JP5151684B2 - Toner manufacturing method and toner - Google Patents

Description

  The present invention relates to an electrostatic image developing toner used for electrophotographic image formation and a method for producing the same, and more specifically, it is produced by a reaction between a colorant compound precursor and a metal-containing compound in the production process. The present invention relates to a toner containing a colorant comprising a reactive compound and a method for producing the same.

In recent years, in an electrophotographic image forming method using toner for developing an electrostatic charge image, an electrostatic latent image corresponding to an original pattern (original image information) is obtained by exposing a dispersed light onto a photosensitive member. It has been put into practical use to form a full color image by forming an image and developing the electrostatic latent image with each color toner.
As a color toner for forming such a color image, a yellow toner, a magenta toner, a cyan toner, or the like containing a binder resin (binder resin) made of a thermoplastic resin and a colorant of each color is used. ing.
Here, the electrophotographic image forming method generally means that an electrostatic latent image is formed by irradiating a photoconductor made of a photoconductive material with light according to image information of a document by various methods. The electrostatic latent image formed on the photosensitive member is developed as a toner image with charged toner, and the toner image is transferred to an image recording medium (for example, plain paper or an intermediate transfer member). A visible image is obtained through a fixing process using a thermal fixing device. In order to form a full-color image, an electrostatic latent image of each color corresponding to each of the image patterns decomposed for each color of yellow, magenta, cyan, and black in the image information of the document is formed on the photoreceptor. These electrostatic latent images are developed with the corresponding color toner.

  Conventionally known organic pigments and oil-soluble dyes are used as the colorant constituting the electrostatic image developing toner. Toners using either organic pigments or oil-soluble dyes, or organic pigments and oil-soluble dyes are used. Toners that are mixed with dyes have been proposed (see, for example, Patent Document 1 and Patent Document 2), but organic pigments and oil-soluble pigments used as colorants each have various drawbacks. Have.

Specifically, organic pigments generally have better heat resistance and light resistance than oil-soluble dyes, but they have a hiding power because they exist in a dispersed state in the toner. And the transparency of the toner is reduced. In addition, since pigments generally have low dispersibility, good dispersibility cannot be obtained, resulting in further reduced transparency, lower saturation, and good color in the formed visible image. There is a problem that reproducibility cannot be obtained.
Here, in the full-color image formed by superimposing the single color toner images, the lowermost one of the superimposed toner images is not concealed by the upper layer, and the lowermost one is not concealed by the uppermost one. In order to make it possible to visually confirm the color of the toner constituting the toner image, the toner needs to be transparent in a fixed state, and to obtain excellent color reproducibility for an original. The colorant constituting the toner needs to have dispersibility and coloring power.

  In addition, a technique for producing a toner by a polymerization method using a nickel chelate oil-soluble dye as a colorant has been proposed (see, for example, Patent Document 3). As a result of the detailed examination conducted by the company, there are problems that the chargeability is reduced due to the generation of weakly charged toner, causing toner scattering, and that good cleaning properties cannot be obtained, and that the image density is stable. It became clear that there was a problem of lacking.

JP-A-5-11504 JP-A-5-34980 JP 2007-14078 A

  The present invention has been made on the basis of the above circumstances, and an object of the present invention is to provide a toner having a good color tone and having excellent transparency, charging property, cleaning property and image density stability, and the toner. It is to provide a manufacturing method.

The method for producing a toner of the present invention is a method for producing a toner for developing an electrostatic image containing a resin and a colorant comprising a colorant compound,
Give a mixture of said colorant compound precursor and the resin, yielding intermediate by warming the mixture was heated by mixing the intermediate with a metal-containing compound, constituting the intermediate It has a coloring agent compound production | generation process which produces | generates a coloring agent compound as a reaction product of a coloring agent compound precursor and a metal containing compound by making a coloring agent compound precursor and a metal containing compound react.

  The toner production method of the present invention includes a resin dispersion in which resin particles are dispersed and a colorant compound precursor dispersion in which particles of a colorant compound precursor are dispersed in a colorant compound generation step. It is preferable to obtain an intermediate composed of an aggregate of resin particles and colorant compound precursor particles by mixing and heating.

In the toner production method of the present invention, the metal-containing compound is preferably a metal coordination compound or an organometallic compound.
In such a toner production method of the present invention, the colorant compound precursor is composed of a compound represented by the general formula (1) or the general formula (2), and the metal-containing compound is represented by the general formula (3). It is preferably made of a metal coordination compound.

[Wherein, R ¹ independently represents a hydrogen atom, a halogen group or a monovalent organic group, R ² represents a —NR ⁴ R ⁵ group (provided that R ⁴ and R ⁵ each independently represents hydrogen Represents an atom, a halogen group or a monovalent organic group.) Or —OR ⁶ group (wherein R ⁶ independently represents a hydrogen atom, a halogen group or a monovalent organic group), and R ^3. 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 ⁷ = group (provided that R ⁷ each independently represents a hydrogen atom, a halogen group 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 at least one An atomic group necessary for forming a 5-membered or 6-membered heterocyclic ring containing an elementary atom is shown, and this atomic group may be unsubstituted or substituted, and the substituent forms a condensed ring. It may be. L ¹ represents a part of a linking group having 1 or 2 carbon atoms or a ring structure, and may be bonded to R ³ to form a 5-membered or 6-membered ring structure. p is an integer of 0-3. ]

[Wherein X ² represents an atomic group necessary for forming an aromatic carbocyclic or heterocyclic ring in which at least one ring is composed of 5 to 7 atoms, and forms a heterocyclic ring. The atomic group necessary for this is that a carbon atom is bonded to the azo bond, and at least one of the adjacent positions of the carbon atom is a nitrogen atom, or the carbon atom in the carbocycle is a nitrogen atom, oxygen atom or sulfur It has a structure that is substituted with atoms. X ³ represents an atomic group necessary for forming an aromatic carbocyclic or heterocyclic ring in which at least one ring is composed of 1 to 7 atoms, and G represents a hydroxyl group, an amino group, a methoxy group A group, a thiol group or a thioalkoxy group. ]

[Wherein, M represents a divalent metal atom, R ⁸ represents a hydrogen atom or a monovalent organic group, and R ⁹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic ring. Group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group or a cyano group, and R ¹⁰ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or A heterocyclic group is shown. ]

  In the toner manufacturing method of the present invention, the toner to be manufactured is preferably a magenta toner.

  The toner of the present invention is a toner for developing an electrostatic image containing a resin and a colorant, and is characterized by being manufactured by the above-described toner manufacturing method.

  In the present invention, the colorant compound constituting the colorant is a reaction compound produced by reacting a colorant compound precursor having a hue different from that of the obtained toner and a metal-containing compound in the production process. Thus, the reactive compound is generated in the presence of the resin constituting the toner, and thus the hue of the obtained toner can be adjusted, so that it has a good color tone and a high charge. Toner, cleaning properties and image density stability, and a method for producing the same can be obtained.

The toner of the present invention comprises particles (hereinafter also referred to as “toner particles”) containing at least a resin and a colorant composed of a colorant compound.
In addition to the resin and the colorant, the toner of the present invention may contain other components such as a release agent (wax) and a charge control agent.

  The toner of the present invention is produced by a pulverization method through a kneading step, a pulverization step, and a classification step in this order, or a polymerization method (wet method) such as an emulsion polymerization method, a suspension polymerization method, or a polyester elongation method. In the production process, a mixture comprising a resin and a colorant compound precursor is obtained, and the mixture and the metal-containing compound are mixed and heated to form a colorant constituting the mixture. It has a coloring agent compound production | generation process which produces | generates a coloring agent compound as a reaction product of a coloring agent compound precursor and a metal containing compound by making a compound precursor and the said metal containing compound react.

As a preferred specific example of the colorant compound precursor that is used for the reaction for generating the colorant compound constituting the toner of the present invention, that is, the colorant compound generation step, a compound represented by the above general formula (1) Or the compound represented by the said General formula (2) is mentioned.
Of these, the compound represented by the general formula (2) is particularly preferable.

<Compound represented by the general formula (1)>
In the general formula (1) indicating the colorant compound precursor, R ¹ represents a hydrogen atom, a halogen group or a monovalent organic group.
This group R ¹ may be an independent group when p is 2 or 3.

Examples of the halogen group representing the group R ¹ include a fluoro group, a chloro group, and a bromo group. Examples of the monovalent organic group representing the group R ¹ include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group). 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, methylothio group, etc.) Xycarbonyl 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 group) Bonyl 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 group Bonylamino 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, ethylsulfinyl group) 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), cyano group and Such as a furnace group, and the like.

In the general formula (1), R ² represents a —NR ⁴ R ⁵ group (where R ⁴ and R ⁵ each independently represents a hydrogen atom, a halogen group or a monovalent organic group) or — OR ⁶ group (where R ⁶ represents a hydrogen atom, a halogen group or a monovalent organic group).
The group R ² is preferably a —NR ⁴ R ⁵ group from the viewpoint of the molar extinction coefficient ε, and is preferably a —OR ⁶ group from the viewpoint of wavelength adjustment.

Further, examples of the halogen group represented by R ⁶ in R ⁴ and R ^5, and -OR ⁶ groups in -NR ⁴ R ⁵ groups according to the group R ^2, a fluoroalkyl group, and a chloro group and a bromo group.
R ⁴ and R ⁵ in -NR ⁴ R ⁵ groups according to the group R ^2, and examples of the monovalent organic group represented by R ⁶ in -OR ⁶ group, those exemplified as the monovalent organic group represented by group R ¹ Is mentioned.
These groups R ^{4 to} R ⁶ 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 (1), R ³ 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 ³ 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 ³ include those exemplified as one type of monovalent organic group representing the group R ¹ .

In the general formula (1), A ^{1 to} A ^{3 each} independently represent —CR ⁷ ═group (where R ⁷ represents a hydrogen atom, a halogen group or a monovalent organic group) or — N = group.
Groups A ¹ and group A ² are each preferably a -CR ⁷ = group.

Examples of the monovalent organic group representing R ⁷ in the group —CR ⁷ = group related to the groups A ¹ to A ³ include those exemplified as the monovalent organic group representing the group R ¹ .
The group R ⁷ is preferably a hydrogen atom, a halogen group or an alkoxycarbonyl group, and particularly preferably a hydrogen atom.

In the general formula (1), 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 (1), L ¹ represents a linking group having 1 or 2 carbon atoms or a part of the ring structure.
A part of the linking group and the ring structure may be bonded to the group R ³ 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 (4).

[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 (1) by one bond and represented by the general formula (1) by the other bond. To R ^{3 in} ]

In this general formula (4), 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 group, an alkoxy group, an amino group, an acylamino group, a sulfonylamino group, and a ureido group, and a halogen group, an alkoxy group, an amino group, and an acylamino group are preferable.
It is also preferable to have a chelatable group as a substituent. The chelatable group 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, a heterocyclic ring. 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 ring 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 and arylthio groups There, 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 (1), 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 (5) to (10).

[In General Formula (5) and General Formula (6), each of R ¹¹ and R ¹³ represents a hydrogen atom, a halogen group 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 (7), R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom, a halogen group or a monovalent organic group, and R ¹⁷ represents a hydroxyl group, an alkoxy group, an aryloxy group, 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 (1).
In the general formula (8), R ¹⁸ represents a hydrogen atom, a halogen group 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 (1).
In the general formula (9), R ²⁰ and R ²¹ each independently represent a hydrogen atom, a halogen group 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 (1).
In the general formula (10), R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen group 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 (1). ]

In the general formula (5) and general formula (6), examples of the monovalent organic group representing R ¹¹ and R ¹³ are those exemplified as the monovalent organic group representing R ¹ in the general formula (1). 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 (5) and the general formula (6), R ¹² and R ¹⁴ are respectively synonymous with R ³ in the general formula (1), and preferred groups are also synonymous.

In the general formula (5) and general formula (6), L ² and L ³ are each the same meaning as L ¹ in the general formula (1), the same meaning applies to the preferred group.

In the general formula (7) and the general formula (8), the monovalent organic group representing R ¹⁵ , R ¹⁶ and R ¹⁸ is a monovalent organic group representing R ¹ in the general formula (1). 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 group, 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 group, 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 (7) and the general formula (8), R ¹⁷ and R ¹⁹ are respectively synonymous with R ³ in the general formula (1), and preferred groups are also synonymous.

In the general formula (7) and the general formula (8), L ⁴ and L ⁵ each has the same meaning as L ¹ in the general formula (1), the same meaning applies to the preferred group.

In the general formula (9) and the general formula (10), the monovalent organic group representing R ²⁰ , R ²¹ , R ²³ and R ²⁴ is a monovalent group representing R ¹ in the general formula (1). 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 general formula (9) and the general formula (10), R ²² and R ²⁵ are each the same meaning as R ³ in the general formula (1), the same meaning applies to the preferred group.

Moreover, in General formula (9) and General formula (10), L < ⁶ > and L < ⁷ > are respectively synonymous with L < ¹ > in the said General formula (1), and are also synonymous about a preferable group.

  Specific examples of the compound represented by the general formula (1) include compounds represented by the following formulas (1-1) to (1-20).

<Compound represented by formula (2)>
In the general formula (2) showing the colorant compound precursor, X ² is necessary to form an aromatic carbocyclic or heterocyclic ring in which at least one ring is composed of 5 to 7 atoms. An atomic group that represents an atomic group and is necessary for forming a heterocyclic ring has a carbon atom bonded to an azo bond, and at least one of the adjacent positions of the carbon atom is a nitrogen atom, or It has a structure in which a carbon atom is substituted with a nitrogen atom, an oxygen atom or a sulfur atom.
The atomic group representing the group X ² may be unsubstituted or have a substituent.

An aromatic carbocyclic or heterocyclic ring formed by an atomic group representing the group X ² and in which at least one ring is composed of 5 to 7 atoms includes a benzene ring, a naphthalene ring, a pyridine ring and a quinoline A ring is preferred.
In addition, preferable substituents related to the atomic group representing the group X ² include alkyl groups (eg, methyl group, ethyl group, etc.), alkoxy groups, cyano groups, nitro groups, thiol groups, thioalkoxy groups, and halogen groups. It is done.

In the general formula (2), X ³ represents an atomic group necessary for forming an aromatic carbocyclic or heterocyclic ring in which at least one ring is composed of 1 to 7 atoms, It may be unsubstituted or may have a substituent.
An aromatic carbocyclic or heterocyclic ring formed by an atomic group representing the group X ³ and in which at least one ring is composed of 1 to 7 atoms includes a benzene ring, a naphthalene ring, a pyridine ring, a quinoline A ring is preferred. Moreover, as a substituent, an alkyl group, an alkoxy group, a cyano group, a nitro group, a hydroxyl group, an amino group, and a halogen group are preferable.

  Moreover, in General formula (2), G shows a hydroxyl group, an amino group, a methoxy group, a thiol group, or a thioalkoxy group.

  Specific examples of the compound represented by the general formula (2) include 1- (2-pyridylazo) -2-naphthol, 2- (2-hydroxyphenylazo) -5-hydroxypyridine, 1- (2-hydroxy Phenylazo) -2-naphthol, 2- (2-hydroxyphenylazo) -5-methoxyphenol, 8- (2-hydroxyphenylazo) -quinoline and the like.

The metal-containing compound that is used for the reaction for generating the colorant compound constituting the toner of the present invention, that is, that is used for the colorant compound generation step, is preferably a metal coordination compound or an organometallic compound. A coordination compound is preferred.
Here, when the metal-containing compound for producing the colorant compound constituting the toner of the present invention is an organometallic compound, in the colorant compound production step, with respect to the reaction with the colorant compound precursor, For example, an inorganic metal salt such as copper sulfate can be provided together with the organic compound instead of the organic metal compound itself.

  Preferable specific examples of the metal coordination compound constituting the metal-containing compound relating to the colorant compound constituting the toner of the present invention include compounds represented by the above general formula (3).

<Compound represented by formula (3)>
In General formula (3) which shows a metal containing compound, M shows a bivalent metal atom, Preferably it is a bivalent transition metal atom.
As the group M, among the divalent transition metal atoms, a colorant compound precursor composed of a compound represented by the general formula (1) or a compound represented by the general formula (2) and a metal coordination compound are generated. From the viewpoint of the stability of the color tone of the finally obtained toner, nickel atoms, copper atoms, and zinc atoms are preferable, and copper atoms are most preferable.

In the general formula (3), R ⁸ represents a hydrogen atom or a monovalent organic group.
Examples of the monovalent organic group representing the group R ⁸ include alkyl groups (for example, methyl group, ethyl group, propyl group, i-propyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group). Group, tetradecyl group, pentadecyl group, chloromethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, pentafluoroethyl group, methoxyethyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), Alkenyl groups (such as vinyl and allyl groups), alkynyl groups (such as ethynyl and propargyl groups), aryl groups (such as phenyl, naphthyl, p-nitrophenyl, p-fluorophenyl, and p-methoxyphenyl) Group), heterocyclic group (for example, furyl group, thienyl group, pyridyl group, Dazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.) Alkoxycarbonyl groups (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl groups (for example, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl groups ( For example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl Group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexyl group) Carbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, benzoyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), carbamoyl group (eg aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylamino) Carbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dode Ruaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecyl) Sulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.) ), Arylsulfonyl groups (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), cyano groups and the like.

The group R ⁸ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, or a cyano group, and most preferably a hydrogen atom, an alkyl group, an aryl group A group, a heterocyclic group, and a cyano group. The monovalent organic groups exemplified as these preferable ones may be unsubstituted or may have a substituent.

In the general formula (3), R ⁹ is a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, sulfinyl group, alkylsulfonyl. A group, an arylsulfonyl group or a cyano group;

Specific examples of each of the organic groups representing the group R ⁹ are exemplified below.
Examples of the alkyl group include methyl, ethyl, propyl, i-propyl, t-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, chloromethyl, trimethyl. Examples thereof include a fluoromethyl group, a trichloromethyl group, a tribromomethyl group, a pentafluoroethyl group, and methoxyethyl.
Examples of the alkenyl group include a vinyl group and an allyl group.
Examples of the alkynyl group include ethynyl group and propargyl group.
Examples of the aryl group include a phenyl group, a naphthyl group, a p-nitrophenyl group, a p-fluorophenyl group, and p-methoxyphenyl.
Heterocyclic groups include furyl, thienyl, pyridyl, pyridazyl, pyrimidyl, pyrazyl, triazyl, imidazolyl, pyrazolyl, thiazolyl, benzoimidazolyl, benzoxazolyl, quinazolyl, phthalazyl Pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group and the like.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group.
Examples of the aryloxycarbonyl group include a phenyloxycarbonyl group and a naphthyloxycarbonyl group.
The carbamoyl group includes an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a propylaminocarbonyl group, a pentylaminocarbonyl group, a cyclohexylaminocarbonyl group, an octylaminocarbonyl group, a 2-ethylhexylaminocarbonyl group, and a dodecylaminocarbonyl group. , Phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group and the like.
The sulfamoyl group includes aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthyl. An aminosulfonyl group, 2-pyridylaminosulfonyl group, etc. are mentioned.
Examples of the sulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a butylsulfinyl group, a cyclohexylsulfinyl group, a 2-ethylhexylsulfinyl group, a dodecylsulfinyl group, a phenylsulfinyl group, a naphthylsulfinyl group, and a 2-pyridylsulfinyl group.
Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a cyclohexylsulfonyl group, a 2-ethylhexylsulfonyl group, and a dodecylsulfonyl group.
Examples of the arylsulfonyl group include phenylsulfonyl, naphthylsulfonyl, 2-pyridylsulfonyl and the like.

The group R ⁹ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group or a cyano group, and most preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or a cyano group. is there. The monovalent organic groups exemplified as these preferable ones may be unsubstituted or may have a substituent.

In the general formula (3), R ¹⁰ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

Specific examples of each organic group representing the group R ¹⁰ are illustrated below.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group.
Examples of the alkenyl group include a vinyl group and an allyl group.
Examples of the alkynyl group include ethynyl group and propargyl group.
Examples of the aryl group include a phenyl group, a naphthyl group, a p-nitrophenyl group, a p-fluorophenyl group, and a p-methoxyphenyl group.
Heterocyclic groups include furyl, thienyl, pyridyl, pyridazyl, pyrimidyl, pyrazyl, triazyl, imidazolyl, pyrazolyl, thiazolyl, benzoimidazolyl, benzoxazolyl, quinazolyl, phthalazyl Pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group and the like.

The group R ¹⁰ is preferably an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and most preferably an alkyl group or an aryl group. The monovalent organic groups exemplified as these preferable ones may be unsubstituted or may have a substituent.

In the general formula (3), R ⁸ and R ⁹ , or R ⁹ and R ¹⁰ may be connected to each other to form a 5- to 6-membered ring.

Furthermore, in this general formula (3), it is more preferable that either one of R ⁸ and R ⁹ is an electron-withdrawing group, and the total of σρ values of R ⁸ and R ⁹ is 0.2-2. Most preferably, it is zero.
Here, the “electron-withdrawing group” is a substituent whose substituent constant ρ according to the Hammett rule can take a positive value. Alternatively, in the para-substituted product, it is defined as σ in Hammett's formula: log (k / k0) = ρσ, which is established when the reaction rate constant between the unsubstituted compound and the compound having a substituent is k0 and k, respectively.
In the Hammett equation, ρ = 1 is the dissociation reaction of benzoic acid and its derivatives in an aqueous solution at 25 ° C. Regarding Hammett's substituent constants, see Journalof Medicinal Chemistry, 1973, Vol. 16, no. 11, 1207-1216 etc. can be referred to.

Specific examples of the electron-withdrawing group include an alkyl group having a substituent (for example, a halogen-substituted alkyl group), an alkenyl group having a substituent (for example, a cyanovinyl group), an unsubstituted or substituted alkynyl group (for example, a trivalent group). Fluoromethylacetylenyl group, cyanoacetylenyl group, etc.), substituted aryl group (eg, cyanophenyl), unsubstituted or substituted heterocyclic group (eg, pyridyl group, triazinyl group, benzoxazolyl) Group), halogen group, cyano group, acyl group (eg acetyl group, trifluoroacetyl group, formyl group etc.), thioacetyl group (eg thioacetyl group, thioformyl group etc.), oxalyl group (eg methyl oxalyl group etc.), oxy Oxalyl group (eg, etoxalyl group), thiooxalyl group (eg, ethyl) Oxalyl group etc.), oxamoyl group (eg methyl oxamoyl group etc.), oxycarbonyl group (eg ethoxycarbonyl group etc.), carboxyl group, thiocarbonyl group (eg ethylthiocarbonyl group etc.), carbamoyl group, thiocarbamoyl group, sulfonyl Group, sulfinyl group, oxysulfonyl group (such as ethoxysulfonyl group), thiosulfonyl group (such as ethylthiosulfonyl group), sulfamoyl group, oxysulfinyl group (such as methoxysulfinyl group), thiosulfinyl group (such as methylthiosulfinyl group) ), Sulfinamoyl group, phosphoryl group, nitro group, imino group, N-carbonylimino group (for example, N-acetylimino group), N-sulfonylimino group (for example, N-methanesulfonylimino group), di Anoechiren group, an ammonium group, a sulfonium group, a phosphonium group, pyrylium group, such as immonium group.
Among these, an alkyl group having a substituent, an aryl group having a substituent, a cyano group, an acyl group, an oxycarbonyl group, a nitro group, and a cyano group are preferable. Specifically, a cyano group, a nitro group, and trichloromethyl are included. A group, a dichloromethyl group, a chloromethyl group, a tribromomethyl group, a dibromomethyl group, a bromomethyl group, an alkoxyacyl group, an acyl group, and an aromatic ring substituted with these organic groups are preferable.

Such a metal coordination compound represented by the general formula (3) is obtained by synthesizing a compound represented by the following general formula (11) and reacting the compound with a compound containing a divalent metal. It is preferable that
Here, the synthesis method of these metal coordination compounds can be synthesized according to the method described in “Chelate Chemistry (5) Complex Chemistry Experimental Method [I] (Edited by Nanedo)” and the like. The compounds containing divalent metals used for this synthesis include nickel chloride, nickel acetate, magnesium chloride, calcium chloride, barium chloride, zinc chloride, zinc acetate, titanium (II) chloride, iron (II) chloride, Examples include copper chloride (II), cobalt chloride, manganese chloride (II), lead chloride, lead acetate, mercury chloride, and mercury acetate. As described above, the compound represented by the general formula (1) or the general formula ( From the viewpoint of producing a colorant compound precursor and a metal coordination compound comprising the compound represented by 2), and from the viewpoint of the stability of the color tone of the finally obtained toner, preferably zinc chloride, zinc acetate, nickel chloride , Nickel acetate, copper chloride, and copper acetate, and most preferably copper acetate.

[Wherein R ⁸ represents a hydrogen atom or a monovalent organic group, and R ⁹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. Carbamoyl group, sulfamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group or cyano group, R ¹⁰ represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group. ]

  Specific examples of the metal coordination compound represented by the general formula (3) include compounds represented by the following formulas (3-1) to (3-14).

The colorant constituting the toner of the present invention includes a colorant compound precursor composed of a compound represented by the general formula (1) or a compound represented by the general formula (2), and a general formula (3). What consists of a coloring agent compound produced | generated when the metal containing compound which consists of a metal coordination compound reacts is preferable.
The content of the colorant is preferably 2 to 11 parts by mass, more preferably 4 to 9 parts by mass with respect to 100 parts by mass of the toner.

The resin constituting the toner of the present invention, that is, the resin existing under the reaction between the colorant compound precursor and the metal-containing compound is not particularly limited, but the tetrahydrofuran (THF) insoluble content is 100% of the toner. And less than 20% can be preferably used. When the THF-insoluble content is excessive, the reaction medium for the resin to produce the colorant compound, specifically, the reaction medium for the colorant compound precursor and the metal-containing compound in the colorant compound production step The uniform dispersion of the colorant composed of the colorant compound in the toner particles is inhibited, and the effects to be obtained by the colorant compound generation step may not be sufficiently exhibited. .
More preferably, a resin comprising a polymer obtained by polymerizing a radical polymerizable monomer is used. This resin is composed of a polymer obtained by polymerizing at least one kind of polymerizable monomer, and even if it is composed of one kind of polymerizable monomer, a plurality of kinds of polymerizable monomers can be used. A combination of monomers may also be used.
Specific examples of the polymer used as the resin include a vinyl polymer in which a vinyl monomer is used as the polymerizable monomer.

  Examples of the vinyl monomer for obtaining the vinyl polymer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-chloro styrene, and 3,4-dichloro styrene. , P-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn- Styrene or styrene derivatives such as decylstyrene and pn-dodecylstyrene; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate Methacrylic acid ester derivatives such as lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, Acrylate derivatives such as isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, and phenyl acrylate; olefins such as ethylene, propylene, and isobutylene; vinyl propionate, vinyl acetate Vinyl esters such as vinyl benzoate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl esters such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl hexyl ketone. Nyl ketones; N-vinyl compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; and other vinyl compounds such as vinyl naphthalene and vinyl pyridine; acrylonitrile, methacrylonitrile, acrylamide And acrylic acid or methacrylic acid derivatives.

In addition, as a polymerizable monomer for obtaining a vinyl polymer, an ionic dissociation group having a functional group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group in the side chain is used together with the vinyl monomer. What has can also be used.
Specific examples of the polymerizable monomer having an ionic dissociation group include those having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, and itacone. Examples include acid monoalkyl esters. Examples of those having a sulfonic acid group include styrene sulfonic acid, allyl sulfosuccinic acid, and 2-acrylamido-2-methylpropane sulfonic acid. Examples of those having a phosphoric acid group include acid phosphooxyethyl methacrylate. It is done.

Moreover, the resin which has a crosslinked structure can also be obtained by using polyfunctional vinyl.
Specific examples of the multifunctional vinyls include, for example, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate. And neopentyl glycol diacrylate.

  The reaction system of the colorant compound precursor and the metal-containing compound in the presence of the resin, that is, the mixing ratio of the resin, the colorant compound precursor and the metal-containing compound used in the colorant compound production step is the toner finally obtained Colorant compound precursor and metal-containing compound are adjusted so that the content ratio of the colorant in (toner particles) is within a desired range and varies depending on the type of colorant compound precursor and metal-containing compound used. Is preferably 2 to 11 parts by mass, more preferably 4 to 9 parts by mass with respect to 100 parts by mass of the toner.

  As described above, the colorant compound generation step included in the production process for producing the toner containing at least the resin, the colorant compound precursor, and the metal-containing compound includes the resin, the colorant compound precursor, and the like. A process for obtaining an intermediate (hereinafter also referred to as “A process”), a process for mixing the intermediate obtained in the A process and a metal-containing compound (hereinafter also referred to as “B process”). The process of heating the mixture of the intermediate and the metal-containing compound obtained in the process B (hereinafter also referred to as “C process”).

In the process A, the intermediate obtained may be a mixture obtained by simply mixing the resin and the colorant compound precursor, but in order to improve the dispersion state of the colorant compound precursor, In order to obtain better characteristics with the obtained toner, it is preferable that the toner is obtained by heating a mixture of a resin and a colorant compound precursor.
In the case where the mixture of the resin and the colorant compound precursor is heated, the heating temperature (heating temperature) is preferably 70 to 147 ° C, more preferably 70 to 145 ° C, The heating time is preferably 2 to 16 hours.

The method for obtaining the intermediate from the resin and the colorant compound precursor varies depending on, for example, the form of the resin subjected to the A process, but is a dry type using a conventionally known mixer such as a Henschel mixer. As a method, a wet method using a known stirring device including a stirring member can be used. In particular, in a wet method, a device provided with a heating means such as a heating jacket, which has a mechanism for heating the mixture, can be suitably used.
Here, in the process A, the resin can be provided in various forms such as a resin powder, a dispersion of resin particles, a resin solution, and a dispersion of a resin solution, depending on the toner production method. Or it is preferable that it is the form of the dispersion liquid of a resin particle. Moreover, what mixed a polymerizable monomer can also be used as needed.

  In the process B, as a technique for mixing the intermediate and the metal-containing compound, a technique similar to the technique for obtaining the intermediate in the step A can be used.

  In the process C, the conditions for heating the mixture of the intermediate and the metal-containing compound vary depending on the type of resin, the type of the colorant compound precursor, the type of the metal-containing compound, the toner production method, and the like. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 0.5 to 8 hours.

  As a method for heating the intermediate and the metal-containing compound, when a dry method is used for mixing in the A process and the B process, for example, a kneader can be used. When this method is used, the stirring device used in the process can be used.

As a specific example of a method for producing a toner having such a colorant compound production step, a method of obtaining a toner by passing through a kneading step, a pulverization step and a classification step in this order (hereinafter also referred to as “pulverization method”), A method of passing through toner by aggregating and fusing resin fine particles made of a resin obtained by polymerizing a polymerizable monomer and fine particles made of other components (hereinafter also referred to as “polymerization method”). Is mentioned.
The pulverization method is based on a conventionally known pulverization method, and the polymerization method is based on a conventionally known emulsion polymerization aggregation method.

Here, when the pulverization method is used, for example, the process of premixing the resin and the colorant compound precursor is referred to as process A. The process of adding and mixing the metal-containing compound to the mixture is referred to as process B. As the mixing apparatus used in the A process and the B process, those capable of adjusting the temperature of the mixture in the mixing tank by heating the jacket of a mixing tank such as a Henschel mixer or controlling hot air are preferable.
When a polymerization technique is used, for example, the process of mixing the resin dispersion and the colorant compound precursor dispersion is referred to as A process, and the resin dispersion and the colorant compound precursor dispersion The process of adding the dispersion liquid of the metal-containing compound after forming the toner particles or the toner particle intermediates by heating the mixed liquid is referred to as B process. The technique of this example is based on the emulsion association method, and the process of continuing stirring while heating, such as a fusion process and a spheronization process, in the conventional emulsion polymerization process is referred to as C process.
In the polymerization method, if a method based on a polymerization method such as a suspension polymerization method or a polyester elongation method is used in the steps A and B, the resin is dissolved in a solvent. .

Specifically showing an example of a manufacturing process when the toner of the present invention is obtained by a pulverization technique,
(1) A first component in which a resin, a colorant compound precursor, and other components such as a release agent and a charge control agent as necessary are mixed using, for example, a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) Mixing process,
(2) a second mixing step in which the metal-containing compound is mixed with the first mixture obtained in the first mixing step;
(3) a kneading step in which the second mixture obtained in the second mixing step is kneaded while being heated using, for example, a twin-screw extrusion kneader,
(4) A pulverization step in which the kneaded product obtained in the kneading step is subjected to a pulverization process using a turbo mill pulverizer (manufactured by Turbo Kogyo Co., Ltd.) after a rough pulverization process using, for example, a hammer mill,
(5) A classification step of subjecting the pulverized product obtained in the pulverization step to fine powder classification using an air classifier utilizing the Coanda effect, for example.
(6) The method includes an external additive addition step of adding an external additive to the toner particles subjected to the fine powder classification process, if necessary.

  In such a pulverization technique, the first mixing step (preliminary mixing step) corresponds to the A process, the second mixing step corresponds to the B process, and the kneading process corresponds to the C process. In the colorant compound production step comprising the first mixing step, the second mixing step and the kneading step, an intermediate comprising a resin and a colorant compound precursor is obtained, and the colorant compound precursor and the metal-containing compound are obtained. As a result, a colorant compound is produced.

In the kneading step (C process), the heating temperature is preferably 70 to 180 ° C, particularly preferably 95 to 115 ° C.
The reason why the heating temperature, that is, the temperature of the kneaded product is preferably maintained at 70 ° C. or higher and 180 ° C. or lower is that when the temperature of the kneaded product exceeds 130 ° C., This is because the melt viscosity is excessively lowered, the shearing force for the colorant and the release agent becomes insufficient, and the uniformity of dispersion cannot be maintained. The reason why the temperature is 70 ° C. or higher is that in the case of the pulverization method, a stable toner color tone can be obtained at 70 ° C. or higher.

In addition, when a preferable example of the production process when the toner of the present invention is obtained by a polymerization technique is specifically shown,
(1) A colorant compound precursor dispersion preparing step for obtaining a colorant compound precursor dispersion in which particles of a colorant compound precursor comprising a colorant compound precursor are dispersed in an aqueous medium,
(2) a metal-containing compound dispersion preparing step for obtaining a metal-containing compound dispersion in which particles of a metal-containing compound comprising a metal-containing compound are dispersed in an aqueous medium;
(3) A polymerizable monomer solution is prepared by dissolving or dispersing toner particle constituents such as a release agent and a charge control agent in the polymerizable monomer to form a resin as necessary. A resin particle polymerization step of obtaining resin particles by adding in a medium, forming oil droplets by applying mechanical energy, and then performing a polymerization reaction in the oil droplets with radicals from a water-soluble radical polymerization initiator,
(4) a first stirring step of adding and stirring the colorant compound precursor dispersion to the resin particle dispersion obtained in the resin particle polymerization step;
(5) Aggregation step of forming an aggregate of resin particles and colorant compound precursor particles by heating the mixed dispersion obtained in the first stirring step,
(6) a second stirring step in which the metal-containing compound dispersion is added to the aggregate dispersion obtained in the aggregation step and stirred;
(7) The mixed dispersion obtained in the second stirring step is heated, and if necessary, the agglomeration is further advanced or an aggregation terminator is added to adjust the circularity while adjusting the toner particles. Obtaining toner particle forming step,
(8) A filtration and washing step for separating the toner particles from the aqueous medium and removing the surfactant from the toner particles.
(9) A drying step of drying the washed toner particles,
(10) an external additive addition step of adding an external additive to the dried toner particles;
Consists of

  Here, the “aqueous medium” is a medium composed of 50 to 100% by mass of water and 0 to 50% by mass of a water-soluble organic solvent, preferably, for example, sodium decyl sulfate, sodium dodecylbenzenesulfonate, It is an aqueous solution containing surfactants, such as other well-known anionic surfactants and nonionic surfactants. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran, and alcohol-based organic solvents that do not dissolve the resulting resin are preferable.

In such a polymerization method, the first stirring step and the aggregation step correspond to the A process, the second stirring step corresponds to the B process, and the toner particle forming step corresponds to the C process. That is, in the colorant compound generation step comprising the first stirring step, the aggregation step, the second stirring step, and the toner particle forming step, the resin dispersion in which resin particles are dispersed, and the colorant compound precursor By mixing and heating the colorant compound precursor dispersion in which the particles are dispersed, an intermediate composed of an aggregate of resin particles and colorant compound precursor particles is obtained, and the colorant compound precursor is obtained. A colorant compound is produced by the body and the metal-containing compound.
The reason why it is preferable to add the metal-containing compound to the system after obtaining the intermediate composed of the aggregate of the resin and the colorant compound precursor in this way is finally obtained. This is because good charging characteristics can be obtained for the toner.

  In the colorant compound precursor dispersion preparation step and the metal-containing compound dispersion preparation step (hereinafter, collectively referred to as “colorant compound generation dispersion step”), the aqueous medium is colored by mechanical energy. A dispersion of fine particles in which each of the agent compound precursor particles and the metal-containing compound particles is dispersed is prepared. The dispersing machine for dispersing oil droplets by mechanical energy is not particularly limited, and a stirring device “CLEAMIX” (manufactured by MTechnic Co., Ltd.) equipped with a rotor that rotates at high speed, an ultrasonic dispersing machine, a machine Examples thereof include a homogenizer, a manton gourin, and a pressure homogenizer.

The colorant compound precursor particles and metal-containing compound particles in the dispersion prepared in the colorant compound-forming dispersion step each have a volume-based median diameter in the range of 50 to 700 nm. More preferably, it is 100-500 nm, Most preferably, it is 150-250 nm.
As a method for controlling the volume-based median diameter of the particles of the colorant compound precursor and the particles of the metal-containing compound to 150 to 250 nm, for example, it can be controlled by adjusting the magnitude of the mechanical energy described above. it can.

  In the toner particle forming step, the temperature of the system is preferably 70 to 97 ° C., particularly preferably 75 to 90 ° C., by adjusting the temperature by heating.

  In this way, the toner of the present invention obtained by passing through the colorant compound production step may contain other constituent components together with the resin and the colorant. Specific examples include polyolefin waxes such as polyethylene wax and polypropylene wax; long-chain hydrocarbon waxes such as paraffin wax and sazol wax; dialkyl ketone waxes such as distearyl ketone; carnauba wax, montan wax, tri Methylolpropane tribehenate, pentaerythritol tetramyristate, pentaerythritol tetrastearate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecane All distearate, trimellitic acid tristearyl, ester waxes such as distearyl maleate; ethylenediamine behenyl amide, an amide-based waxes such as trimellitic acid tristearyl amide.

The release agent used as the constituent material of the toner of the present invention has a melting point of usually 40 to 125 ° C., preferably 50 to 120 ° C., more preferably 60 to 90 ° C.
By using a release agent having a melting point in the above range, the heat-resistant storage stability of the toner of the present invention is ensured, and there is a problem that cold offset occurs even when performing low-temperature fixing. And stable image formation can be performed.
Further, the content ratio of the release agent in the toner of the present invention is preferably 1 to 30% by mass, more preferably 5 to 20% by mass in the whole toner.

The toner of the present invention preferably has a volume-based median diameter (D50v) of 3 μm or more and 8 μm or less.
By setting the volume-based median diameter in the above range, it is possible to faithfully reproduce a very minute dot image having a level of, for example, 1200 dpi (number of dots per inch (2.54 cm)). As a result, it is possible to form a photographic image having a high definition equal to or higher than that of an image formed by printing ink. Therefore, even when a photographic image is formed as a visible image, the image has a high color. Reproducibility can be obtained. Thus, particularly in the light printing field, a full-color image including a high-definition photographic image can be easily formed even with a small amount of several hundred to several thousand parts.

  The volume-based median diameter of the toner of the present invention is measured using a measuring apparatus in which a computer system for data processing (manufactured by Beckman Coulter) is connected to "Coulter Multisizer TA-III" (manufactured by Beckman Coulter).・ It can be calculated. Specifically, 0.02 g of toner is added to 20 mL of a surfactant solution (for example, a surfactant solution in which a neutral detergent containing a surfactant component is diluted 10-fold with pure water for the purpose of dispersing the toner). Then, ultrasonic dispersion was performed for 1 minute to prepare a toner dispersion, and this toner dispersion was placed in a beaker containing “ISOTON II” (manufactured by Beckman Coulter) in a sample stand. Pipette until the indicated concentration is 8%. Here, a reproducible measurement value can be obtained by setting the concentration range. In the measurement apparatus, the measurement particle count is 25000, the aperture diameter is 50 μm, the frequency value is calculated by dividing the measurement range of 1 to 30 μm into 256, and the volume integrated fraction is 50 % Particle diameter is defined as the volume-based median diameter.

In the toner of the present invention, the coefficient of variation (CV value) in the volume-based particle size distribution is preferably 2% or more and 21% or less, particularly 5% or more and 15% or less. It is preferable.
The coefficient of variation in the volume-based particle size distribution indicates the degree of dispersion in the particle size distribution of the toner particles on the volume basis, and is calculated by the following mathematical formula (1).
This CV value indicates that the smaller the value is, the sharper the particle size distribution is. Therefore, it means that the toner particles have the same size.

  By setting the CV value within the above range, the toner has a uniform toner particle size, so that it is possible to reproduce the fine dots and fine lines required in digital image formation with higher accuracy. Become. Moreover, as a photographic image, an image having high definition equivalent to or higher than that of an image formed with printing ink can be formed.

The toner of the present invention has a softening point temperature (Tsp) of 70 ° C. or higher and preferably 110 ° C. or lower, particularly preferably 70 ° C. or higher and 100 ° C. or lower. By setting the softening point temperature within the above range, it is possible to reduce adverse effects caused by heat applied during fixing, and as a result, an image can be formed without imposing a large burden on the colorant. A wider and more stable color reproducibility can be obtained in a visible image. .
In addition, since fixing at a very low fixing temperature can be performed without causing any harmful effects, it is possible to perform environment-friendly image formation with reduced power consumption.

  The softening point temperature of the toner of the present invention is, for example, (1) adjusting the type and composition ratio of the polymerizable monomer for obtaining the resin, and (2) in the toner production process, for example, linked to the process of obtaining the resin. Using a transfer agent, adjusting the molecular weight of the resin according to the type and amount used, (3) adjusting the type and amount used of a constituent material such as a release agent, or these (1) to (3) It is possible to control by combining these methods.

As for the softening point temperature of the toner of the present invention, for example, “Flow Tester CFT-500” (manufactured by Shimadzu Corporation) is used, and a cylindrical body having a height of 10 mm is formed from the toner. A pressure of 1.96 × 10 ⁶ Pa is applied by a plunger while heating at 6 ° C./min to push out from a nozzle having a diameter of 1 mm and a length of 1 mm, whereby the relationship between the amount of descent from the plunger and the temperature Is measured by obtaining a softening flow curve indicating that the temperature at a drop of 5 mm is the softening point temperature.

  The toner of the present invention may be composed only of toner particles. As an external additive (external additive), particles such as inorganic fine particles and organic fine particles having a number average primary particle size of 4 to 800 nm. Alternatively, it may be configured such that a lubricant is added to the toner particles. 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 4.5% 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 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.

  When used as a two-component developer, for example, a tandem type image forming apparatus to be described later can obtain a full color image having good image quality at high speed without causing any harmful effects. Further, by appropriately selecting the constituent material of the toner, it can be suitably used for so-called low temperature fixing in which the paper temperature at the time of fixing is about 100 ° C.

  When the toner of the present invention is used as a two-component developer, the carrier is made of a conventionally known material such as a metal such as iron, ferrite, or magnetite, or an alloy of such a metal with a metal such as aluminum or lead. Magnetic particles 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. .

In the toner of the present invention described above, the reaction that the compound constituting the colorant is produced by reacting the colorant compound precursor having a hue different from that of the obtained toner and the metal-containing compound in the production process. The reaction compound is produced in the presence of a resin constituting the toner, and thus the hue of the toner obtained can be adjusted, thus having a good color tone, High chargeability, cleanability and image density stability can be obtained.
In particular, according to the present invention, as in Patent Document 3, as compared with the case where a metal chelate compound having a high viscosity is produced as a colorant, a good color tone can be obtained and sufficient concentration stability can be obtained. In addition, the charging property, the cleaning property, and the transparency of the toner image are good.

  The reason why the toner of the present invention has excellent characteristics such as having a good color tone and high chargeability, cleaning properties, and stability of image density is specifically described using a resin as a medium. In the case where a polymerization method is used for the production, a relatively small molecular weight colorant compound precursor and a metal-containing compound for producing a colorant compound in a portion extending from near the surface layer to the inside of the resin particles. Since the reaction proceeds, the colorant is stably taken into and contained in the toner particles as compared with the case where a compound having a large molecular weight is added as the colorant. As a result, the colorant is liberated. It is presumed that this is because the probability of being exposed or exposed to the surface is reduced. That is, since the colorant is prevented from being exposed on the surface of the toner particles, the toner particles are uniformly charged, and excellent fluidity is obtained and the cleaning property is improved, and the photosensitive member is obtained. It is presumed that excessive adhesion force was suppressed against the occurrence of the above.

The toner of the present invention and the manufacturing method thereof can be suitably applied to magenta toner from the viewpoint of color tone control.
Further, when the toner of the present invention is a magenta toner, a magenta organic pigment is supplementarily contained as a colorant constituting the magenta toner together with a reaction product of a colorant compound precursor and a metal-containing compound. It may be. In this case, the content ratio of the magenta organic pigment is preferably 10 to 30% with respect to the entire colorant from the viewpoint of ensuring a high color tone.

  Hereinafter, a fixing device suitably used for image formation using the toner of the present invention will be described.

  FIG. 1 is a cross-sectional view showing an example of the configuration of a fixing device used for image formation using the toner of the present invention. The fixing device 10 includes a heating roller 12 that is heated by an induction heating mechanism 14 that is an external heating mechanism, a fixing roller 13 that is spaced apart from the heating roller 12 and extends in parallel, and the heating roller 12 and the fixing roller 13. The fixing belt 11 is formed of an endless heat-resistant belt that is stretched and rotates counterclockwise by the rotation of either the heating roller 12 or the fixing roller 13, and the fixing belt 11 is rotated by being driven by the fixing roller 13. And a pressure roller 15 that forms a fixing nip portion N by being brought into pressure contact with the fixing roller 13. The fixing belt 11 is heated via a heating roller 12 heated by an induction heating mechanism 14.

  The heating roller 12 has a hollow cylindrical shape made of a magnetic metal such as iron, cobalt, nickel, or an alloy thereof, and has an outer diameter of, for example, 20 to 40 mm and a wall thickness of 0.3 to 1.0 mm. In addition, the heat capacity is low and the temperature can be increased easily.

  The fixing roller 13 includes a metal core 13a made of, for example, stainless steel, and an elastic member 13b covered with a core 13a made of heat-resistant silicone rubber in a solid or foamed form. The outer diameter of the fixing roller 13 is about 20 to 40 mm and is larger than the outer diameter of the pressure roller 15. The thickness of the elastic member 13b is about 4 to 6 mm. The fixing roller 13 has an Asker C hardness of 10 to 50 degrees measured at a load of 9.8 N using an Asker-C type measuring instrument manufactured by Kobunshi Keiki Co., Ltd.

  In the fixing device 10, the fixing belt 11 is heated at a contact portion W with the heating roller 12 heated by the induction heating mechanism 14, and the inner surface of the fixing belt 11 is rotated by the rotation of the heating roller 12 and the fixing roller 13. The belt is continuously heated, and as a result, the fixing belt 11 is heated throughout.

The fixing belt 11 has a configuration in which, for example, a heat generation layer, an intermediate elastic layer, and a release layer are formed in this order on a metal substrate. The thickness of the release layer is preferably about 10 to 300 μm, particularly preferably about 200 μm.
Further, as the base material of the fixing belt 11, a resin substrate having heat resistance such as a fluorine resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a PEEK resin, a PES resin, or a PPS resin may be used instead of the metal substrate. Good.

The pressure roller 15 includes, for example, a metal core 15a made of a metal cylindrical member having high thermal conductivity such as copper or aluminum, and an elastic layer 15b having high heat resistance and releasability provided on the surface of the metal core 15a. It is composed of. SUS (stainless steel) may be used as a material constituting the metal core 15a.
The pressure roller 15 has an Asker C hardness of 80 to 100 degrees, an outer diameter of 20 to 40 mm, and an elastic layer thickness of 0.5 to 2.0 mm.

  The induction heating mechanism 14 heats the heating roller 12 by an electromagnetic induction method, and includes an exciting coil 16 that is a magnetic field generating means and a coil guide plate 17 around which the exciting coil 16 is wound. . The coil guide plate 17 has a semi-cylindrical shape that is disposed close to the outer peripheral surface of the heating roller 12, and the excitation coil 16 is formed of a single long excitation coil wire along the coil guide plate 17 in the axial direction of the heating roller 12. It is one that is wound around alternately. The excitation coil 16 is connected to a drive power supply (not shown) whose oscillation circuit has a variable frequency.

  Outside the exciting coil 16, a semi-cylindrical exciting coil core 18 made of a ferromagnetic material having a relative permeability of 2500 such as ferrite is fixed to the core support member 18 </ b> A and is arranged close to the exciting coil 16. .

  In this fixing device 10, a high frequency alternating current of 10 kHz to 1 MHz, preferably a high frequency alternating current of 20 kHz to 800 kHz is supplied to the exciting coil 16 from a driving power source, thereby generating an alternating magnetic field and fixing with the heating roller 12. The alternating magnetic field acts on the heating roller 12 and the heat generating layer of the fixing belt 11 in the contact area W with the belt 11 and the vicinity thereof, and an eddy current generated in a direction that prevents the change of the alternating magnetic field inside the heating roller 12 and the fixing belt 11. Joule heat corresponding to the resistance of the heat generating layer of the fixing belt 11 is generated, and the heating roller 12 and the fixing belt 11 are heated by electromagnetic induction mainly in the contact area W and its vicinity. The temperature detecting means comprising a thermosensitive element such as a thermistor in which the fixing belt 11 heated in this manner is disposed in contact with the inner surface of the fixing belt 11 in the vicinity of the inlet side of the fixing nip N. 19, the belt inner surface temperature is detected. Then, the fixing process is performed in the fixing nip portion N by the heat from the heated fixing belt 11.

An example of fixing conditions by the fixing device shown in FIG. 1 is that the fixing temperature (surface temperature of the fixing belt 11 at the fixing nip portion N) is 70 to 210 ° C., and the nip width of the fixing nip portion N is 5 to 40 mm. , Preferably 11 to 30 mm. Here, the fixing nip N refers to a contact width between the toner image T formed on the image support P and the surface of the fixing belt 11. The contact load between the fixing roller 13 and the pressure roller 15 is 40 to 350 N, preferably 50 to 300 N.
Further, image formation can be performed when the moving speed of the image support (hereinafter also referred to as “printing speed”) in the fixing nip portion is in the range of 230 to 500 mm / sec.

FIG. 2 is a cross-sectional view showing another example of the configuration of the fixing device used for image formation using the toner of the present invention.
The fixing device 20 includes a fixing pressure roller 23 in which an elastic layer 23 b made of an elastic foam material is formed on the outer peripheral surface of a core metal 23 a around which the fixing belt 21 is wound, and fixing via the fixing belt 21. An induction heating mechanism 24 provided to face the pressing roller 23 and a pressure roller 25 pressed against the fixing pressing roller 23 via the fixing belt 21 are provided.

The fixing belt 21 is obtained by forming a release layer having a thickness of 10 μm or more on a heat generating base material layer having a thickness of 40 μm or less. The heat capacity of the fixing belt 21 is 0.017 to 0.077 J. / K / cm ² .
Further, the fixing belt 21 is provided by guide members (not shown) arranged at both ends in the axial direction (direction perpendicular to the paper surface in FIG. 2) so that the substantially cylindrical shape is maintained even when the fixing pressing roller 23 rotates. Guided.

The pressure roller 25 is provided with a hard foam layer 25b on a core metal 25a. The hardness of the pressure roller 25 is greater than the hardness of the fixing pressure roller 23. The outer diameter of the pressure roller 25 is substantially the same as the outer diameter of the fixing pressure roller 23.
The hard foam layer 25b has a heat insulating structure, and can be, for example, a silicone rubber foam or a silicone layer filled with hollow fibers or hollow particles.

  In FIG. 2, 29 is a temperature detection sensor such as a thermistor disposed in contact with or close to the outer peripheral surface of the fixing belt 21, and induction heating is performed based on the temperature detected by the temperature detection sensor 29. The output of the mechanism 24 is controlled.

  In the fixing device 20 having such a configuration, the pressure roller 25 is rotationally driven, for example, counterclockwise by a driving mechanism (not shown), so that the fixing belt 21 is driven and rotated clockwise, whereby the toner image T The image support P on which the toner image is formed passes through the fixing nip N, and the toner image is fixed on the image support P by heat and pressure. The fixing pressure roller 23 rotates with the rotation of the fixing belt 21.

  The above fixing device 20 can perform fixing under the same conditions as the fixing device 10 shown in FIG.

FIG. 3 is a cross-sectional view showing still another example of the configuration of the fixing device used for image formation using the toner of the present invention.
The fixing device 30 is pressed against a fixing roller 31 disposed so as to be in contact with one surface of the image support P on which an unfixed toner image is formed (for example, the upper surface of the image support P in FIG. 3). A pressure roller 33 provided in such a manner, an external heating rotator 35 provided so as to be in contact with the surface of the fixing roller 31, and a forced peeling means 37 provided so that a tip edge thereof is in contact with the pressure roller 33. A fixing nip portion N is formed by a pressure contact portion between the fixing roller 31 and the pressure roller 33. In FIG. 3, 39a and 39b are non-contact type temperature detecting means.

  The fixing roller 31 includes a heating source HLa made of a heater lamp such as a halogen lamp, for example, and includes a cylindrical cored bar 31a in which the heating source HLa is disposed, and an outer peripheral surface of the cored bar 31a. And a coating layer formed on the surface of the heat-resistant elastic layer 31b through an adhesive layer (not shown) made of, for example, a mixture obtained by applying and baking a mixed latex of fluorine rubber and fluorine resin. A soft roller composed of 31c.

  Here, the heating source HLa is disposed inside the cored bar 31a so as to extend in the length direction of the fixing roller 31, and the temperature of the outer peripheral surface of the fixing roller 31 that is a direct heating target is maintained in the set temperature range. Thus, based on the surface temperature of the fixing roller 31 detected by the temperature detection means 39a, for example, the lighting state is on / off controlled by a control means (not shown).

Examples of the heat-resistant elastic material constituting the heat-resistant elastic layer 31b include silicone rubber, foamed silicone rubber, and fluorine rubber, and it is particularly preferable to use silicone rubber. The heat-resistant elastic layer 31b preferably has a thickness in the range of 1.0 mm to 4.0 mm. When the thickness of the heat-resistant elastic layer 31b is 0.2 mm or less, the surface of the fixing roller 31 becomes difficult to follow the unevenness of the surface of the image support P carrying the toner image to be heat-fixed, resulting in high image quality. The visible image may not be formed. Further, when the thickness of the heat resistant elastic layer 31b is less than 1.0 mm, the fixing roller 31 is convex with respect to the pressure roller 33, and it is difficult to secure the width of the fixing nip portion N.
On the other hand, when the thickness of the heat-resistant elastic layer 31b is excessive, it is possible to sufficiently ensure the thermal responsiveness when the surface of the fixing roller 31 is heated by the heating source HLa disposed inside the cored bar 31a. It may not be possible.

  Although it does not specifically limit as a material which comprises the metal core 31a, Metals, such as aluminum, iron, copper, or those alloys can be mentioned.

  The coating layer 31c is a layer having a function as a toner release layer for preventing the toner from adhering, and is a polytetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene and perfluoroalkoxyethylene ( PFA), a release resin containing a fluororesin selected from a copolymer (FEP) of tetrafluoroethylene and hexafluoropropylene, and the thickness thereof is preferably 50 μm or less.

  Since the covering layer 31c is made of a fluororesin, the surface releasability of the fixing roller 31 with respect to the toner itself is enhanced by the releasing action, so that fixing is performed without applying a release oil such as silicone oil to the fixing roller 31. During processing, the deposits derived from the toner are less likely to adhere to the surface of the fixing roller 31, and the peelability of the image support P from the fixing roller 31 is increased.

By setting the thickness of the coating layer 31c to 50 μm or less, the surface of the fixing roller 31 can easily follow the unevenness of the surface of the image support P on which the unfixed toner image is formed. it can.
In addition, in order to make it easy to form the uniform coating layer 31c, the thickness is more preferably 20 μm or more.

  Specifically, the coating layer 31c is formed to have a thickness of 20 to 50 μm by, for example, (1) coating and baking a release resin in a dispersion state, and (2) being formed to a thickness of 20 to 50 μm. It can be formed by covering and releasing a release resin tube.

  The fixing roller 31 has an Asker C hardness of 60 to 85 degrees measured with a load of 9.8 N using an Asker-C type measuring instrument manufactured by Kobunshi Keiki Co., Ltd.

As shown in FIG. 3, the pressure roller 33 is formed on, for example, a cylindrical cored bar 33a, a heat resistant elastic layer 33b formed on the outer peripheral surface of the cored bar 33a, and a surface of the heat resistant elastic layer 33b. A soft roller comprising the coating layer 33c can be used.
In the example of this figure, the pressure roller 33 has a built-in heating source HLa, like the fixing roller 31. This heating source HLa is arranged inside the metal core 33a so as to extend in the length direction of the pressure roller 33, and the temperature of the outer peripheral surface of the pressure roller 33, which is a direct heating target, is maintained within a set temperature range. Thus, based on the surface temperature of the pressure roller 33 detected by the temperature detection means 39b, for example, the lighting state is on / off controlled by a control means (not shown).

Examples of the heat-resistant elastic material constituting the heat-resistant elastic layer 33b include silicone rubber, foamed silicone rubber, and fluorine rubber, and it is particularly preferable to use silicone rubber. The heat-resistant elastic layer 33b is thinner than the heat-resistant elastic layer 31b of the fixing roller 31 if the heat-resistant elastic layer 31b and the heat-resistant elastic layer 33b are of similar hardness. 5 to 3 mm.
Since the heat-resistant elastic layer 33 b of the pressure roller 33 is thinner than the heat-resistant elastic layer 31 b of the fixing roller 31, the fixing roller 31 that is one fixing rotating body in the fixing nip portion N is the other. It is possible to obtain a shape in which the pressure roller 33 which is the fixing rotator is convex.

  Although it does not specifically limit as a material which comprises the metal core 33a, Metals, such as aluminum, iron, copper, or those alloys can be mentioned.

Specific examples of the material constituting the coating layer 33c include, for example, polytetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene and perfluoroalkoxyethylene (PFA), and a copolymer of tetrafluoroethylene and hexafluoropropylene. Examples thereof include a resin mainly composed of a fluororesin such as coalescence (FEP).
Specifically, the covering layer 33c is formed to have a thickness of 20 to 50 μm by, for example, (1) coating and firing a fluororesin in a dispersion state, and (2) fluorine formed to have a thickness of 20 to 50 μm. The resin tube can be formed by covering the cored bar 33a.

  The pressure roller 33 preferably has a hardness equal to or higher than that of the fixing roller 31. For example, the pressure roller 33 has an Asker C hardness of 65 to 90 degrees.

  As the external heating rotator 35, for example, a cylindrical cored bar having a built-in heating source HLa made of a halogen heater lamp or the like and a coating layer formed on the outer peripheral surface of the cored bar can be used.

  As the forced peeling means 37, for example, a plate-like member in which a release layer is formed by laminating a thin film made of a fluororesin such as polytetrafluoroethylene (PTFE) on a thin stainless steel plate having a thickness of 0.2 mm. That is, the tip edge thickness is 0.2 mm, and the straightness (shift in linearity of the plate-like member) is 0.5 mm or less.

  The above fixing device 30 can perform fixing under the same conditions as the fixing device 10 shown in FIG.

FIG. 4 is a schematic diagram showing an example of the configuration of an image forming apparatus used for image formation using the toner of the present invention.
The image forming apparatus 40 is a tandem color image forming apparatus, and includes a plurality of image forming units 50Y, 50M, 50C, and 50K provided along a belt-like intermediate transfer member 46, a paper feed cassette 42, And a fixing device 49. In FIG. 4, reference numeral 41 denotes an operation unit, and reference numerals 47Y, 47M, 47C, and 47K denote toner cartridges for respective colors.

  The image forming unit 50Y forms a yellow toner image, and includes a photoreceptor 51Y. Around the photoreceptor 51Y, a charging unit 52Y, an exposure unit 53Y, a developing device 54Y, a primary transfer unit 57Y, and a cleaning unit are provided. The means 58Y is arranged and configured.

The image forming units 50M, 50C, and 50K have the same configuration as the image forming unit 50Y except that magenta, cyan, and black toner images are formed instead of forming yellow toner images.
Here, a yellow toner image is formed by the image forming unit 50Y, a magenta toner image is formed by the image forming unit 50M, and a cyan toner image is formed by the image forming unit 50C. According to the image forming unit 50K, a black toner image is formed.

  The intermediate transfer member 46 is stretched around a plurality of support rollers 46A, 46B, and 46C, and is supported so as to be able to circulate.

In this image forming apparatus, the toner images of the respective colors formed by the image forming units 50Y, 50M, 50C, and 50K are sequentially primary transferred and superimposed on the intermediate transfer body 46 that is circulated by the primary transfer unit. A color toner image is formed.
On the other hand, the image support P accommodated in the paper feed cassette 42 is fed one by one by the paper feed roller 43, conveyed to the secondary transfer means 57A by the registration roller 44, and the color support on the image support P. The toner image is secondarily transferred.
Next, the image support P is conveyed to the fixing device 49 and subjected to a fixing process. Thereafter, the image support P is sandwiched between the discharge rollers 45 and discharged onto the discharge tray 48 outside the apparatus.

  Here, as the image support, plain paper from thin paper to thick paper, high-quality paper, coated printing paper such as art paper or coated paper, commercially available OA Japanese paper or postcard paper, plastic film for OHP, Although various kinds, such as cloth, can be mentioned, it is not limited to these.

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

(Magenta toner production example 1: toner production by pulverization method)
<First mixing step (Process A)>
100 parts by mass of a polyester resin (bisphenol A-ethylene oxide adduct, condensate of terephthalic acid and trimellitic acid, weight average molecular weight 20000) and 2 parts by mass of the compound represented by the formula (1-16) as a colorant compound precursor Part, 6 parts by mass of a release agent composed of pentaerythritol tetrastearate, and 1 part by mass of a charge control agent composed of boron dibenzylate are added to a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) equipped with a jacket and stirred. The peripheral speed of the wings was set to 25 m / sec and mixed for 5 minutes. During the mixing process, the temperature of the mixture was maintained at 25 ° C. or lower by circulating 9 ° C. cooling water through the jacket of the Henschel mixer.

<Second mixing step (B process)>
Into the Henschel mixer, 0.8 parts by mass of the metal coordination compound represented by the formula (3-4) as a metal-containing compound is added, and the peripheral speed of the stirring blade is set to 40 m / sec over 30 minutes. Mixed processing was performed. During this mixing process, hot water of 40 ° C. was passed through the jacket of the Henschel mixer, and the temperature of the mixture was 47 ° C.

<Kneading process (C process)>
The obtained mixture was kneaded while being heated to 140 ° C. by a twin screw extrusion kneader. During this kneading process, the temperature of the kneaded material in the discharge part of the kneader was 145 ° C. Thereafter, the kneaded product was allowed to cool for 6 hours.

<Crushing process>
When the temperature of the kneaded product reaches 28 ° C., it is coarsely pulverized by a hammer mill, then pulverized by a turbo mill pulverizer (manufactured by Turbo Kogyo Co., Ltd.), and further finely classified by an airflow classifier utilizing the Coanda effect. As a result, toner particles having a volume-based median diameter of 5.4 μm were obtained.

<External additive addition process>
External addition consisting of 0.6 parts by mass of hexamethylsilazane-treated silica (average primary particle size 12 nm) and 0.8 parts by mass of n-octylsilane-treated titanium dioxide (average primary particle size 24 nm) was added to the obtained toner particles. Magenta toner is added by an external addition process using a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) and mixing with a stirring blade peripheral speed of 35 m / sec, a processing temperature of 35 ° C., and a processing time of 15 minutes. (Hereinafter referred to as “magenta toner (1)”).
The shape and particle size of the toner particles did not change with the addition of the external additive.

(Comparative Magenta Toner Production Example 1: Toner Production by Crushing Method)
In the first mixing step of Production Example 1 of magenta toner, a color formed of a compound represented by the following formula (A-1) instead of the compound represented by the formula (1-16) (colorant compound precursor) The volume-based median diameter was obtained in the same manner as in Magenta Toner Production Example 1 except that 2.8 parts by mass of the agent was used, and after this first mixing step, the mixture proceeded to the kneading step without passing through the second mixing step. Toner particles having a particle size of 5.5 μm were obtained, and an external additive was added to the obtained toner particles to obtain a magenta toner (hereinafter referred to as “comparative magenta toner (H1)”).

(Manufacture example 2 of comparative magenta toner: manufacture of toner by pulverization method)
In Production Example 1 of magenta toner, a compound represented by the formula (1-1) is used as a colorant compound precursor, a metal coordination compound represented by the formula (1-1) is used as a metal-containing compound, and a polyester resin. A compound represented by formula (1-1) as a colorant compound precursor, a metal coordination compound represented by formula (3-5) as a metal-containing compound, a release agent, a charge control agent, In the same manner as in Magenta Toner Production Example 1 except that these are mixed together, that is, these raw materials are put into a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.), and the peripheral speed of the stirring blade is set to 25 m / sec. By setting and mixing for 5 minutes, a magenta toner (hereinafter referred to as “comparative magenta toner (H2)”) was obtained.

(Magenta Toner Production Example 2: Toner Production by Emulsion Association Method)
(1) Preparation Example 1 of Colorant Compound Precursor 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, 20 parts by mass of the compound represented by the formula (1-3) is gradually added as a colorant compound precursor, and then “CLEARMIX W-Motion CLM-0.8” (M Technique Co., Ltd.). The colorant compound precursor dispersion in which the particles of the colorant compound precursor are dispersed (hereinafter referred to as “colorant compound precursor dispersion (1)”) is prepared. did.
The volume-based median diameter of the colorant compound precursor particles in the colorant compound precursor dispersion (1) was measured to be 221 nm.
The volume-based median diameter is “MICROTRAC UPA-150” (manufactured by HONEYWELL), sample refractive index 1.59, sample specific gravity 1.05 (in terms of spherical particles), solvent refractive index 1.33, solvent viscosity. The measurement was performed by adjusting the zero point by introducing ion-exchanged water into the measurement cell under the measurement conditions of 0.797 (30 ° C.) and 1.002 (20 ° C.).

(2) Preparation example 1 of metal-containing compound dispersion
In Preparation Example 1 of the colorant compound precursor dispersion, the metal represented by the formula (3-8) as a metal-containing compound instead of the compound represented by the formula (1-3) (colorant compound precursor) A metal-containing compound dispersion in which particles of a metal-containing compound are dispersed by the same method as in Preparation Example 1 of the colorant compound precursor dispersion except that 19.4 parts by mass of the coordination compound is used (hereinafter referred to as “metal-containing compound”). Compound dispersion (1) ") was prepared.
With respect to the particle diameter of the metal-containing compound particles in this metal-containing compound dispersion (1), the volume-based median diameter was measured under the same measurement conditions as in Preparation Example 1 of the colorant compound precursor fine particle dispersion. there were.

(3) Preparation example 1 of toner particles
(A) Preparation of resin particles for core part (a) First-stage polymerization Sodium dodecyl sulfate (C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) was added to a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introducing device. ₂ SO ₃ Na) and 4 parts by mass of an anionic surfactant dissolved in 3040 parts by mass of ion-exchanged water are charged, and 10 parts by mass of potassium persulfate (KPS) is added to 400 parts by mass of ion-exchanged water. After adding the dissolved polymerization initiator solution 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 16.4 parts by mass of n-octyl mercaptan. After the dropwise addition of the polymerizable monomer solution consisting of 1 part over 1 hour, polymerization (first stage polymerization) is carried out by heating and stirring at 75 ° C. for 2 hours, and a resin containing resin particles (1h) Particle dispersion (1H) was prepared.
The obtained resin particles (1h) had a weight average molecular weight of 16,500.

(B) Second-stage polymerization In a flask equipped with a stirrer, 101.1 parts by mass of styrene, 62.2 parts by mass of n-butyl acrylate, 12.3 parts by mass of methacrylic acid and 1.75 parts by mass of n-octyl mercaptan After adding a polymerizable monomer solution comprising 93.8 parts by weight of paraffin wax “HNP-57” (manufactured by Nippon Wax Co., Ltd.), the internal temperature is raised to 90 ° C. and dissolved. A meter solution was prepared.
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 98 ° 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 paraffin wax, By using a mechanical disperser “CLEAMIX” (manufactured by M Technique Co., Ltd.) having a circulation path, the emulsified particle dispersion containing emulsified particles (oil droplets) having a dispersed particle diameter of 340 nm is obtained by mixing and dispersing for 8 hours. 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 98 ° C. for 12 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 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 was added to the resin particle dispersion (1HM) obtained in the second-stage polymerization. A 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 under a temperature condition of 80 ° C. . 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.

(B) Preparation of Resin Particles for Shell 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 16.4 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 the parts by mass were used, thereby obtaining resin particles for shell (1).

(C) Preparation of toner particles (a) Formation of core part <First stirring step and aggregation step (A process)>
In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introducing device, 420.7 parts by mass of resin particles for core (1), 900 parts by mass of ion-exchanged water, and a colorant compound precursor dispersion (1) After 42 parts by mass were charged and stirred to adjust the internal temperature to 30 ° C., the pH was adjusted to 9 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.

<Second stirring step (process B)>
In the above state, 42 parts by mass of the metal-containing compound dispersion (1) was further added, followed by stirring.

<Toner particle formation process (C process)>
Thereafter, the average particle diameter of the associated particles was measured with “Coulter Multisizer 3” (manufactured by Beckman Coulter Inc.). When the volume-based median diameter reached 6.5 μm, 40.2 parts by mass of sodium chloride was added. An aqueous solution dissolved in 1000 parts by mass of ion-exchanged water 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, whereby the core part (1) The core part containing liquid (1) containing this was obtained.
With respect to the obtained core part (1), the average circularity was measured using “FPIA2100” (manufactured by Sysmec), and it was 0.912.

(B) Formation of Shell After adjusting the core-containing liquid (1) to 65 ° C., 96 parts by mass of resin particles for shell (1) were added, and 2 parts by mass of magnesium chloride hexahydrate was added to ion-exchanged water. An aqueous solution dissolved in 1000 parts by mass is added over 10 minutes, the temperature is raised to 70 ° C., and the mixture is stirred for 1 hour to fuse the resin particles for shell (1) to the surface of the core (1). After that, an aging treatment was performed at a liquid temperature of 75 ° C. for 20 hours to form a shell.
Thereafter, an aging treatment (shell formation) was stopped by adding an aqueous solution in which 40.2 parts by mass of sodium chloride was dissolved in 1000 parts by mass of ion-exchanged water, and then cooled to 30 ° C. at 8 ° C./min. The produced particles were filtered, washed with ion exchange water at 45 ° C. repeatedly, and dried with hot air at 40 ° C. to obtain toner particles having a structure in which a shell was formed on the surface of the core.

(4) External addition treatment To the obtained toner particles, hexamethylsilazane-treated silica (average primary particle size 12 nm) 0.6 parts by mass and n-octylsilane-treated titanium dioxide (average primary particle size 24 nm) 0.8 Add external additive consisting of parts by mass, and use Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) to mix externally with stirring blades at a peripheral speed of 35 m / sec, a processing temperature of 35 ° C., and a processing time of 15 minutes. As a result, a magenta toner (hereinafter referred to as “magenta toner (2)”) was obtained.
The shape and particle size of the toner particles did not change with the addition of the external additive.

(Magenta Toner Production Examples 3 to 17: Toner Production by Emulsion Association Method)
In Production Example 2 of magenta toner, Preparation Example 1 of Colorant Compound Precursor Dispersion and Preparation Example 1 of Metal Containing Compound Dispersion were used except that the colorant compound precursor and metal-containing compound shown in Table 1 below were used. Similarly, a colorant compound precursor dispersion and a metal-containing compound dispersion were obtained, respectively, and toner particle preparation examples except that the obtained colorant compound precursor dispersion and metal-containing compound dispersion were used. In the same manner as in No. 1, toner particles are obtained, and the obtained toner particles are further subjected to an external addition treatment, whereby magenta toners (hereinafter referred to as “magenta toners (3) to (17)”). Got.

(Comparative Magenta Toner Production Example 3)
In the first stirring step and the aggregation step according to Magenta Toner Production Example 2, instead of the colorant precursor dispersion (1), the colorant fine particle dispersion obtained in Preparation Example 1 of the following colorant fine particle dispersion is used. 200 parts by mass of the liquid was used for comparison in the same manner as in Preparation Example 1 of the toner particles, except that after the first stirring step and the aggregation step, the process proceeded to the toner particle forming step without passing through the second stirring step. The toner particles thus obtained were further subjected to an external addition treatment, whereby a comparative magenta toner (hereinafter referred to as “comparative magenta toner (H3)”) was obtained.

(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 a colorant composed of a compound represented by the following formula (A-2) is gradually added, and then “Cleamix W Motion CLM-0.8” (manufactured by M Technique Co., Ltd.). ) To prepare a colorant fine particle dispersion in which colorant fine particles are dispersed (hereinafter referred to as “colorant fine particle dispersion (1)”).
The volume-based median diameter of the colorant fine particles in the colorant fine particle dispersion (1) was measured and found to be 545 nm.
The volume-based median diameter is “MICROTRAC UPA-150” (manufactured by HONEYWELL), sample refractive index 1.59, sample specific gravity 1.05 (in terms of spherical particles), solvent refractive index 1.33, solvent viscosity. The measurement was performed by adjusting the zero point by introducing ion-exchanged water into the measurement cell under the measurement conditions of 0.797 (30 ° C.) and 1.002 (20 ° C.).

(Developer Production Examples 1-17 and Comparative Developers 1-3 Production Examples)
Each of the magenta toners (1) to (17) and the comparative magenta toners (H1) to (H3) is coated with a silicone resin-coated ferrite carrier having a volume average particle diameter of 60 μm, and the concentration of the magenta toner is 6% by mass. By mixing so that developers (1) to (17) and comparative developers (H1) to (H3) were obtained.

[Examples 1 to 17 and Comparative Examples 1 to 3]
For the developer, the following (1) to (4) were evaluated in the magenta monochromatic mode using an image forming apparatus “bizhub PRO C6500” (manufactured by Konica Minolta Business Technologies, Inc.). The results are shown in Table 1.

(1) Image density stability An image with a pixel rate of 10% was formed on an A4 size image support (transfer paper), and a spectrophotometer “Gretag Macbeth Spectrolino” (Gretag Macbeth) was formed every 2000 images formed. ), Measure the density of the solid image of magenta, and if the amplitude of the image density is within ± 0.05 (1.2 ± 0.05) Was evaluated as “◯” as good when “±” was more than ± 0.05 and not more than ± 0.1, and “x” was evaluated as bad when the image density was more than ± 0.1.
The toner adhesion amount on the transfer paper of the solid image was fixed at 4 g / m ² at the start of the test, and the density measurement image was sampled. The density fluctuation was processed with the data fluctuation of up to 200,000 sheets from the start of the live-action test.
Here, the image density is a D50 light source as a light source, a φ4 mm reflection measurement aperture, a viewing angle (observer) of 2 °, a UV cut filter, a dedicated white tile for reference alignment, and a measurement mode “Reflect”. It is measured under the condition of “Tance”.

(2) Toner scattering (chargeability)
After forming 100,000 images, the developing device is taken out, the developing device is set on the idle rotating machine, A4 paper is placed around the sleeve of the developing device, and the idle rotating is performed for 60 minutes (developing device). Rotation speed of the sleeve is 620 mm / second), the amount of toner dropped on the paper is measured, “A” when the amount of toner on the paper surface is 3 mg or less, “B” when the amount exceeds 3 mg and less than 6 mg, 6 mg The case of exceeding 9 mg and less than 9 mg was evaluated as “C”, the case of exceeding 9 mg and less than 12 mg as “D”, the case of exceeding 12 mg and less than 15 mg as “E”, and the case of exceeding 15 mg as “F”.
Here, the case where the evaluation is A to C is a level having no practical problem.

(3) Transparency An image with a toner adhesion amount of 4 g / m ² is formed on an OHP sheet, and the image on the OHP is used with a “330 type magnetic spectrophotometer” manufactured by Hitachi, Ltd. The visible spectral transmittance was measured using an unsupported OHT sheet as a reference to obtain a spectral transmittance at a wavelength of 650 nm, and the transparency of the image on the OHP was evaluated based on the spectral transmittance.
This evaluation of transparency by spectral transmittance shows that the larger the value, the better the transparency. In this test, 65% or more was judged to be a level having good transparency.

(4) Cleaning property An image is formed on 800,000 or more image supports (transfer papers) under the same conditions as the image forming conditions relating to the evaluation of image density stability, and each of these images is magenta solid. The presence or absence of white spot-like image defects in the image is visually confirmed, and the number of generated images is 80 based on the number of images formed when the image defects are confirmed (hereinafter also referred to as “number of generated images”). “◎” as excellent when the number is 10,000 or more, “good” when the number is 500,000 or more and less than 800,000, and “bad” when the number is less than 500,000 Evaluated as “x”.

  In Table 1, (2-3) in the column of the colorant compound precursor represents 1- (2-hydroxyphenylazo) -2-naphthol, and (2-5) represents 8- (2-hydroxyphenylazo). ) -Quinoline.

FIG. 3 is a cross-sectional view illustrating an example of a configuration of a fixing device used in image formation using the toner of the present invention. FIG. 6 is a cross-sectional view illustrating another example of a configuration of a fixing device used in image formation using the toner of the present invention. FIG. 10 is a cross-sectional view showing still another example of the configuration of a fixing device used in image formation using the toner of the present invention. FIG. 3 is a schematic diagram illustrating an example of an image forming apparatus used in image formation using the toner of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Fixing device 11 Fixing belt 12 Heating roller 13 Fixing roller 13a Core metal 13b Elastic member 14 Induction heating mechanism 15 Pressure roller 15a Core metal 15b Elastic layer 16 Excitation coil 17 Coil guide plate 18 Excitation coil core 18A Core support member 19 Temperature detection means 20 fixing device 21 fixing belt 23 fixing pressure roller 23a core metal 23b elastic layer 24 induction heating mechanism 25 pressure roller 25a core metal 25b hard foam layer 29 temperature detection sensor 30 fixing device 31 fixing roller 31a core metal 31b heat resistant elastic layer 31c Covering layer 33 Pressure roller 33a Core metal 33b Heat resistant elastic layer 33c Covering layer 35 External heating rotator 37 Forced peeling means 39a, 39b Temperature detection means HLa Heating source 40 Image forming apparatus 41 Operation unit 42 Paper feed cassette 43 Paper feed roller 44 Registration roller 45 Paper discharge roller 46 Intermediary transfer member 46D Cleaning means 46A, 46B, 46C Support rollers 50Y, 50M, 50C, 50K Image forming unit 51Y Photoreceptor 52Y Charging means 53Y Exposure means 54Y Developing device 57Y Primary transfer means 57A Secondary transfer means 58Y Cleaning means N Fixing Nip part P Image support T Toner image

Claims (6)

A method for producing a toner for developing an electrostatic image comprising a resin and a colorant comprising a colorant compound,
Give a mixture of said colorant compound precursor and the resin, yielding intermediate by warming the mixture was heated by mixing the intermediate with a metal-containing compound, constituting the intermediate A toner having a colorant compound generation step of generating a colorant compound as a reaction product of a colorant compound precursor and a metal-containing compound by reacting the colorant compound precursor with a metal-containing compound. Production method. In the colorant compound generation step, the resin dispersion in which the resin particles are dispersed and the colorant compound precursor dispersion in which the colorant compound precursor particles are dispersed are mixed and heated. The toner manufacturing method according to claim 1, wherein an intermediate comprising an aggregate of resin particles and colorant compound precursor particles is obtained.   The method for producing a toner according to claim 1, wherein the metal-containing compound is a metal coordination compound or an organometallic compound.   The colorant compound precursor is composed of a compound represented by the general formula (1) or the general formula (2), and the metal-containing compound is composed of a metal coordination compound represented by the general formula (3). Item 4. The method for producing a toner according to Item 3.

[In the formula, R ¹ Each independently represents a hydrogen atom, a halogen group or a monovalent organic group, R ² Is -NR ^Four R ^Five Group (however, R ^Four And R ^Five Each independently represents a hydrogen atom, a halogen group or a monovalent organic group. ) Or -OR ⁶ Group (however, R ⁶ Each independently represents a hydrogen atom, a halogen group or a monovalent organic group. ) And R ^Three Represents a hydroxyl group, alkoxy group, aryloxy group, amino group, amide group, alkylsulfonylamino group or arylsulfonylamino group; ¹ ~ A ^Three Is independent of -CR ⁷ = Group (however, R ⁷ Each independently represents a hydrogen atom, a halogen group or a monovalent organic group. ) Or -N = group, X ¹ Represents an atomic group necessary for forming a 5-membered or 6-membered aromatic ring or heterocyclic ring; ¹ Represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring containing at least one nitrogen atom, and this atomic group may be unsubstituted or substituted, and the substituent May form a condensed ring. L ¹ Represents a part of a linking group having 1 or 2 carbon atoms or a ring structure, and R ^Three And may form a 5-membered or 6-membered ring structure. p is an integer of 0-3. ]

[Where X ² Represents an atomic group necessary to form an aromatic carbocyclic or heterocyclic ring in which at least one ring is composed of 5 to 7 atoms, and atoms necessary to form a heterocyclic ring In the group, a carbon atom is bonded to the azo bond, and at least one of the adjacent positions of the carbon atom is a nitrogen atom, or the carbon atom in the carbocycle is substituted with a nitrogen atom, an oxygen atom or a sulfur atom. It has a structure. X ^Three Represents an atomic group necessary for forming an aromatic carbocyclic or heterocyclic ring in which at least one ring is composed of 1 to 7 atoms, G is a hydroxyl group, an amino group, a methoxy group, A thiol group or a thioalkoxy group is shown. ]

[Wherein M represents a divalent metal atom, R ⁸ Represents a hydrogen atom or a monovalent organic group, R ⁹ Is a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, sulfinyl group, alkylylsulfonyl group, arylsulfonyl group or cyano group, R ^Ten Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. ]   5. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the produced toner is a magenta toner.   A toner for developing an electrostatic image containing a resin and a colorant,
  A toner produced by the toner production method according to claim 1.

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