JP5077118B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention relates to an electrostatic charge image developing toner used for electrophotographic image formation.

In recent years, an image forming apparatus that forms an image by an electrophotographic method using toner for developing an electrostatic image has been widely used as a copying machine in an office or the like, and can form a high-quality color image particularly at high speed. The color image forming apparatus that can be used is also referred to as a “digital printing machine”, and is suitably used for creating a document on which variable information such as direct mail and a billing statement is to be printed, and further, no printing plate is required. Therefore, it has begun to spread as an alternative to the offset printing press that has been mainly used for commercial printing.
Various image forming apparatuses having new functions have been proposed. Particularly, those having high speed and high function have a high usage rate and a large number of printed sheets. Along with this, the consumption rate of consumables such as toner is increased, and studies for differentiating from others are being actively conducted.

In an image forming apparatus called a digital printing machine, since the formed image itself is a product, there are various demands on the image quality. One of them is the stability of image density and color tone. Can be mentioned. Specifically, for example, when a large number of catalogs and brochures are created, stable image quality cannot be obtained for each of a large number of formed images, and fluctuations in image density and color tone may occur. If there is something wrong, the value of the product will be significantly reduced.
In addition, since a small lot image may be formed, for example, in order to complete image formation in a short period of several days or several hours, a part of the image forming apparatus (specifically, for example, a photosensitive member). It is also desired to shorten the time required for replacement.
Here, in the image forming apparatus, parts that require replacement such as a photosensitive member that contacts the toner are oil-less fixing toner containing a large amount of a release agent in addition to wear and deterioration of charging characteristics in recent years. Is widely used, it is necessary to replace the toner even when filming occurs due to the release of the release agent component from the toner.

  On the other hand, as the electrostatic image developing toner, a so-called “chemical toner” that can obtain an image quality equivalent to an image by offset printing has been proposed (for example, see Patent Documents 1 to 3). It is used.

  However, such chemical toner uses a metal salt as an aggregating agent or the like in its production process (for example, see Patent Document 2), or a titanium catalyst as a catalyst or the like. (For example, refer to Patent Document 3) Metal ions derived from the metal salt or titanium catalyst are present in the toner, and the chargeability of the toner fluctuates due to the hydration of the metal ions. As a result, especially in a high-temperature and high-humidity environment, toner scattering occurs and density stability cannot be obtained in the resulting image. There is a problem that subtle fluctuations in image density due to humidity dependency cannot be suppressed.

JP 2002-148848 A JP 2001-117269 A JP 2007-279653 A

  The present invention has been made based on the above circumstances, and an object thereof is to form an image with stable image quality regardless of an image forming environment and to suppress the occurrence of toner filming. It is an object of the present invention to provide a toner for developing an electrostatic charge.

The electrostatic image developing toner of the present invention contains a resin, a colorant, a release agent and a metal element selected from the group consisting of copper, zinc, titanium, aluminum and calcium in a proportion of 300 ppm to 5000 ppm. In toner for image development,
The release agent comprises a compound having a molecular weight distribution peak value of 400 or more and 1800 or less,
It contains a metal deactivator comprising a compound represented by the following general formula (1).

[Wherein, R ¹ and R ² each represents an alkyl group having 12 or less carbon atoms having a tertiary carbon atom or an arylalkyl group having a tertiary carbon atom, and the other being a tertiary carbon atom. An alkyl group having no atom, an ester residue having an alkyl group having no tertiary carbon atom, a sulfo group or a sulfonic acid group. R ³ represents a hydrogen atom or a chlorine atom. ]

  In the electrostatic image developing toner of the present invention, the release agent is a mixture of a branched paraffin compound and a linear paraffin compound, and preferably has an endothermic peak in the range of 60 to 105 ° C.

According to the toner for developing an electrostatic charge image of the present invention, a specific metal inactive agent is contained, and the metal inactive action of the metal inactive agent based on adsorption to metal ions present in the toner. Therefore, it is possible to suppress a change in the charging characteristics of the toner due to the hydration of metal ions, and the metal deactivator has a metal deactivating action and is dispersed in the toner. Suppressing the occurrence of filming due to the release of the release agent component in the image forming process by improving the adhesion strength between the mold agent phase and the resin phase. Therefore, it is possible to form an image with stable image quality regardless of the image forming environment, and to suppress the occurrence of toner filming.
Therefore, according to the toner for developing an electrostatic charge image of the present invention, it is possible to suppress the occurrence of image contamination due to toner scattering even when an image is formed over a long period of time in a high temperature and high humidity environment. In the forming apparatus, it is possible to reduce the frequency with which replacement of the photosensitive member, the intermediate transfer belt, and the like is required, and the parts that come into contact with the toner due to filming, that is, the replacement cycle can be lengthened. Become.

  The electrostatic image developing toner of the present invention comprises toner particles containing a resin, a colorant, and a release agent. The release agent constituting the toner particles has a molecular weight distribution peak value of 400 to 1800. The toner particles are composed of a compound, and the toner particles contain a metal element selected from the group consisting of copper, zinc, titanium, aluminum, and calcium (hereinafter also referred to as “specific metal element”) at a ratio of 300 to 5000 ppm. And a metal deactivator comprising a compound represented by the general formula (1) (hereinafter also referred to as “specific benzotriazole compound”).

In the general formula (1) showing the specific benzotriazole compound constituting the metal deactivator relating to the electrostatic image developing toner of the present invention, either one of R ¹ and R ² has a tertiary carbon atom. An ester residue having an alkyl group having 12 or less carbon atoms or an arylalkyl group having a tertiary carbon atom, the other having an alkyl group having no tertiary carbon atom or an alkyl group having no tertiary carbon atom A group (hereinafter also referred to as “specific esterified alkyl group”), a sulfo group or a sulfonic acid group;

Examples of the alkyl group having 12 or less carbon atoms having a tertiary carbon atom representing the group R ¹ or R ² include a tert-butyl group, a 1,1-dimethyldecyl group, a tert-octyl group, a neopentyl group, 2, 2-dimethylhexyl group, 2,2-dimethyloctyl group, 2,2-dimethyldecyl group, —C (CH ₃ ) ₂ C ₆ H ₁₁ group and the like can be mentioned.
Examples of the arylalkyl group having a tertiary carbon atom representing the group R ¹ or the group R ² include a —C (CH ₃ ) ₂ C ₆ H ₅ group.

Examples of the alkyl group having no tertiary carbon atom that represents the group R ¹ or R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a sec-butyl group, a 2-ethylhexyl group, 2, 4-dimethylhexyl group, dodecyl group, etc. are mentioned.
Specific esterified alkyl groups representing the group R ¹ or R ² include, for example, —CH ₂ CH ₂ COOCH ₃ group, —CH ₂ CH ₂ COOC ₈ H ₁₇ group, —CH ₂ COOCH ₃ group, —CH ₂ COO ( CH ₂ ) ₃ CH ₃ group and the like.
Examples of the sulfonic acid group representing the group R ¹ or the group R ² include —SO ₃ Na group and —SO ₃ H group.

In the general formula (1), R ³ represents a hydrogen atom or a chlorine atom.

Preferable specific examples of the specific benzotriazole compound constituting the metal deactivator represented by the general formula (1) include the following compounds (1-1) to (1-6).
Among these, the compounds (1-1) and (1-3) are particularly preferable.

(1-1) Compound wherein R ¹ is a tert-butyl group, R ² is a methyl group, and R ³ is a chlorine atom (1-2) R ¹ is a —C (CH ₃ ) ₂ C ₉ H ₁₉ group, R ² (1-3) wherein R ³ is a hydrogen atom, R ¹ is a tert-butyl group, R ² is a —CH ₂ CH ₂ COOCH ₃ group, and R ³ is a chlorine atom (1-4) R ¹ is tert- butyl group, R ² is -CH ₂ CH ₂ COOC ₈ H ₁₇ group, and R ³ is a chlorine atom (1-5) wherein R ¹ is tert- butyl group, R ² is -SO ₃ Na A compound in which R ³ is a hydrogen atom (1-6) a compound in which R ¹ is a sec-butyl group, R ² is a -tert-butyl group, and R ³ is a hydrogen atom

  The content ratio of the metal deactivator in the toner for developing an electrostatic charge image of the present invention is preferably 0.5 to 5% by mass, and particularly preferably 1 to 3% by mass with respect to the whole toner.

If the content of the metal deactivator is excessive, good low-temperature fixability may not be obtained.
On the other hand, if the content of the metal deactivator is too small, the effect of suppressing the occurrence of toner filming may not be exhibited.

The release agent constituting the toner for developing an electrostatic charge image of the present invention is required to be composed of a compound having a molecular weight distribution peak value in the range of 400 or more and 1800 or less. It is preferable that it consists of a compound which exists in the range of 400-1400.
Here, the peak value of the molecular weight distribution relating to the release agent can be measured by gel permeation chromatography (Gel Permeation Chromatography) under the following measurement conditions. In particular, when detecting from the toner, first, the THF (tetrahydrofuran) soluble content of the toner is obtained, and after confirming that the fraction is a release agent, the molecular weight distribution of the compounds constituting the release agent The maximum value is selected, and the maximum value is taken as the “peak value of the molecular weight distribution of the compound constituting the release agent”.
(Measurement condition)
Column: Tosoh Corporation TSKgel G200HXL (exclusion limit molecular weight 1 × 10 ⁴ ) × 3, 40 ° C.
Eluent: THF 1.0 (ml / min)
Detection: RI
Injection volume: 100 μl
Calibration curve: standard polystyrene, n-hexylbenzene

When the peak value of the molecular weight distribution of the compound constituting the release agent is less than 400, the release agent component is volatilized in the fixing device in the fixing step related to the image forming process, thereby constituting the image forming apparatus. Stable image quality cannot be obtained due to contamination of the optical system member.
On the other hand, when the peak value of the molecular weight distribution of the compound constituting the release agent exceeds 1800, the melt viscosity is not sufficiently lowered, and as a result, the release agent supply for applying silicone oil to the image forming apparatus is performed. It will be necessary to provide means.

  Further, the compound constituting the release agent has an endothermic peak, that is, an endothermic main peak value in a DSC endothermic curve within a range of 60 to 105 ° C., from the viewpoint of preventing gloss uniformity and toner filming. It is preferable that it has in the range of 70-90 degreeC. Moreover, it is preferable that the compound which comprises a mold release agent is a thing whose tangential separation temperature in a DSC endothermic curve is 40 degreeC or more.

Preferable specific examples of the release agent include those obtained by mixing a branched paraffin compound and a linear paraffin compound.
In the mixture of the branched paraffin compound and the linear paraffin compound, the mixing ratio (branched paraffin compound: linear paraffin compound) is 10: 1 from the viewpoint of preventing gloss uniformity and toner filming. It is preferable that it is 90-30: 70 (mass ratio).
Here, the mixing ratio of the branched paraffin compound and the linear paraffin compound can be confirmed by C ¹³ NMR measurement.

  In addition to the mixture of the branched paraffin compound and the linear paraffin compound, as the mold release agent, for example, synthetic ester wax such as behenyl behenate, stearyl stearate, glycerin tribehenate ester, tribehenate citrate, carnauba wax, Natural waxes such as rice wax and candelilla wax can be used.

  The content of the release agent in the toner for developing an electrostatic charge image of the present invention is preferably 2 to 25% by mass, particularly 4 to 16% by mass, based on the whole toner.

  The toner for developing an electrostatic charge image of the present invention contains a specific metal element selected from the group consisting of copper, zinc, titanium, aluminum and calcium, and the content ratio is preferably 300 ppm or more and 5000 ppm or less. Is 600 ppm or more and 1800 ppm or less.

The specific metal element is derived from the toner constituent material and the additive compound used in the toner manufacturing process. As a preferred specific example of the presence state, the specific metal element in the resin constituting the toner particle as a metal ion or the like is used. In a dispersed state.
Specific examples of the toner constituent materials and additives that cause the specific metal element to be introduced are shown in (1) to (5) below.

(1) When the specific metal element is copper, its presence is derived from a metal-containing compound used as a toner constituent material.
(2) When the specific metal element is zinc, its presence is derived from a metal cross-linking agent, a dispersion stabilizer or a flocculant used for obtaining a resin.
(3) When the specific metal element is titanium, its presence is derived from a catalyst used in a reaction system for obtaining a resin.
(4) When the specific metal element is aluminum, its presence is derived from a dispersion stabilizer or a flocculant.
(5) When the specific metal element is calcium, its presence is derived from a dispersion stabilizer and a flocculant.

  The content ratio of the specific metal element in the toner for developing an electrostatic charge image of the present invention can be measured by atomic absorption spectrometry.

  When the content ratio of the specific metal element is excessive, the function of the metal deactivator made of the specific benzotriazole compound may not be sufficiently exhibited.

The resin constituting the electrostatic image developing toner of the present invention is not particularly limited, and various resins can be used.
Specific examples of such resins include styrene resins, acrylic resins such as alkyl acrylates and alkyl methacrylates, vinyl polymers such as styrene-acrylic copolymer resins, olefin resins, polyester resins, and epoxy resins. In particular, in order to improve transparency and color reproducibility of a superimposed image, a styrene resin or an acrylic resin having high transparency, low melting property, and high sharp melt property is preferable. Can be mentioned. These can be used alone or in combination of two or more.

  Further, as a polymerizable monomer for obtaining a resin, for example, a styrene monomer such as styrene, methyl styrene, methoxy styrene, butyl styrene, phenyl styrene; methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid (Meth) acrylic acid ester monomers such as ethylhexyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and ethylhexyl methacrylate; carboxylic acid monomers such as acrylic acid and fumaric acid can be used. . These can be used alone or in combination of two or more.

  Further, as the colorant constituting the toner for developing an electrostatic charge image of the present invention, it is preferable to use a colorant composed of a compound represented by the following general formula (2).

[Wherein, R ⁴ independently represents a hydrogen atom, a halogen atom or a monovalent organic group, R ⁵ represents a —NR ⁷ R ⁸ group (provided that R ⁷ and R ⁸ independently represent hydrogen An atom, a halogen atom or a monovalent organic group) or —OR ⁹ group (wherein R ⁹ independently represents a hydrogen atom, a halogen atom or a monovalent organic group), and R ⁶ Represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an amide group, an alkylsulfonylamino group or an arylsulfonylamino group, and A ^{1 to} A ^{3 each} independently represents —CR ¹⁰ = group (provided that R ¹⁰ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group.) Or —N = group, and X ¹ forms a 5-membered or 6-membered aromatic ring or heterocyclic ring. represents an atomic group necessary, Z ¹ is less Represents an atomic group necessary for forming a 5-membered or 6-membered heterocyclic ring containing one nitrogen atom, and this atomic group may be unsubstituted or substituted, and may be condensed by the substituent. A ring may be formed. L ¹ represents a linking group having 1 or 2 carbon atoms or a part of a ring structure, and may be bonded to R ⁶ to form a 5-membered or 6-membered ring structure. p is an integer of 0-3. ]

In the general formula (2), R ⁴ represents a hydrogen atom, a halogen atom or a monovalent organic group. The group R ⁴ may be an independent group when p is 2 or 3.

Examples of the halogen atom representing the group R ⁴ include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the monovalent organic group representing the group R ⁴ include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group). Group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), aryl group (for example, vinyl group, allyl group, etc.), alkenyl group (for example, ethynyl group, propargyl group, etc.), alkynyl group ( For example, phenyl group, naphthyl group, etc.), heteroaryl group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyridyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group) Group, quinazolyl group, phthalazyl group, etc.), Telocyclic group (eg pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.) , Cycloalkoxy groups (eg cyclopentyloxy group, cyclohexyloxy group etc.), aryloxy groups (eg phenoxy group, naphthyloxy group etc.), alkylthio groups (eg methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group) Octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyl) Oxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl) Group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylamino Sulfonyl group, etc.), acyl group (eg acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexyl) Rubonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octyl) Carbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, trifluoromethylcarbonylamino group, phenyl Carbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group) , Dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dresylureido group) Phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfide group) Nyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-methylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group) Cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (eg phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group etc.), amino group (eg amino group, ethylamino group, dimethyl) Amino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group and Such as the Toro group, and the like.

In the general formula (2), R ⁵ is -NR ⁷ R ⁸ group (. However, R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom or a monovalent organic group) or - OR ⁹ group (where R ⁹ represents a hydrogen atom, a halogen atom or a monovalent organic group).
This group R ⁵ is preferably a —NR ⁷ R ⁸ group from the viewpoint of the molar extinction coefficient ε, and is preferably a —OR ⁹ group from the viewpoint of wavelength adjustment.

As the halogen atom shown an R ⁹ in R ⁷ and R ^8, and -OR ⁹ groups in -NR ⁷ R ⁸ groups according to the group R ^5, a fluorine atom, a chlorine atom and a bromine atom.
R ⁷ and R ⁸ in -NR ⁷ R ⁸ groups according to the group R ^5, and examples of the monovalent organic group represented by R ⁹ in the -OR ⁹ group, those exemplified as the monovalent organic group represented by group R ⁴ Is mentioned.
These groups R ^{7 to} R ⁹ are each preferably a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group and a heterocyclic group, and particularly a hydrogen atom, an alkyl group, an aryl group and an acyl group. Preferably there is.

In the general formula (2), R ⁶ represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an amide group, an alkylsulfonylamino group or an arylsulfonylamino group.
This group R ⁶ is preferably a hydroxyl group, an alkoxy group, an amino group, an amide group and an alkylsulfonyl group.

Examples of the alkoxy group, aryloxy group, amino group, alkylsulfonylamino group and arylsulfonylamino group representing the group R ⁶ include those exemplified as one type of monovalent organic group representing the group R ⁴ .

In the general formula (2), A ^{1 to} A ^{3 each} independently represent —CR ¹⁰ = group (where R ¹⁰ represents a hydrogen atom, a halogen atom or a monovalent organic group) or — N = group.
The group A ¹ and the group A ² are each preferably —CR ¹⁰ = group.

Examples of the monovalent organic group representing R ¹⁰ in —CR ¹⁰ = group related to the groups A ¹ to A ³ include those exemplified as the monovalent organic group representing the group R ⁴ .
The group R ¹⁰ is preferably a hydrogen atom, a halogen atom and an alkoxycarbonyl group, and particularly preferably a hydrogen atom.

In the general formula (2), X ¹ represents an atomic group necessary for forming a 5-membered or 6-membered aromatic ring or heterocyclic ring.

The 5-membered or 6-membered aromatic ring or heterocyclic ring formed by the atomic group representing the group X ¹ includes benzene ring, naphthalene ring, pyridine ring, pyrazine ring, furan ring, thiophene ring, imidazole ring, thiazole ring And preferred are a benzene ring, a pyridine ring and a thiophene ring.

In the general formula (2), L ¹ represents a part of a linking group having 1 or 2 carbon atoms or a ring structure.
A part of the linking group and the ring structure may be bonded to the group R ⁶ to form a 5-membered or 6-membered ring structure.

Examples of the linking group having 1 or 2 carbon atoms representing the group L ¹ include a methylene group, an ethylene group and an ethyne group which are unsubstituted or have a substituent.
As the part of the ring structure showing the group L ^1, include groups represented by the following general formula (3).

[In the formula, Z ² represents a 5-membered or 6-membered aromatic ring or heterocyclic ring, and is bonded to Z ¹ in the general formula (2) by one bond and represented by the general formula (2) by the other bond. It binds to R ^{6 in} ]

In this general formula (3), Z ² represents a 5-membered or 6-membered aromatic ring or heterocyclic ring, and these aromatic ring and heterocyclic ring have a substituent even if they are unsubstituted. There may be.
Examples of the substituent include a halogen atom, an alkoxy group, an amino group, an acylamino group, a sulfonylamino group, and a ureido group, and a halogen atom, an alkoxy group, an amino group, and an acylamino group are preferable.
Moreover, it is also preferable to have a group capable of coordinating to a metal atom as a substituent. The group capable of coordinating to the metal atom is a substituent containing an atom having an unshared electron pair, and specifically includes a heterocyclic group, a hydroxy group, a carbonyl group, an oxycarbonyl group, a carbamoyl group, an alkoxy group. Group, heterocyclic oxy group, carbonyloxy group, urethane group, sulfonyloxy group, amino group, imino group, sulfonylamino group, sulfamoylamino group, acylamino group, ureido group, sulfonyl group, sulfamoyl group, alkylthio group, arylthio Group, and heterocyclic thio group, preferably hydroxy group, carbonyl group, oxycarbonyl group, carbamoyl group, alkoxy group, carbonyloxy group, urethane group, sulfonyloxy group, amino group, imino group, sulfonylamino group, acylamino group , Ureido group, alkylthio group and aryl An O group, particularly preferably a hydroxy group, a carbonyl group, a carbamoyl group, an alkoxy group, a sulfonylamino group and an acylamino group.

In the general formula (2), Z ¹ represents an atomic group necessary for forming a 5-membered or 6-membered heterocyclic ring containing at least one nitrogen atom.
The atomic group representing the group Z ¹ may be unsubstituted or substituted, and the substituent may form a condensed ring.

The 5- or 6-membered heterocyclic ring containing at least one nitrogen atom formed by the atomic group representing the group Z ¹ includes a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazole ring, an imidazole ring, a pyrrole ring and a pyrazolidine. Examples include rings (for example, rings derived from pyrazolidine-3,5-dione), those having a substituent on these rings, and those having a condensed ring formed by this substituent.
Preferable specific examples of this group Z ¹ include groups represented by the following general formulas (4) to (9).

[In General Formula (4) and General Formula (5), R ¹¹ and R ¹³ each represent a hydrogen atom, a halogen atom or a monovalent organic group, and R ¹² and R ¹⁴ represent a hydroxyl group, an alkoxy group, an aryl group. An oxy group, an amino group, an amide group, an alkylsulfonylamino group, or an arylsulfonylamino group; L ² and L ^{3 each} represent a linking group having 1 or 2 carbon atoms or a part of a ring structure; ) At the site indicated by A ¹ and *.
In the general formula (6), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, and R ¹⁷ represents a hydroxyl group, an alkoxy group, an aryloxy group or an amino group. Represents an amide group, an alkylsulfonylamino group or an arylsulfonylamino group. L ⁴ represents a part of a linking group having 1 or 2 carbon atoms or a ring structure, and is bonded at a site indicated by A ¹ and * in the general formula (2).
In the general formula (7), R ¹⁸ represents a hydrogen atom, a halogen atom or a monovalent organic group, and R ¹⁹ represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an amide group, an alkylsulfonylamino group. Or an arylsulfonylamino group; L ⁵ represents a linking group having 1 or 2 carbon atoms or a part of the ring structure, and is bonded at the site indicated by A ¹ and * in the general formula (2).
In the general formula (8), R ²⁰ and R ²¹ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, and R ²² represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, An amide group, an alkylsulfonylamino group or an arylsulfonylamino group; L ⁶ represents a part of a linking group having 1 or 2 carbon atoms or a ring structure, and is bonded at a site indicated by A ¹ and * in the general formula (2).
In the general formula (9), R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, and R ²⁵ represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, An amide group, an alkylsulfonylamino group or an arylsulfonylamino group; L ⁷ represents a linking group having 1 or 2 carbon atoms or a part of the ring structure, and is bonded at the site indicated by A ¹ and * in the general formula (2). ]

In the general formula (4) and general formula (5), examples of the monovalent organic group representing R ¹¹ and R ¹³ are those exemplified as the monovalent organic group representing R ⁴ in the general formula (2). Is mentioned.
The groups R ¹¹ and R ¹³ are each a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group. Group, aryloxy group, ureido group, alkoxycarbonylamino group, carbamoyl group, carboxyl group or alkoxycarbonyl group, more preferably alkyl group, carboxyl group, alkoxyl group and carbamoyl group, particularly preferably An alkyl group (particularly a methyl group, a tert-butyl group, a trifluoromethyl group), a carbamoyl group, and an alkoxycarbonyl group.

In the general formula (4) and the general formula (5), R ¹² and R ¹⁴ are respectively synonymous with R ⁶ in the general formula (2), and preferred groups are also synonymous.

In general formula (4) and general formula (5), L ² and L ³ are each the same meaning as L ¹ in the general formula (2), which is also synonymous the preferred group.

In the general formula (6) and general formula (7), as the monovalent organic group representing R ¹⁵ , R ¹⁶ and R ¹⁸ , respectively, as the monovalent organic group representing R ⁴ in the general formula (2) What was illustrated can be mentioned.
This group R ¹⁵ is preferably a hydrogen atom, alkyl group, aryl group, heterocyclic group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, sulfamoyl group, alkylsulfonyl group or arylsulfonyl group, More preferred are an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, and a cyano group.
The group R ¹⁶ is preferably a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, an alkoxycarbonyl group, an amino group, an alkylthio group, or an arylthio group, more preferably a hydrogen atom, a halogen atom, an alkyl group, or an acylamino group. It is a group.
The group R ¹⁸ is a hydrogen atom, alkyl group, aryl group, heterocyclic group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxyl group, aryloxy group, ureido Group, an alkoxycarbonylamino group, an acyl group, an alkoxycarbonyl group or a carbamoyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group or an alkoxy group.

In the general formula (6) and the general formula (7), R ¹⁷ and R ¹⁹ are respectively synonymous with R ⁶ in the general formula (2), and preferred groups are also synonymous.

In the general formula (6) and the general formula (7), L ⁴ and L ⁵ each has the same meaning as L ¹ in the general formula (2), which is also synonymous the preferred group.

In the general formula (8) and the general formula (9), the monovalent organic group representing R ²⁰ , R ²¹ , R ²³ and R ²⁴ is a monovalent organic group representing R ⁴ in the general formula (2). What was illustrated as an organic group can be mentioned.
The group R ²⁰ and the group R ²¹ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxyl group, a cyano group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group. Group or a nitro group, more preferably an alkoxycarbonyl group or a cyano group.

The group R ²³ is a hydrogen atom, alkyl group, aryl group, heterocyclic group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxyl group, aryloxy group, ureido Group, alkoxycarbonylamino group, acyl group, carboxyl group, alkoxycarbonyl group or carbamoyl group, more preferably a hydrogen atom, alkyl group, aryl group, acyl group, acylamino group, alkoxycarbonyl group or carbamoyl group. It is.

In the general formula (8) and general formula (9), R ²² and R ²⁵ are each the same meaning as R ⁶ in the general formula (2), which is also synonymous the preferred group.

In the general formula (8) and general formula (9), L ⁶ and L ⁷ are each the same meaning as L ¹ in the general formula (2), which is also synonymous the preferred group.

Specific examples of the compound represented by the general formula (2) include compounds represented by the following formulas (2-1) to (2-13).
Here, the compounds represented by (2-1) to (2-7), (2-10), (2-12) and (2-13) are each a 5-membered ring containing a nitrogen atom ( A trans isomer may be mixed in addition to a cis isomer related to a C═C double bond portion bonded to (including a ring constituting a polycyclic system).

  When the compound represented by the general formula (2) having such a structure is used as a colorant, it is preferable to use a metal-containing compound as a colorant.

In addition to the compound represented by the general formula (2), a known inorganic or organic colorant can also be used as the colorant constituting the electrostatic image developing toner of the present invention. Specific colorants are shown below.
Examples of the black colorant include carbon black such as furnace black, channel black, acetylene black, thermal black and lamp black, and magnetic powder such as magnetite and ferrite.
Examples of the colorant for magenta include C.I. I. Solvent Red 1, C.I. I. Solvent Red 3, C.I. I. Solvent Red 8, C.I. I. Solvent Red 23, C.I. I. Solvent Red 24, C.I. I. Solvent Red 25, C.I. I. Solvent Red 27, C.I. I. Solvent Red 30, C.I. I. Solvent Red 49, C.I. I. Solvent Red 52, C.I. I. Solvent Red 58, C.I. I. Solvent Red 63, C.I. I. Solvent Red 81, C.I. I. Solvent Red 82, C.I. I. Solvent Red 83, C.I. I. Solvent Red 84, C.I. I. Solvent Red 100, C.I. I. Solvent Red 109, C.I. I. Solvent Red 111, C.I. I. Solvent Red 121, C.I. I. Solvent Red 122, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, C.I. I. Solvent Violet 13, C.I. I. Solvent Violet 14, C.I. I. Solvent Violet 21, C.I. I. Solvent violet 27,
C. I. Oil-soluble dyes such as Disperse Violet 1; I. Basic Red 1, C.I. I. Basic Red 2, C.I. I. Basic Red 9, C.I. I. Basic Red 12, C.I. I. Basic Red 13, C.I. I. Basic Red 14, C.I. I. Basic Red 15, C.I. I. Basic Red 17, C.I. I. Basic Red 18, C.I. I. Basic Red 22, C.I. I. Basic Red 23, C.I. I. Basic Red 24, C.I. I. Basic Red 27, C.I. I. Basic Red 29, C.I. I. Basic Red 32, C.I. I. Basic Red 34, C.I. I. Basic Red 35, C.I. I. Basic Red 36, C.I. I. Basic Red 37, C.I. I. Basic Red 38, C.I. I. Basic Red 39, C.I. I. Basic Red 40, C.I. I. Basic Violet 1, C.I. I. Basic Violet 3, C.I. I. Basic Violet 7, C.I. I. Basic Violet 10, C.I. I. Basic Violet 14, C.I. I. Basic Violet 15, C.I. I. Basic Violet 21, C.I. I. Basic Violet 25, C.I. I. Basic Violet 26, C.I. I. Basic Violet 27, C.I. I. And basic dyes such as basic violet 28.
These dyes can be used alone or in combination with a pigment. Examples of the colorant for orange or yellow include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 68, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, and the like.
Examples of the colorant for cyan include pigments and C.I. I. Solvent Blue 25, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 60, C.I. I. Solvent Blue 70, C.I. I. Solvent Blue 93, C.I. I. And dyes such as Solvent Blue 95.
These can be used alone or in combination with a pigment and a dye.

The above colorants can be used alone or in combination of two or more.
The addition amount of the colorant is in the range of 1 to 30% by mass, preferably 2 to 20% by mass with respect to the whole toner.

  As the colorant, a surface-modified one can also be used. As the surface modifier, conventionally known ones can be used, and specifically, silane coupling agents, titanium coupling agents, aluminum coupling agents and the like can be preferably used.

  The toner for developing an electrostatic charge image of the present invention may contain an internal additive such as a charge control agent in addition to a resin, a colorant, a release agent, a specific metal element and a metal deactivator.

The toner for developing an electrostatic charge image of the present invention may be composed only of toner particles, but as an external additive (external additive), inorganic fine particles having a number average primary particle diameter of 4 to 800 nm or Particles such as organic fine particles or a structure in which a lubricant is added to colored particles may be used.
By adding an external additive, fluidity and chargeability are improved, and cleaning properties and transfer properties are improved.

  As the inorganic fine particles, conventionally known ones can be used. For example, silica fine particles, titania fine particles, alumina fine particles, strontium titanate fine particles and the like can be suitably used. Moreover, what hydrophobized these inorganic fine particles can also be used.

Specific examples of the silica fine particles include, for example, “R-805”, “R-976”, “R-974”, “R-972”, “R-812”, “R-809” manufactured by Nippon Aerosil Co., Ltd .; "HVK-2150", "H-200" manufactured by Hoechst, "TS-720", "TS-530", "TS-610", "H-5", "MS-5" manufactured by Cabot Is mentioned.
Specific examples of the titania fine particles include “T-805” and “T-604” manufactured by Nippon Aerosil Co., Ltd .; “MT-600S”, “MT-100B”, “MT-500BS”, “MT” manufactured by Teica. -600 "," MT-600SS "," JA-1 ";" TA-300SI "," TA-500 "," TAF-130 "," TAF-510 "," TAF-510T "manufactured by Fuji Titanium ; “IT-S”, “IT-OA”, “IT-OB”, “IT-OC” manufactured by Idemitsu Kosan Co., Ltd.
Specific examples of the alumina fine particles include “RFY-C” and “C-604” manufactured by Nippon Aerosil Co., Ltd. and “TTO-55” manufactured by Ishihara Sangyo Co., Ltd.

  As the organic fine particles, spherical particles having a number average primary particle diameter of 10 to 2000 nm can be used. Specific examples include homopolymers such as styrene and methyl methacrylate and copolymers thereof. It is done.

  As the lubricant, metal salts of higher fatty acids can be used. Specifically, salts of zinc stearate, aluminum, copper, magnesium, calcium, etc .; zinc oleate, manganese, iron, copper, magnesium, etc. Salts: salts of palmitic acid zinc, copper, magnesium, calcium, etc .; zincs of linoleic acid, salts of calcium, etc .; salts of ricinoleic acid zinc, calcium, etc.

  The addition amount of the external additive is preferably 0.1 to 10.0% by mass in the whole toner.

  In the method of adding the external additive, various known mixing apparatuses such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer can be used.

  The electrostatic image developing toner of the present invention can be used as a magnetic or non-magnetic one-component developer, but can also be mixed with a carrier and used as a two-component developer.

  In the case where the toner for developing an electrostatic charge image according to the present invention is used as a two-component developer, the carrier is conventionally a metal such as iron, ferrite, or magnetite, or an alloy of such a metal with a metal such as aluminum or lead. From the above, magnetic particles made of a known material can be used, and ferrite particles are particularly preferable. The carrier preferably has a volume average particle diameter of 15 to 100 μm, particularly preferably 25 to 80 μm.

  Further, when used as a non-magnetic one-component developer, since the toner constituting the developer is charged by being rubbed and pressed against the charging member or the developing roller surface, the developing device Therefore, the entire image forming apparatus can be made compact, so that it is possible to form a full-color image having excellent color reproducibility even in a space-limited work environment. .

The electrostatic image developing toner of the present invention can be produced by a conventionally known method.
That is, a pulverization method that goes through a kneading step, a pulverization step and a classification step in this order, a so-called polymerization method in which a polymerizable monomer is polymerized and particles are formed while controlling the shape and size in the polymerization step (specifically, For example, an emulsion polymerization method, a suspension polymerization method, a polyester elongation method, or the like can be used.

According to the electrostatic image developing toner of the present invention as described above, a metal used as a raw material for producing a metal catalyst such as a flocculant, a metal catalyst such as a titanium catalyst, or a colorant used in the production process. A metal deactivator comprising a specific benzotriazole compound, even if a metal ion derived from an atom-containing compound exists and the metal ion hydrates adversely affects the charging characteristics of the toner. Due to the metal deactivation effect of this metal deactivator based on the adsorption to the metal ions present in the toner, the charging characteristics of the toner change as the metal ions hydrate. The generation of the metal deactivator can be distributed between the dispersed release agent phase and the resin phase in the toner. Thus, the adhesion improving effect that increases the adhesive strength can suppress the occurrence of filming due to the release of the release agent component in the image forming process, so that it can be performed regardless of the image forming environment. An image with stable image quality can be formed and toner filming can be suppressed.
Therefore, according to the toner for developing an electrostatic charge image of the present invention, it is possible to suppress the occurrence of image contamination due to toner scattering even when an image is formed over a long period of time in a high temperature and high humidity environment. In the forming apparatus, it is possible to reduce the frequency with which replacement of the photosensitive member, the intermediate transfer belt, and the like is required, and the parts that come into contact with the toner due to filming, that is, the replacement cycle can be lengthened. Become.

Here, the reason why the metal deactivator made of a specific benzotriazole compound has a metal inactive action is that the lone pair of nitrogen atoms constituting the specific benzotriazole compound is an electron orbit of a specific metal element (metal ion) ( d orbital), and is considered to exert an adhesive force. The specific benzotriazole compound has an alkyl group having no tertiary carbon atom, a specific esterified alkyl group, a sulfo group or a sulfone. The acid group (the group represented by either R ¹ or R ² in the general formula (1)) enhances the dispersibility and mobility of the specific benzotriazole compound in the resin, whereby the specific benzotriazole compound Resulting in good contact with the specific metal element (metal ion), It is assumed that fluctuations in the charging characteristics of the toner are suppressed.
The reason why the metal deactivator has an adhesion improving action is that the specific benzotriazole compound has an alkyl group having 12 or less carbon atoms having a tertiary carbon atom or an arylalkyl group having a tertiary carbon atom ( The group represented by the other of R ^{1 and} R ² in the general formula (1) is presumed to be for increasing the adhesive force between the release agent domain and the resin.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

[Toner Production Example 1 (Production Example of Toner Containing Copper as Specific Metal Element)]
(1) Preparation Example 1 of Colorant Fine Particle Dispersion
A surfactant aqueous solution was prepared by stirring and dissolving 11.5 parts by mass of sodium n-dodecyl sulfate in 160 parts by mass of ion-exchanged water. To this surfactant aqueous solution, 2 parts by mass of the compound represented by the formula (2-13) is gradually added as a colorant, and then “Cleamix W Motion CLM-0.8” (manufactured by M Technique Co., Ltd.) is added. By using and dispersing, a colorant fine particle dispersion in which colorant fine particles are dispersed (hereinafter referred to as “colorant fine particle dispersion (1)”) was prepared.
With respect to the particle diameter of the colorant fine particles in this colorant fine particle dispersion (1), the volume-based median diameter was measured and found to be 221 nm.
The volume-based median diameter is “MICROTRAC UPA 150” (manufactured by HONEYWELL), sample refractive index 1.59, sample specific gravity 1.05 (in terms of spherical particles), solvent refractive index 1.33, solvent viscosity 0 Measurement was performed by adjusting the zero point by introducing ion-exchanged water into the measurement cell under the measurement conditions of .797 (30 ° C.) and 1.002 (20 ° C.).

(2) Preparation Example 1 of metal-containing compound fine particle dispersion
In Preparation Example 1 of the colorant fine particle dispersion, the colorant fine particle dispersion was used except that 8 parts by mass of a compound represented by the following chemical formula (A) containing a copper element as a metal-containing compound was used instead of the colorant. A metal-containing compound fine particle dispersion in which metal-containing compound fine particles are dispersed (hereinafter referred to as “metal-containing compound fine particle dispersion (1)”) was prepared by the same method as in Preparation Example 1.
With respect to the particle diameter of the metal-containing compound fine particles in this metal-containing compound fine particle dispersion (1), the volume-based median diameter was measured by the same method as in Preparation Example 1 of the colorant fine particle dispersion, and found to be 987 nm.

(3) Preparation Example of Core Part Resin Particles (a) First-stage polymerization (formation of core particles)
Anionic surfactant 4 made of sodium dodecyl sulfate (C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ SO ₃ Na) in a 5 L reaction vessel equipped with a stirrer, temperature sensor, condenser, and nitrogen introducing device A surfactant aqueous solution having mass parts dissolved in 3040 mass parts of ion-exchanged water is charged, and while stirring at a stirring speed of 230 rpm under a nitrogen stream, the internal temperature is raised to 80 ° C., and potassium persulfate (KPS) 10 masses. After adding a polymerization initiator solution in which 400 parts by mass of ion-exchanged water are dissolved and raising the liquid temperature to 75 ° C., 532 parts by mass of styrene, 200 parts by mass of n-butyl acrylate, 68 parts by mass of methacrylic acid And a polymerizable monomer solution consisting of 16.4 parts by mass of n-octyl mercaptan was added dropwise over 1 hour, followed by heating and stirring at 75 ° C. for 2 hours for polymerization (first Polymerization was conducted), the resin particle dispersion containing resin particles (1h) to (1H) was prepared.
The obtained resin particles (1h) had a weight average molecular weight of 16,500.

(B) Second stage polymerization (formation of intermediate layer)
Illustrated as 101.1 parts by weight of styrene, 62.2 parts by weight of n-butyl acrylate, 12.3 parts by weight of methacrylic acid, 1.75 parts by weight of n-octyl mercaptan and metal deactivator in a flask equipped with a stirrer A polymerizable monomer solution containing 30 parts by mass of the compound (1-1) is charged, and then a mixture of a branched paraffin compound and a linear paraffin compound as a release agent. The endothermic peak is 81 ° C. and the molecular weight distribution peak. 93.8 parts by weight of paraffin wax (hereinafter also referred to as “release agent compound (A)”) having a value of 910 and a mixing ratio (branched paraffin compound: linear paraffin compound) of 19:81 was added. A monomer solution containing a release agent was prepared by heating to 80 ° C. and dissolving.
Here, in the release agent compound (A), the endothermic peak is confirmed by DSC measurement, the peak value of the molecular weight distribution is confirmed by gel permeation chromatography measurement, and the mixing ratio of the branched paraffin compound and the linear paraffin compound is C ^It was confirmed by ¹³ NMR measurement. In the following, the endothermic peak, the peak value of the molecular weight distribution, and the mixing ratio of the compound relating to the release agent are measured by the same method.

On the other hand, a surfactant aqueous solution in which 3 parts by mass of the anionic surfactant used in the first stage polymerization was dissolved in 1560 parts by mass of ion-exchanged water was charged and heated so that the internal temperature became 80 ° C. After adding 32.8 parts by mass (in terms of solid content) of resin particles (1h) obtained in the first-stage polymerization to this surfactant aqueous solution, and further adding a monomer solution containing a release agent An emulsified particle dispersion containing emulsified particles (oil droplets) having a dispersed particle diameter of 340 nm by mixing and dispersing for 8 hours using a mechanical disperser “CLEAMIX” (manufactured by M Technique Co., Ltd.) having a circulation path Was prepared.
Next, a polymerization initiator solution in which 6 parts by mass of potassium persulfate was dissolved in 200 parts by mass of ion-exchanged water was added to this dispersion, and the system was polymerized by heating and stirring at 80 ° C. for 3 hours. Two-stage polymerization) was performed to prepare a resin particle dispersion (1HM) containing resin particles (1 hm).
In addition, the weight average molecular weight of the obtained resin particle (1 hm) was 23000.

(C) Third stage polymerization (formation of outer layer)
A polymerization initiator solution in which 5.45 parts by mass of potassium persulfate was dissolved in 220 parts by mass of ion-exchanged water as a polymerization initiator was added to the resin particle dispersion (1HM) obtained in the second stage polymerization, and 80 ° C. The polymerizable monomer solution consisting of 293.8 parts by mass of styrene, 154.1 parts by mass of n-butyl acrylate and 7.08 parts by mass of n-octyl mercaptan was added dropwise over 1 hour. After completion of the dropwise addition, polymerization (third stage polymerization) was performed by heating and stirring for 2 hours, followed by cooling to 28 ° C. to obtain a resin particle dispersion containing the core part resin particles (1).
The weight average molecular weight of the obtained resin particles for core part (1) was 26800, and the glass transition temperature (Tg) was 28.1 ° C.
In addition, it was 125 nm when the mass mean particle diameter of the resin particle for core parts (1) in this resin particle dispersion was measured.

(4) Preparation Example of Resin Particles for Shell Layer In the first-stage polymerization, 624 parts by mass of styrene, 120 parts by mass of 2-ethylhexyl acrylate, 56 parts by mass of methacrylic acid, and n-octyl mercaptan are used as the polymerizable monomer. Polymerization was carried out in the same manner as in the first-stage polymerization except that 16.4 parts by mass were used, thereby obtaining resin particles (1) for shell layer.
The weight average molecular weight of the obtained resin particles for shell layer (1) was 16400, and the glass transition temperature (Tg) was 62.6 ° C.
In addition, it was 95 nm when the mass mean particle diameter of the resin particle (1) for shell layers in this resin particle dispersion was measured.

(5) Preparation Example of Toner Particles (a) Formation of Core Portion Resin particle for core portion (1) 420.7 parts by mass, ion exchange in a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introducing device 900 parts by mass of water, 12.9 parts by mass of the colorant fine particle dispersion (1) (in terms of solid content) and 12.8 parts by mass of the metal-containing compound fine particle dispersion (1) (in terms of solid content) were charged and stirred. After adjusting the temperature to 30 ° C., the pH was adjusted to 10.0 by adding an aqueous sodium hydroxide solution having a concentration of 5 mol / liter.
Next, an aqueous solution in which 2 parts by mass of magnesium chloride hexahydrate was dissolved in 1000 parts by mass of ion-exchanged water was added at 30 ° C. over 10 minutes with stirring. After standing for 3 minutes, the temperature was raised and the system was heated to 65 ° C. over 60 minutes. In this state, the average particle diameter of the associated particles was measured with “Coulter Multisizer III” (manufactured by Beckman Coulter), and when the volume-based median diameter became 5.5 μm, 40.2 mass of sodium chloride. An aqueous solution in which 1000 parts by mass of ion-exchanged water is dissolved is added to stop particle growth, and further, fusion is continued by heating and stirring at a liquid temperature of 70 ° C. for 1 hour. A core part-containing liquid (1) containing 1) was obtained.
With respect to the obtained core part (1), the average circularity was measured using “FPIA2100” (manufactured by Sysmex Corporation), and it was 0.912.

(B) Formation of Shell Layer After adjusting the core part-containing liquid (1) to 65 ° C., 96 parts by mass of resin particles (1) for the shell layer are added, and 2 parts by mass of magnesium chloride hexahydrate is ionized. An aqueous solution dissolved in 1000 parts by mass of exchange water is added over 10 minutes, the temperature is raised to 70 ° C. (shelling temperature), and the mixture is stirred for 1 hour, whereby the shell layer resin is formed on the surface of the core part (1). After fusing the particles (1), a shell layer was formed by performing an aging treatment at a liquid temperature of 75 ° C. for 20 minutes.
Then, after aging treatment (shell layer formation) was stopped by adding 40.2 parts by mass of sodium chloride, the mixture was cooled to 30 ° C. at 6 ° C./min, and the produced particles were filtered. Washing with ion exchange water at 0 ° C. and drying with hot air at 40 ° C. to form toner particles having a shell layer formed on the surface of the core (hereinafter referred to as “toner particles (1)”). Got.

(6) External addition treatment To the obtained toner particles (1), 0.6 parts by mass of hexamethylsilazane-treated silica (average primary particle size 12 nm) and n-octylsilane-treated titanium dioxide (average primary particle size 24 nm) An external additive consisting of 0.8 parts by mass is added and mixed using a Henschel mixer (made by Mitsui Miike Mining Co., Ltd.) under the conditions of a peripheral speed of a stirring blade of 35 m / sec, a treatment temperature of 35 ° C., and a treatment time of 15 minutes. By performing the addition process, a toner (hereinafter referred to as “toner (1)”) was obtained.
The shape and particle size of the toner particles (1) did not change depending on the addition of the external additive.

[Toner Production Example 2 (Production Example of Toner Containing Zinc as Specific Metal Element)]
(1) Preparation Example 2 of Colorant Fine Particle Dispersion
In Preparation Example 1 of the colorant fine particle dispersion according to Toner Production Example 1, 17.5 parts by mass of C.I. I. Pigment Yellow 65 and 7.5 parts by mass of C.I. I. Colorant fine particle dispersion (hereinafter, referred to as “colorant fine particle dispersion”) in which the colorant fine particles are dispersed by the same method as in Preparation Example 1 of the colorant fine particle dispersion except that each pigment yellow 83 is gradually added to the surfactant aqueous solution. “Colorant fine particle dispersion (2)” was prepared.
With respect to the particle diameter of the colorant fine particles in this colorant fine particle dispersion (2), the volume-based median diameter was measured by the same method as in Preparation Example 1 of the colorant fine particle dispersion, and found to be 221 nm.

(2) Preparation Example of Core Part Resin Particles In the preparation example of core part resin particles according to Toner Production Example 1, a branched paraffin compound is used as a release agent during the second stage polymerization (intermediate layer formation) process. Paraffin wax comprising a mixture of linear paraffin compounds, an endothermic peak of 62 ° C., a molecular weight distribution peak value of 430, and a mixing ratio (branched paraffin compound: linear paraffin compound) of 11:89 (hereinafter referred to as “release agent”) Resin particles containing the core part resin particles (2) in the same manner as in the preparation example of the core part resin particles according to Production Example 1 of the toner except that the compound (B) is used. A dispersion was obtained.
The weight average molecular weight of the obtained resin particles for core part (2) was 26800, and the glass transition temperature (Tg) was 28.1 ° C.
In addition, it was 125 nm when the mass mean particle diameter of the resin particle for core parts (2) in this resin particle dispersion was measured.

(3) Preparation Example of Toner Particles (a) Formation of Core Part Resin particle for core part (2) 420.7 parts by mass, ion exchange in a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introducing device After adding 900 parts by mass of water and 200 parts by mass of the colorant fine particle dispersion (2) and stirring the mixture so that the internal temperature becomes 30 ° C., the pH is adjusted by adding a 5 mol / liter sodium hydroxide aqueous solution. Was adjusted to 10.0.
Next, an aqueous solution in which 2 parts by mass of zinc chloride was dissolved in 1000 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After standing for 3 minutes, the temperature was raised and the system was heated to 65 ° C. over 60 minutes. In this state, the average particle diameter of the associated particles was measured with “Coulter Multisizer III” (manufactured by Beckman Coulter), and when the volume-based median diameter became 5.5 μm, 40.2 mass of sodium chloride. An aqueous solution in which 1000 parts by mass of ion-exchanged water is dissolved is added to stop particle growth, and further, fusion is continued by heating and stirring at a liquid temperature of 70 ° C. for 1 hour. A core part-containing liquid (2) containing 2) was obtained.
With respect to the obtained core part (2), the average circularity was measured by using “FPIA2100” (manufactured by Sysmex Corporation), and it was 0.912.

(B) Formation of Shell Layer After adjusting the core part-containing liquid (2) to 65 ° C., 96 parts by mass of the resin particles (1) for the shell layer are added, and 2 parts by mass of zinc chloride is added to 1000 parts by mass of ion-exchanged water. The aqueous solution dissolved in the part is added over 10 minutes, the temperature is raised to 70 ° C. (shell formation temperature), and the mixture is stirred for 1 hour, whereby the resin particles for the shell layer (1) are formed on the surface of the core part (2). After fusing, a aging treatment was performed at a liquid temperature of 75 ° C. for 20 minutes to form a shell layer.
Then, after aging treatment (shell layer formation) was stopped by adding 40.2 parts by mass of sodium chloride, the mixture was cooled to 30 ° C. at 6 ° C./min, and the produced particles were filtered. Washing with ion exchange water at 0 ° C. and drying with hot air at 40 ° C. to form toner particles having a shell layer formed on the surface of the core (hereinafter referred to as “toner particles (2)”). Got.

(4) External Addition Treatment Toner (hereinafter referred to as “toner (2)”) is obtained by subjecting the obtained toner particles (2) to an external addition treatment in the same manner as in Toner Production Example 1. Obtained.
The shape and particle size of the toner particles (2) did not change with the addition of the external additive.

[Toner Production Example 3 (Production Example of Toner Containing Titanium as Specific Metal Element)]
(1) Synthesis Example of Titanium Catalyst In a reaction vessel equipped with a cooling tube, a stirring device, and a nitrogen introducing tube capable of bubbling in liquid, 1617 parts by mass of titanium diisopropoxybis (triethanolaminate) and 126 ion-exchanged water Titanium dihydroxy was prepared by charging the mass part and gradually raising the temperature in the reaction vessel to 90 ° C. while bubbling in liquid with nitrogen gas, followed by reaction (hydrolysis) at 90 ° C. for 4 hours. Bis (triethanolaminate) was obtained.

(2) Synthesis Example of Amorphous Polyester Resin In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 350 parts by mass of EO2 mol adduct of bisphenol A, 326 parts by mass of PO3 mol adduct of bisphenol A, 278 parts by mass of terephthalic acid, 40 parts by mass of phthalic anhydride, 2 parts by mass of titanium dihydroxybis (triethanolamate) as a condensation catalyst, and 50 parts by mass of the exemplified compound (1-2) as a metal deactivator were charged at a temperature of 230 The reaction was carried out over 10 hours while distilling off the water produced under a nitrogen stream under the condition of ° C. Further, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, the temperature in the reaction vessel was cooled to 180 ° C., and then 62 parts by mass of trimellitic anhydride was added and sealed at normal pressure. The reaction product was taken out after making it react for 2 hours under. The obtained reaction product was cooled to room temperature and then pulverized to obtain a non-linear polyester resin (1).
The obtained non-linear polyester resin (1) does not contain tetrahydrofuran insolubles, has an acid value of 35, a hydroxyl value of 17, a glass transition temperature (Tg) of 69 ° C., a number average molecular weight (Mn ) Is 3920, molecular weight distribution (Mw / Mn) is 4.5, Mp is 11200, storage modulus is 7.8 × 104 Pa at 100 ° C. and 4.5 × 103 Pa at 150 ° C., softening point temperature is 143 ° C. Met. The ratio of components having a molecular weight of 1500 or less was 0.9%.

(3) Preparation Example of Toner Particles Nonlinear polyester resin (1) 100 parts by mass, release agent compound (A) 7 parts by mass as a release agent, and carbon black 10 parts by mass as a colorant, using a Henschel mixer Mixing for 20 minutes under the conditions of a temperature of 37 ° C. and a peripheral speed of a stirring blade of 20 m / s, kneading with a biaxial extruder, and then pulverizing with an airflow pulverizer, and airflow classification using the Coanda effect By classifying with a machine, toner particles having a volume-based median diameter of 6.5 μm (hereinafter referred to as “toner particles (3)”) were obtained.

(4) External Addition Treatment Toner (hereinafter referred to as “toner (3)”) is obtained by subjecting the obtained toner particles (3) to an external addition treatment in the same manner as in Toner Production Example 1. Obtained.
The shape and particle size of the toner particles (3) did not change with the addition of the external additive.

[Toner Production Example 4 (Production Example of Toner Containing Aluminum as Specific Metal Element)]
In Toner Production Example 2, the exemplified compound (1-2) was used as a metal deactivator during the second stage polymerization (formation of the intermediate layer) according to the preparation example of the core part resin particles, and as a release agent. A mixture of a branched paraffin compound and a linear paraffin compound, an endothermic peak of 103 ° C., a molecular weight distribution peak value of 1760, and a mixing ratio (branched paraffin compound: linear paraffin compound) of 28:72 (hereinafter, “ The toner production example 2 except that aluminum sulfate was used instead of zinc chloride during the process of forming the core part according to the toner particle preparation example. In the same manner, toner particles having a structure in which a shell layer is formed on the surface of the core (hereinafter referred to as “toner particles (4)”) were obtained.
The toner particles (4) thus obtained were subjected to an external addition treatment in the same manner as in Toner Production Example 1 to obtain a toner (hereinafter referred to as “toner (4)”).
The shape and particle size of the toner particles (4) did not change with the addition of the external additive.

[Toner Production Example 5 (Production Example of Toner Containing Calcium as Specific Metal Element)]
In Toner Production Example 2, the exemplified compound (1-3) was used as a metal deactivator during the second-stage polymerization (intermediate layer formation) process according to the preparation example of the core part resin particles, and as a release agent. The same procedure as in toner production example 2 except that the release agent compound (A) was used, and calcium chloride was used instead of zinc chloride during the process of forming the core part according to the toner particle preparation example. As a result, toner particles having a shell layer formed on the surface of the core (hereinafter referred to as “toner particles (5)”) were obtained.
The toner particles (5) thus obtained were subjected to an external addition treatment in the same manner as in Toner Production Example 1 to obtain a toner (hereinafter referred to as “toner (5)”).
The shape and particle size of the toner particles (5) did not change with the addition of the external additive.

[Toner Production Examples 6 and 7 (Production Example of Toner Containing Copper as Specific Metal Element)]
In the toner production example 1, the compounds shown in Table 1 were used as the metal deactivator and the release agent during the second stage polymerization (formation of the intermediate layer) according to the preparation example of the resin particles for the core part. Is a toner particle having a structure in which a shell layer is formed on the surface of the core (hereinafter, referred to as “toner particle (6)” and “toner particle (7)”, respectively, in the same manner as in the toner production example 1. .)
Each of the obtained toner particles (6) and toner particles (7) is subjected to an external addition treatment in the same manner as in Toner Production Example 1, whereby toner (hereinafter referred to as "toner (6)" and “Toner (7)” was obtained.
The shape and particle size of toner particles (6) and toner particles (7) did not change with the addition of external additives.

[Toner Production Example 8 (Production Example of Toner Containing Zinc as Specific Metal Element)]
In Toner Production Example 2, except that Exemplified Compound (1-6) was used as the metal deactivator during the second stage polymerization (formation of the intermediate layer) according to the preparation example of the core part resin particles. By a method similar to that in Toner Production Example 2, toner particles having a shell layer formed on the surface of the core (hereinafter referred to as “toner particles (8)”) were obtained.
The toner particles (8) thus obtained were subjected to an external addition treatment in the same manner as in Toner Production Example 1 to obtain a toner (hereinafter referred to as “toner (8)”).
The shape and particle size of the toner particles (8) did not change with the addition of the external additive.

[Toner Production Example 9 (Production Example of Toner Containing Aluminum as Specific Metal Element)]
In Toner Production Example 4, the exemplified compound (1-1) was used as a metal deactivator during the second stage polymerization (formation of an intermediate layer) according to the preparation example of the core part resin particles, and as a release agent. A toner particle (hereinafter referred to as “toner particle (9)”) having a structure in which a shell layer is formed on the surface of the core portion by the same method as in Production Example 4 of the toner except that the release agent compound (A) is used. And obtained.
The toner particles (9) thus obtained were subjected to an external addition treatment in the same manner as in Toner Production Example 1 to obtain a toner (hereinafter referred to as “toner (9)”).
The shape and particle size of the toner particles (9) did not change with the addition of the external additive.

[Comparative Toner Production Examples 1 to 3]
In the toner production example 1, the compounds shown in Table 1 were used as the metal deactivator and the release agent during the second stage polymerization (formation of the intermediate layer) according to the preparation example of the resin particles for the core part. Is a toner particle having a structure in which a shell layer is formed on the surface of the core portion in the same manner as in Production Example 1 of the toner (hereinafter referred to as “comparative toner particle (1)” to “comparative toner particle (3 ) ”.
Each of the obtained comparative toner particles (1) to comparative toner particles (3) is subjected to an external addition treatment in the same manner as in Toner Production Example 1, thereby producing a toner (hereinafter referred to as “comparison toner”). Toner (1) ”to“ Comparative toner (3) ”were obtained.
The shape and particle size of the comparative toner particles (1) to the comparative toner particles (3) were not changed by the addition of the external additive.

<Measurement of specific metal element content>
For each of the toners according to Production Example 1 to Toner Production Example 9 and Comparative Toner Production Example 1 to Comparative Toner Production Example 3 obtained, 1 g of toner was added in 20 ml of methanol over 2 minutes. After sonic dispersion, the mixture was allowed to stand for 6 hours, after which a residue from which the supernatant from which the external additive was suspended was removed, and the content of the metal element was measured by atomic absorption spectrometry. The results are shown in Table 1.

[Examples 1 to 9 and Comparative Examples 1 to 3]
For each of the toners according to Production Example 1 to Toner Production Example 9 and Comparative Toner Production Example 1 to Comparative Toner Production Example 3 obtained, a developer was produced by the following method, and the following actual machine Evaluation was performed. The results are shown in Table 1.

(Developer Production Examples 1 to 9 and Comparative Developer Production Examples 1 to 3)
Each of toner (1) to toner (9) and comparative toner (1) to comparative toner (3) is coated with a silicone carrier-coated ferrite carrier having a volume average particle diameter of 60 μm, and the toner concentration is 6 mass%. By mixing so as to obtain developer (1) to developer (9) and comparative developer (1) to comparative developer (3).

<Evaluation of toner scattering under high temperature and high humidity>
Using an image forming apparatus “bizhub PRO C6500” (manufactured by Konica Minolta Business Technologies, Inc.), image formation is performed in a high-temperature and high-humidity environment (temperature 33 ° C., relative humidity 80%). The occurrence of toner spillage due to toner scattering, that is, the number of continuous prints until the image smears due to the scattered toner accumulating on the members constituting the developing device and spilling on the transfer paper is confirmed. “◎” indicates that image smear does not occur even when the number of sheets reaches 1,000,000, and although slight image smear occurs until the number of continuous prints reaches 1,000,000, image smear does not occur until 800,000. “○” as good as the case, and “×” as bad when the image smudges before the number of continuous prints reaches 800,000. evaluated.

<Toner filming evaluation>
Using the image forming apparatus “bizhub PRO C6500” (manufactured by Konica Minolta Business Technologies Co., Ltd.), image formation was performed 1 million times continuously in a high temperature and high humidity environment (temperature 33 ° C., relative humidity 80%). The occurrence of density unevenness in the printed image, that is, the presence or absence of image density unevenness due to toner filming on the photosensitive member is visually confirmed, and even when the number of continuous prints reaches 1,000,000 “◎” as excellent when there is no image, and “○” as good when no image density unevenness occurs until 700,000, although slight image density unevenness occurs until the number of continuous prints reaches 1 million. There is a practical problem when image density unevenness does not occur until 500,000, although slight image density unevenness occurs until the number of continuous prints reaches 700,000. "△" as there is no was evaluated as "×" a case where continuous printing number has occurred uneven image density before reaching the 500,000 as bad.

In Table 1, the metal deactivator “Comparative 1” according to Comparative Example 1 is a compound in which R ¹ and R ² are both tert-butyl groups and R ³ is a hydrogen atom. The activator “Comparative 2” is a compound in which R ¹ is a hydrogen atom, R ² is a methyl group, and R ³ is a hydrogen atom. In the same table, the release agent “release agent compound D” according to Comparative Example 1 is composed of a mixture of a branched paraffin compound and a linear paraffin compound, and has an endothermic peak of 57 ° C. and a peak value of molecular weight distribution of 1840, It is a paraffin wax having a mixing ratio (branched paraffin compound: linear paraffin compound) of 8:92, and the release agent “release agent compound E” according to Comparative Example 2 is a mixture of a branched paraffin compound and a linear paraffin compound. The paraffin wax has an endothermic peak of 108 ° C., a molecular weight distribution peak value of 820, and a mixing ratio (branched paraffin compound: linear paraffin compound) of 33:67.

Claims (2)

In an electrostatic charge image developing toner containing a resin, a colorant, a release agent and a metal element selected from the group consisting of copper, zinc, titanium, aluminum and calcium in a proportion of 300 ppm to 5000 ppm,
The release agent comprises a compound having a molecular weight distribution peak value of 400 or more and 1800 or less,
A toner for developing an electrostatic charge image, comprising a metal deactivator comprising a compound represented by the following general formula (1).

[Wherein, R ¹ and R ² each represents an alkyl group having 12 or less carbon atoms having a tertiary carbon atom or an arylalkyl group having a tertiary carbon atom, and the other being a third carbon atom. An alkyl group having no secondary carbon atom, an ester residue having an alkyl group having no tertiary carbon atom, a sulfo group, or a sulfonic acid group. R ³ represents a hydrogen atom or a chlorine atom. ]   2. The electrostatic image developing toner according to claim 1, wherein the release agent is a mixture of a branched paraffin compound and a linear paraffin compound, and has an endothermic peak in the range of 60 to 105 ° C. .