JP2002287407A - Method for forming image, image forming device and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming an image, an image forming device and a process cartridge so that countermeasures to improve black spots, irregularity due to fog, cleaning property, buckling property of a blade or the like are obtained while keeping sharpness by using a specified toner and so that performances with high picture quality are stably obtained even for long-term use. SOLUTION: The method for forming an image includes a developing process to develop an electrostatic latent image formed on an electrophotographic photoreceptor having a photosensitive layer with an intermediate layer interposed on a conductive supporting body with an electrostatic charge image developing toner containing at least a resin and a coloring agent. In the method, the intermediate layer contains at least one of organometallic compounds or a silane coupling agent. The toner contains a metal salt of a fatty acid as an external additive to color particles obtained by forming particles in a water- based medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method, an image forming apparatus, and a process cartridge used for a copying machine, a printer, and the like.

[0002]

2. Description of the Related Art At present, most image forming apparatuses that require high-speed and high-quality images employ an image forming method in which an electrostatic latent image is formed on an electrophotographic photosensitive member and developed with dry toner. I have.

The reason is that high-quality images can be formed at high speed, the performance is stable even when used for a long period of time, and color images can be formed. Therefore, it is considered that this field will continue to occupy a large area in the future, but it is also true that there are some demands for improving the performance. The biggest among them is further improvement in image quality.

The most effective countermeasures in studying high image quality are to reduce the particle size of the toner and to make the shape and surface properties of the toner uniform, and many technical studies have been made at present. .

[0005] The typical inventions developed therein include, for example, the following. By using a toner composed of toner particles containing a fatty acid metal salt (hereinafter also referred to as “toner A”), abrasion of a cleaning blade, slippage of toner on a photoreceptor surface during cleaning, image blur due to toner adhesion, and the like. , And fluctuation of image density due to temperature and humidity environment during use can be eliminated, and a high-quality image can be formed for a long period of time.

Further, by using a toner composed of toner particles containing inorganic fine particles (hereinafter, also referred to as “toner B”), environment dependency is reduced, the charge distribution is uniform, and fine dot dust is reduced. Small and sharp images are obtained, excellent in fluidity, no image contamination due to toner granules and toner scattering even under severe use conditions, and there is little decrease in halftone homogeneity due to embedding of toner external additives, and stable images are obtained. . In addition, paper that effectively exerts the abrasiveness of the external additive itself, removes substances that cause image deletion such as moisture adhering to the surface of the photoreceptor, and further generates streak-like or spot-like image defects. Filming due to powder or toner is prevented, and excellent image developability and fine line reproducibility, and a high-quality image can be formed over a long period of time. Further, even when used in an image forming apparatus incorporating a toner recycling system, failures such as black spots do not occur in the image, and there is no decrease in toner fluidity or fluctuation in chargeability. Therefore, the image density is high, there is no fog, High-quality images can be formed over a long period of time.

Further, toner particles containing inorganic / organic composite fine particles having inorganic fine particles having a primary average particle diameter of 5 to 100 nm fixed on the surface of organic fine particles having an average particle diameter of 0.1 to 5.0 μm. Toner (hereinafter, “toner C”)
), The wear of the cleaning blade, toner slip through the photoconductor surface during cleaning,
It eliminates image blur due to toner adhesion, eliminates fluctuations in image density due to temperature and humidity environment during use, and is excellent in developability and fine line reproducibility, and can form high-quality images for a long period of time.

[0008]

The above-mentioned toner A,
B and C eliminate wear of the cleaning blade, toner slippage on the photoreceptor surface at the time of cleaning, image blur due to toner sticking, etc., eliminate fluctuation in image density due to temperature and humidity environment during use, and provide high quality images for a long time. Formed, less dependent on the environment, uniform charge distribution, less fine dot dust, sharp image, excellent fluidity,
Even under severe usage conditions, there is no image contamination due to toner granules and toner scattering, little decrease in halftone homogeneity due to toner external additive burial, stable images can be obtained, and high quality images can be formed for a long time. I can,
It has become clear that there is a problem in practical use.

Especially, the photosensitive layer is worn out under high temperature and high humidity, and the photosensitive layer
When it is about μm, black spots increase sharply, potential stability under high temperature and high humidity is poor, fog unevenness, etc.When durability of tens of thousands of copies or more is required, the above advantages are not utilized. is there.

Further, when the diameter and uniformity of the toner are reduced, the driving torque at the time of cleaning tends to be excessively large because the adhesive force to the electrophotographic photosensitive member surface is high. In addition, there is a high probability that the toner will pass through the cleaning blade, resulting in poor cleaning, poor adhesion near the intermediate layer under high temperature and high humidity, and peeling off of the film at the end of the drum. It has been found that the occurrence of abnormally vibrating or turning up of the cleaning causes a problem.

An object of the present invention is to find a method for improving black spots, fog spots, cleaning properties, blade turning, etc., while ensuring sharpness with the above-mentioned specific toner, and stably provide high image quality even in long-term use. An object of the present invention is to provide an image forming method, an image forming apparatus, and a process cartridge having high performance.

[0012]

Means for Solving the Problems The inventors of the present invention ensure the sharpness of the toner according to the present invention while maintaining the sharpness of black spots, fog spots,
As a result of intensive studies to improve the cleaning property and blade turn-up, etc., the thickness of the photosensitive layer was reduced to about 15 μm by using a curable intermediate layer as the intermediate layer of the electrophotographic photosensitive member (also simply referred to as a photosensitive member). It has been found that the above-mentioned disadvantages can be overcome, and the present invention has been achieved.

That is, the object of the present invention is achieved by adopting one of the following constitutions. [1] An electrostatic latent image formed on an electrophotographic photoreceptor having a photosensitive layer on a conductive support via an intermediate layer is formed by an electrostatic image developing toner containing at least a resin and a colorant. In an image forming method including a developing step of developing a visible image, the intermediate layer is a layer containing at least one of an organometallic compound and a silane coupling agent, and the toner is obtained by forming particles in an aqueous medium. An image forming method, characterized in that the colored particles contain at least a fatty acid metal salt as an external additive.

[2] The fatty acid metal salt has a water content of 0.1 to 2.5% by mass and a free fatty acid content of 0.01 to 0.1%.
The image forming method according to [1], wherein the content is 7% by mass.

[3] The image forming method according to [1] or [2], wherein the fatty acid metal salt is a fatty acid calcium.

[4] The image forming method according to [1] or [2], wherein the fatty acid metal salt is zinc stearate.

[5] An electrostatic latent image formed on an electrophotographic photosensitive member having a photosensitive layer on a conductive support via an intermediate layer is developed into an electrostatic image containing at least a resin and a colorant. In an image forming method including a developing step of visualizing with a toner for use, the intermediate layer is a layer containing at least one of an organometallic compound and a silane coupling agent, and the toner forms particles in an aqueous medium. An image forming method, comprising using a toner containing at least inorganic fine particles as an external additive in the colored particles obtained as described above.

[6] The inorganic fine particles have an average particle size of 0.1.
005 to 0.020 μm [5]
2. The image forming method according to 1.,

[7] The inorganic fine particles have an average particle size of 0.1.
The image forming method according to [6], wherein the thickness is 50 to 5.0 μm.

[8] The image forming method according to [5], [6] or [7], wherein the inorganic fine particles are silica.

[0021]

[9] The image forming method according to [5], [6] or [7], wherein the inorganic fine particles are titania.

[10] An electrostatic latent image formed on an electrophotographic photosensitive member having a photosensitive layer on a conductive support via an intermediate layer is developed into an electrostatic image containing at least a resin and a colorant. In an image forming method including a developing step of visualizing with a toner for use, the intermediate layer is a layer containing at least one of an organometallic compound and a silane coupling agent, and the toner forms particles in an aqueous medium. The colored particles obtained as described above, at least as an external additive, have an average particle size of 0.1 to 5.0 μm.
m having an average primary particle size of 5 to 100 n
m. An image forming method comprising using a toner containing, as an external additive, inorganic / organic composite fine particles to which inorganic fine particles are fixed.

[11] The image forming method according to [10], wherein the organic fine particles are an acrylic polymer.

[12] The image forming method according to [10], wherein the inorganic fine particles are titania.

[13] At least two of the above-mentioned fatty acid metal salts, inorganic fine particles, or inorganic / organic composite fine particles are used [1], [5] or [1].
0].

[14] The image forming method according to [1], wherein the organic metal compound contained in the intermediate layer is a metal alkoxide or an organic metal chelate.

[15] The image forming method according to [5] or [10], wherein the intermediate layer is a layer containing an organic metal chelate and a silane coupling agent.

[16] The image forming method according to [14] or [15], wherein the organometallic chelate contained in the intermediate layer is represented by the following general formula (1).

Formula (1) (R ₁ O) _g -M- (K) _m (where R ₁ is an alkyl group, M is zirconium,
A chelating group K representing titanium or aluminum
Represents an acetoacetic acid ester group or a β-diketone group,
g and m represent an integer of 1 or more. However, when M is zirconium or titanium, g + m is 4, and when M is aluminum, g + m is 3. [17] The image forming method according to [15], wherein the silane coupling agent contained in the intermediate layer is represented by the following general formula (2).

Formula (2) (Q) _p —Si (Y) _q — (A) _r (wherein Q represents a halogen atom, an alkoxy group or an amino group, A represents an alkyl group or an aryl group, and functional group Y -BOOC (R ') C = CH 2, -BNHR " or .R representing the -BNH _2' represents an alkyl group, R" represents an alkyl group or an aryl group, B is an alkylene radical - Represents an alkylene group containing O-, -NH-, -CO-, p and q represent an integer of 1 or more, r represents an integer of 0 or more, and p + q + r is 4.) [18] The photosensitive layer Contains a hindered amine or a hindered phenol compound [1]
-The image forming method according to any one of [17].

[19] The toner according to [1] to [18], wherein the variation coefficient of the shape factor of the colored particles is 16% or less, and the number variation coefficient in the number particle size distribution is 27% or less. The image forming method according to claim 1.

[20] In the toner, the ratio of the colored particles having a shape factor of the colored particles in the range of 1.0 to 1.6 is 6%.
5% or more by number [1] to [19]
The image forming method according to claim 1.

[21] In the toner, the ratio of the colored particles whose shape factor is in the range of 1.2 to 1.6 is 6%.
5% or more by number [1] to [20]
The image forming method according to claim 1.

[22] The image forming method according to any one of [1] to [21], wherein the toner has a ratio of colored particles having no corners of 50% by number or more.

[23] The toner according to [1], wherein the number average particle diameter of the colored particles is 3 to 8 μm.
[22] The image forming method according to any one of [22].

[24] When the particle diameter of the colored particles of the toner is D (μm), the natural logarithm InD is plotted on the horizontal axis, and the horizontal axis is divided into a plurality of classes at intervals of 0.23. In the histogram showing the particle size distribution, the sum (M1) of the relative frequency (m1) of the colored particles included in the most frequent class and the relative frequency (m2) of the colored particles included in the class having the second highest frequency after the most frequent class ) Is 70% or more, the image forming method according to any one of [1] to [23].

[25] The image according to any one of [1] to [24], wherein the toner is obtained by coloring at least a polymerizable monomer in an aqueous medium. Forming method.

[26] The image forming method according to any one of [1] to [25], wherein the toner is obtained by associating colored particles with at least resin particles in an aqueous medium.

[27] An image forming apparatus using the image forming method according to any one of [1] to [26].

[28] The image forming method according to any one of [1] to [26], wherein a photosensitive member, a charger, an image exposing unit, a developing unit, a transferring unit, a separating unit and a cleaning unit are used. A process cartridge, which is made by combining at least one of them, and is detachably attached to a main body device.

[0041]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail.

<Intermediate Layer Used in the Present Invention> The photoreceptor of the present invention is provided with a conductive support for ensuring excellent image quality when an image is formed and adhesion between the conductive support and the photosensitive layer. It is characterized in that an intermediate layer containing at least one of an organometallic compound and a silane coupling agent is provided between the body and the photosensitive layer.

<< Organic metal compound, silane coupling >>
Examples of the organometallic compound contained in the intermediate layer of the photoreceptor of the present invention include alkoxide compounds such as zirconium tetra-n-propylate, aluminum isopropylate, mono-sec-butoxyaluminum-i-propylate, and aluminum-sec-butylate. And a group 1a, a group 1b, or a group 2a of the periodic table.
Group, group 3a, group 3b, group 4a, group 4b, group 5a
Group, group 5b and group 8 and a metal atom selected from the group consisting of acetoacetate, β-diketone, acetylacetone, catechol, ethylenediamine, o-phenylenebisdimethylaniline and the like as chelating agents in the range of 3, 4, 6, 8; An organic metal chelate compound formed by molecular coordination may be used.

However, in the intermediate layer of the photoreceptor of the present invention, the organometallic chelate compound represented by the general formula (1) is used as the organometallic compound, and the silane coupling agent represented by the general formula (2) is used. Is preferably contained in combination.

In the general formula (1), R ₁ is a lower alkyl group, M represents a metal atom such as zirconium, titanium or aluminum, the chelating group K represents an acetoacetic ester group or a β-diketone group, g and m represent an integer of 1 or more. However, when M is zirconium or titanium, g + m is 4, and when M is aluminum, g + m is 3.

Specific examples of the organic metal chelate compound represented by the general formula (1) include, for example, diisopropoxytitanium (methylacetoacetate) isobutoxytitanium tri (methylacetoacetate) tributoxytitanium acetyl Acetonate diisopropoxyaluminum (methylacetoacetonate) dibutoxytitanium bis (ethylacetoacetonate) isobutoxyaluminum (acetylacetonate);

Next, in the silane coupling agent represented by the general formula (2), Q represents a halogen atom, an alkoxy group or an amino group which may have a substituent, and A represents an alkyl group, a phenyl group or a naphthyl. Represents an aryl group such as a group, and the organic functional group Y is -BOOC (R ') C = CH
_2, -BNHR "or -BNH represents a ₂ .R 'represents an alkyl group, R" represents an aryl group such as an alkyl group or a phenyl group or naphthyl group, B is an alkylene group or -O -, - NH- , -CO-. p and q represent an integer of 1 or more, r represents an integer of 0 or more, and p + q + r is 4.

Specific examples of the silane coupling agent represented by the general formula (2) include, for example, γ-methacryloxypropyltrimethoxysilane γ-methacryloxypropyltriethoxysilane γ-methacryloxypropylmethyldimethoxysilane Etc. can be given.

In the present invention, the thickness of the intermediate layer is from 0.1 to
10 μm is preferable, and particularly preferably 0.1 to 5 μm.

<Layer Structure of Photoreceptor> The layer structure of the photoreceptor of the present invention comprises a charge generation material (CG) on a conductive support via an intermediate layer.
M) -containing charge generation layer (CGL), a charge transport layer (CTL) containing a charge transport substance (CTM), and a surface layer (as a protective layer) may be provided in this order, or via an intermediate layer. CGL containing CGM and surface layer (C
TL) may be provided in this order, or a surface layer (as a photosensitive layer) containing CGM may be provided via an intermediate layer. Further, CGM may be provided via an intermediate layer.
And a photosensitive layer and a surface layer (as a protective layer) containing both CTM and CTM may be provided in this order.

However, in the present invention, from the viewpoint of practicability, a structure in which CGL containing CGM, CTL containing CTM, and a surface layer (as a protective layer) are provided in this order on a conductive support via an intermediate layer. Is particularly important.

<< CGM and CTM contained in the photosensitive layer >> Examples of the CGM contained in the photosensitive layer of the present invention include phthalocyanine pigments, polycyclic quinone pigments, azo pigments, perylene pigments, indigo pigments, quinacridone pigments, and azurenium pigments. And squarylium dyes, cyanine dyes, pyrylium dyes, thiopyrylium dyes, xanthene dyes, triphenylmethane dyes, styryl dyes, and the like. These CGMs are used alone or in combination with an appropriate binder resin to form a layer.

As the CTM contained in the photosensitive layer,
For example, oxazole derivatives, oxadiazole derivatives,
Thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives,
Imidazoline derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, benzidine compounds, pyrazoline derivatives, stilbene compounds, amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, amino Examples include stilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, and the like. In these CTMs, a layer is usually formed together with a binder resin.

<< Binder Resin for Photosensitive Layer >> As the binder resin contained in the CGL and CTL in the case of a single-layered photosensitive layer and a laminated structure, polycarbonate resin, polyester resin, polystyrene resin, methacrylic resin,
Acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl butyral resin, polyvinyl acetate resin, styrene-butadiene resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-maleic anhydride copolymer resin, urethane resin, silicone Resins, epoxy resins, silicone-alkyd resins, phenol resins, polysilane resins, polyvinyl carbazole, and the like.

In the present invention, the ratio of CGM to binder resin in CGL is preferably from 1: 5 to 5: 1 by mass. The thickness of the CGL is preferably 5 μm or less, particularly preferably 0.05 to 2 μm.

The CTL is formed by dissolving the CTM and the binder resin in an appropriate solvent, and applying and drying the solution. The mixing ratio of CTM and the binder resin is preferably from 3: 1 to 1: 3 by mass ratio.

The thickness of the CTL is preferably 5 to 50 μm, particularly preferably 10 to 40 μm. When a plurality of CTLs are provided, the thickness of the upper layer of the plurality of CTLs is preferably 10 μm or less. It is preferable that the thickness be smaller than the thickness of all the CTLs provided under the plurality of CTLs.

<< Solvent and Dispersant for Photosensitive Layer >> As the solvent or dispersant used for the photosensitive layer, intermediate layer and protective layer of the photoreceptor of the present invention, n-butylamine, diethylamine, ethylenediamine, isopropanolamine, tripropanolamine Ethanolamine, triethylenediamine, N, N-dimethylformamide, acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloromethane,
1,2-dichloroethane, 1,2-dichloropropane,
1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane,
Tetrahydrofuran, dioxolan, dioxane, methanol, ethanol, butanol, isopropanol,
Ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve and the like can be mentioned. Although the present invention is not limited to these, dichloromethane, 1,2-dichloroethane, methyl ethyl ketone and the like are preferably used. In addition, these solvents can be used alone or as a mixed solvent of two or more kinds.

<< Conductive Support >> Next, the conductive support of the electrophotographic photoreceptor of the present invention includes: 1) a metal plate such as an aluminum plate or a stainless plate, or 2) a support such as paper or a plastic film. ,
A thin metal layer such as aluminum, palladium, or gold provided by lamination or vapor deposition. 3) On a support such as paper or plastic film,
A conductive polymer, a layer provided with a conductive compound such as indium oxide, tin oxide or the like by coating or vapor deposition; 4) alumite, particularly a sealed anodized substrate;

The material of the conductive support used in the present invention is mainly aluminum, copper, brass, steel,
A belt-shaped or drum-shaped metal material such as stainless steel or another plastic material is used. Among them, aluminum excellent in cost, workability and the like is preferably used, and a thin-walled cylindrical aluminum tube usually formed by extrusion or drawing is often used.

The shape of the support may be a drum shape, a sheet shape or a belt shape, and may be any shape suitable for the electrophotographic apparatus to be applied.

<< Antioxidant added to the surface layer >>
In the present invention, in order to sufficiently prevent fatigue deterioration of the electrophotographic performance of the photoreceptor in the process of repeated image formation, an antioxidant is preferably contained in the surface layer, and hindered amine, hindered phenol compound, phosphorous It is preferable to contain a compound or a sulfur compound.

Among the above antioxidants, hindered phenol-based and hindered amine-based antioxidants are particularly effective in preventing fog and image blurring at high temperature and high humidity.

The content of the hindered phenol or hindered amine antioxidant in the resin layer is 0.01 to 2
0% by mass is preferred. When the content is less than 0.01% by mass, there is no effect on fogging and image blur at high temperature and high humidity, and when the content is more than 20% by mass, the charge transporting ability in the resin layer is reduced, and the residual potential tends to increase. In addition, a decrease in film strength occurs.

Here, the hindered phenol type refers to compounds having a branched alkyl group at the position ortho to the hydroxyl group of the phenol compound and derivatives thereof (however, the hydroxyl group may be modified to alkoxy).

The hindered amine compound is a compound having a bulky organic group near an N atom. As the bulky organic group, there is a branched alkyl group, and for example, a t-butyl group is preferable. For example, compounds having an organic group represented by the following structural formula are preferable.

[0067]

Embedded image

R ₁₃ in the formula is a hydrogen atom or a monovalent organic group,
R ₁₄ , R ₁₅ , R ₁₆ and R _{17 each} represent an alkyl group, and R ₁₈ represents a hydrogen atom, a hydroxyl group or a monovalent organic group.

Examples of the antioxidant having a hindered phenol partial structure include compounds described in JP-A-1-118137 (P7 to P14), but the present invention is not limited thereto.

As an antioxidant having a hindered amine partial structure, for example, JP-A-1-118138 (P.
7 to P9), but the present invention is not limited thereto.

The following are examples of typical antioxidant compounds.

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

As the organic phosphorus compound, for example,
A compound represented by the general formula RO-P (OR) -OR is a representative one. Here, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group or aryl group.

Further, as the organic sulfur compound, for example, there is a compound represented by the general formula RSR. Here, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group or aryl group.

The following compounds may be used as commercialized antioxidants, for example, “Irganox 107”.
6, Irganox 1010, Irganox 1098, Irganox 245, Irganox 1330, Irganox 3114, Irganox 1076, 3,5-di-t-butyl- 4
-Hydroxybiphenyl "or more hindered phenols," Sanol LS2626 "," Sanol LS76 "
5, "Sanol LS770", "Sanol LS74"
4, "Tinuvin 144", "Tinuvin 622LD",
"Mark LA57", "Mark LA67", "Mark L
A62 "," mark LA68 ", and" mark LA63 "or more.

<< Coating Method >> Next, as a coating method for producing the electrophotographic photoreceptor of the present invention, coating methods such as dip coating, spray coating, and circular amount control type coating are used. The coating process on the surface layer side of the layer does not dissolve the lower layer film as much as possible, and in order to achieve a uniform coating process, a coating process such as a spray coating or a circular volume control type (a typical example is a circular slide hopper type). It is preferable to use The spray coating is described in detail in, for example, JP-A-3-90250 and JP-A-3-269238, and the circular amount control type coating is described in detail in, for example, JP-A-58-189061. I have.

In the present invention, a coating for compensating for surface defects of the support is provided between the support and the intermediate layer. A conductive layer for the purpose of preventing generation and the like can be provided. This conductive layer is made of carbon black,
It can be formed by applying and drying a solution in which conductive powder such as metal particles or metal oxide particles is dispersed in a suitable binder resin. The thickness of the conductive layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.

<Toner Used in the Present Invention><< Method of Manufacturing Toner >> The toner of the present invention is a toner obtained by forming colored particles in an aqueous medium. In particular, it is preferable that the toner is made of colored particles formed by using resin particles and colorant particles obtained by polymerizing a polymerizable monomer in an aqueous medium. Hereinafter, the method for producing the toner of the present invention will be described in detail.

In the description of the present invention, the colored particles and the toner are distinguished from each other unless otherwise misunderstood.

That is, the colored particles are particles formed by using at least a resin and a colorant and having a shape and a particle size suitable for use as particles for developing an electrostatic latent image, and an external additive. In addition to the above, what is actually used as “toner” is called toner or toner particles. However, when it is used as a normal expression method and does not cause misunderstanding from the common technical knowledge, from the above, what should be described as colored particles may be described as toner or toner particles.

The colored particles according to the present invention may be prepared by a suspension polymerization method or in a liquid to which an emulsion of necessary additives is added (in an aqueous medium).
And then polymerizing the monomers to prepare fine polymer particles (resin particles), and then adding an organic solvent, an aggregating agent, and the like, and associating the resin particles. Here, “association” means that a plurality of the resin particles are fused together, and also includes a case where the resin particles are fused with other particles (for example, colorant particles).

One example of the method for producing the toner of the present invention is as follows. A coloring agent and a releasing agent, if necessary, are added to a polymerizable monomer.
Various constituent materials such as a charge control agent and a polymerization initiator are added, and the various constituent materials are dissolved or dispersed in the polymerizable monomer using a homogenizer, a sand mill, a sand grinder, an ultrasonic disperser or the like. The polymerizable monomer in which these various constituent materials are dissolved or dispersed is dispersed in an aqueous medium containing a dispersion stabilizer into oil droplets of a desired size as a toner using a homomixer, a homogenizer, or the like. Thereafter, the stirring mechanism is moved to a reaction device (stirring device), which is a stirring blade described later, and heated to cause the polymerization reaction to proceed. After the completion of the reaction, the dispersion stabilizer is removed, filtered, washed, and dried to prepare the colored particles according to the present invention. The “aqueous medium” in the present invention refers to a medium containing at least 50% by mass of water.

Further, as a method of producing the colored particles according to the present invention, a method of preparing resin particles by associating or fusing them in an aqueous medium can also be mentioned. This method is not particularly limited, and examples thereof include the methods described in JP-A-5-265252, JP-A-6-329947, and JP-A-9-15904. That is, a method of associating a plurality of resin particles and dispersed particles of a constituent material such as a colorant, or a plurality of fine particles composed of a resin and a colorant, particularly, after dispersing these in water using an emulsifier, the critical aggregation concentration At the same time as adding the above flocculant and salting out, the formed polymer itself is heated and fused at a temperature equal to or higher than the glass transition temperature to gradually form a fused particle, thereby gradually growing the particle size. At this point, a large amount of water was added to stop the growth of the particle diameter, and the surface was smoothened by heating and stirring to control the shape. The colored particles according to the invention can be formed. Here, a solvent that is infinitely soluble in water may be added together with the coagulant.

As the polymerizable monomers constituting the resin, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4- Dichlorostyrene,
p-phenylstyrene, p-ethylstyrene, 2,4-
Dimethylstyrene, p-tert-butylstyrene, p
-N-hexylstyrene, pn-octylstyrene,
pn-nonylstyrene, pn-decylstyrene, p
Styrene or a styrene derivative such as -n-dodecylstyrene, methyl methacrylate, ethyl methacrylate,
N-butyl methacrylate, isopropyl methacrylate,
Methacrylate derivatives such as isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, and dimethylaminoethyl methacrylate. , Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate,
Acrylic ester derivatives such as n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, etc .; olefins such as ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, vinyl bromide , Vinyl fluoride, halogenated vinyls such as vinylidene fluoride, vinyl esters such as vinyl propionate, vinyl acetate, vinyl benzoate, vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, vinyl methyl ketone, vinyl ethyl ketone , Vinyl ketones such as vinylhexyl ketone, N-vinyl compounds such as N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone, vinyl compounds such as vinylnaphthalene and vinylpyridine, acrylonitrile, Acrylonitrile, there are acrylic acid or methacrylic acid derivatives such as acrylamide. These vinyl monomers can be used alone or in combination.

It is more preferable to use a polymerizable monomer constituting the resin in combination with one having an ionic dissociating group. For example, those having a substituent such as a carboxyl group, a sulfonic acid group, and a phosphate group as a constituent group of the monomer, specifically, acrylic acid, methacrylic acid,
Maleic acid, itaconic acid, cinnamic acid, fumaric acid, monoalkyl maleate, monoalkyl itaconate, styrenesulfonic acid, allylsulfosuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxyethyl Methacrylate,
3-chloro-2-acid phosphooxypropyl methacrylate and the like.

Further, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate,
Polyfunctional vinyls such as neopentyl glycol diacrylate can be used to form a crosslinked resin.

These polymerizable monomers can be polymerized using a radical polymerization initiator. In this case, an oil-soluble polymerization initiator can be used in the suspension polymerization method. As the oil-soluble polymerization initiator, 2,2'-azobis- (2,4
-Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvalero Azo or diazo polymerization initiators such as nitrile and azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide , Dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis-
Examples include peroxide-based polymerization initiators such as (4,4-t-butylperoxycyclohexyl) propane and tris- (t-butylperoxy) triazine, and polymer initiators having a peroxide in a side chain. . When an emulsion polymerization method is used, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, and hydrogen peroxide.

Examples of dispersion stabilizers include tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, and calcium sulfate. , Barium sulfate,
Bentonite, silica, alumina and the like can be mentioned. Further, a surfactant generally used as a surfactant such as polyvinyl alcohol, gelatin, methyl cellulose, sodium dodecylbenzenesulfonate, ethylene oxide adduct, and higher alcohol sodium sulfate can be used as a dispersion stabilizer.

The resin excellent in the present invention preferably has a glass transition point of 20 to 90 ° C. and a softening point of 8 ° C.
The thing of 0-220 ° C is preferred. The glass transition point is measured by a differential calorimetric analysis method, and the softening point can be measured by a Koka flow tester. Furthermore, these resins have a number average molecular weight (Mn) of 10 as measured by gel permeation chromatography.
00 to 100000, weight average molecular weight (Mw) 200
Those having 0 to 1,000,000 are preferred. Further, as a molecular weight distribution, Mw / Mn is 1.5 to 100, particularly 1.8.
-70 are preferred.

The flocculant used for associating the resin particles in the aqueous medium is not particularly limited, but those selected from metal salts are preferably used.
Specifically, as a monovalent metal, for example, a salt of an alkali metal such as sodium, potassium, and lithium, and as a divalent metal, for example, a salt of an alkaline earth metal such as calcium and magnesium, or a divalent metal such as manganese or copper And salts of trivalent metals such as iron and aluminum. Specific examples of the salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Can be mentioned. These may be used in combination. It is preferable that these coagulants are added at a critical coagulation concentration or higher. The critical aggregation concentration is an index relating to the stability of the aqueous dispersion, and indicates the concentration at which aggregation occurs when a coagulant is added. This critical aggregation concentration varies greatly depending on the emulsified component and the dispersant itself. For example, it is described in "Polymer Chemistry 17, 601 (1960), edited by The Society of Polymer Science, Japan" by Seizo Okamura et al., And a detailed critical aggregation concentration can be obtained. As another method, a desired salt is added to the target particle dispersion at a different concentration, the 、 (zeta) potential of the dispersion is measured, and the salt concentration at which this value changes is defined as the critical aggregation concentration. You can also ask. The amount of the coagulant of the present invention may be at least the critical coagulation concentration, but is preferably 1.2 times or more, more preferably 1.5 times or more the critical coagulation concentration.

As the "solvent infinitely soluble in water" used together with the coagulant, a solvent which does not dissolve the resin to be formed is selected. Specific examples include alcohols such as methanol, ethanol, propanol, isopropanol, t-butanol, methoxyethanol and butoxyethanol, nitriles such as acetonitrile, and ethers such as dioxane. Particularly, ethanol, propanol and isopropanol are preferred. The addition amount of the solvent infinitely soluble in water is preferably 1 to 100% by volume based on the polymer-containing dispersion to which the flocculant has been added. In order to make the particle shape uniform, it is preferable to prepare a colored particle, and after the filtration, it is preferable to fluidly dry a slurry in which 10% by mass or more of water is present with respect to the particle. Those having a polar group therein are preferred. It is considered that the reason for this is that the existing water exerts an effect of slightly swelling the polymer in which the polar group is present, so that the shape is particularly easily uniformized.

The colored particles according to the present invention contain at least a resin and a colorant, but may contain a releasing agent or a charge control agent as a fixing property improving agent, if necessary.

As the colorant used in the colored particles according to the present invention, carbon black, magnetic substance, dye, pigment and the like can be arbitrarily used. As the carbon black, channel black, furnace black, acetylene black, thermal black and the like can be used. , Lamp black and the like are used. As the magnetic material, ferromagnetic metals such as iron, nickel, and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys that do not contain ferromagnetic metals but show ferromagnetism by heat treatment, For example, an alloy of a type called a Heusler alloy such as manganese-copper-aluminum, manganese-copper-tin, chromium dioxide, or the like can be used.

As the dye, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 1
22, C.I. I. Solvent Yellow 19, 44, 7
7, 79, 81, 82, 93, 98, 10
3, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 9
5 and the like, and a mixture thereof can also be used. Examples of the pigment include C.I. I. Pigment Red 5,
48: 1, 53: 1, 57: 1, 122, 1
39, 144, 149, 166, 177, 1
78, 222, C.I. I. Pigment Orange 31, 43 and C.I. I. Pigment Yellow 14, 17, 17
3, 94, 138, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 3, can be used by the same 60 or the like, can be also used a mixture thereof. The number average primary particle size varies depending on the type, but generally ranges from 10 to
About 200 nm is preferable.

As a method of adding a colorant, a method of adding polymer particles prepared by an emulsion polymerization method at the stage of aggregating by adding an aggregating agent to color the polymer, a method of polymerizing a monomer, or the like. And a method of adding a colorant, polymerizing, and forming colored particles can be used. When the colorant is added at the stage of preparing the polymer, it is preferable to use the colorant after treating the surface with a coupling agent or the like so as not to inhibit the radical polymerizability.

Further, low molecular weight polypropylene (number average molecular weight = 1500 to 9000) or low molecular weight polyethylene as a fixing property improving agent may be added. Similarly, various known charge control agents, which can be dispersed in water, can be used. Specific examples include a nigrosine dye, a metal salt of naphthenic acid or a higher fatty acid, an alkoxylated amine, a quaternary ammonium salt compound, an azo metal complex, a metal salt of salicylic acid or a metal complex thereof. The particles of the charge control agent and the fixability improver preferably have a number average primary particle diameter of about 10 to 500 nm in a dispersed state.

In a suspension polymerization method toner in which a toner component such as a colorant is dispersed or dissolved in a so-called polymerizable monomer is suspended in an aqueous medium and then polymerized to obtain colored particles. The shape of the colored particles can be controlled by controlling the flow of the medium in the reaction vessel to be performed.

In the toner of the present invention, the ratio of the colored particles having no corners is preferably 50% by number or more. Also, preferably, it is composed of colored particles having a shape coefficient variation coefficient of 16% or less and a number variation coefficient in the number particle size distribution of 27% or less. Further, in the toner used in the present invention, the ratio of the colored particles having a shape factor in the range of 1.0 to 1.6 is 65% by number or more, and more preferably the shape factor is 1.2 to 1.6. The proportion of colored particles in the range is 65
It is good to be composed of colored particles of not less than a few%.

<< Shape Factor of Colored Particles >> In the toner of the present invention, the “shape factor” of the colored particles is represented by the following formula, and indicates the degree of roundness of the colored particles.

Shape factor = ((maximum diameter / 2) ² × π) / projected area Here, the maximum diameter means that the projected image of the colored particles on the plane is 2
The width of a particle at which the distance between the parallel lines is the largest when sandwiched between the parallel lines. The projection area refers to an area of a projected image of the colored particles on a plane.

In the present invention, the shape factor is determined by taking a photograph obtained by enlarging the colored particles by 2000 times with a scanning electron microscope, and then referring to the “SCCANNING” based on the photograph.
The measurement was performed by analyzing a photographic image using "IMAGE ANALYZER" (manufactured by JEOL Ltd.). At this time, the shape factor of the present invention was measured by the above calculation formula using 100 colored particles.

The method for controlling the shape factor is not particularly limited. For example, a method of spraying colored particles in a hot air flow, a method of repeatedly applying mechanical energy due to an impact force in a gaseous phase in a gas phase, a method of adding a colored particle to a solvent that does not dissolve the colored particles to impart a swirling flow, and the like. To prepare colored particles having a shape factor of 1.0 to 1.6 or 1.2 to 1.6, and then add them to ordinary colored particles so as to fall within the range of the present invention. There is a way.

In the step of preparing colored particles for a so-called polymerization toner, the colored particles whose overall shape is controlled and whose shape factor is adjusted to 1.0 to 1.6 or 1.2 to 1.6 are prepared. Similarly, there is a method of adjusting the content by adding it to ordinary colored particles. Among the above-mentioned methods, it is preferable to use a so-called polymerization toner to produce colored particles by a production method in terms of simplicity and excellent surface uniformity as compared with colored particles produced by a pulverization method.

<< Coefficient of Variation of Shape Factor of Colored Particle >> The “coefficient of variation of shape factor” of the colored particles of the present invention is calculated from the following equation.

Coefficient of variation (%) = (S ₁ / K) × 100 (where S ₁ represents the standard deviation of the shape coefficients of 100 colored particles, and K represents the average value of the shape coefficients). In the colored particles according to the invention, the coefficient of variation of the shape factor is 16% or less, preferably 14% or less. When the variation coefficient of the shape coefficient is 16% or less, the toner layer (powder layer) developed and transferred by this
Are reduced, the fixing property is improved, and offset hardly occurs. Further, the charge amount distribution becomes sharp, and the image quality is improved.

In order to uniformly control the shape factor of the colored particles and the variation coefficient of the shape coefficient without variation in lots, resin particles (polymer particles) constituting the colored particles of the present invention are prepared (polymerized). In the step of fusing and controlling the shape of the resin particles, an appropriate process end time may be determined while monitoring the characteristics of the colored particles being formed. Monitoring means that a measuring device is incorporated in-line and process conditions are controlled based on the measurement result. That is, by incorporating measurement such as shape in-line, for example, for colored particles formed by associating or fusing resin particles in an aqueous medium, the shape and particle Is measured, and the reaction is stopped when the desired shape is obtained. Although the monitoring method is not particularly limited, a flow type particle image analyzer FPIA-2 is used.
000 (manufactured by Toa Medical Electronics Co., Ltd.) can be used.
This apparatus is suitable because the shape can be monitored by performing image processing in real time while passing the sample liquid. That is, a pump or the like is used from the reaction field to constantly monitor and measure the shape and the like, and stop the reaction when the desired shape and the like are obtained.

<< Coefficient of Number Variation of Colored Particles >> The number particle size distribution and the number variation coefficient of the colored particles of the present invention are measured by a Coulter Counter TA-II or a Coulter Multisizer (manufactured by Coulter). In the present invention, a Coulter Multisizer was used by connecting an interface (manufactured by Nikkaki Co., Ltd.) for outputting a particle size distribution and a personal computer. The aperture used in the Coulter Multisizer is 1
Using the thing of 00 μm, the volume of the toner of 2 μm or more,
The number was measured to calculate the particle size distribution and the average particle size. The number particle size distribution represents the relative frequency of the toner particles with respect to the particle size, and the number average particle size represents the median size in the number particle size distribution. The “number variation coefficient in the number particle size distribution” of the colored particles is calculated from the following equation.

Coefficient of number variation (%) = (S ₂ / D _n ) × 100 (where S ₂ represents a standard deviation in the number particle size distribution,
D _n denotes the number average particle diameter ([mu] m). The colored particles of the present invention have a number variation coefficient of preferably 27% or less, more preferably 25% or less. Since the number variation coefficient is 27% or less, it is developed by this,
The voids in the transferred toner layer (powder layer) are reduced, so that the fixability is improved, and offset is less likely to occur. Further, the charge amount distribution is sharpened, the transfer efficiency is increased, and the image quality is improved.

The method for controlling the number variation coefficient of the colored particles of the present invention is not particularly limited. For example,
Although a method of classifying colored particles by wind force can be used, classification in a liquid is effective for further reducing the number variation coefficient. As a method of classifying in a liquid, there is a method of using a centrifugal separator, controlling the number of revolutions, and separating and collecting the colored particles according to the difference in sedimentation velocity caused by the difference in the diameter of the colored particles. In particular, in the case of producing colored particles by a suspension polymerization method, a classification operation is indispensable in order to reduce the number variation coefficient in the number particle size distribution to 27% or less. In the suspension polymerization method, it is necessary to disperse the polymerizable monomer into oil droplets of a desired size as colored particles in an aqueous medium before polymerization. That is, mechanical shearing by a homomixer, a homogenizer, or the like is repeated for a large oil droplet of the polymerizable monomer to reduce the oil droplet to a size of about a colored particle. In the method based on the appropriate shearing, the number and particle size distribution of the obtained oil droplets becomes wide, and accordingly, the particle size distribution of the colored particles obtained by polymerizing the oil droplets becomes wide. For this reason, a classification operation is required.

<< Ratio of Colored Particles without Corners >> In the present invention, the percentage of colored particles without corners in the colored particles is preferably at least 50% by number, more preferably at least 70% by number.

When the ratio of the colored particles having no corners is 50% by number or more, the voids of the toner layer (powder layer) developed and transferred by the toner produced by this method are reduced, and the fixability is improved. However, the offset hardly occurs. Also, wear,
The number of easily breakable toner particles and toner particles having portions where charges are concentrated are reduced, the charge amount distribution is sharpened, the chargeability is stabilized, and good image quality can be formed over a long period of time.

Here, “toner particles having no corners” (referred to as “toner particles because the characteristics of the toner are not a color particle but a problem”) are referred to as toner particles due to protrusions or stresses where electric charges are concentrated. It refers to toner particles having substantially no protrusions, and specifically, the following toner particles are referred to as toner particles having no corners.

FIG. 1 is a diagram for explaining a toner particle having no corner and a toner particle having a corner. As shown in FIG. 1A, when the major axis of the toner particles T is L, the radius (L /
In the circle of 10), when the inside is rolled while contacting the inside at one point with respect to the peripheral line of the toner particle, the case where the circle does not substantially protrude outside the toner is referred to as “toner particle having no corner”. " “Cases that do not substantially protrude” refer to cases where there are no more than one protrusion having a protruding circle.
Further, “the major axis of the toner particles” refers to the width of the particle at which the interval between the parallel lines is the largest when the projected image of the toner particles on the plane is sandwiched between two parallel lines. FIG.
(B) and (c) show projected images of the toner particles having corners, respectively.

The ratio of the colored particles having no corners was measured as follows. First, a photograph in which the colored particles were enlarged by a scanning electron microscope was taken, and further enlarged to 15,000.
Obtain a double photographic image. Next, the presence or absence of the corners is measured for this photographic image. This measurement was performed for 100 colored particles.

The method for obtaining colored particles having no corners is not particularly limited. For example, as described above as a method of controlling the shape factor, a method of spraying colored particles in a hot air flow, or a method of repeatedly applying mechanical energy by impact force in a gas phase, or a method of applying colored particles. It can be obtained by adding to a solvent that does not dissolve and imparting a swirling flow.

Further, in a so-called polymerization toner in which colored particles are formed by associating or fusing resin particles, the surface of the fused particles has many irregularities at the stage of stopping the fusion, and the surface is not smooth. , Temperature in the shape control process,
By adjusting the conditions such as the number of rotations of the stirring blade and the stirring time, colored particles having no corners can be obtained. These conditions vary depending on the physical properties of the resin particles.For example, at a temperature higher than the glass transition temperature of the resin particles, by setting the rotation speed higher, the surface becomes smooth and colored particles without corners can be formed. .

<< Particle Size of Colored Particles >> The particle size of the colored particles of the present invention (usually referred to as the particle size of toner) is preferably 3 to 8 μm in number average particle size. In the case where the colored particles are formed by a polymerization method, the particle size is determined by the method of producing the colored particles described in detail below, in which the concentration of the coagulant or the amount of the organic solvent added, or the fusing time, and even the polymer itself. It can be controlled by the composition. Number average particle size is 3-8μ
In the fixing step, toner particles having a large adhesive force that fly and adhere to the heating member to generate an offset in the fixing step are reduced, and the transfer efficiency is increased to improve the halftone image quality. The image quality of dots and the like is improved.

As the colored particles of the present invention, when the particle diameter of the colored particles is D (μm), the natural logarithm InD is plotted on the horizontal axis, and the horizontal axis is divided into a plurality of classes at intervals of 0.23. In the histogram showing the particle size distribution of (i), the sum of the relative frequency (m1) of the colored particles included in the most frequent class and the relative frequency (m2) of the colored particles included in the class having the highest frequency after the most frequent class (m2) It is preferable that the colored particles have M) of 70% or more.

When the sum (M) of the relative frequency (m1) and the relative frequency (m2) is 70% or more, the dispersion of the particle size distribution of the colored particles becomes narrow, and the colored particles are used in the image forming step. As a result, the occurrence of selective development can be reliably suppressed. In the present invention, the histogram showing the number-based particle size distribution includes a natural logarithm lnD (D: particle size of individual toner particles) in a plurality of classes (0 to 0.23: 0.23 to 0.23) at intervals of 0.23. 0.46: 0.46-0.
69: 0.69-0.92: 0.92-1.15: 1.
15-1.38: 1.38-1.61: 1.61-1.
84: 1.84 to 2.07: 2.07 to 2.30: 2.
30 to 2.53: 2.53 to 2.76...) Is a histogram showing the number-based particle size distribution, which is based on the following conditions. Diameter data is
The data is transferred to a computer via the / O unit, and is created by the computer using a particle size distribution analysis program.

[Measurement conditions] (1) Aperture: 100 μm (2) Sample preparation method: Electrolyte (ISOTON R-1)
1 (Coulter Scientific Japan)
An appropriate amount of a surfactant (neutral detergent) is added to 50 to 100 ml and stirred, and 10 to 20 mg of a measurement sample is added thereto. This system is prepared by subjecting it to a dispersion treatment with an ultrasonic disperser for 1 minute.

<< Comparison with Conventionally Known Colored Particles (Toner) >> The colored particles according to the present invention have a shape coefficient, a variation coefficient of a shape factor, a ratio of colored particles having no corners, and a number variation coefficient in a number particle size distribution. It is distinguished from conventionally known and widely used colored particles.

Regarding the numerical values in the above range according to the present invention,
The numerical values of the coloring particles that have been widely known conventionally will be described. This numerical value differs depending on the manufacturing method and further depending on the manufacturing conditions, but will be described in comparison with a typical one.

In the case of a so-called pulverized toner, the proportion of colored particles having a shape factor of 1.2 to 1.6 is about 60% by number. The variation coefficient of the shape factor is about 20%. Further, in the pulverization method, in order to reduce the particle size while repeating crushing, the colored particles have many corners, and the ratio of colored particles having no corners is 30% by number or less. Therefore, in order to obtain colored particles having a uniform shape and no rounded corners and a round shape, it is necessary to perform a process of forming a spherical shape by heat or the like as described above as a method of controlling the shape factor. In addition, the number variation coefficient in the number particle size distribution is about 30% when the classification operation after the pulverization is performed once, and the classification operation needs to be further repeated to reduce the number variation coefficient to 27% or less. There is.

In the case of the colored particles obtained by the suspension polymerization method, since they are conventionally polymerized in a laminar flow, substantially spherical colored particles are obtained. For example, in the toner described in JP-A-56-130762, The proportion of colored particles having a shape factor of 1.2 to 1.6 is about 20% by number, the variation coefficient of the shape coefficient is also about 18%, and the proportion of colored particles without corners is also about 85% by number. . Further, as described above as a method for controlling the number variation coefficient in the number particle size distribution, mechanical shearing is repeated for a large oil droplet of a polymerizable monomer to reduce the oil droplet to a size of a target colored particle. In order to reduce the particle size distribution of the oil droplets, the particle size distribution of the obtained colored particles is wide and the number variation coefficient is 32%.
The classification operation is necessary to reduce the number variation coefficient.

In a polymerization method toner formed by associating or fusing resin particles, for example, Japanese Unexamined Patent Publication No.
In the toner described in Japanese Patent No. 186253, the proportion of colored particles having a shape coefficient of 1.2 to 1.6 is about 60% by number, the coefficient of variation of the shape coefficient is about 18%, The proportion of uncolored particles is also about 44% by number. Furthermore, the particle size distribution of the colored particles is wide and the coefficient of variation in number is about 30%, and a classifying operation is required to reduce the coefficient of variation in number.

<External Additive Used in the Present Invention><< Fatty Acid Metal Salt (Lubricant) >> In the toner A of the present invention, a fatty acid metal salt is used as an external additive. Fatty acid metal salts act as lubricants and include higher fatty acid metal salts. Further, the water content of the fatty acid metal salt is preferably 0.1 to 2.5% by mass, and the free fatty acid amount is preferably 0.01 to 0.7% by mass.

The fatty acid metal salt of the present invention is obtained by reacting a fatty acid with a metal salt, and the free fatty acid refers to a product remaining in the fatty acid metal salt as an unreacted product with the metal salt. . The free fatty acid amount refers to the amount of unreacted fatty acid in the reaction product of the fatty acid and the metal salt.

In general, the metal salt of a fatty acid is preferably a metal salt of a saturated or unsaturated fatty acid having 10 or more carbon atoms. Specific examples of such fatty acid metal salts include zinc stearate, aluminum stearate, copper stearate, magnesium stearate, calcium stearate and the like; zinc oleate, calcium oleate,
Metal oleates such as manganese oleate, iron oleate, copper oleate and magnesium oleate; metal palmitates such as zinc palmitate, copper palmitate, magnesium palmitate and calcium palmitate;
Metal salts of linoleic acid such as zinc linoleate and calcium linoleate; metal salts of ricinoleic acid such as zinc ricinoleate and calcium ricinoleate, and others such as calcium undecylate, calcium laurate, calcium tridecylate, calcium dodecylate, calcium myristate And calcium long-chain fatty acids such as calcium palmitate, calcium pentadecylate, calcium behenate, calcium heptadecylate, calcium arachiate, calcium montanate, calcium arachidate, and calcium behenate. Among them, fatty acid zinc,
Fatty acid calcium is preferred. More specifically, zinc stearate is preferable as the fatty acid zinc, and calcium stearate is preferable as the fatty acid calcium. The external addition amount is preferably 0.005 to 0.3% by mass of the toner mass.

Taking calcium stearate as an example, the production method includes a melting method in which a fatty acid and calcium oxide or calcium hydroxide are melt-reacted at a temperature equal to or higher than the melting point of the resulting fatty acid calcium salt, a fatty acid and calcium oxide or hydroxide. Any method such as a semi-melting method in which a calcium slurry is semi-molten below the melting point of the fatty acid calcium salt to be produced, a metathesis method in which an aqueous solution of an inorganic metal salt is added to an aqueous solution of a fatty acid sodium salt, and sodium is replaced with calcium, and the like. Good.

The preferred amounts of water and free fatty acids to be contained are substantially as follows.

The water content of the fatty acid metal salt is preferably from 0.1 to 2.5% by mass from the viewpoint of improving the humidity stability of charging.
0.2 to 1.2% by weight is particularly preferred. The amount of free fatty acid is preferably 0.01 to 0.7% by mass, and 0.02 to 0.5% by mass.
% By weight is particularly preferred. When the water content is more than 2.5% by mass and the free fatty acid content is more than 0.7% by mass, there is a possibility that a charging member such as a carrier and a developer carrying member (developing roll surface) may be contaminated, and If the amount is less than 0.1% by mass and the amount of free fatty acid is less than 0.01% by mass, the blade wear tends to increase, and the life of the cleaning blade may be shortened.

[0134] Taking calcium fatty acid as an example, the amount of water contained and the amount of free fatty acid were measured as follows.

1) Measurement of water content The water content is measured by the Karl Fischer method.

As a specific measuring method, there is a measuring method using a Hiranuma trace moisture meter (AQS-712: manufactured by Hiranuma Sangyo) under the following conditions.

Sample heating temperature: 110 ° C. Sample heating time: 1 minute Nitrogen gas flow rate: 150 ml / min 2) Measurement of free fatty acid 1 g of a sample was precisely weighed and mixed with ethanol and ethyl ether at a ratio of 1: 1.
The mixture was dissolved in one mixture, neutralized and titrated with an aqueous solution of potassium hydroxide using phenolphthalein as an indicator, and the content of free fatty acids was expressed in terms of mass percentage of stearic acid.

The amount of the fatty acid metal salt to be added is 0.005 to 0.3% by mass, more preferably 0.01 to 0.3% by mass, based on the colored particles.
It is preferably from 0 to 0.2% by mass.

When the content of the fatty acid metal salt is less than 0.005% by mass, the transfer from the toner surface to the photoreceptor surface becomes insufficient, and it is difficult to form a thin film on the photoreceptor surface. 0.3
When the amount is more than the mass%, the adhesion of paper powder to the fatty acid metal salt thin film formed on the surface of the photoreceptor increases, and image blur is likely to occur.

<< Inorganic Fine Particles >> In the toner B of the present invention, inorganic fine particles are used as an external additive.

As the material constituting the inorganic fine particles, various inorganic oxides, nitrides, borides and the like are preferably used.
For example, silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, manganese oxide, Examples thereof include boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride. Among them, silica and titania are preferable. In order to improve the flow characteristics (also referred to as a flowable external additive), a combination system of silica and / or titania is preferred. Further, it is preferable to externally add two kinds of silica particles having different number average particle diameters and / or two kinds of titanium oxide (titania) having different number average particle diameters.

Examples of the silica particles having different number average particle diameters include the following: a) The number average particle diameter is 0.005 to 0.05.
15 μm silica (hereinafter also referred to as small diameter silica), and b) silica having a number average particle diameter of 0.020 to 0.080 μm (hereinafter also referred to as large diameter silica).

The above inorganic fine particles may be used in combination with alumina, tin oxide, iron oxide or the like, if necessary. Further, it is preferable that the above-mentioned inorganic fine particles have been subjected to a hydrophobic treatment. When performing hydrophobic treatment, various titanium coupling agents,
It is preferable to carry out a hydrophobic treatment with a so-called coupling agent such as a silane coupling agent or a silicone oil.

Examples of the treating agent for performing the hydrophobizing treatment include titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, and bis (dioctyl pyrophosphate). ) Oxyacetate titanate. Further, as the silane coupling agent, γ-
(2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-amino Propyltrimethoxysilane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxy Examples include silane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane and the like. Examples of fatty acids and metal salts thereof include undecylic acid, lauric acid, tridecylic acid, dodecylic acid, Long-chain fatty acids such as stinic acid, palmitic acid, pentadecylic acid, stearic acid, heptadecylic acid, arachinic acid, montanic acid, oleic acid, linoleic acid, and arachidonic acid are listed. And salts with metals such as calcium, sodium and lithium. Further, as the silicone oil, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil and the like can also be mentioned as surface treatment agents.

These compounds are preferably added and coated in an amount of 1 to 10% by mass with respect to the inorganic fine particles.
It is 3 to 7% by mass. Further, these materials can be used in combination.

The degree of the hydrophobizing treatment is not particularly limited, but a methanol wettability of 40 to 95 is preferred. Methanol wettability is to evaluate the wettability to methanol. In this method, inorganic fine particles to be measured are added to 50 ml of distilled water placed in a beaker having a capacity of 200 ml.
Weigh 2 g and add. Methanol is slowly dropped from a burette whose tip is immersed in the liquid until the whole of the inorganic fine particles becomes wet while being slowly stirred. When the amount of methanol required to completely wet the inorganic fine particles is a (ml), the degree of hydrophobicity is calculated by the following equation.

Degree of hydrophobicity = (a / (a + 50)) × 100 The amount of the external additive to be added is 0.1 to 5.
0 mass%, preferably 0.5 to 4.0 mass%. Various external additives may be used in combination.

In order to improve the polishing characteristics (also referred to as an abrasive external additive), the number average particle size is 0.5 to 5.0 μm.
Inorganic fine particles or inorganic / organic composite fine particles described later are used.

This abrasive external additive was added to the colored particles in an amount of 0.1%.
The content is preferably from 02 to 2.0 parts by mass. More preferably, the content is 0.04 to 1.0 part by mass. 2.0
If the amount is more than the mass part, the amount of wear of the blade increases, and the cleaning property decreases. On the other hand, if the amount is less than 0.02 parts by mass, the effect of preventing toner filming on the photoconductor is reduced.

<< Inorganic / Organic Composite Fine Particles >> In the toner C of the present invention, inorganic fine particles having a primary average particle size of 5 to 100 nm are formed on the surface of organic fine particles having an average particle size of 0.1 to 5.0 μm as an external additive. A composite type abrasive containing fixed inorganic / organic composite fine particles (referred to as HFP) is used.

The primary average particle diameter of the inorganic fine particles constituting the inorganic / organic composite fine particles is preferably from 5 to 100 nm from the viewpoint of improving the cleaning property, the polishing property and the filming resistance. In addition, the primary average particle diameter of the inorganic fine particles refers to the number-based average particle diameter measured by image analysis under observation with a scanning electron microscope.

The constituent materials of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, cerium oxide, tungsten oxide, antimony oxide, copper oxide, tellurium oxide, manganese oxide, barium titanate, and titanate. Strontium, magnesium titanate, silicon nitride, carbon nitride and the like are used. Particularly preferably used is titanium oxide (titania).

The organic fine particles constituting the inorganic / organic composite fine particles are preferably resin particles made of an acrylic acid polymer, a styrene polymer, a styrene-acrylic acid copolymer or the like.

The acrylic acid polymer constituting the organic fine particles is a homopolymer or a copolymer obtained by polymerizing a monomer selected from acrylic acid or an acrylic ester, methacrylic acid or a methacrylic ester. . Examples of the acrylic acid monomer used to obtain such an acrylic acid polymer include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, and n-acrylic acid. Octyl, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-chloromethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid Propyl, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-methacrylic acid
Examples include ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate. An acrylic acid-based polymer can be obtained from one or more of the above-described acrylic acid-based monomers. In the present invention, one or more other monomers are copolymerized as necessary. It may be something. In this case, it is preferable to use the acrylic acid-based monomer in a proportion of 50% by mass or more in the monomer composition.

The styrene-based monomers used to obtain the styrene-based polymer constituting the organic fine particles include:
Styrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-
Nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, and the like can be mentioned. A styrene-based polymer can be obtained from one or more of the above-mentioned styrene-based monomers. In the present invention, one or more other monomers are copolymerized as necessary. There may be. In this case, it is preferable to use a styrene-based monomer in a proportion of 50% by mass or more in the monomer composition.

The styrene-acrylic acid-based copolymer constituting the organic fine particles is obtained by using one or more of the above-mentioned acrylic monomers and one or more of the above-mentioned styrene monomers. However, if necessary, one other monomer
It may be one or two or more copolymerized. In this case, in the monomer composition, it is preferable to use the acrylic acid-based monomer and the styrene-based monomer in a total amount of 50% by mass or more.

Examples of the other monomers include acrylic compounds such as acrylonitrile, methacrylonitrile and acrylamide; vinyl esters such as vinyl acetate, vinyl butyrate and vinyl benzoate; and vinyl ethers such as vinyl methyl ether and vinyl ethyl ether. , Vinyl ketones such as vinyl methyl ketone, dienes such as butadiene and isoprene, unsaturated carboxylic acids such as maleic acid and fumaric acid, and the like.

The average particle size of the organic fine particles constituting the inorganic / organic composite fine particles is from 0.1 to 5.0 μm from the viewpoints of improvement in cleaning properties and stability of triboelectric charging.
2-3.0 μm is preferred. The average particle diameter of the organic fine particles can be measured by a laser diffraction particle size distribution analyzer “HELOS” equipped with a wet disperser (SYMPATEK (SYMP)
ATEC) manufactured by ATEC Co., Ltd.). However, before the measurement, a pretreatment was performed in which 10 mg of organic fine particles were dispersed in 50 ml of water together with a surfactant, and then dispersed with an ultrasonic homogenizer (output 150 W) for 1 to 10 minutes while paying attention to reaggregation due to heat generation.

The inorganic / organic composite fine particles are constituted by fixing the inorganic fine particles treated with the above-mentioned specific treatment compound on the surface of the organic fine particles. Here, the term “fixed” refers to a state in which the length of a portion of the inorganic fine particles embedded in the organic fine particles is 5% to 95%, instead of being simply attached to the organic fine particles by the electrostatic force. Such a condition
It can be confirmed by observing the surface of the inorganic / organic composite fine particles with a transmission electron microscope or a normal electron microscope. In fixing the inorganic fine particles to the surface of the organic fine particles, it is preferable to first make the organic fine particles spherical, and then to fix the inorganic fine particles to the surface of the organic fine particles.
This is because when the organic fine particles are spherical, the inorganic fine particles are uniformly fixed, and the release of the inorganic fine particles is effectively prevented. Means for spheroidizing the organic fine particles include a method in which the organic fine particles are once melted by heat and then spray granulation, a method in which the hot-melted organic fine particles are jetted into water and spheroidized, a suspension polymerization method, A method of synthesizing spherical organic fine particles by an emulsion polymerization method may, for example, be mentioned.

The means for fixing the inorganic fine particles on the surface of the organic fine particles include a method of mixing the organic fine particles and the inorganic fine particles and then applying heat, and a so-called mechanochemical method of mechanically fixing the inorganic fine particles on the surface of the organic fine particles. Method is used. Specifically, the organic fine particles and the inorganic fine particles are mixed and stirred and mixed by a Henschel mixer, a V-type mixer, a turbular mixer, etc., and the inorganic fine particles are adhered to the surface of the organic fine particles by electrostatic force. A method in which the organic fine particles having the fine particles attached thereto are introduced into a heat treatment apparatus such as a nitro atomizer or a spray drier, and heat is applied to soften the surface of the organic fine particles to fix the inorganic fine particles to the surface. After attaching the inorganic fine particles, the impact-type pulverizer is modified to fix the inorganic fine particles on the surface of the organic fine particles by using a device capable of imparting mechanical energy, for example, a device such as an ang mill, a free mill, and a hybridizer. And the like.

In obtaining the inorganic / organic composite fine particles, the compounding amount of the inorganic fine particles with respect to the organic fine particles may be an amount capable of uniformly covering the surface of the organic fine particles. Specifically, although it depends on the specific gravity of the inorganic fine particles, it is usually 5 to 100% by mass, preferably 5 to 80% by mass based on the organic fine particles.
Inorganic fine particles are used in a ratio of mass%. If the proportion of the inorganic fine particles is too small, the cleaning property tends to decrease, and if the proportion of the inorganic fine particles is too large, the inorganic fine particles are easily released.

The above-mentioned inorganic / organic composite fine particles are added to and mixed with the colored particles to form a toner. The mixing ratio of the inorganic / organic composite fine particles is determined from the viewpoints of improvement in cleaning properties and stability of triboelectric charging. 0.01 to colored particles
5.0 mass% is preferable, and especially 0.01 to 2.0 mass% is preferable.

<Step of Adding External Additive> This step is a step of adding the above external additive to the dried colored particles.

Examples of a device used for adding an external additive to the above-mentioned colored particles include various known mixing devices such as a turbular mixer, a Henschel mixer, a Nauta mixer, and a V-type mixer.

<Developer> When the toner of the present invention contains a magnetic material and is used as a one-component magnetic toner, for example,
When used as a two-component developer by mixing with a so-called carrier, there may be cases where a non-magnetic toner is used alone, etc., and any of them can be preferably used. It is preferably used as a two-component developer.

<Developing Method> The developing method in which the toner of the present invention can be used is not particularly limited. An example in which the present invention is applied to a non-contact developing method will be described. In the non-contact developing method, a developer layer formed on a developer carrying member (developer conveying member) does not come into contact with a photoreceptor. In order to constitute this developing method, the developer layer is a thin layer. It is preferable to be formed by. In this method, the development area on the surface of the developer carrier
A developer layer of 0 to 500 μm is formed, and the gap between the photoreceptor and the developer carrier has a larger gap than the developer layer. The thin layer is formed by a magnetic blade using a magnetic force or a method of pressing a developer layer regulating rod against the surface of the developer carrier. Furthermore, there is a method in which a urethane blade, a phosphor bronze plate or the like is brought into contact with the surface of the developer carrier to regulate the developer layer. The pressing force of the pressing regulating member is 10 to 1
50 mN / mm is preferred. When the pressing force is small, the conveyance is likely to be unstable because the regulating force is insufficient. On the other hand, when the pressing force is large, the stress on the developer is increased, and the durability of the developer is likely to be reduced. A preferred range is 30 to 100 mN / mm. The gap between the developer carrier and the surface of the photoconductor needs to be larger than the developer layer. Further, when a developing bias is applied at the time of development, either a method of applying only a DC component or a method of applying an AC bias may be used.

In the present invention, it is preferable to apply an alternating electric field between the developer carrying member (developer conveying member) and the electrostatic latent image holding member (photosensitive member). By applying this alternating electric field, the toner can fly effectively. The condition of this alternating electric field is that the AC frequency f is 200 to
8000 Hz, and an AC voltage Vp-p of 500 to 30
It is preferably 00V. When this alternating electric field is used, it is necessary that the toner has a uniform chargeability. That is, when the chargeability is distributed between the toners, the effect of pulling back the weakly chargeable toner or the like due to the alternating electric field is offset, and as a result, the effect of improving the image quality is reduced.

As the developer carrier used in the present invention, those having a built-in magnet inside the carrier are often used, and the developer is developed by rotating the surface (sleeve) of the developer carrier. It is transported to the area. Aluminum or stainless steel whose surface is oxidized is used as the sleeve. The diameter of the developer carrier is 10 to 10 mm.
40 mm is preferred. When the diameter is small, the mixing of the developer is insufficient, and it is difficult to ensure sufficient mixing to give sufficient charge to the toner. When the diameter is large, the centrifugal force on the developer becomes large. , The problem of toner scattering is likely to occur.

When the toner of the present invention is used in a non-contact developing system, it is preferable to use it as a two-component developer by mixing it with a carrier. As the carrier constituting the two-component developer, magnetic particles made of conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead can be used. Particularly, ferrite particles are preferable. The magnetic particles have a volume average particle size of 15 to 100 μm,
More preferably, the thickness is 25 to 60 μm. The volume average particle size of the carrier is typically measured by a laser diffraction type particle size distribution analyzer “HELOS (HELO) equipped with a wet disperser.
S) "(manufactured by SYMPATEC). The carrier is preferably a carrier further coated with a resin or a so-called resin-dispersed carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited,
For example, an olefin resin, a styrene resin, a styrene / acrylic resin, a silicone resin, an ester resin, a fluorine-containing polymer resin, or the like is used. The resin for constituting the resin dispersion type carrier is not particularly limited, and known resins can be used.
For example, styrene acrylic resin, polyester resin, fluorine resin, phenol resin, and the like can be used.

FIG. 2 is a schematic diagram for explaining an example of the non-contact developing system. Hereinafter, the non-contact developing method will be described with reference to FIG. FIG. 2 is a schematic view of a non-contact developing type developing unit that can be suitably used in the image forming method of the present invention. 10 is a cylindrical photoreceptor, 74 is a developer carrier, 75 is a sleeve, 7
Reference numeral 6 denotes a magnet, 77 denotes a two-component developer containing the toner of the present invention, 78 denotes a developer layer regulating member, 79 denotes a development area, 80 denotes a developer layer, and 81 denotes a power supply for forming an alternating electric field. The two-component developer 77 containing the toner of the present invention is carried by the magnetic force of a developer carrier 74 having a magnet 76 therein, and is conveyed to a development area 79 by movement of a sleeve 75. During this transport, the thickness of the developer layer 80 is regulated by the developer layer regulating member 78 so that the developer layer 80 does not come into contact with the cylindrical photoreceptor 10 in the developing region 79. The minimum gap (Dsd) of the developing area 79 is equal to the thickness (about 50 to 300 μm) of the developer layer 80 conveyed to the area.
m, preferably 100 to 1000 μm (preferably 100 to 500 μm).
m). The power supply 81 is a power supply for forming an alternating electric field, and has a frequency of 200 to 8000 Hz and a voltage of 500.
AC of ~ 3000 Vp-p is preferred. The power supply 81 may have a configuration in which DC is added to AC in series as needed. In that case, the DC voltage is preferably 300 to 800V. Further, when the toner of the present invention is used in the contact type development, the layer thickness of the developer having the toner of the present invention is 0.1 to 8 mm in the development area, particularly 0.4 to 8 mm.
It is preferably about 5 mm. Further, the gap between the photoconductor and the developer carrier is 0.15 to 7 mm, particularly 0.2 to 7 mm.
It is preferably 4 mm.

Although the developing method has been described by taking the non-contact method as an example, the present invention relates to a contact developing method, that is, a method in which a photosensitive layer is brought into contact with a developer layer formed on a developer carrying member. It goes without saying that the present invention can be applied to a method of forming an image on the top.

<Fixing Method> As a preferable fixing method used in the present invention, a so-called contact heating method can be mentioned. In particular, examples of the contact heating method include a heat and pressure fixing method, a heat roll fixing method, and a pressure contact heat fixing method in which fixing is performed by a rotating pressing member including a fixedly disposed heating element.

In the heat roll fixing method, a heat source is often provided inside a metal cylinder made of iron, aluminum, or the like whose surface is coated with tetrafluoroethylene or polytetrafluoroethylene-perfluoroalkoxyvinyl ether copolymer or the like. It is formed of an upper roller and a lower roller made of silicone rubber or the like. A typical example of the heat source is one having a linear heater and heating the surface temperature of the upper roller to about 120 to 200 ° C. In the fixing section, pressure is applied between the upper roller and the lower roller to deform the lower roller and form a so-called nip. The nip width is 1 to 10 mm, preferably 1.
5-7 mm. The fixing linear velocity is 40 mm / sec to 60
0 mm / sec is preferable. If the nip is narrow, heat cannot be uniformly applied to the toner, causing uneven fixing. On the other hand, when the nip width is large, the melting of the resin is promoted, and a problem occurs that the fixing offset becomes excessive. A fixing cleaning mechanism may be provided for use. As this method, a method in which a silicone oil is supplied to a roller or a film after fixing, or a method in which a silicone oil-impregnated pad, roller, web or the like is used for cleaning can be used.

Next, a description will be given of a fixing method using a rotating pressing member including a fixedly disposed heating element used in the present invention. This fixing method is a method in which a heating member fixedly disposed and a pressing member which is opposed to and pressed against the heating member and adheres the recording material to the heating member via a film through a film are used to perform pressure-contact heating and fixing. In this press-contact heat fixing device, the heating element has a smaller heat capacity than a conventional heating roller, and has a linear heating section in a direction perpendicular to the recording material passing direction. 300 ° C. The press-contact heat fixing is a method of fixing an unfixed toner image by pressing the unfixed toner image against a heating source, such as a method of passing a recording material having unfixed toner between a heating member and a pressing member as usually used. is there. By doing so, the heating is performed quickly, so that the fixing speed can be increased. However, it is difficult to control the temperature, and the so-called residual toner is adhered to the unfixed toner directly, such as the surface of the heating source, where the unfixed toner is pressed. There is also a problem that a toner offset is likely to occur, and a failure such as the recording material wrapping around the fixing device is also likely to occur.

Next, FIG. 3 shows an example of a sectional view of the structure of the fixing device. In FIG. 3A, reference numeral 84 denotes a low-heat-capacity linear heating element fixedly supported by the apparatus. As an example, a resistance material 86 is attached to an alumina substrate 85 having a height of 1.0 mm, a width of 10 mm, and a length of 240 mm. Is applied to a width of 1.0 mm, and electricity is supplied from both ends in the longitudinal direction. Energization is performed, for example, at a DC voltage of 100 V, usually in a pulse-like waveform with a period of 20 msec, and is controlled by a signal from the temperature detecting element 87 to maintain a predetermined temperature. For this reason, the pulse width is changed in accordance with the energy release amount, and the range is, for example, 0.5 to 5 msec.

The recording paper (recording material) P carrying the unfixed toner image 93 is brought into contact via the film 88 moved to the heating element 84 controlled in this way, and the toner is thermally fixed.
The film 88 used here moves without generating wrinkles while being tensioned by the driving roller 89 and the driven roller 90. Reference numeral 95 denotes a pressure roller having a rubber elastic layer formed of silicone rubber or the like, and presses the heating body through the film at a total pressure of 40 to 200N. The unfixed toner image 93 on the recording material P is
The fixing image is guided to the fixing unit 6 and a fixed image is obtained by the above-described heating.

In this fixing method, the low-heat-capacity linear heating element fixedly supported by the apparatus has a thickness of 0.2 to 5.0 mm.
0 mm, more preferably 0.5 to 3.5 mm and width 10
A resistance material is applied to an alumina substrate having a length of 240 to 400 mm and a length of 240 to 400 mm, and is supplied with electricity from both ends. Energization is performed at a cycle of 15 to 25 DC100V.
With a pulse waveform of msec, the pulse width is changed according to the temperature / energy release amount controlled by the temperature sensor. In the case of the temperature T1 detected by the temperature sensor in the low heat capacity linear heating element, the surface temperature T2 of the film facing the resistance material is lower than T1. Here, T1 is preferably 120 to 220 ° C., and the temperature of T2 is preferably 0.5 to 10 ° C. lower than the temperature of T1. Further, the film material surface temperature T3 at a portion where the film is separated from the toner surface is substantially equal to T2. The film moves in the direction of the arrow in FIG. 3A by contacting the heating body whose energy and temperature are controlled in this manner. Those used as fixing films are heat-resistant films having a thickness of 10 to 35 μm, for example, polyester, polyperfluoroalkoxy vinyl ether, polyimide, and polyetherimide, and in many cases, conductive films such as Teflon (registered trademark). It is an endless film in which a material is added and a release agent layer is covered with 5 to 15 μm.

In driving the film, a driving force and a tension are applied by a driving roller and a driven roller, and the film is transported in the direction of the arrow without wrinkles and twists. The linear velocity of the fixing device is preferably 40 to 600 mm / sec. The pressure roller has a rubber elastic layer with high release properties such as silicone rubber,
At a total pressure of 20 to 300 N, it is pressed against the heating element via the film material, and rotates under pressure.

In the above description, an example using an endless film has been described. However, as shown in FIG. Good. Further, it may be a simple cylindrical member having no drive roller or the like inside.

The above fixing device may be provided with a cleaning mechanism. As a cleaning method, a method of supplying various silicone oils to the fixing film or a method of cleaning with a pad, a roller, a web or the like impregnated with various silicone oils is used. As the silicone oil, polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane and the like can be used. Further, a siloxane containing fluorine can also be suitably used.

<Image Forming Apparatus and Process Cartridge>
FIG. 4 is a diagram illustrating a configuration of a digital image forming apparatus (hereinafter, also simply referred to as an image forming apparatus) applied to the present invention.

In the figure, an image forming apparatus 1 includes an automatic document feeder (ADF) A, a document image reading unit B for reading an image of a document conveyed by the automatic document feeder, and a read document image. Image control board C to be processed
A writing unit 12 for writing on a cylindrical photoreceptor 10 as an image carrier in accordance with data after image processing
And an image including image forming means such as a cylindrical photoreceptor 10, a charging electrode 14, a developing means 16 composed of a magnetic brush type developing device, a transfer electrode 18, a separation electrode 20, and a cleaning means 21. It has a forming section E and a storage section F for paper feed trays 22 and 24 for storing recording paper P.

The automatic document feeder A is provided with a document table 26
Switching means for appropriately switching the roller group including the roller R1 and the movement path of the document (no reference symbol)
And a document transport processing unit 28 including

The original image reading section B is located below the platen glass G and can move back and forth while maintaining the optical path length, a fixed imaging lens (hereinafter simply referred to as a lens) 33, and a line-shaped image forming section. Image sensor (hereinafter referred to as CCD
The writing unit D includes a laser light source 40, a polygon mirror (polarizer) 42, and the like.

When viewed from the moving direction of the recording paper P as a transfer material, R10 shown on the front side of the transfer electrode 18 is a registration roller, and H shown on the downstream side of the separation electrode 20 is a fixing means.

In the embodiment, the fixing means H is composed of a roller having a built-in heating source and a pressure roller which rotates while pressing the roller.

Further, Z is a cleaning means for the fixing means H, and has a cleaning web provided so as to be wound up as a main element.

One original (not shown) placed on the original placing table 26 is transported by the original transport processor 28,
While passing under the roller R1, exposure by the exposure means L is performed.

The light reflected from the original passes through the mirror units 30 and 31 and the lens 33 at the fixed position and passes through the CCD 3.
5 and is read.

The image information read by the document image reading section B is processed by the image processing means, encoded, and stored in a memory provided on the image control board C.

Further, the image data is called in accordance with the image formation, and the laser light source 40 in the writing section D is driven according to the image data, so that the cylindrical photosensitive member 10 is exposed.

Prior to the exposure, the cylindrical photoreceptor 10 rotating in the direction of the arrow (counterclockwise) is given a predetermined surface potential by the corona discharge action of the charging electrode 14. The potential decreases according to the exposure amount, and as a result, an electrostatic latent image corresponding to the image data is formed on the cylindrical photoconductor 10.

The electrostatic latent image is reversely developed by the developing means 16 to be a visible image (toner image).

On the other hand, before the leading end of the toner image on the cylindrical photoreceptor 10 reaches the transfer area, for example,
One of the recording sheets P in 2 is fed and conveyed, reaches the registration roller R10, and is regulated at the leading end.

The recording paper P is conveyed toward a transfer area by a registration roller R10, which starts rotating in synchronization with the toner image, that is, an image area on the cylindrical photoreceptor 10, in a synchronized manner.

In the transfer area, the toner image on the cylindrical photoreceptor 10 is transferred onto the recording paper P by the urging of the transfer electrode 18, and the recording paper P is then urged by the separation electrode 20. Separated from 10.

Thereafter, the fixing unit H is pressurized and heated to
The toner image is fused and fixed on the recording paper P, and the recording paper P
Is discharged onto a discharge tray T via a discharge path 78 and a discharge roller 79.

The reference symbol Sp on the paper feed tray 24 is
The free end is a movable plate that is constantly urged upward by an urging means such as a coil spring (not shown). As a result, the uppermost sheet comes into contact with a delivery roller described later.

The paper feed tray 22 has the same configuration as that described above. In the embodiment, the paper feed trays 22 and 24 are arranged in two stages in the vertical direction, but may be provided with more paper feed trays.

[0200] Of the paper feed trays, the bottom (the same as the bottom wall) of the paper feed tray 24 arranged at the lower stage (in the embodiment, the paper feed tray is a two-stage stack, so the lower stage is used, but the lower stage is meant). A space 25 having a predetermined gap is formed between the apparatus and the bottom wall of the apparatus main body.

The space 25 is used in a mode (mode) in which images are formed on both sides of the recording paper P, and is cooperated with a second transport path 80 (described later) for reversing the recording paper. To achieve the reverse of the front and back.

Reference numerals 50 and 53 above the respective leading ends (corresponding to the leading ends of the recording sheets P stored in the sheet feeding direction) of the sheet feeding trays 22 and 24 denote sheet feeding means comprising rollers (hereinafter referred to as feed-out means). Rollers), 51 and 54 are feed rollers, and 52 and 55 are double feed prevention rollers.

The feed roller (50, 53) and the feed roller (51, 54) are unitized, and a drive shaft connected to a drive source provided on the apparatus main body side or a locking means provided on a paper feed unit. It has a configuration that can be easily attached to and detached from

The double feed prevention rollers (52, 55) are also unitized, and have a structure that can be easily attached to and detached from a fixing member provided on a fixing portion of the apparatus main body.

Reference numeral 60 denotes a manual paper feed tray of the manual paper feed unit, which can be opened and closed with the lower end serving as a fulcrum with respect to the main body side wall of the image forming apparatus 1.

Numeral 61 denotes a feed roller composed of a roller for feeding the recording paper placed on the manual paper feed tray 60 with image formation, and 63 denotes a feed roller 61.
A feed roller 65 provided downstream of the feed tray 65 is a double feed prevention roller for pressing against the feed roller 63 to prevent a plurality of feeds of the recording paper P.
It has substantially the same configuration as the case of 2, 24.

Reference numeral 66 denotes a conveyance path for the recording paper P sent out from the manual feed tray 60, which communicates with a later-described junction via a pair of conveyance rollers immediately to the left of the feed roller 63.

Reference numeral 70 denotes a first conveyance path for forming an image on the recording paper P by transfer, and extends upward from below when viewed from the moving direction of the recording paper sent from an appropriate paper feed tray. .

Reference numeral 72 denotes a paper feed path for recording paper stored in the upper paper feed tray 22, reference numeral 74 denotes a paper feed path for recording paper stored in the lower paper feed tray 24, and reference numeral 76 denotes both trays 2.
It is a merging portion (a part of the first conveyance path 70) where the recording papers P sent from 2 and 24 merge.

[0210] Reference numeral 78 denotes a paper discharge path for discharging the recording paper on which a predetermined image has been formed onto the paper discharge tray T.

Numeral 80 denotes a second transport path for reversing the recording paper used for forming images on both sides of the recording paper.
The upper part of the figure communicates with the first transport path.

The second transport path 80 extends downward from above when viewed from the direction of movement of the recording paper.

The lower end of the second conveying path 80 is a conveying path that extends substantially vertically, and the lower end extends below the sheet feeding section of the lower sheet feeding tray 24.
0 (connected).

As understood from the above, the first transport path 7
0 and the second transport path 80 form a long loop in the longitudinal direction on one side wall side of the apparatus main body.

At the connection between the first transport path 70 and the second transport path 80, a transport means R20 (also serving as a switchback roller) comprising a pair of reversible rotatable rollers is provided.

The connection section is not a section in which the recording paper P is continuously conveyed from the second conveyance path 80 to the first conveyance path 70, and thus can be said to be a branch section for separating the two conveyance paths.

A path leading to the space 25 is provided below the switchback roller R20. When the recording paper P is turned upside down, the recording paper P moving through the second transport path 80 is moved to the space 25. Used to go to.

In the image forming process, the second transport path 8
0, when the recording paper P is sent out toward the space 25, the rear end of the recording paper P is configured to be gripped by the switchback roller R20. 25 stores a part of the recording paper.

Reference numeral 90 denotes an (upper) branch guide which directs the recording paper P, on which an image has been formed on the first surface, to the paper discharge passage 78,
Alternatively, it is controlled so as to be directed to the second transport path 80.

In other words, the image forming apparatus is controlled according to the image forming mode set by the user (the mode of forming an image on only one side of the recording paper or the mode of forming an image on both sides of the recording paper).
It can be said that the recording paper transport path is switched.

When an image is formed in the image forming section E configured as described above, first, the surface of the cylindrical photosensitive member 10 is charged by the discharging action of the charging electrode 14 as the cylindrical photosensitive member 10 rotates. Next, an image is written in the writing section D to form an electrostatic latent image. The electrostatic latent image is developed by the developing means 16 to form a toner image. On the other hand, the paper feed trays 22, 2
4 or the recording paper P fed from the manual paper feed tray 60, the toner image is transferred by the transfer electrode 18, the recording paper P is separated by the separation electrode 20, fixed by the fixing unit H, and fixed on the discharge tray T. Is discharged to

A process cartridge is formed by combining the photosensitive member with at least one of a charger, an image exposing unit, a developing unit, a transferring unit, a separating unit and a cleaning unit, and the image forming unit E is detachably mountable to the main unit. The preferred embodiment of the present invention is one of the preferred embodiments of the present invention.

FIG. 5 is a sectional view of the cleaning means used in the image forming apparatus of the present invention.

In FIG. 5, the cylindrical photoreceptor 10 is installed in the image forming apparatus such that the central axis of the cylinder is substantially horizontal. The term “substantially horizontal” refers to a horizontality at which the angle at which the central axis of the cylinder intersects the horizontal plane is within ± 10 degrees. A cleaning unit 21 is provided above the cylindrical photoconductor 10. As shown in the figure, the cleaning blade 211 is disposed above a line HL passing through the rotation center 10A of the cylindrical photoreceptor 10, and a position perpendicular to the central axis of the cylindrical photoreceptor 10 is set to 0 degree. When the central angle (β) is within ± 30 degrees, the tip of the cleaning blade 211 is pressed against the surface of the photoconductor to clean the toner on the photoconductor.

On the side of the frame 218 of the cleaning means 21, a sheet-like conductive member 219 and a separating claw 217 are provided on the upstream side of the cleaning blade. Both the sheet-like conductive member 219 and the separating claw 217 are cylindrical. Photoreceptor 10
Touching the surface.

Further, a support 212 is rotatably supported by a shaft 213 in the frame 218, and a base of the cleaning blade 211 is fixed to one end of the support 212. The other end 222 of the support 212 is provided so as to be exposed outside from the frame 218.

In the operating state of the cleaning means 21, the tip of the cleaning blade 211 is pressed against the cylindrical photoreceptor 10 by the elastic force of the spring S provided at the other end of the support 212. On the rear end side of the cleaning blade 211, and
An elastic plate 214 is provided at one end of the support 212 so as to be located downstream of the shaft 213 with respect to the rotation direction of the cylindrical photoconductor 10, and one end thereof is fixed. Works to prevent. Elastic plate 21
4 is preferably made of an elastic plate such as polyurethane rubber or polyethylene terephthalate.

After the toner image is transferred onto the recording paper P in the frame 218, when the residual toner on the cylindrical photoreceptor 10 is cleaned by the cleaning blade 211, the frame 2
The toner discharge members 215 and 216 for sequentially discharging the residual toner to the outside from inside 18 are provided.

FIG. 6 is a diagram illustrating the setting of the cleaning blade, the sheet-shaped conductive member and the cylindrical organic photoreceptor of the present invention in more detail.

In FIG. 6, the cleaning blade 211
Is 0 degrees above the central axis of the cylindrical photoconductor 10, the photoconductor cylinder center angle (β) is within ± 30 degrees,
It is in pressure contact with the photoconductor surface (contact point A).

In the present invention, the cleaning blade 21
Preferred values of the contact load P and the contact angle θ on the photoconductor 1 are P = 5 to 40 N / m and θ = 5 to 35 °.

The free length L of the cleaning blade represents the length from the end of the support 212 to the tip of the blade before deformation, as shown in FIG. A preferred value of the free length is L = 5 to 15 mm. The thickness of the cleaning blade is preferably 0.5 to 4 mm.

The contact load P is the cleaning blade 211
Is the vector value in the normal direction of the pressing force P ′ when the abutment is brought into contact with the cylindrical photoconductor 10.

The contact angle θ is the tangent X at the contact point A of the photosensitive member and the blade before deformation (shown by a two-dot chain line in the drawing).
And the angle formed by

The sheet-shaped conductive member 219 is provided on the side of the frame 218 of the cleaning means 21 and on the upstream side of the cleaning blade (with respect to the rotation direction of the photosensitive member). Is in contact with the photoreceptor surface. As a result, the charge on the toner and the photoreceptor is removed, and as a result, the cleaning property is improved, and an excessive load is not applied to the cleaning blade, and the blade failure such as turning over of the blade and squealing of the blade is prevented.

In FIG. 6, reference numeral 220 denotes a backing member (a folded polyethylene terephthalate sheet or the like) of a sheet-shaped conductive member, and 221 denotes a toner guide (a sheet such as a polyethylene terephthalate sheet). Prevents scattering to the outside. Further, in order to effectively remove the charge of the toner or the photoconductor, it is preferable that the sheet-shaped conductive member 219 is grounded (grounded).

In the present invention, it is preferable that the contact width of the cleaning blade (the width in the direction parallel to the axis of the cylindrical photosensitive member) is set longer than the photosensitive layer width of the organic photosensitive member. If the cleaning blade contact width is set shorter than the width of the photosensitive layer, toner is likely to slip through on both sides of the cylindrical photoconductor, and cleaning failure is likely to occur.

The cleaning blade used in the present invention is preferably an elastic rubber blade. The physical properties of the cleaning blade are controlled simultaneously by controlling the rubber hardness and the rebound resilience. Can be suppressed. Blade J at 25 ± 5 ° C
When the ISA hardness is less than 65, reversal of the blade is likely to occur, and when it is more than 80, the cleaning performance decreases. When the rebound resilience exceeds 80, reversal of the blade tends to occur, and when the rebound resilience is 20 or less, the cleaning performance deteriorates. More preferable rebound resilience is 20 or more and 80.
It is as follows. The Young's modulus is preferably in the range of 294 to 588 N / cm ² . (Both the JISA hardness and the rebound resilience are measured based on the vulcanized rubber physical test method of JIS K6301. The value of the rebound resilience indicates%.) As the material of the elastic rubber blade used for the cleaning blade, urethane rubber, silicone rubber, Fluorine rubber, chloropyrene rubber, butadiene rubber, and the like are known, and among these, urethane rubber is particularly preferable because it has excellent wear characteristics as compared with other rubbers. For example,
Urethane rubbers obtained by reacting and curing polycaprolactone esters and polyisocyanates described in JP-A-59-30574 are preferred.

In the image forming method having the above-described cleaning means, the toner scraped off by the cleaning blade does not easily separate from the surface of the photoreceptor, and cleaning failure often occurs. In particular, when the above-described cleaning means is employed in an image forming apparatus using a polymerized toner and an organic photoreceptor, poor cleaning tends to occur.

[0240]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

A. Photoreceptor Preparation of Photoreceptor P1 The following coating solutions were sequentially applied on an aluminum drum support having a length of 380 mm and a diameter of 60 mm to prepare a photoreceptor P1.

<< Intermediate Layer >> Organometallic compound; titanium chelate compound (TC-750, manufactured by Matsumoto Pharmaceutical Co., Ltd.) 300 g Silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) 170 g 2-propanol 1500 ml Cylindrical using the above coating solution On a conductive support, a film thickness of 0.
It was applied to a thickness of 5 μm.

<< CGL >> Y-type titanyl phthalocyanine (a titanyl phthalocyanine having a maximum peak at 27.2 degrees with a Bragg angle of 2θ (± 0.2) in Cu-Kα characteristic X-ray diffraction spectrum measurement) 600 g silicone-modified butyral resin ( X-40-1211M (Shin-Etsu Chemical Co., Ltd.) 7000 g 2-butanone 20000 ml was mixed and dispersed using a sand mill for 10 hours to prepare a charge generation layer coating solution. This coating solution was applied on the intermediate layer by a dip coating method to form a 0.2 μm-thick charge generation layer.

<< CTL >> Charge transport substance; N- (4-methylphenyl) -N- {4- (β-phenylstyryl) phenyl} -p-toluidine 225 g Polycarbonate (viscosity average molecular weight 30,000) 300 g Antioxidant (Exemplified Compound 1-3) 6 g of dichloromethane and 2,000 ml of dichloromethane were mixed and dissolved to prepare a charge transport layer coating solution. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a dry film thickness of 20 μm.

Preparation of Photoconductor P2 A photoconductor P2 was prepared in the same manner as P1, except that the intermediate layer of the photoconductor P1 was replaced with the following materials.

<< Intermediate Layer >> Organometallic compound; zirconium chelate compound “ZC-540” (manufactured by Matsumoto Pharmaceutical Co., Ltd.) 200 g Silane coupling agent “KBM-903” (manufactured by Shin-Etsu Chemical Co., Ltd.) 100 g methanol 700 ml ethanol 300 ml Coated on aluminum support, 150
It dried at 30 degreeC and 30 minutes, and formed the 0.5-micrometer-thick intermediate | middle layer.

Preparation of Photoreceptor P3 A photoreceptor P3 was prepared in the same manner as P1 except that the intermediate layer of photoreceptor P1 was replaced with the following materials.

<< Intermediate Layer >> Silane coupling agent “KBM-903” (manufactured by Shin-Etsu Chemical Co., Ltd.) 300 g water 30 ml ethanol 1000 ml Preparation of photoconductor P4 Same as P1 except that the intermediate layer of photoconductor P1 was changed to the following material As a result, a photoconductor P4 was manufactured.

<< Intermediate Layer >> Organometallic compound: Titanium chelate compound “TC-100” (manufactured by Matsumoto Pharmaceutical Co., Ltd.) 200 g Silane coupling agent “KBM-903” (manufactured by Shin-Etsu Chemical Co., Ltd.) 130 g Toluene 1000 ml Water 30 ml Photoconductor P5 Production (Comparative Photoreceptor) A photoreceptor P5 was produced in the same manner as P1 except that the intermediate layer of the photoreceptor P1 was changed to the following material.

<< Intermediate Layer >> Polyamide resin “CM-8000” (manufactured by Toray Industries, Inc.) 150 g 2-propanol 1500 ml Methanol 8500 ml 9. Production of Colored Particles and Toner Production of Colored Particles and Toner T1: Example of Emulsion Polymerization Association Method 0.90 kg of sodium n-dodecyl sulfate and pure water
0 liter was added and dissolved by stirring. To this solution was added Regal 330R (carbon black manufactured by Cabot Corporation) 1.20.
kg was gradually added, and the mixture was stirred well for 1 hour, and then continuously dispersed for 20 hours using a sand grinder (medium type disperser). This is referred to as “colorant dispersion liquid 1”. Also,
Sodium dodecylbenzenesulfonate 0.055kg
And a solution composed of 4.0 liters of ion-exchanged water is referred to as “anionic surfactant solution A”. A solution consisting of 0.014 kg of nonylphenol polyethylene oxide adduct of 10 mol and 4.0 liters of ion-exchanged water is referred to as “nonionic surfactant solution B”. Potassium persulfate 223.8
g in 12.0 liters of ion-exchanged water is referred to as "initiator solution C".

A WAX emulsion (polypropylene emulsion having a number average molecular weight of 3,000: a number average primary particle diameter of 120) was placed in a 100-liter GL (glass lining) reactor equipped with a temperature sensor, a cooling pipe, and a nitrogen introducing device.
3.41 kg), the whole amount of “anionic surfactant solution A” and the whole amount of “nonionic surfactant solution B” were added, and stirring was started. Next, 44.0 liters of ion-exchanged water was added.

Heating was started, and when the liquid temperature reached 75 ° C., the entire amount of “initiator solution C” was added dropwise. Then, while controlling the liquid temperature to 75 ° C. ± 1 ° C., the styrene 1
2.1 kg, 2.88 kg of n-butyl acrylate, 1.04 kg of methacrylic acid, and t-dodecyl mercaptan 54
8 g were added dropwise.

After the completion of the dropwise addition, the liquid temperature was raised to 80 ° C. ± 1 ° C., and the mixture was heated and stirred for 6 hours. Subsequently, the liquid temperature was cooled to 40 ° C. or lower, stirring was stopped, and the mixture was filtered with a pole filter to obtain a latex. This is designated as "latex-A".
In addition, the glass transition temperature of the resin particles in the latex-A was 57 ° C, the softening point was 121 ° C, the molecular weight distribution was 12700, and the weight average particle size was 120 nm.

A solution obtained by dissolving 0.055 kg of sodium dodecylbenzenesulfonate in 4.0 liters of ion-exchanged pure water is referred to as “anionic surfactant solution D”. A solution obtained by dissolving 0.014 kg of a 10 mol adduct of nonylphenol polyethylene oxide in 4.0 liters of ion-exchanged water is referred to as “nonionic surfactant solution E”.
A solution obtained by dissolving 200.7 g of potassium persulfate (manufactured by Kanto Chemical Co., Ltd.) in 12.0 liters of ion-exchanged water is referred to as “initiator solution F”.

A 100 liter GL reactor equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a comb baffle was charged with W.
3.41 kg of AX emulsion (polypropylene emulsion having a number average molecular weight of 3,000: number average primary particle diameter of 120 nm, solid content concentration of 29.9%), the total amount of “anionic surfactant solution D” and the total amount of “nonionic surfactant solution E” And stirring was started. Next, ion-exchanged water 44.
0 liter was charged. Start heating, liquid temperature 70 ° C
Was reached, "Initiator solution F" was added. Then, 11.0 kg of styrene and n-butyl acrylate4.
A solution prepared by previously mixing 00 kg, 1.04 kg of methacrylic acid, and 9.02 g of t-dodecylmercaptan was added dropwise.

After the completion of the dropwise addition, the mixture was heated and stirred for 6 hours while controlling the liquid temperature at 72 ° C. ± 2 ° C. Further, when the liquid temperature is 80
After heating to 12 ° C for 12 hours, the solution temperature was cooled to 40 ° C or less, and the stirring was stopped. The solution is filtered through a pole filter, and this filtrate is referred to as “latex-B”. The glass transition temperature of the resin particles in latex-B is 5
8 ° C., softening point 132 ° C., molecular weight distribution was weight average molecular weight 245,000, and weight average particle size was 110 nm.

Sodium chloride as salting-out agent 5.36k
g in 20.0 liters of ion-exchanged water is referred to as "sodium chloride solution G". A solution obtained by dissolving 1.00 g of a fluorine-based nonionic surfactant in 1.00 liter of ion-exchanged water is referred to as “nonionic surfactant solution H”.

A 100-liter SUS reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introduction device, and a particle size and shape monitoring device (reactor having a two-stage stirring blade, crossing angle α of the blade was 25 °) 2) kg of latex-A and 5.2 kg of latex-B prepared above.
And 0.4 kg of the colorant dispersion 1 and ion-exchanged water.
And stirred.

Then, the mixture was heated to 40 ° C., and sodium chloride solution G, isopropanol (manufactured by Kanto Chemical Co., Ltd.) 6.00 k
g, Nonionic surfactant solution H were added in this order. Then, after leaving it for 10 minutes, the temperature was started and the liquid temperature was 8
The temperature was raised to 5 ° C. in 60 minutes, and heated and stirred at 85 ± 2 ° C. for 0.5 to 3 hours to grow the particle size while salting out / fusing.
Next, 2.1 liters of pure water was added to stop the particle size growth.

A 5-liter reaction vessel equipped with a temperature sensor, a cooling pipe, and a particle size and shape monitoring device (reactor having a two-stage stirring blade, crossing angle α of blade was 20)
In (°), 5.0 kg of the fused particle dispersion prepared above was added, and the mixture was heated and stirred at a liquid temperature of 85 ° C. ± 2 ° C. for 0.5 to 15 hours to control the shape. Thereafter, the mixture was cooled to 40 ° C. or lower and the stirring was stopped.

Next, classification is performed in the liquid by a centrifugal sedimentation method using a centrifugal separator, and the liquid is filtered through a sieve having an opening of 45 μm, and this filtrate is used as an associated liquid. Next, non-spherical particles in the form of a wet cake were collected by filtration from the associated liquid using a Nutsche. Thereafter, the substrate was washed with ion-exchanged water. The non-spherical particles were dried at a suction air temperature of 60 ° C. using a flash jet drier, and then dried at a temperature of 60 ° C. using a fluidized bed drier.

In the monitoring of the salting-out / fusion step and the shape control step, the number of rotations of the stirrer and the heating time are controlled to control the variation coefficient of the shape and the shape coefficient. And the coefficient of variation of the particle size distribution is arbitrarily adjusted to obtain colored particles T1- comprising colored particles having the shape characteristics and the particle size distribution characteristics shown in Table 1.
1 to -15 were obtained.

Table 2 was added to 100 parts by mass of the obtained colored particles.
Of the toner T1-1 to -1 by the emulsion polymerization association method using a specified mass part of the external additive
5 was obtained.

Production of Colored Particles and Toner T2: Example of Suspension Polymerization Method 165 g of styrene, 35 g of n-butyl acrylate, 10 g of carbon black, 2 g of metal di-t-butylsalicylate, and 8 g of styrene-methacrylic acid copolymer
and 20 g of paraffin wax (mp = 70 ° C.), heated to 60 ° C., and uniformly dissolved and dispersed at 12,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).

To this, 10 g of 2,2'-azobis (2,4-valeronitrile) as a polymerization initiator was added and dissolved to prepare a polymerizable monomer composition. Then, 450 g of a 0.1 mol / l sodium phosphate aqueous solution was added to 710 g of ion-exchanged water, and 1300
While stirring at 0 rpm, 68 g of 1.0 mol / L calcium chloride was gradually added to prepare a suspension in which tricalcium phosphate was dispersed.

The above polymerizable monomer composition was added to the suspension, and the mixture was stirred with a TK homomixer at 10,000 rpm for 20 minutes to granulate the polymerizable monomer composition. Then 2
The reaction was performed at 75 to 95 ° C. for 5 to 15 hours using a reactor having a stage with a stirring blade configuration (blade intersection angle α was 45 °).

Tricalcium phosphate was dissolved and removed with hydrochloric acid, and then classified in a liquid by a centrifugal sedimentation method using a centrifuge, followed by filtration, washing and drying to obtain colored particles. By monitoring during the polymerization, controlling the liquid temperature, the number of rotations of the stirring, and the heating time, the variation coefficient of the shape and the shape coefficient is controlled, and further, the variation coefficient of the particle size and the particle size distribution can be arbitrarily determined by submerging. Adjust to
Colored particles T2-1 to T5 having the shape characteristics and the particle size distribution characteristics shown in Table 1 were obtained.

Further, 100 parts by mass of the obtained colored particles was
Toners T2-1 to T5 were obtained by suspension polymerization using external additives shown in Table 2 and using a specified mass part with a Henschel mixer.

Production of Colored Particles and Toner T3: Example of Grinding Method Styrene-n-butyl acrylate copolymer resin 100 k
g, carbon black 10kg and polypropylene 4kg
Premixed with a Henschel mixer, melt-kneaded with a twin-screw extruder, coarsely pulverized with a hammer mill, pulverized with a jet pulverizer, and the obtained powder is heated with a hot air Disperse in the flow (200
(~ 300 ° C for 0.05 seconds) to obtain colored particles whose shape was adjusted.

The particles were repeatedly classified by an air classifier until the target particle size distribution was obtained. In this way, the shape and the coefficient of variation of the shape coefficient were controlled, and the coefficient of variation of the particle size and the particle size distribution were adjusted. Colored particles T3-1 and -2 having the shape characteristics and the particle size distribution characteristics shown in Table 1 were obtained.

Table 2 was added to 100 parts by mass of the obtained colored particles.
Using a specified mass part of the external additive, the external additive was mixed with a Henschel mixer to obtain toners T3-1 and T-2 by a pulverizing method.

[0272]

[Table 1]

[0273]

[Table 2]

C. Production of external additive Fatty acid metal salt Solid content concentration 12.6% by mass, BET specific surface area 10 m ² /
g of lime milk slurry was prepared. This lime milk slurry was prepared using a Dynomill (Simmer Enterprises:
(KDL-pilot type) to obtain a lime milk slurry having a BET specific surface area of 20 m ² / g and a sedimentation volume of 80 ml / 60 minutes. This lime milk slurry has a solid concentration of 40%.
Dehydrated so as to become.

On the other hand, 10 in a 3 liter kneader
Stearic acid heated to 0 ° C and melted (neutralization number 197) 57
0 g was prepared, and 222 g of lime milk having a solid content concentration of 40% and 97.6 g of water were added to the molten stearic acid. This compounding ratio is, when converted, higher fatty acid / Ca
(OH) ₂ / water (molar ratio) = 2 / 1.2 / 12.8. In this state, the mixture was mixed for 5 to 30 minutes to terminate the reaction between stearic acid and calcium hydroxide.

The reaction product was dried at 100 ° C. under reduced pressure to obtain a calcium soap. Calcium soaps resulting was IR analysis, peaks of the carboxyl groups of 1700 cm ^-1 is, has changed to the peak of carboxylate 1600 cm ^-1, it was confirmed that calcium stearate is formed.

By changing the reaction time and the drying time under reduced pressure, calcium stearate PM1 to PM3 shown in Table 3 were obtained. In a similar reaction, fatty acid calcium obtained by reacting calcium hydroxide with a fatty acid of a 70/30 mixture of stearic acid / palmitic acid is converted to PM4, and zinc stearate obtained by reacting stearic acid with a zinc salt. Is PM5, and lithium stearate obtained by reacting stearic acid with a lithium salt is PM6. Table 3 shows the water content and the free fatty acid content.

[0278]

[Table 3]

Fluid External Additive <Preparation Example of Hydrophobic Silica> Hydrophobic Silica a1 100 parts by mass of fumed silica having a primary particle diameter of 0.007 μm is placed in a container having a high-speed mixer, and rotated at 8500 rpm in a nitrogen atmosphere. While stirring, 20 parts by mass of dimethyldichlorosilane is sprayed, and stirring is further continued for 5 minutes. Then, the obtained powder liquid is put under a nitrogen stream for 200 minutes.
Reflux stirring was performed at ℃ for 3 hours. Thereafter, the mixture was cooled to room temperature to obtain powdery hydrophobic silica a1.

Hydrophobic silica a2 In the preparation example of the hydrophobic silica a1, the primary particle diameter was 0.0
The primary particle size is 0.1 μm instead of the 0.7 μm fumed silica.
012 μm of fumed silica was replaced with hydrophobic silica a1 in the same manner as hydrophobic silica a1 except that octyltrimethoxysilane was used instead of dimethyldichlorosilane.
2 was obtained.

Hydrophobic Silica b1 In the preparation example of the hydrophobic silica a1, the primary particle diameter was 0.0
The primary particle size is 0.1 μm instead of the 0.7 μm fumed silica.
Hydrophobic silica b in the same manner as hydrophobic silica a1 except that fumed silica of 033 μm was replaced with octyltrimethoxysilane instead of dimethyldichlorosilane.
1 was obtained.

Hydrophobic silica b2 In the preparation example of the hydrophobic silica a1, the primary particle diameter was 0.0
The primary particle size is 0.1 μm instead of the 0.7 μm fumed silica.
A hydrophobic silica b2 was obtained in the same manner as the hydrophobic silica a1, except that fumed silica of 030 μm was replaced with hexamethyldisilazane instead of dimethyldichlorosilane.

<Preparation Example of Hydrophobic Titanium Oxide> Hydrophobic Titanium Oxide c1 (Titania c1) 5 parts of titanium oxide (number-averaged) dried at 110 ° C. for 24 hours in a round bottom flask equipped with a magnetic stirrer and a trap 150 parts of dehydrated toluene and 1.5 parts of normal butyltrimethoxysilane were added to 0.030 μm particle size anatase type titanium oxide), and 0.5 part of acetic acid was further added as a buffer.

The suspension obtained was refluxed at 50-60 ° C. for 7 hours, cooled to room temperature and then filtered by suction. Subsequently, the residue was washed with toluene and dried at 110 ° C. for 4 hours. Then, suction filtration, this time suction filtration with ethanol, dried at 110 ° C. for 4 hours, pulverized in an agate mortar,
A white powder was obtained. The obtained white powdery substance is referred to as hydrophobic titanium oxide c1.

Hydrophobic titanium oxide c2 (titania c2) In the production of titanium oxide c1, a number average particle size of 0.03
A titanium oxide having a number average particle size of 0.021 μm (rutile, anatase ratio of 10:90) was used in place of 0 μm anatase type titanium oxide, and isobutyltrimethoxysilane was used in place of normal butyltrimethoxysilane. Thus, hydrophobic titanium oxide c2 was obtained.

Hydrophobic titanium oxide d1 (titania d1) In the production of titanium oxide c1, a number average particle size of 0.03
A titanium oxide having a number average particle size of 0.092 μm (rutile, anatase ratio 60:40) was used in place of 0 μm anatase-type titanium oxide, and octyltrimethoxysilane was used in place of normal butyltrimethoxysilane. As a result, a hydrophobic large particle diameter titanium oxide d1 was obtained.

Hydrophobic titanium oxide d2 (titania d2) In the production of titanium oxide c1, the number average particle diameter was 0.03.
A hydrophobic large particle size titanium oxide is prepared in the same manner except that rutile type titanium oxide having a number average particle size of 0.112 μm is used instead of 0 μm anatase type titanium oxide and hexyl trimethoxysilane is used instead of normal butyl trimethoxysilane. d2 was obtained.

Hydrophobic silicas a1 and a2, b1 and b
Table 2 below shows fluid external additives obtained by combining 2, hydrophobic titanium c1 and c2, d1 and d2, and the like.

[0289]

[Table 4]

Abrasive External Additive <Metal Oxide> 600 g of strontium carbonate and 320 g of titanium oxide were wet-mixed in a ball mill for 8 hours and then filtered and dried. This mixture was molded by applying a force of 50 N / cm ² and calcined at a temperature of 1100 ° C. for 8 hours.

Thereafter, the mixture was mechanically pulverized to a number average particle size of 0.7 μm.
m, strontium titanate powder was obtained. It is shown in Table 5.

[0292]

[Table 5]

[0293] Inorganic / organic composite particles having an average particle size of 1.0μm styrene - acrylic organic fine primary particle size with respect to (the electric resistivity ^{6.6 × 101 3 Ω · cm)} 100g was tin oxide treatment on the surface of 30nm oxide ET-300W (trade name, manufactured by Ishihara Sangyo Co., Ltd.)
0 g was added and mixed with a turbula mixer. Next, a hybridizer with a modified crusher (Nara Machinery Co., Ltd.)
For 3 minutes at a peripheral speed of 100 m / sec to produce inorganic / organic composite fine particles having titanium oxide fixed on the surface of the organic fine particles. This is called HFP1. The addition amount was 1 part by mass with respect to 100 parts by mass of the colored particles.

The electric resistance (specific resistance) of the inorganic / organic composite fine particles was 4.8 × 10 ⁸ Ω · cm.

D. Production of Developer Each of the toners T1-1 to T3-2 and a 45 μm ferrite carrier coated with a styrene-methacrylate copolymer are mixed at a ratio of 200 g of the carrier to 20 g of the toner, so that the development for evaluation is performed. An agent was manufactured.

E. Characteristics Evaluation As shown in Table 6, a combination of a photoreceptor, a developer and the like was set, and a digital copying machine (corona charging, laser exposure, reversal development,
(Including electrostatic transfer, nail separation, and cleaning blade). However, before the above evaluation was started, in order to make the photoconductor and the cleaning blade familiar, the setting powder (polyvinylidene fluoride powder) was sprayed on the photoconductor and the cleaning blade, and the photoconductor was rotated for 1 minute.

The copying conditions were as follows: 200,000 copies were continuously made in a high-temperature and high-humidity environment (30 ° C., 80% RH), which is considered to be the most severe. The maximum density, fog unevenness and sharpness of the copied image were evaluated for the following evaluation criteria for black spots. Was evaluated.

In the evaluation, a character image having a pixel ratio of 7%, a portrait image of a person, a solid white image, and a solid black image each having an equal size of 1/4 were copied on A4 neutral paper.
Solid white image, solid black image, thin line image,
The image (black spot-like defect: black spot) was evaluated. Regarding the maximum density and fog unevenness, the density of each image is RD manufactured by Macbeth.
The absolute reflection density was measured using -918. For the fine line image, the number of fine lines per 1 mm that can be determined from the copy image of the fifth generation was visually determined. The evaluation of the black pot is based on the image analysis system "Omnicon 3000" (manufactured by Shimadzu Corporation).
Was used to determine the particle size and number of black spots, and the number of black spots of 0.1 mm or more per 100 cm ² was determined.
Regarding the cleaning property, 10 copies of the original image having a ratio of solid black image 4: solid white image 1 of A3 paper were continuously copied 10 times, and it was determined whether or not cleaning failure occurred in the solid white portion. The number of blade turnovers during 200,000 copies was counted.

Fog unevenness: Judgment based on solid white image density A: 0.005 or less (good) O: Greater than 0.005 and less than 0.01 (a level that does not cause a problem in practical use) X: 0.01 or more (a problem occurs in practical use) Sharpness: Judgment by fine line image (the number of fine lines per 1 mm of the test chart is 8.0, 7.1, 5.6, 5.0)
(Measured in (lines / mm)) ◎: 8 lines / mm or more (good) ○: 5.6 lines / mm or more, 7.1 lines / mm or less (a level that does not cause a practical problem) ×: 5 lines / mm or less ( Cleaning performance: Judgment based on the occurrence of poor cleaning in solid white areas ◎: No toner slippage occurs on 200,000 sheets ○: No toner slippage occurs up to 100,000 sheets ×: Less than 100,000 sheets Occurrence of toner slippage Blade turnover ◎: No occurrence up to 200,000 sheets ○: Nearly 200,000 sheets and a little occurrence, but practically acceptable △: Minor partial turnover ×: Blade turnover Black spots ◎: 0.1 mm or more Black spots of 1/100 cm ² or less: good ○: Black spots of 0.1 mm or more: 2 to 3 pieces / 100 cm
² : Level not causing a problem in practical use ×: 4 black dots of 0.1 mm or more / 100 cm ² or more: There is a problem in practical use Other evaluation conditions Other evaluation conditions of the above digital copying machine were set as follows.

Charging Conditions Charger: Scorotron charger, initial charging potential is -750
V.

Exposure conditions The exposure amount was set so that the exposure portion potential was -50V.

Development conditions DC bias: -550V.

Transfer electrode: A corona charging system was used. Table 6 shows the evaluation results.

[0304]

[Table 6]

As is clear from Table 6, in the examples satisfying the conditions of the present invention, image characteristics such as black spots, fog unevenness, sharpness, and uniformity are clearly improved.

[0306]

According to the present invention, 1) toner A: toner composed of toner particles containing a fatty acid metal salt, 2) toner B: toner composed of toner particles containing inorganic fine particles, 3) toner C : Composed of toner particles containing inorganic / organic composite fine particles having inorganic fine particles having a primary average particle diameter of 5 to 100 nm fixed on the surface of organic fine particles having an average particle diameter of 0.1 to 5.0 μm. The practical problems can be improved while using any one of the toners and utilizing the characteristics of the toners.

That is, according to the present invention, the toners A, B,
Using a specific toner represented by C, we found a way to improve black spots, fog spots, cleaning properties, blade turning, etc., while ensuring sharpness. A forming method, an image forming apparatus, and a process cartridge can be provided.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a toner particle having no corner and a toner particle having a corner.

FIG. 2 is a schematic diagram illustrating an example of a non-contact developing method.

FIG. 3 is a diagram illustrating an example of a fixing method to which the present invention is applied.

FIG. 4 is a configuration diagram of a digital image forming apparatus applied to the present invention.

FIG. 5 is a sectional view of a cleaning unit used in the image forming apparatus of the present invention.

FIG. 6 is a diagram illustrating settings of a cleaning blade, a sheet-shaped conductive member, and a cylindrical organic photoconductor of the present invention.

DESCRIPTION OF SYMBOLS 1 Image forming apparatus 10 Cylindrical photoreceptor 14 Charging electrode 16 Developing means 18 Transfer electrode 20 Separation electrode 22, 24, 60 Paper feed tray 40 Laser light source A Automatic document feeder (commonly called ADF) B Document image reading Section C Image control board D Writing section P Recording paper (recording material) R10 Registration roller

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 5/14 101 G03G 5/14 101F 9/087 9/08 384 (72) Inventor Ken Omura Hachioji, Tokyo 2970, Ishikawacho, Ishikawa-cho Konica Corporation (72) Inventor Mao Asano 2970, Ishikawacho, Hachioji-shi, Tokyo Konica Corporation F-term (reference) 2H005 AA08 AA15 AB03 AB06 CA02 CA14 CA30 CB07 CB13 EA05 EA10 2H068 AA16 AA44 BA05 BA12 BA57 BA58

Claims (28)

[Claims] 1. An electrostatic latent image formed on an electrophotographic photosensitive member having a photosensitive layer on a conductive support via an intermediate layer,
In an image forming method including a developing step of developing an image with an electrostatic image developing toner containing at least a resin and a colorant, the intermediate layer is a layer containing at least one of an organometallic compound and a silane coupling agent. An image forming method, wherein the toner comprises colored particles obtained by forming particles in an aqueous medium, and at least a fatty acid metal salt as an external additive. 2. The fatty acid metal salt has a water content of 0.1 to 0.1.
2.5% by mass, free fatty acid amount of 0.01 to 0.7% by mass
2. The image forming method according to claim 1, wherein: 3. The image forming method according to claim 1, wherein the fatty acid metal salt is a fatty acid calcium. 4. The image forming method according to claim 1, wherein the fatty acid metal salt is zinc stearate. 5. An electrostatic latent image formed on an electrophotographic photosensitive member having a photosensitive layer on a conductive support via an intermediate layer,
In an image forming method including a developing step of developing an image with an electrostatic image developing toner containing at least a resin and a colorant, the intermediate layer is a layer containing at least one of an organometallic compound and a silane coupling agent. An image forming method, characterized in that the toner uses a toner containing at least inorganic fine particles as an external additive in colored particles obtained by forming particles in an aqueous medium. 6. An inorganic fine particle having an average particle size of 0.005.
The image forming method according to claim 5, wherein the thickness is from 0.020 μm. 7. An inorganic fine particle having an average particle size of 0.50 to 0.50.
The image forming method according to claim 6, wherein the thickness is 5.0 μm. 8. The image forming method according to claim 5, wherein the inorganic fine particles are silica. 9. The image forming method according to claim 5, wherein the inorganic fine particles are titania. 10. An electrostatic latent image formed on an electrophotographic photosensitive member having a photosensitive layer on a conductive support via an intermediate layer for developing an electrostatic image containing at least a resin and a colorant. In an image forming method including a developing step of visualizing with a toner, the intermediate layer is a layer containing at least one of an organometallic compound and a silane coupling agent, and the toner is formed by forming particles in an aqueous medium. In the obtained colored particles,
As an external additive, inorganic / organic composite fine particles having inorganic fine particles having a primary average particle diameter of 5 to 100 nm fixed on the surface of organic fine particles having an average particle diameter of at least 0.1 to 5.0 μm as at least an external additive. An image forming method using a toner. 11. The image forming method according to claim 10, wherein the organic fine particles are an acrylic polymer. 12. The image forming method according to claim 10, wherein the inorganic fine particles are titania. 13. The image forming method according to claim 1, wherein at least two kinds of said fatty acid metal salt, inorganic fine particles, and inorganic / organic composite fine particles are used. 14. The image forming method according to claim 1, wherein the organometallic compound contained in the intermediate layer is a metal alkoxide or an organic metal chelate. 15. The image forming method according to claim 5, wherein the intermediate layer is a layer containing an organic metal chelate and a silane coupling agent. 16. The image forming method according to claim 14, wherein the organometallic chelate contained in the intermediate layer is represented by the following general formula (1). General formula (1) (R ₁ O) _g -M- (K) _m (wherein R ₁ is an alkyl group, M is zirconium,
A chelating group K representing titanium or aluminum
Represents an acetoacetic acid ester group or a β-diketone group,
g and m represent an integer of 1 or more. However, when M is zirconium or titanium, g + m is 4, and when M is aluminum, g + m is 3. ) 17. The image forming method according to claim 15, wherein the silane coupling agent contained in the intermediate layer is represented by the following general formula (2). Formula (2) (Q) _p -Si (Y) _q- (A) _r (wherein Q represents a halogen atom, an alkoxy group or an amino group, A represents an alkyl group or an aryl group, and the organic functional group Y alkylene or -O- is -BOOC (R ') C = CH 2, -BNHR " or .R representing the -BNH _2' represents an alkyl group, R" represents an alkyl group or an aryl group, B is Represents an alkylene group containing -NH-, -CO-, p and q represent an integer of 1 or more, r represents an integer of 0 or more, and p + q + r is 4.) 18. The image forming method according to claim 1, wherein the photosensitive layer contains a hindered amine or a hindered phenol compound. 19. The toner according to claim 1, wherein the variation coefficient of the shape factor of the colored particles is 16% or less, and the number variation coefficient in the number particle size distribution is 27% or less. Item 2. The image forming method according to Item 1. 20. The toner according to claim 1, wherein the proportion of the colored particles having a shape factor of the colored particles in the range of 1.0 to 1.6 is 65% by number or more. Item 2. The image forming method according to Item 1. 21. The toner according to claim 1, wherein the proportion of the colored particles having a shape factor of the colored particles in the range of 1.2 to 1.6 is 65% by number or more. Item 2. The image forming method according to Item 1. 22. The toner according to claim 1, wherein the ratio of the colored particles having no corners is 50% by number or more.
22. The image forming method according to any one of 21. 23. The toner according to claim 1, wherein the number average particle diameter of the colored particles is 3 to 8 μm.
The image forming method according to claim 1. 24. The toner according to claim 1, wherein the particle diameter of the colored particles is D.
(Μm), the natural logarithm lnD is taken on the horizontal axis, and the horizontal axis is divided into a plurality of classes at intervals of 0.23. The frequency (m1) and the relative frequency (m) of the colored particles contained in the class having the highest frequency next to the mode
24. The image forming method according to claim 1, wherein the sum (M) of 2) is 70% or more. 25. The image forming method according to claim 1, wherein the toner is obtained by polymerizing at least a polymerizable monomer in an aqueous medium. 26. The image forming method according to claim 1, wherein the toner is obtained by associating colored particles with at least resin particles in an aqueous medium. 27. An image forming apparatus using the image forming method according to claim 1. Description: 28. A photoconductor, and at least one of a charger, an image exposure device, a developing device, a transfer device, a separator, and a cleaning device, using the image forming method according to claim 1. Description: And a process cartridge detachably mounted on the main body device.