JP5106988B2 - Electrophotographic toner carrier and method for producing the same, electrophotographic developer, and image forming method - Google Patents

Description

  The present invention relates to a carrier for an electrophotographic toner and a method for producing the same, an electrophotographic developer, and an image forming method.

  Conventionally, in an image forming method using an electrophotographic copying apparatus or the like, a two-component developing method in which development is performed using a two-component developer including a magnetic latent electrostatic image developing carrier and toner, and only toner is used. And a one-component development method in which development is performed.

  The two-component developing method usually uses a developing device that includes a developing roller that is a cylindrical developer carrying member that is provided with a magnet roller including a magnet body having a plurality of magnetic poles therein and is rotatably supported. While carrying the carrier with the toner attached to the surface of the developing sleeve, it is transported to a developing region that is opposite to the electrostatic latent image carrier and developed with a magnetic brush made of a two-component developer. .

  In such a two-component development method, charging is performed by stirring and mixing the carrier and the toner, so that the chargeability of the toner is stable and a relatively stable and good image can be obtained. On the other hand, regarding the carrier, formation of a uniform carrier surface, prevention of surface oxidation, prevention of moisture sensitivity deterioration, extension of the developer life, prevention of carrier adhesion to the surface of the photoreceptor, protection from scratches or abrasion by the carrier of the photoreceptor, For the purpose of controlling the charge polarity or adjusting the charge amount, a hard and high-strength coating layer is usually provided by coating with a resin material.

  As a carrier for solving these problems, many carriers have been proposed, for example, those coated with a specific resin material (see Patent Document 1), and those in which various additives are added to the coating layer ( Patent Documents 2 to 8), those in which an additive is attached to the carrier surface (see Patent Document 9), those in which conductive particles larger than the coating layer thickness are contained in the coating layer (see Patent Document 10), etc. It has been known. Further, Patent Document 11 includes a carrier using a benzoguanamine-n-butyl alcohol-formaldehyde copolymer as a main component for a coating layer, and Patent Document 12 includes a carrier using a cross-linked product of a melamine resin and an acrylic resin as a coating material. Are listed.

On the other hand, the prevention of spent toner components on the carrier surface is also an important issue. For this purpose, for example, in Patent Documents 13 to 15, the particle size of fine particles contained in the coating layer is larger than the thickness of the coating layer. It has been proposed to select one. In Patent Document 16, it is considered to increase the contact charging opportunity with the toner and reduce the adhesion between the carrier and the toner by forming irregularities based on the fine particles contained in the coating layer on the surface. ing.
JP 58-108548 A JP 54-1555048 A JP 57-40267 A JP 58-108549 A JP 59-166968 A Japanese Patent Publication No. 1-19584 Japanese Examined Patent Publication No. 3-628 JP-A-6-202381 JP-A-5-273789 JP-A-9-160304 JP-A-8-6307 Japanese Patent No. 2683624 Japanese Patent No. 3600219 Japanese Patent No. 3737060 JP 2004-226784 A JP 2002-287431 A

  However, conventionally known carriers such as the above-mentioned carriers still have insufficient durability and carrier adhesion suppression, and particularly regarding durability, the spent on the carrier surface of the toner and the charge amount associated therewith Destabilization of the coating resin, reduction of the coating layer due to coating film scraping, and accompanying resistance reduction, and the like, a good image can be obtained initially, but as the number of copies increases, the quality of the copied image Since this is a problem, it needs to be improved.

  Even in the above-described carrier for the purpose of preventing spent toner components on the surface, although reduction in toner spent can be expected, the dispersion state of the fine particles in the coating layer of the carrier is not necessarily good, and the fine particles are localized. As a result, the composition of the coating layer becomes non-uniform, and the coating layer easily peels off and wears. Also, the presence of fine particles protruding on the surface of the carrier tends to be a point that receives stress during stirring intensively, especially when the coating layer is thin. Wear is likely to occur.

  Thus, in order to satisfy both the toner spent on the carrier and the reduction in abrasion of the coating layer, further improvement of the carrier is required, and the localization of the fine particles contained in the coating layer on the carrier surface is required. In addition, reduction of protrusion to the surface is also important in solving the problem.

  The object of the present invention is based on the above-mentioned problems, and uses a carrier that realizes prevention of toner spent on the carrier and reduces the abrasion of the coating layer, a method for producing the carrier, a developer containing the carrier, and the developer. An image forming method is provided.

In order to solve the above problems, the present inventors have completed the following invention.
The present invention provides a carrier for an electrophotographic toner having a volume resistance of 10 ¹¹ to 10 ¹⁵ Ω · cm , wherein the core material is coated with a coating layer containing at least a binder resin and fine particles. A coating liquid containing at least one of the binder resin and the binder resin precursor, fine particles having a volume average particle diameter Dv in terms of a sphere diameter, and a solvent is applied to the material surface, and the following formula ( A first step of forming coated particles having a coating layer with an average film thickness h satisfying the relationship of 1);
Dv / h ≦ 0.3 (1)
The coated particles are produced by a production method comprising a second step of stirring and surface-treating the coated particles with a stirring device having no stirring blade , the fine particles are metal oxide fine particles, and the binder resin precursor Is a carrier for an electrophotographic toner comprising an amino resin, an acrylic resin having a hydroxyl value of at least 30 mg KOH / g and capable of crosslinking with the amino resin, and a silicone resin .

  A preferred embodiment of the carrier for electrophotographic toner according to the present invention is characterized in that an average film thickness h of the coating layer of the coating particles is 1 μm or more, and a mass ratio of the coating layer to the carrier is 5 mass% or more. is there.

The reference invention is the carrier of the electrophotographic toner, wherein the binder resin contains at least a silicone resin.

The reference invention is the carrier for an electrophotographic toner, wherein the binder resin contains at least an acrylic resin.

The reference invention is the carrier of the electrophotographic toner, wherein the binder resin is a resin having a silicone resin component and an acrylic resin component.

  In a preferred embodiment of the present invention, the electrophotographic toner carrier is characterized in that the coating layer contains an aminosilane coupling agent.

  In a preferred embodiment of the present invention, the electrophotographic toner carrier is characterized in that the fine particles are metal oxide fine particles.

  In a preferred embodiment of the present invention, the electrophotographic toner carrier is characterized in that the metal oxide is alumina or titanium oxide.

  In a preferred aspect of the present invention, the electrophotographic toner carrier is characterized in that the fine particles are conductive fine particles having a conductive surface.

The reference invention is the carrier for an electrophotographic toner, wherein the volume resistance is 10 ¹⁰ to 10 ¹⁶ Ω · cm.

  In a preferred embodiment of the present invention, the electrophotographic toner carrier has a volume average particle diameter of 20 to 65 μm.

The present invention relates to a method for producing a carrier for an electrophotographic toner having a volume resistance of 10 ¹¹ to 10 ¹⁵ Ω · cm, wherein the surface of a core material is coated with a coating layer containing at least a binder resin and fine particles. A first step of forming a coated particle by applying a coating liquid containing at least one of the binder resin and the binder resin precursor, fine particles, and a solvent to the surface of the core material; and the coated particle A second step of performing surface treatment by stirring with a stirrer not having a stirring blade, the fine particles are metal oxide fine particles, and the binder resin precursor is an amino resin, The average film thickness h of the coating layer of the coated particles, which contains at least a hydroxyl value of 30 mg KOH / g or more and a silicone resin, and can be crosslinked with the amino resin, and is coated with a coating liquid in the first step, Fine particles Between the volume average particle diameter Dv in the spherical diameter in terms, relations Dv / h ≦ 0.3 · · · formula formula (1) (1)
The method for producing a carrier for an electrophotographic toner characterized by satisfying the above.

In the present invention, preferably, the coating liquid in the first step is represented by the following formula (2):
| T ₆ h (%) − T ₀ h (%) | ≦ 30 (%) (2)
The method for producing a carrier for an electrophotographic toner according to claim 1, wherein:
However, the formula (2) _in, T 0 h (%) represents the transmittance of light having a wavelength of 550nm in immediately after preparing the coating liquid. T ₆ h (%) represents the transmittance of light having a wavelength of 550 nm after standing for 6 hours immediately after preparing the coating solution.

  The present invention provides an electrophotographic developer comprising the electrophotographic toner carrier and the electrophotographic toner.

  The present invention relates to an electrostatic latent image forming step for forming an electrostatic latent image on an electrostatic latent image carrier, and a developing step for developing the electrostatic latent image using the developer to form a visible image. And a transfer step of transferring the visible image to a recording medium to form a transfer image, and a fixing step of fixing the transfer image transferred to the recording medium. .

  According to the present invention, there are provided a carrier that realizes prevention of occurrence of toner spent on the carrier and a reduction in wear of the coating layer, a manufacturing method thereof, a developer including the carrier, and an image forming method using the developer. can do.

  The best mode for carrying out the present invention will be described with reference to the drawings as necessary. Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description is an example of a preferred embodiment of the present invention, and does not limit the scope of the claims.

(Career)
The carrier of the present invention is an electrophotographic toner carrier in which the surface of a core material is coated with a coating layer containing at least a binder resin and fine particles, and the binder resin and the binder resin are coated on the core material surface. A coating liquid containing at least one of the above precursors, fine particles having a volume average particle diameter Dv in terms of a sphere diameter, and a solvent is applied, and the relationship of the following formula (1) Dv / h ≦ 0.3 ..Formula (1)
By a production method comprising a first step of forming coated particles having a coating layer having an average film thickness h that satisfies the above, and a second step of stirring the coated particles with a stirrer having no stirring blade to surface-treat This is a carrier of manufactured electrophotographic toner.

  More preferably, the carrier of the present invention satisfies Dv / h ≦ 0.2. If Dv / h exceeds 0.3, in the surface treatment of the coated particles in the second step described later, the fine particles in the coating layer are easily detached or irregularities derived from the fine particles are formed on the surface of the coating layer. It is not preferable because it becomes easy.

The carrier preferably has a volume average particle size of 20 to 100 μm and a volume resistance of 10 ¹⁰ to 10 ¹⁶ Ω · cm. Furthermore, the coating layer of the coated particles preferably has an average film thickness of 1 μm or more and 5% by mass or more of the mass of the carrier.

<Core>
The core material of the carrier of the present invention is not particularly limited, and can be appropriately selected according to the purpose from core materials used as known two-component carriers for electrophotography. For example, ferrite, Suitable examples include magnetite, iron, nickel and the like. Further, in consideration of environmental aspects that have been remarkably advanced in recent years, if it is a ferrite, it is not a conventional copper-zinc ferrite, for example, Mn ferrite, Mn-Mg ferrite, Mn-Mg-Sr ferrite, copper-zinc ferrite It is preferable to use lithium-based ferrite or the like.

  For the purpose of controlling the core material resistance and the purpose of improving the production stability, as other core material composition components, for example, Li, Na, K, Ca, Ba, Y, Ti, Zr, V, Ag, Ni , Cu, Zn, Al, Sn, Sb, Bi, or other composition component elements may be added. As these compounding quantities, it is preferable that it is 5 atomic% or less of the total amount of metal elements, and it is more preferable that it is 3 atomic% or less.

  The core material preferably has a volume average particle size of 20 μm or more from the viewpoint of prevention of carrier adhesion (scattering) to the electrostatic latent image carrier. From the viewpoint of prevention of image quality deterioration such as prevention of carrier streaks. Those having a size of 100 μm or less are preferable, and in particular, for the recent high image quality, the volume average particle size is more preferably 20 μm to 50 μm.

  Here, the volume average particle diameter of the core material can be measured, for example, using “Microtrac particle size analyzer SRA” manufactured by Nikkiso Co., Ltd., with a range setting of 0.7 μm to 125 μm.

<Coating layer>
The coating layer can be formed by applying a coating solution on the surface of the core material. The coating liquid contains at least one of a binder resin and a precursor of the binder resin, fine particles, and a solvent, and further contains an aminosilane coupling agent and other components as necessary.

-Binder resin, binder resin precursor-
The binder resin is not particularly limited and can be appropriately selected according to the purpose. For example, the binder resin includes a crosslinkable copolymer including styrene, acrylic resin, acrylonitrile, vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether and the like. Polymers: Silicone resins composed of organosiloxane bonds or modified products thereof (for example, modified products by alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.); Polyamide; Polyester; Polyurethane; Polycarbonate; Urea resin; Melamine resin: Benzoguanamine resin An epoxy resin; an ionomer resin; a polyimide resin, or a derivative thereof.

The binder resin precursor is a monomer that can form the binder resin, a macromonomer, a polymer having a reactive group, and the like, after attaching a coating liquid containing the binder resin precursor to the surface of the core material, heating, Alternatively, a binder resin having desired characteristics can be formed as a coating layer by causing a polymerization reaction such as radical polymerization or condensation polymerization by a crosslinking agent, a polymerization initiator, or the like.
As the binder resin, since the acrylic resin has strong adhesiveness with the fine particles contained in the core material and the coating layer and is low in brittleness, it has very excellent properties against peeling of the coating layer, It is preferable that deterioration such as peeling hardly occurs. Furthermore, the acrylic resin can maintain the coating layer stably, and can firmly adhere the core material and the coating layer due to strong adhesiveness, and particles contained in the coating layer such as conductive particles. Can be held firmly. In particular, a powerful effect can be exhibited in holding particles having a particle size larger than the film thickness of the coating layer.

  The glass transition temperature (Tg) of the acrylic resin is preferably 20 ° C to 100 ° C, more preferably 25 ° C to 80 ° C. By setting the glass transition temperature (Tg) of the acrylic resin within this range, it is considered that the acrylic resin has appropriate elasticity and reduces the impact received by the carrier during the frictional charging of the developer, and the coating layer is not damaged. Deterred.

  By making the binder resin a cross-linked product of an acrylic resin and an amino resin, it is possible to prevent the so-called blocking between the resins that tend to occur when the acrylic resin alone is used while maintaining appropriate elasticity. Since it can do, it is much more preferable.

  As the amino resin, conventionally known amino resins can be used, and among them, guanamine and melamine can be used more preferably because the charge imparting ability of the carrier can be improved. Further, when it is necessary to appropriately control the charge imparting ability of the carrier, at least one of guanamine and melamine may be used in combination with another amino resin.

As the acrylic resin capable of crosslinking with such an amino resin, the above-mentioned binder resin precursor having a hydroxyl group or a carboxylic acid group can be used, improving adhesion to the core material and the fine particles, and dispersing the fine particles. From the viewpoint that | T ₆ h (%) − T ₀ h (%) | can be kept at 30% or less, those having a hydroxyl group are more preferably used. The hydroxyl value at this time is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more. When the hydroxyl value is less than 30 mgKOH / g, the | T ₆ h (%) − T ₀ h (%) | tends to be 30% or more, and the dispersibility of the fine particles in the binder resin is insufficient. As a result, the fine particles on the surface of the carrier coating layer are localized, and the carrier coating layer is greatly scraped and peeled off during long-term stirring. Examples of such commercially available acrylic resins that can react with amino resins include Hitaroid 3012X, 3368 (manufactured by Hitachi Chemical Co., Ltd.). Since this acrylic resin reacts with the amino resin to finally form a binder resin layer, the acrylic resin itself is considered to be the aforementioned “binder resin precursor”.

  By including a silicone resin component as a constituent unit, the binder resin or binder resin precursor can reduce the surface energy itself of the carrier surface and suppress the occurrence of toner spent itself. Can be maintained for a longer period of time.

  The silicone resin component preferably contains at least one of a methyltrisiloxane unit, a dimethyldisiloxane unit, and a trimethylsiloxane unit. This silicone resin component may be chemically bonded to other resin components, may be in a blended state with other resins as a single resin, or may be multilayered.

  In the case of the blend or multilayer structure, it is preferable to use at least one of a silicone resin and a modified product thereof as the silicone resin component. By having at least the structural unit represented by the following formula (3), problems such as specific wear, abrasion, and detachment of the silicone resin component or other resin components can be suppressed.

_{^{- (SiR 1 R 2 O)}} a - (SiR 3 X 1 O) b - ··· formula (3)
However, in said formula (3), R < ¹ > -R < ³ > may mutually be the same, may differ, and represents at least any one of a hydrocarbon group and its derivative (s), and X < ¹ > is a condensation reaction group. A and b represent integers.

X ¹ as the condensation reaction group includes a hydroxyl group, an alkoxy group, a methyl ethyl ketoxime group, and the like, and a condensation reaction takes place at the site by moisture or heating in the atmosphere, and can take a three-dimensional network structure. The silicone resin having such a condensation reactive group is the “binder resin precursor” because it forms a final binder resin by performing a condensation reaction after coating the carrier core material.

  Examples of the silicone resin include a straight silicone resin having only an organosiloxane bond having a structural unit represented by the formula (3), or a modified silicone resin modified with alkyd, polyester, epoxy, acrylic, urethane, or the like.

  Commercially available products can be used as the straight silicone resin. Examples of the commercially available products include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.); SR2400, SR2405, SR2406 (Toray Dow) Corning Silicone Co., Ltd.).

  Examples of the modified silicone resin include epoxy-modified products (for example, ES-1001N), acrylic-modified silicone (for example, KR-5208), polyester-modified products (for example, KR-5203), alkyd-modified products (for example, KR-206), urethane-modified products ( For example, KR-305) (both manufactured by Shin-Etsu Chemical Co., Ltd.); epoxy-modified products (for example, SR2115), alkyd-modified products (for example, SR2110) (all manufactured by Toray Dow Corning Silicone Co., Ltd.), and the like. .

  As the binder resin, the acrylic resin and the silicone resin may be contained in the coating layer in a form in which they are chemically bonded to each other. For example, a method of copolymerizing a monomer having a methacrylic group at one end of the silicone skeleton represented by the formula (3) with a monomer constituting the acrylic resin as a macromonomer, copolymerizing a silicone having a mercapto group and an acrylic monomer And a method in which an acrylic resin having an alkoxysilyl group is reacted with the condensation reaction group of the alkoxysilyl group and the silicone resin.

  Examples of such a binder resin in which an acrylic resin and a silicone resin are copolymerized include silicone grafts such as X-22-8004, X22-8212, X22-8195X, and X-24-798A manufactured by Shin-Etsu Chemical Co., Ltd. An acrylic resin etc. are mentioned.

  The binder resin precursor can be used alone, or a crosslinking reactive component can be used at the same time. Examples of the crosslinking reactive component include a silane coupling agent. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, aminosilane coupling agent, and the like. Of these, aminosilane coupling agents are particularly preferred.

  As the aminosilane coupling agent, those represented by the following structural formula are suitable.

0.001-20 mass% is preferable and, as for content in the said coating layer of the said aminosilane coupling agent, 0.001-10 mass% is more preferable. By containing the aminosilane coupling agent in the coating layer, by increasing the bonding strength between the particles and the binder resin of the carrier core material and a coating layer, to improve the dispersibility of the fine particles, the above | T ₆ h (%) − T ₀ h (%) | can be suppressed to 30% or less, and film peeling of the carrier coating layer due to stress when the developer is stirred can be suppressed.
<Fine particles>
The fine particles can remarkably improve the strength of the coating layer by selecting an appropriate content and particle size with respect to the thickness of the coating layer.

  There is no restriction | limiting in particular as said fine particle, According to the objective, it can select suitably from a conventionally well-known material, The particle | grains of an inorganic compound, especially a metal oxide are used preferably. Examples thereof include particles of alumina, titanium oxide, zinc oxide, silica, potassium titanate, aluminum borate, calcium carbonate, tin oxide, indium oxide, and the like. Among these, fine particles of titanium oxide and fine particles of alumina are particularly preferable from the viewpoint that the toner is negatively charged and the resistance value of the coating layer is easily controlled within a desired range. These may be used individually by 1 type and may use 2 or more types together.

  It is preferable that the fine particles further exhibit a desired conductivity by being subjected to a conductive treatment. Examples of such a conductive treatment method include a metal or an alloy thereof, a metal oxide, a method of depositing a metal or a metal oxide thereof on the surface of the fine particles, aluminum, zinc, copper, chromium, nickel, stainless steel, silver, Or an alloy thereof, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony-doped tin oxide and zirconium oxide in the form of solid solution or fusion. A method of coating the surface of the film may be used. Among these, it is particularly preferable to conduct the conductive treatment using tin oxide, indium oxide, indium oxide doped with tin, or tin oxide doped with antimony.

  Although the content of the fine particles is appropriately selected depending on the material constituting the coating layer, it is preferably 1% by mass to 70% by mass and more preferably 10% by mass to 50% by mass with respect to the mass of the coating layer. When the content is less than 1% by mass, the effect of improving the strength of the film and the resistance adjustment of the coating layer by the fine particles may not be sufficient. When the content exceeds 70% by mass, the fine particles are removed from the coating layer. Separation is likely to occur, which may cause problems in durability.

Incidentally, the covering layer for the purpose of the electric resistance adjusting, conductive ZnO, metal powder such as Al, SnO ₂ doped with various SnO ₂ or various elements manufactured by the method; borides (e.g., TLB _{2, ZnB 2, MoB 2)} ; silicon carbide, conductive polymers (e.g., polyacetylene, polyparaphenylene, poly (para - phenylene sulfide), polypyrrole, parylene, etc.), it may contain fine particles such as carbon black .

  The solvent is not particularly limited as long as it can dissolve or disperse at least one of the binder resin and the binder resin precursor and the fine particles, and can be appropriately selected according to the purpose. hydrocarbons such as n-hexane, cyclohexane, toluene, xylene, benzene; alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, 3-methyl-3-methoxybutanol; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as cyclohexanone and isophorone; halogen-containing compounds such as carbon tetrachloride, methylene chloride, 1,2-dichloromethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloromethylidene; methyl acetate, acetic acid Echi Esters such as butyl acetate, isobutyl acetate, cellosolve acetate; ethers such as methyl ethyl ether, diethyl ether, ethyl cellosolve, butyl cellosolve, isopropyl cellosolve, ethyl carbitol; acetonitrile, pyridine, N-methylpyrrolidone, dimethylformamide, etc. Nitrogen-containing compounds; water, and the like. These solvents may be used alone or in combination of two or more.

(Carrier manufacturing method)
In the method for producing a carrier for an electrophotographic toner of the present invention, a coating layer containing at least a binder resin and fine particles is coated. At that time, a first step of forming coated particles by applying a coating liquid containing at least one of the binder resin and the binder resin precursor, fine particles, and a solvent to the surface of the core material; A second step of surface-treating the coated particles with a stirring device having no stirring blade, and the average film thickness h of the coating layer of the coated particles formed in the first step is: Between the volume average particle diameter Dv in terms of the spherical diameter of the fine particles, the relationship of the following formula (1) Dv / h ≦ 0.3 Formula (1)
Meet.

Furthermore, in the carrier manufacturing method of the present invention, the coating liquid in the first step is a condition of the following formula (2): | T ₆ h (%) − T ₀ h (%) | ≦ 30 (%) Formula (2)
It is preferable to satisfy. However, the formula (2) _in, T 0 h (%) represents the transmittance of light having a wavelength of 550nm in immediately after preparing the coating liquid. T ₆ h (%) represents the transmittance of light having a wavelength of 550 nm after standing for 6 hours immediately after preparing the coating solution.

In the formula (2), | T ₆ h (%) − T ₀ h (%) | is more preferably 15% or less. When | T ₆ h (%) − T ₀ h (%) | exceeds 30%, the coating liquid immediately after the dispersion treatment has settled with time, and the dispersibility is insufficient. That is, T ₆ h which is the light transmittance of the supernatant is increased, and the light transmittance fluctuation with T ₀ h is increased. At this time, it is difficult to form a coating layer in which the fine particles are uniformly dispersed when forming the coating layer, which is not preferable.

  In order to improve the dispersibility of the fine particles in such a coating liquid and satisfy the condition of the formula (2), as described later, a binder resin having a functional group capable of improving the dispersibility of the fine particles and a precursor thereof It is possible to control using at least one of the above, a dispersant, a silane coupling agent, and the like.

Here, the method of measuring the above | T ₆ h (%) − T ₀ h (%) | is not particularly limited as long as it is a spectrophotometer capable of measuring the transmittance of light having a wavelength of 550 nm. For example, a UV-VIS spectrophotometer (UV-3100, manufactured by Shimadzu Corporation) may be used.

<First step>
There is no restriction | limiting in particular as a coating method of the coating liquid in a 1st process, A conventionally well-known method can be used, The method of apply | coating the said coating liquid to a core material surface by means, such as a spraying method or a dipping method, is mentioned. By heating the core material coated with the coating liquid in this manner, it is preferable to accelerate the polymerization reaction of the coating liquid to form a coating layer.

  The heating may be performed in the coating layer forming apparatus after the coating liquid is applied to the core material, or another heating means such as a normal electric furnace or a baking kiln after the coating liquid is applied to the core material. The coated particles may be formed by.

  The heating temperature varies depending on the coating layer material to be used, and is not generally determined, but is preferably 120 ° C to 350 ° C, preferably a temperature equal to or lower than the decomposition temperature of the coating resin, and an upper limit temperature up to about 220 ° C. The heating time is preferably 5 minutes to 120 minutes.

At this time, the particle diameter Dv of the fine particles in the coating layer and the thickness h of the coating layer are expressed by the following formula 1. Dv / h ≦ 0.3 Formula (1)
By satisfying the condition, the surface treatment in the second step described later can be promptly and reliably advanced. Here, Dv is the volume average particle diameter of the fine particles in terms of a sphere, and h is the film thickness of the coating layer of the coated particles.

  Further, the value of Dv / h in the formula (1) is set to 0.3 or less, preferably 0.2 or less. If this value exceeds this range and is too large, fine particles in the carrier coating layer after the surface treatment described later can easily be detached, or irregularities derived from the fine particles can be easily formed on the surface of the carrier coating layer. As a result, the carrier life is reduced, which is not preferable.

  The volume average particle diameter Dv of the fine particles in order to satisfy the formula (1) is preferably 0.01 μm to 0.3 μm. When the volume average particle diameter Dv of the fine particles is less than 0.01 μm, it must be added more than necessary with respect to the weight required for the coating liquid, and the viscosity of the coating liquid increases, It may be difficult to coat the core material with the coating liquid in one step.

  Here, the thickness h of the coating layer of the coated particles is, for example, 50 by using a transmission electron microscope (TEM) and a scanning transmission electron microscope (STEM) after creating a cross section of the coated particle with FIB (focused ion beam). It can be calculated as an average value of the film thickness obtained by observing the cross section of the coated particle at a point or more. The volume average particle diameter Dv of the fine particles in spherical form can be measured by, for example, Nikkiso Co., Ltd., Nanotrack particle size distribution measuring device UPA-EX150.

<Second step>
In the second step, the coated particles obtained in the first step are stirred using a stirrer that does not have a stirring blade inside, and the surface treatment of the coated particles is performed. By this surface treatment, fine particles of the coated particles protruding from the surface of the coating layer are removed, the coating layer is made uniform, and the carrier surface can be prevented from being scraped or peeled off during mixing and stirring with the carrier toner. The reason for stirring using a stirring device that does not have a stirring blade is that, if vigorous stirring is performed with a stirring blade, the coating layer of the coated particles is excessively worn and a normal carrier cannot be produced.

  In general, in an image forming apparatus, an electrophotographic developer is excessively stressed on a convex portion of a carrier with long-term agitation, and peeling and abrasion of the carrier coating layer proceed. In contrast, the coating layer formed in the first step smoothes the contact site by weak stress between the carriers by applying a surface treatment using a stirrer, so that the coating layer can be peeled off. Abrasion can be suppressed.

  Examples of the stirring device having no stirring blade include a V-type mixer, a double cone type mixer, a rocking mixer, a Laedige mixer, and a tumbler mixer, but are not limited thereto. Among these, a stirring blade such as a rocking mixer or a tumbler mixer is provided because it is necessary to apply a relatively weak load so that the coating layer does not peel or wear, and the coating layer can be efficiently and uniformly smoothed. Particularly preferred is a container rotating type mixer.

  The content of the coating layer in the carrier is preferably 5% by mass or more, and more preferably 5% by mass or more and 10% by mass or less. The thickness h of the coating layer is preferably 1.0 μm or more, and more preferably 1.0 μm or more and 2.0 μm or less. When the coating layer is 5% by mass or less or the film thickness is 1.0 μm or less, the strength of the coating layer is not sufficient in the second step, and before the carrier surface is smoothened. The coating layer may be partially peeled off or worn out, and the core material may be easily exposed. When the coating layer exceeds 2.0 μm, the strength of the coating layer is improved and the wear resistance is excellent, but a carrier having a desired resistance value can be obtained even if the conductive fine particles are contained. It may not be easy, and as a result, maintaining the image quality may not be easy.

(Physical properties of the carrier)
The volume resistance of the carrier is preferably 10 (log Ω · cm) or more and 16 (log Ω · cm) or less, and more preferably 11 (log Ω · cm) or more and 15 (log Ω · cm) or less (logarithm display of volume resistance). Is, for example, 15 (log Ω · cm) represents 10 ¹⁵ (Ω · cm).

  When the volume resistance is less than 10 (log Ω · cm), carrier adhesion may occur in the non-image area, and when it exceeds 16 (log Ω · cm), the image density at the edge portion is emphasized during development. The so-called edge effect becomes remarkable. The volume resistance can be adjusted as necessary within the range of the volume resistance by adjusting the thickness of the coating layer and the content of the conductive fine particles to be contained.

Here, as a measuring method of the volume resistance, as shown in FIG. 1, a cell 3 composed of a fluororesin container containing an electrode 1 and an electrode 2 having a distance between electrodes of 0.2 cm and a surface area of 2.5 cm × 4 cm is used. Then, the carrier 4 is filled, and the drop height is 1 cm, the tapping speed is 30 times / min, and the tapping frequency is 10 times. Next, a DC voltage of 1000 V was applied between both electrodes, and the resistance value after 30 seconds was measured with a high resistance meter 4329A (manufactured by Yokogawa Hewlett-Packard Co., Ltd., High Resistance Meter), and the obtained resistance value r ( Ω), the following formula: R = Log [r × (2.5 cm × 4 cm) ÷ 0.2 cm]
The volume resistance R [Log (Ω · cm)] in logarithm can be calculated by calculating as follows.

  The volume average particle size of the carrier is preferably 20 μm to 65 μm, and more preferably 20 μm to 50 μm. When the volume average particle size is less than 20 μm, carrier adhesion due to a decrease in uniformity of the core material may occur. When the volume average particle size exceeds 65 μm, reproducibility of image details is poor and fine. An image may not be obtained.

  Here, the method for measuring the volume average particle size is not particularly limited as long as it is a device capable of measuring the particle size distribution, and can be appropriately selected according to the purpose. For example, a microtrack particle size distribution meter (model HRA9320- X100).

(Developer)
The developer of the present invention is a two-component developer containing the carrier of the present invention described above and a toner. The mixing ratio of the toner and the carrier in this developer is preferably 1.0 part by mass to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier. The toner includes at least a binder resin and a colorant, and further includes a release agent, a charge control agent, and other components as necessary.

<Toner>
The method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose. It is a pulverization method, a suspension in which an oil phase is emulsified, suspended or aggregated in an aqueous medium to form toner base particles. Examples include a polymerization method, an emulsion polymerization method, and a polymer suspension method.

-Binder resin-
The binder resin for the toner is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene such as polystyrene, poly-p-styrene, polyvinyltoluene, or a substitution product thereof may be used. Polymer, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-methacrylic Acid Copolymer Corps, Styrene-Methyl Methacrylate Copolymer, Styrene-Ethyl Methacrylate Copolymer, Styrene-Butyl Methacrylate Copolymer, Styrene-α-Chloromethacrylate Methyl Copolymer, Styrene- Acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrene copolymers such as luketone copolymer, styrene-butadiene copolymer, styrene-isopropyl copolymer, styrene-maleic acid ester copolymer, polythyme methacrylate resin, polybutyl methacrylate resin, polyvinyl chloride resin , Polyvinyl acetate resin, polyethylene resin, polyester resin, polyurethane resin, epoxy resin, polyvinyl butyral resin, polyacrylic acid resin, rosin resin, modified rosin resin, terpene resin, phenol resin, aliphatic or aromatic hydrocarbon resin, aromatic Family petroleum resin. These may be used individually by 1 type and may use 2 or more types together.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G , G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR ), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cadmium Mummer Curry Red, Antimony Zhu, Permanent Red 4R, Parare , Phi Sae Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake B, rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil Quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue , Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid Examples include lean lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and litbon. These may be used individually by 1 type and may use 2 or more types together.

  The content of the colorant in the toner is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, styrene copolymer, polymethyl methacrylate resin, polybutyl Methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polypropylene resin, polyester resin, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin and the like. These may be used individually by 1 type and may use 2 or more types together.

-Release agent-
There is no restriction | limiting in particular as a mold release agent for toners, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.

  Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, long chain hydrocarbons, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.

  Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.

Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40 to 160 degreeC is preferable, 50 to 120 degreeC is more preferable, and 60 to 90 degreeC is further. preferable. When the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.

  The melt viscosity of the release agent is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as measured at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  There is no restriction | limiting in particular as content in a toner of a mold release agent, Although it can select suitably according to the objective, 1-40 mass% is preferable and 3-30 mass% is more preferable. When the content of the release agent exceeds 40% by mass, the fluidity of the toner may be deteriorated.

-Charge control agent-
The charge control agent is not particularly limited, and a positive or negative charge control agent can be appropriately selected and used depending on whether the charge charged on the photoconductor is positive or negative.
As the negative charge control agent, for example, a resin or compound having an electron donating functional group, an azo dye, a metal complex of an organic acid, or the like can be used. Specifically, Bontron (product numbers: S-31, S-32, S-34, S-36, S-37, S-39, S-40, S-44, E-81, E-82, E -84, E-86, E-88, A, 1-A, 2-A, 3-A) (all manufactured by Orient Chemical Co., Ltd.); Kaya Charge (product numbers: N-1, N-2) Kaya Set Black (Part No .: T-2, 004) (all manufactured by Nippon Kayaku Co., Ltd.); Eisenspiron Black (T-37, T-77, T-95, TRH, TNS-2) (all Also manufactured by Hodogaya Chemical Co., Ltd.); FCA-1001-N, FCA-1001-NB, FCA-1001-NZ (all manufactured by Fujikura Chemical Co., Ltd.), and the like.

As the positive charge control agent, for example, basic compounds such as nigrosine dyes, cationic compounds such as quaternary ammonium salts, metal salts of higher fatty acids, and the like can be used. Specifically, Bontron (part numbers: N-01, N-02, N-03, N-04, N-05, N-07, N-09, N-10, N-11, N-13, P -51, P-52, AFP-B) (all manufactured by Orient Chemical Co., Ltd.); TP-302, TP-415, TP-4040 (all manufactured by Hodogaya Chemical Co., Ltd.); Copy Blue PR , Copy charge (part numbers: PX-VP-435, NX-VP-434) (both manufactured by Hoechst); FCA (part numbers: 201, 201-B-1, 201-B-2, 201-B-3) , 201-PB, 201-PZ, 301) (all manufactured by Fujikura Kasei Co., Ltd.); PLZ (part numbers: 1001, 2001, 6001, 7001) (all manufactured by Shikoku Kasei Kogyo Co., Ltd.), and the like. .
These may be used individually by 1 type and may use 2 or more types together.

  The addition amount of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited. However, with respect to 100 parts by mass of the binder resin, 0.1-10 mass parts is preferable and 0.2-5 mass parts is more preferable. If the addition amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is reduced, the image When the concentration is less than 0.1 part by mass, the charge rise property and the charge amount are not sufficient, and the toner image may be easily affected.

  In addition to binder resin, release agent, colorant, and charge control agent, inorganic fine particles, fluidity improver, cleaning improver, magnetic material, metal soap, etc. are added to the toner material as necessary. can do.

  The inorganic fine particles are not particularly limited and can be appropriately selected according to the purpose.For example, silica, titania, alumina, cerium oxide, strontium titanate, calcium carbonate, magnesium carbonate, calcium phosphate, and the like can be used. It is more preferable to use silica fine particles hydrophobized with silicone oil or hexamethyldisilazane or titanium oxide subjected to a specific surface treatment.

  As silica fine particles, for example, Aerosil (Product No .: 130, 200V, 200CF, 300, 300CF, 380, OX50, TT600, MOX80, MOX170, COK84, RX200, RY200, R972, R974, R976, R805, R811, R812, T805) , R202, VT222, RX170, RXC, RA200, RA200H, RA200HS, RM50, RY200, REA200) (all manufactured by Nippon Aerosil Co., Ltd.); HDK (Part Nos .: H20, H2000, H3004, H2000 / 4, H2050EP, H2015EP, H3050EP, KHD50), HVK2150 (all manufactured by Wacker Chemical Co., Ltd.); Cabogil (Part No .: L-90, LM-130, LM-150, M-5, PTG, MS-5) , H-5, HS-5, EH-5, LM-150D, M-7D, MS-75D, TS-720, TS-610, TS-530) (all manufactured by Cabot Corporation), etc. it can.

  The addition amount of the inorganic fine particles is preferably 0.1 to 5.0 parts by mass, and more preferably 0.8 to 3.2 parts by mass with respect to 100 parts by mass of the toner base particles.

<Toner production method>
The method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a pulverization method, a monomer composition containing a specific crystalline polymer and a polymerizable monomer. A polymerization method (suspension polymerization method, emulsion polymerization method) in which water is directly polymerized in a water phase, and a composition containing a specific crystalline polymer and an isocyanate group-containing prepolymer directly in the water phase with amines. And a polyaddition reaction method using an isocyanate group-containing prepolymer, a method of dissolving with a solvent, removing the solvent and pulverizing, a melt spraying method, and the like.

  The pulverization method is, for example, a method of obtaining the toner base particles by melting or kneading the toner material, pulverizing, classifying or the like. In the case of the pulverization method, for the purpose of increasing the average circularity of the toner, the shape may be controlled by applying a mechanical impact force to the obtained toner base particles. In this case, the mechanical impact force can be applied to the toner base particles using a device such as a hybridizer or mechanofusion.

  The above toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial continuous kneader, a biaxial continuous kneader, or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay, PCM type twin screw extruder manufactured by Ikegai Co., Ltd. Used for. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature is performed with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

  In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion by a cyclone, a decanter, centrifugation, or the like.

  After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like to produce a toner having a predetermined particle size.

  The suspension polymerization method is an oil-soluble polymerization initiator, an emulsification method described later in an aqueous medium in which a colorant, a release agent, etc. are dispersed in a polymerizable monomer and a surfactant, other solid dispersant, and the like are contained. To emulsify and disperse. Thereafter, a polymerization reaction is performed to form particles, and then wet processing for attaching inorganic fine particles to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to wash the excess surfactant or the like and apply the treatment to the removed toner particles.

  Examples of the polymerizable monomer include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride; acrylamide, Methacrylamide, diacetone acrylamide, or their methylol compounds; vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate and other (meth) acrylates with amino groups are used on the toner particle surface. Functional groups can be introduced.

  Further, by selecting a dispersant having an acid group or a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

  As an emulsion polymerization method, a water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by an ordinary emulsion polymerization method. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, wet processing of inorganic fine particles described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer used in the suspension polymerization method.

  Among these, since the selectivity of the resin is high, the low-temperature fixability is high, the granulation property is excellent, and the particle size, particle size distribution, and shape can be easily controlled. And a polymer capable of reacting with the active hydrogen group-containing compound is dissolved or dispersed in an organic solvent to prepare a toner solution, and then the toner solution is emulsified or dispersed in an aqueous medium. In the aqueous medium, the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted to form an adhesive substrate in the form of particles, and the organic solvent is What is obtained by removing is suitable.

  Examples of the toner material include an adhesive base obtained by reacting an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, a binder resin, a charge control agent, and a colorant. And, if necessary, other components such as resin fine particles and a release agent.

  Further, in order to improve the fluidity, storage stability, developability and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner base particles produced as described above. For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

  The shape, size, etc. of the toner are not particularly limited and can be appropriately selected according to the purpose. The average circularity, volume average particle size, volume average particle size and number are as follows. It is preferable to have a ratio to the average particle size (volume average particle size / number average particle size).

  The average circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected shape as the toner shape by the perimeter of the actual particles, and is preferably 0.900 to 0.980, for example, 0.950 to 0 .975 is more preferred. Note that particles having an average circularity of less than 0.94 are preferably 15% or less.

  If the average circularity is less than 0.900, satisfactory transferability and a high-quality image free from dust may not be obtained. If the average circularity exceeds 0.980, image formation employing blade cleaning or the like is employed. In the system, defective cleaning occurs on the photoconductor and the transfer belt, and in the case of image formation with a high image area ratio such as a photographic image, an untransferred image is formed due to defective paper feeding, etc. The accumulated toner may become a transfer residual toner on the photoconductor, resulting in background smearing of the image, or it may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.

  The average circularity is measured using a flow particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation), and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). It was. Specifically, 0.1 to 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, and each toner 0 is added. 0.1 to 0.5 g was added, and the mixture was mixed with a micropartel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the concentration of the dispersion reached 5,000 to 15,000 / μL. In this measurement method, it is important that the concentration of the dispersion is 5,000 / μL to 15,000 / μL from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the concentration of the dispersion, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated, and if it is too small, the toner cannot be sufficiently wetted. It will be enough. The amount of toner added varies depending on the particle size, and is small when the particle size is small, and needs to be increased when the particle size is large. When the toner particle size is 3 μm to 10 μm, the toner amount is 0.1 g to 0.00 g. By adding 5 g, the dispersion concentration can be adjusted to 5,000 / μl to 15,000 / μl.

The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 3 μm to 10 μm, and more preferably 3 μm to 8 μm.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. Therefore, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle diameter may increase.
The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, more preferably 1.10 to 1.25.

  The volume average particle diameter and the ratio between the volume average particle diameter and the number average particle diameter (volume average particle diameter / number average particle diameter) are measured using a particle size measuring device (“Multisizer III” manufactured by Beckman Coulter, Inc.). Then, measurement was performed with an aperture diameter of 100 μm, and analysis was performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml beaker made of glass, and 0.5 g of each toner is added. The mixture was stirred with a micropartel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

  The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

(Container with developer)
The developer-containing container contains the developer of the present invention in a container. There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a developer container main body and a cap etc. are mentioned suitably. The size, shape, structure, material and the like of the developer container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. A spiral unevenness is formed on the peripheral surface, and the developer as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, Etc. are particularly preferred. The material of the developer container main body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable, and among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like. The developer-containing container is easy to store and transport, has excellent handleability, and can be suitably used for replenishing the developer by being detachably attached to a process cartridge, an image forming apparatus, and the like described later.

(Process cartridge)
The process cartridge using the developer of the present invention uses an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using the developer. Development means for developing and forming a visible image at least, and other means appropriately selected as necessary.

  The developing means includes at least a developer container that contains the developer of the present invention, and a developer carrier that carries and conveys the developer contained in the developer container. In addition, a layer thickness regulating member for regulating the toner layer thickness to be carried may be provided if necessary. The process cartridge can be detachably provided in various electrophotographic image forming apparatuses, and particularly preferably detachably provided in an image forming apparatus used in the image forming method of the present invention described later.

  For example, as shown in FIG. 2, the process cartridge includes a photosensitive member 101, includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and further includes other members as necessary. Become. In FIG. 2, reference numeral 103 denotes exposure by exposure means, and a light source capable of writing with high resolution is used. Reference numeral 105 denotes a recording medium. As the photoreceptor 101, the same one as an image forming apparatus described later can be used. An arbitrary charging member is used as the charging unit 102.

  Next, the image forming process using the process cartridge shown in FIG. 2 will be described. The photoconductor 101 is exposed to the surface by charging by the charging means 102 and exposure 103 by the exposure means (not shown) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the image is formed. The electrostatic latent image is developed with toner by the developing unit 104, and the toner image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. , Including recycling process, control process, etc.

  The image forming apparatus used in the image forming method of the present invention has at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and is further necessary. Other means appropriately selected according to the above, for example, a static elimination means, a cleaning means, a recycling means, a control means, and the like.

<Electrostatic latent image forming step and electrostatic latent image forming means>
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
―Electrostatic latent image carrier―
The electrostatic latent image carrier (sometimes referred to as “electrophotographic photosensitive member” or “photosensitive member”) is not particularly limited in terms of material, shape, structure, size, etc. Although it can be selected as appropriate, the shape thereof is preferably a drum shape, and examples of the material thereof include inorganic photoreceptors such as amorphous silicon and selenium, organic photoreceptors (OPC) such as polysilane and phthalopolymethine, and the like. Is mentioned. Among these, amorphous silicon or the like is preferable in terms of long life.

―Electrostatic latent image formation process―
The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

  The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger. The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons. The charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying a direct current and an alternating voltage. Further, the charger is a charging roller disposed in a non-contact proximity to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is carried by applying a direct current and an alternating voltage to the charging roller. Those that charge the body surface are preferred.

  The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device. The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used. In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Development process and development means>
The development step is a step of developing the electrostatic latent image using the developer of the present invention to form a visible image (toner image). The visible image can be formed, for example, by developing the electrostatic latent image using the developer of the present invention, and can be performed by the developing unit. The developing means is not particularly limited as long as it can be developed using, for example, the developer of the present invention, and can be appropriately selected from known ones, for example, containing the developer of the present invention. It is preferable to have at least a developing device capable of bringing the developer into contact or non-contact with the electrostatic latent image, and a developing device including the developer-containing container is more preferable.

  The developing unit may be of a dry development type, may be of a wet development type, may be a single color developer, or may be a multicolor developer. Suitable examples include those having a stirrer for charging the developer by frictional stirring and a rotatable magnet roller.

  In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor). The developer accommodated in the developing device is the developer of the present invention.

<Transfer process and transfer means>
The transfer step is a step of transferring a visible image onto a recording medium. An intermediate transfer member is used to primarily transfer the visible image onto the intermediate transfer member, and then the visible image is transferred onto the recording medium. A mode of subsequent transfer is preferable, and a primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably a full color toner as the toner, and the composite transfer image And a secondary transfer step of transferring the image onto a recording medium is more preferable.

  The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photosensitive member) with the transfer charger using the visible image, and can be performed by a transfer unit. The transfer unit includes a primary transfer unit that transfers a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer unit that transfers the composite transfer image onto a recording medium. Is preferred. The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

  The transfer means (the primary transfer means and the secondary transfer means) includes at least a transfer device that peels and charges the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. Is preferred. There may be one transfer means, or two or more. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. In addition, there is no restriction | limiting in particular as a recording medium, It can select suitably from well-known recording media (recording paper).

<Fixing process and fixing means>
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the developer for each color is transferred to the recording medium, or for each color developer. You may perform this simultaneously in the state which laminated | stacked this. The fixing device is not particularly limited and may be appropriately selected depending on the intended purpose. However, a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.

  The fixing device includes a heating body provided with a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and between the film and the pressure member It is preferable that the recording medium on which an unfixed image is formed is passed and heated and fixed. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.

  In the present invention, for example, a known optical fixing device may be used together with or instead of the fixing step and the fixing unit depending on the purpose.

<Static elimination process and static elimination means>
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit. There are no particular restrictions on the static elimination means, and any neutralization bias can be applied to the electrostatic latent image carrier, and any suitable static elimination device can be selected. For example, a static elimination lamp or the like is suitable. It is mentioned in.

<Cleaning process and cleaning means>
The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit. There is no particular limitation on the cleaning means, and it is sufficient that the toner remaining on the electrostatic latent image carrier can be removed, and it can be appropriately selected from known cleaners. For example, a magnetic brush cleaner, static Preferred examples include an electric brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.

<Recycling process and recycling means>
The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit. There is no restriction | limiting in particular as a recycle means, A well-known conveyance means etc. are mentioned.

<Control process and control means>
A control process is a process of controlling each said process, and can perform each process suitably by a control means. The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

<Embodiment of Image Forming Method>
—Example 1—
Here, one mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 3 includes a photosensitive drum 10 (photosensitive member 10) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and an exposure device 30 as the exposure unit. A developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed so as to be movable in the direction of the arrow in the figure by three rollers 51 that are arranged on the inner side and stretch the belt. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. An intermediate transfer member cleaning blade 90 is disposed in the vicinity of the intermediate transfer member 50, and a transfer bias for transferring a visible image (toner image) to the recording medium 95 (secondary transfer) is applied. Possible transfer rollers 80 as the transfer means are arranged to face each other. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is connected to the electrostatic latent image carrier 10 in the rotation direction of the intermediate transfer member 50. The contact portion between the intermediate transfer member 50 and the contact portion between the intermediate transfer member 50 and the recording medium 95 is disposed.

  The developing device 40 includes a developing belt 41 as a developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. Yes. The black developing unit 45K includes a developer accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. Further, the developing belt 41 is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10. Here, the developer of the present invention described above is used as the developer.

  In the image forming apparatus 100 shown in FIG. 3, for example, the charging roller 20 uniformly charges the photosensitive drum 10. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

—Example 2—
Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 4 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 3, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and the like around the photoconductor 10. Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 4, the same components as those in FIG. 3 are denoted by the same reference numerals.

—Example 3—
Still another embodiment for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The tandem type image forming apparatus shown in FIG. 5 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

  The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 5. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. Here, the developer of the present invention described above is used in at least one developing unit of the tandem developing unit 120.

  An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.

  In the tandem type image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image bearing member 10 is uniformly charged, and the electrostatic latent image bearing member is exposed (L in FIG. 6) for each color image corresponding to each color image information. An exposure device that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) Develop with A developing device 61 for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a static eliminator 64 are provided. Each single color image (black image, yellow image, magenta image, and cyan image) can be formed based on the color image information.

  The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 145, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  The image forming method of the present invention uses the developer of the present invention that has high mechanical strength, is free of toner scattering and background contamination, and can form an image with a high image density, so that high-quality images can be formed efficiently over a long period of time. it can.

[Example]
Examples of the present invention will be described below, but the present invention is not limited to these examples.
(Preparation of Toner 1)
<Synthesis of organic fine particle emulsion>
In a reaction vessel in which a stirrer and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 166 methacrylic acid When a mass part, 110 mass parts of butyl acrylate, and 1 mass part of ammonium persulfate were prepared and stirred for 30 minutes at 3,800 rpm, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Subsequently, 30 parts by mass of a 1% by mass aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 6 hours. A dispersion [fine particle dispersion 1] was synthesized.

  The obtained [Fine Particle Dispersion 1] was measured with a particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.), and the volume average particle size was 110 nm. Further, a portion of the obtained [fine particle dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 58 ° C., and the weight average molecular weight was 130,000.

<Preparation of aqueous phase>
990 parts by weight of water, 83 parts by weight of [fine particle dispersion 1], 37 parts by weight of a 48.3% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and ethyl acetate 90 parts by mass were mixed and stirred to obtain a milky white liquid. This is designated [Aqueous Phase 1].

<Synthesis of low molecular weight polyester>
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propylene oxide 3-mole adduct, 208 parts by mass of terephthalic acid, adipic acid 46 parts by mass and 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 7 hours under normal pressure. Next, after 5 hours of reaction at a reduced pressure of 10 mmHg to 15 mmHg, 44 parts by weight of trimellitic anhydride was placed in the reaction vessel and reacted at 180 ° C. for 3 hours under normal pressure to synthesize [low molecular weight polyester 1]. did.

  The obtained [Low molecular weight polyester 1] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25 mgKOH / g.

<Synthesis of Intermediate Polyester and Prepolymer>
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, anhydrous [Intermediate polyester 1] was synthesized by adding 22 parts by mass of trimellitic acid and 2 parts by mass of dibutyltin oxide and reacting at 230 ° C. for 7 hours under normal pressure and further reacting under reduced pressure of 10 mmHg to 15 mmHg for 5 hours. . The obtained [Intermediate polyester 1] had a number average molecular weight of 2,200, a weight average molecular weight of 9,700, a glass transition temperature (Tg) of 54 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 52 mgKOH / g. .

  Next, 410 parts by mass of [Intermediate Polyester 1], 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. By reacting for a period of time, [Prepolymer 1] was synthesized. The obtained [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Synthesis of ketimine>
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 hours and half to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

<Preparation of master batch (MB)>
1,200 parts by mass of water, 540 parts by mass of carbon black (Printex 35, manufactured by Dexa, DBP oil absorption = 42 ml / 100 mg, pH = 9.5) and 1,200 parts by mass of polyester resin were added, and Henschel mixer (Mitsui Mine) was added. The mixture was kneaded at 110 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to prepare [Masterbatch 1].

<Production of oil phase>
In a container in which a stir bar and a thermometer are set, 378 parts by mass of [low molecular weight polyester 1], 100 parts by mass of carnauba wax, and 947 parts by mass of ethyl acetate are charged, and the temperature is raised to 80 ° C. with stirring. After being kept for 5 hours, it was cooled to 30 ° C. at 1 hour. Next, 500 parts by mass of [Masterbatch 1] and 500 parts by mass of ethyl acetate were charged into the container and mixed for 1 hour to prepare [Raw material solution 1].

  1324 parts by mass of the obtained [Raw Material Solution 1] was transferred into a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), the liquid feed speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm zirconia. Filling with 80% by volume of beads, carbon black and wax were dispersed under conditions of 3 passes. Next, 1324 parts by mass of a 65% by mass ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes using the bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. The obtained [Pigment / Wax Dispersion 1] had a solid content (130 ° C., 30 minutes) of 50% by mass.

<Emulsification and solvent removal>
[Pigment / Wax Dispersion 1] 749 parts by mass, [Prepolymer 1] 115 parts by mass, and [Ketimine Compound 1] 2.9 parts by mass are placed in a container, and TK homomixer (manufactured by Tokushu Kika Co., Ltd.) is used. After mixing at 5,000 rpm for 2 minutes, 1,200 parts by mass of [Aqueous Phase 1] is added to the container, and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [Emulsion Slurry 1]. It was.

  [Emulsion slurry 1] was put into a container in which a stirrer and a thermometer were set, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 40 ° C. for 24 hours to obtain [Dispersion slurry 1].

<Washing and drying>
[Dispersion Slurry 1] After 100 parts by mass of filtration under reduced pressure, the following washing treatment was performed.
(1) 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2) 100 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. (3) 100 parts by mass of 10 mass% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4) Add 300 parts by mass of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filter twice to perform [Filter cake 1]. Obtained.

  The obtained [Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, the mixture was sieved with a mesh of 75 μm to prepare [Toner Base Particle 1] having a volume average particle size of 6.1 μm, a number average particle size of 5.4 μm, and an average circularity of 0.972.

<External toner addition>
Next, 0.7 parts by mass of hydrophobic silica and 0.3 parts by mass of hydrophobic titanium oxide were mixed with 100 parts by mass of the obtained [Toner Base Particle 1] using a Henschel mixer to produce “Toner 1”. did.

Example 1
-Production of carrier 1-
The following materials were put into a homomixer and dispersed for 10 minutes to prepare a coating liquid (1).
Acrylic resin solution (Hitaloid Chemical Co., Ltd., Hitaroid 3012X, hydroxyl value 50 mgKOH / g, solid content 50% by mass): 3.56 parts by mass Guanamine solution (Mitsui Cytec Co., Ltd., Mycoat 106, solid content 77) (Mass%): 1.20 parts by mass Silicone resin solution (Toray Dow Corning, SR2405, solid content 50% by mass): 7.11 parts by mass Aminosilane coupling agent (Toray Dow Corning, SH6020, solid content 100% by mass): 0.09 parts by mass / alumina fine particles (manufactured by Sumitomo Chemical Co., Ltd., volume average particle size 0.3 μm in spherical conversion): 5.93 parts by mass / toluene: 71.11 Parts by mass.

  Next, ferrite powder (saturation magnetic moment 65 emu / g at 1 k gauss) is used as a core material, and a rolling fluid type coating apparatus is used so that the coating liquid (1) has a thickness of 1.5 μm on the core material surface. Applied and dried. The obtained carrier was baked by standing at 150 ° C. for 1 hour in an electric furnace, and after cooling, the ferrite powder bulk was pulverized using a sieve having an opening of 90 μm to obtain coated particles 1. Next, the obtained coated particles 1 were placed in a tumbler shaker mixer T2F type (manufactured by Shinmaru Enterprises Co., Ltd.) so that the volume filling rate was 60 vol%, and stirred for 10 hours at a rotational speed of 96 min-1 [Carrier 1 ] Was obtained.

  When the particle size distribution of the obtained “Carrier 1” was measured with a Microtrac particle size distribution analyzer (model HRA9320-X100), the weight average particle size (Dw) was 39.6 μm, and the number average particle size (Dn) was 34.2 μm. Dw / Dn was 1.16. The volume resistance of “Carrier 1” was 14.8 (log Ω · cm).

(Example 2)
-Production of carrier 2-
The following materials were put into a homomixer and dispersed for 10 minutes to prepare a coating liquid (2).
Acrylic resin solution (Hitaloid Chemical Co., Ltd., Hitaroid 3012X, hydroxyl value 50 mgKOH / g, solid content 50% by mass): 3.56 parts by mass Guanamine solution (Mitsui Cytec Co., Ltd., Mycoat 106, solid content 77) (Mass%): 1.20 parts by mass Silicone resin solution (Toray Dow Corning, SR2405, solid content 50% by mass): 7.11 parts by mass Aminosilane coupling agent (Toray Dow Corning, SH6020, solid content 100% by mass): 0.09 parts by mass / alumina fine particles (manufactured by Nippon Aerosil Co., Ltd., volume average particle size 0.013 μm in terms of sphere): 5.93 parts by mass / toluene: 71.11 parts by mass .

  Next, in the same manner as in Example 1 except that the surface of the core material was coated with the coating liquid (2) instead of the coating liquid (1) in Example 1, “coated particles 2”, “carrier 2” Was made.

  When the particle size distribution of the obtained “Carrier 2” was measured with a Microtrac particle size distribution analyzer (model HRA9320-X100), the weight average particle size (Dw) was 39.4 μm and the number average particle size (Dn) was 34.5 μm. Dw / Dn was 1.14. The volume resistance of “Carrier 2” was 14.3 (log Ω · cm).

(Example 3)
-Production of carrier 3-
The following materials were put into a homomixer and dispersed for 10 minutes to prepare a coating liquid (3).
Acrylic resin solution (Hitaloid Chemical Co., Ltd., Hitaroid 3012X, hydroxyl value 50 mgKOH / g, solid content 50% by mass): 3.56 parts by mass Guanamine solution (Mitsui Cytec Co., Ltd., Mycoat 106, solid content 77) (Mass%): 1.20 parts by mass Silicone resin solution (Toray Dow Corning, SR2405, solid content 50% by mass): 7.11 parts by mass Aminosilane coupling agent (Toray Dow Corning, SH6020, solid content 100% by mass): 0.09 parts by mass. Titanium oxide fine particles (manufactured by Ishihara Sangyo Co., Ltd., volume average particle size 0.03 μm in terms of sphere): 5.93 parts by mass. Toluene: 71.11 parts by mass Department.

Next, “coated particles 3” and “carrier 3” were obtained in the same manner as in Example 1 except that the coating liquid (3) was used instead of the coating liquid (1) in Example 1 to coat the surface of the core material. Was made.
When the particle size distribution of the obtained “Carrier 3” was measured with a Microtrac particle size distribution analyzer (model HRA9320-X100), the weight average particle size (Dw) was 39.2 μm, and the number average particle size (Dn) was 34.1 μm. Dw / Dn was 1.15. The volume resistance of “Carrier 3” was 13.9 (log Ω · cm).

Example 4
-Production of carrier 4-
The following materials were put into a homomixer and dispersed for 10 minutes to prepare a coating solution (4).
Silicone graft acrylic resin solution (Shin-Etsu Chemical Co., Ltd., X-22-8004, solid content 40% by mass): 8.44 parts by mass Guanamine solution (Mitsui Cytec Co., Ltd., Mycoat 106, solid content 77 mass) %): 3.62 parts by mass Aminosilane coupling agent (manufactured by Dow Corning Toray, SH6020, solid content 100% by mass): 0.10 parts by mass Alumina fine particles (manufactured by Nippon Aerosil Co., Ltd., volume in spherical form) Average particle diameter: 0.012 μm): 6.03 parts by mass. Methyl ethyl ketone: 72.31 parts by mass.

Next, “coated particles 4” and “carrier 4” were obtained in the same manner as in Example 1 except that the coating liquid (4) was used instead of the coating liquid (1) in Example 1 to coat the surface of the core material. Was made.
When the particle size distribution of the obtained “Carrier 4” was measured with a Microtrac particle size distribution analyzer (model HRA9320-X100), the weight average particle size (Dw) was 39.9 μm and the number average particle size (Dn) was 34.5 μm. Dw / Dn was 1.16. The volume resistance of “Carrier 4” was 14.6 (log Ω · cm).

(Comparative Example 1)
-Production of carrier 5-
The following materials were put into a homomixer and dispersed for 10 minutes to prepare a coating liquid (5).
Acrylic resin solution (Hitaloid Chemical Co., Ltd., Hitaroid 3012X, hydroxyl value 50 mgKOH / g, solid content 50% by mass): 3.56 parts by mass Guanamine solution (Mitsui Cytec Co., Ltd., Mycoat 106, solid content 77) (Mass%): 1.20 parts by mass Silicone resin solution (Toray Dow Corning, SR2405, solid content 50% by mass): 7.11 parts by mass Aminosilane coupling agent (Toray Dow Corning, SH6020, solid content: 100% by mass): 0.09 parts by mass Alumina particles (Sumitomo Chemical Co., Ltd., volume average particle size in terms of sphere: 0.4 μm): 5.93 parts by mass Toluene: 71.11 parts by mass Department.

Next, in the same manner as in Example 1 except that the coating liquid (5) was used instead of the coating liquid (1) in Example 1 to coat the surface of the core material so that the film thickness was 0.5 μm. “Coated particles 5” and “carrier 5” were prepared.
When the particle size distribution of the obtained “Carrier 5” was measured with a Microtrac particle size distribution analyzer (model HRA9320-X100), the weight average particle size (Dw) was 38.3 μm, and the number average particle size (Dn) was 33.3 μm. Dw / Dn was 1.15. The volume resistance of “Carrier 5” was 13.2 (log Ω · cm).

(Comparative Example 2)
-Production of carrier 6-
The following materials were put into a homomixer and dispersed for 10 minutes to prepare a coating solution (6).
Acrylic resin solution (Hitaloid Chemical Co., Ltd., Hitaroid 3012X, hydroxyl value 50 mgKOH / g, solid content 50% by mass): 3.56 parts by mass Guanamine solution (Mitsui Cytec Co., Ltd., Mycoat 106, solid content 77) (Mass%): 1.20 parts by mass Silicone resin solution (Toray Dow Corning, SR2405, solid content 50% by mass): 7.11 parts by mass Aminosilane coupling agent (Toray Dow Corning, SH6020, solid content 100% by mass): 0.09 parts by mass / alumina fine particles (manufactured by Nippon Aerosil Co., Ltd., volume average particle size 0.013 μm in terms of sphere): 5.93 parts by mass / toluene: 71.11 parts by mass .

Next, in Example 1, the coating liquid (6) was used instead of the coating liquid (1) to coat the surface of the core material, and the stirring treatment by the tumbler, shaker, and mixer was not added. In the same manner as in Example 1, “coated particles 6” and “carrier 6” were produced.
When the particle size distribution of the obtained “Carrier 6” was measured with a Microtrac particle size distribution analyzer (model HRA9320-X100), the weight average particle size (Dw) was 40.1 μm and the number average particle size (Dn) was 34.6 μm. Dw / Dn was 1.16. The volume resistance of “Carrier 6” was 15.1 (log Ω · cm).

(Comparative Example 3)
-Production of carrier 7-
The following materials were put into a homomixer and dispersed for 10 minutes to prepare a coating solution (7).
・ Acrylic resin solution (manufactured by Hitachi Chemical Co., Ltd., Hitaroid 3546-3, hydroxyl value 15 mgKOH / g, solid content 50 mass%): 3.56 parts by mass ・ Guanamine solution (Mitsui Cytec Co., Ltd., Mycoat 106, solid 77 mass%): 1.20 parts by mass Silicone resin solution (manufactured by Toray Dow Corning Co., Ltd., SR2405, solid content 50 mass%): 7.11 parts by mass Aminosilane coupling agent (Toray Dow Corning Co., Ltd.) Manufactured by SH6020, solid content 100% by mass): 0.09 parts by mass / alumina fine particles (manufactured by Nippon Aerosil Co., Ltd., volume average particle diameter 0.013 μm in terms of sphere): 5.93 parts by mass / toluene: 71.11 Parts by mass.

Next, “coated particles 7” and “carrier 7” were obtained in the same manner as in Example 1 except that the coating liquid (1) was replaced with the coating liquid (7) in Example 1 to coat the surface of the core material. Was made.
When the particle size distribution of the obtained “Carrier 7” was measured with a Microtrac particle size distribution analyzer (model HRA9320-X100), the weight average particle size (Dw) was 39.2 μm, and the number average particle size (Dn) was 33.9 μm. Dw / Dn was 1.16. The volume resistance of “Carrier 7” was 13.6 (log Ω · cm).

(Comparative Example 4)
-Production of carrier 8-
The following materials were put into a homomixer and dispersed for 10 minutes to prepare a coating liquid (8).
Acrylic resin solution (Hitaloid Chemical Co., Ltd., Hitaroid 3012X, hydroxyl value 50 mgKOH / g, solid content 50% by mass): 3.56 parts by mass Guanamine solution (Mitsui Cytec Co., Ltd., Mycoat 106, solid content 77) (Mass%): 1.20 parts by mass Silicone resin solution (Toray Dow Corning, SR2405, solid content 50% by mass): 7.11 parts by mass Aminosilane coupling agent (Toray Dow Corning, SH6020, solid content 100% by mass): 0.09 parts by mass / alumina fine particles (manufactured by Nippon Aerosil Co., Ltd., volume average particle size 0.013 μm in terms of sphere): 5.93 parts by mass / toluene: 71.11 parts by mass .

Next, the surface of the core material was coated with the coating liquid (8) instead of the coating liquid (1) in Example 1, and the volume filling rate was applied to the paint shaker (manufactured by Asada Steel) instead of the tumbler, shaker, and mixer. “Coated particles 8” and “carrier 8” were prepared in the same manner as in Example 1 except that the carrier was filled so as to be 50 vol%, and a stirring treatment was added for 3 hours without adding beads.
When the particle size distribution of the obtained “Carrier 8” was measured with a Microtrac particle size distribution analyzer (model HRA9320-X100), the weight average particle size (Dw) was 38.1 μm, and the number average particle size (Dn) was 32.5 μm. Dw / Dn was 1.17. The volume resistance of “Carrier 8” was 13.2 (log Ω · cm).

[Measurement of physical properties of carriers, etc.]
(Measurement of coating layer thickness of coated particles)
The film thickness (h) of the coating layer of the coated particles 1 to 8 is determined by cutting the coated particle with FIB (focused ion beam) to create a coated particle cross section, and then using a transmission electron microscope (TEM), a scanning transmission electron microscope ( STEM) was used to calculate the average value of film thicknesses obtained by observing cross sections of 50 or more coated particles. Table 1 shows the calculated film thickness (h) of the coating layer of the coated particles 1 to 8.

(Measurement of volume average particle diameter of fine particles and calculation of Dv / h)
The volume average particle diameter Dv in terms of spherical shape of the fine particles was measured using a nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd. Calculate the volume average particle diameter (Dv) of the fine particles used in each example and [volume average particle diameter (Dv) of the fine particles / film thickness (h) of the coating layer of the coated particles] of the coated particles 1 to 8. It is shown in Table 1.

(Measurement of light transmittance of coating liquid)
The prepared coating liquids 1 to 8 were prepared using a UV-VIS spectrophotometer (UV-3100, manufactured by Shimadzu Corporation) with a light transmittance T ₀ h (%) immediately after production with respect to a light beam having a wavelength of 550 nm. After leaving still for 6 hours, the light transmittance T ₆ h (%) after that was calculated, and the difference | T ₆ h (%) − T ₀ h (%) | was calculated. The results are shown in Table 1.

[Production of developer]
The prepared toner 1 is added to the carriers 1 to 8 while adjusting the carrier coverage to 50%, and stirred with a tumbler mixer (manufactured by Shinmaru Enterprises Co., Ltd.). ~ 8 were made. Developers 1 to 4 were developers of Examples 1 to 4, and developers 5 to 8 were developers of Comparative Examples 1 to 4.

(Developer evaluation)
Using the obtained developers 1 to 8, peeling and scraping of the coating layer, image density, toner scattering property, and background stain were evaluated as follows. The results are shown in Table 1.

<Evaluation of peeling and shaving of coating layer>
-Evaluation methods-
Using the tandem color image forming apparatus (image Neo Neo450, manufactured by Ricoh Co., Ltd.), the produced developers 1 to 8 were subjected to 200,000 running evaluations, and the resistance reduction amount of the carrier after running was reduced to 200,000 sheets. The resistance ratio before and after running was evaluated. Here, the amount of resistance reduction refers to an initial carrier introduced between resistance measuring parallel electrodes: electrodes having a gap of 2 mm, and a resistance value after 30 sec after applying DC 200 V is measured with a high resist meter (manufactured by Yokogawa Hewlett-Packard Co., Ltd., High Resistance). The carrier obtained by removing the toner in the developer after running 200,000 sheets by the blow-off device from the value (R1) obtained by converting the value measured by (Meter) into the volume resistance is the same method as the resistance measuring method. The target value is 2.0 [Log (Ω · cm)] or less.

The cause of the decrease in resistance is the detachment of the carrier from the core material of the coating layer, and therefore the peeling and scraping of the coating layer were evaluated according to the following evaluation criteria based on the ratio of resistance values.
-Evaluation criteria-
A: Ratio of [resistance after 200,000 sheets run / resistance at the beginning of run] is 1/10 or more. O: ratio of [resistance after 200,000 sheets run / resistance at the beginning of run] is less than 1/10 and 1/100 or more Δ: Ratio of [resistance after 200,000 sheets run / resistance at initial stage of run] is less than 1/100 1/1000 or more ×: ratio of [resistance after 200,000 sheets run / resistance at initial stage of run] is less than 1/1000 .

<Evaluation of image density>
Next, each developer obtained was attached to copy paper (TYPE6000 <70W>, manufactured by Ricoh Co., Ltd.) using a tandem color image forming apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.). A solid image having an amount of 1.00 ± 0.05 mg / cm ² was formed. The solid image was repeatedly formed on 200,000 copy sheets. The image density of the obtained solid image was observed visually at the initial stage and after endurance of 200,000 sheets, and evaluated based on the following criteria. Note that the higher the image density obtained, the higher the density image can be formed. This evaluation also corresponds to an embodiment of the image forming method of the present invention.
-Evaluation criteria-
A: The image density did not change at the initial stage and after the endurance of 200,000 sheets, and high image quality was obtained.
◯: After 200,000 sheets were used, the image density was slightly reduced, but high image quality was obtained.
(Triangle | delta): After 200,000 sheets endurance, the image density fell and the image quality fell.
X: After the endurance of 200,000 sheets, the image density was remarkably lowered and the image quality was greatly lowered.

<Evaluation of toner scattering property>
The degree of toner contamination in the machine when the chart with an image area ratio of 5% is output continuously by 200,000 sheets using a tandem color image forming apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.) is visually observed according to the following criteria. Evaluation was made in 4 stages.
-Evaluation criteria-
A: There is no toner contamination in the image forming apparatus and it is in an excellent state.
◯: There is no toner contamination in the image forming apparatus and it is in a good state.
Δ: There is toner contamination in the image forming apparatus, but it is a practically usable level.
X: Toner contamination in the image forming apparatus is severe, and the actual use is impossible.

<Evaluation of dirt>
The chart below shows the degree of background contamination of the image background portion when 200,000 sheets of a 5% image area ratio chart is continuously output using a tandem type color image forming apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.). It was evaluated with.
-Evaluation criteria-
○: No background stains in the image background.
Δ: Soil is slightly generated in the background portion of the image.
X: Soil is generated in the background portion of the image.

<Comprehensive evaluation>
From the above evaluation results, the following criteria were evaluated as a comprehensive evaluation.
-Evaluation criteria-
A: Very good B: Good x: Bad

From the results shown in Table 1, after coating so that the film thickness h of the coating layer of the coated particles and the particle diameter of the fine particles Dv / h is 0.3 or less and the film thickness is 1.0 μm, with a weak stirring force Example in which mechanical treatment is applied to smooth the surface, and | T ₆ h (%) − T ₀ h (%) | is lower than 30%, and the dispersibility of the fine particles in the coating liquid is good. It can be seen that all of Nos. 1 to 4 have less peeling and scraping of the coating layer than Comparative Examples 1 to 4 and are good against toner scattering properties and background stains, and a high image density can be obtained.

All the carriers in Examples 1 to 4 satisfy the constituent requirements of the present invention, and the evaluation results are also good. In contrast, the carrier of Comparative Example 1 is smoothed in the second step because the particle diameter of the fine particles is larger than the film thickness h of the coating layer of the coated particles and the film thickness is 1.0 μm or less. It has been found that the coating layer peels off before the toner advances, the film strength decreases, and accordingly, the toner scattering property and the background stain are also deteriorated. Comparative Example 2 is a case where the second step of Example 2 is not applied, but the coating layer is subjected to strong stress before the coating layer is smoothed, and the coating layer is peeled off. The result was worse. In Comparative Example 3, | T ₆ h (%) − T ₀ h (%) | is higher than 30%, and the dispersibility of the fine particles in the coating layer is not good. It was not sufficient, and the surface condition of the clothing layer was difficult to be uniform. Further, Comparative Example 4 is an example in which smoothing was attempted using a stirrer having a strong stirring force as the second step, but the shear and impact due to stirring became excessive, causing significant peeling of the coating layer, and thereafter Even in the developer evaluation, the actual use was impossible.

The carrier of the present invention is suitably used for the developer of the present invention because it prevents the coating layer from being scraped and peeled off due to stress caused by agitation over a long period of time, and has an excellent charge imparting ability to the toner.
The developer of the present invention includes the carrier of the present invention and a toner. By using the developer, it is possible to form an image with a high image density without toner scattering and background contamination.
In the image forming method of the present invention, the mechanical strength is high, there is no scattering of toner and background stains, a high-quality image with high image density and high sharpness can be obtained, and the image forming method is suitably used for various electrophotographic image forming apparatuses. .

FIG. 1 is a schematic diagram showing a measuring instrument used for measuring the volume resistance of a carrier. FIG. 2 is a schematic configuration diagram showing an example of a process cartridge used in the present invention. FIG. 3 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus. FIG. 4 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus. FIG. 5 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by an image forming apparatus (tandem color image forming apparatus). 6 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.

Explanation of symbols

1 Electrode 2 Electrode 3 Cell 4 Carrier 10 Electrostatic latent image carrier (photosensitive drum)
10K Electrostatic latent image carrier for black 10Y Electrostatic latent image carrier for yellow 10M Electrostatic latent image carrier for magenta 10C Electrostatic latent image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device DESCRIPTION OF SYMBOLS 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling body 34 Second Traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Development roller La 44Y Development roller 44M Development roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching Claw 56 Discharge Roller 57 Discharge Tray 58 Corona Charger 60 Cleaning Device 61 Developer 62 Transfer Charger 63 Photoconductor Cleaning Device 64 Charger 70 Charger Lamp 80 Transfer Roller 90 Cleaning Device 95 Transfer Paper 100 Image Forming Device 101 Electrostatic Latent image carrier (photoconductor)
DESCRIPTION OF SYMBOLS 102 Charging means 103 Exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 110 Carrier processing tank 112 Raw material recovery tank 113 Carbon dioxide cylinder 114 Stirrer 115 Stirrer 116 Entrainer tank 117 Cooling jacket 118 Temperature control jacket 120 Tandem developer 121 Heating roller 122 Fixing roller 123 Fixing belt 124 Pressure roller 125 Heating source 126 Cleaning roller 127 Temperature sensor 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copier Main Body 160 Charging Device 200 Paper Feed Table 300 Scanner 400 Automatic Document Feeder (ADF)

Claims (11)

An electrophotographic toner carrier having a volume resistance of 10 ¹¹ to 10 ¹⁵ Ω · cm, wherein the surface of the core material is coated with a coating layer containing at least a binder resin and fine particles.
A coating liquid containing the binder resin precursor, fine particles having a volume average particle diameter Dv in terms of a sphere diameter, and a solvent is applied to the surface of the core material, and the relationship of the following formula (1) is satisfied. A first step of forming coated particles having a coating layer having an average film thickness h;
Dv / h ≦ 0.3 (1)
The coated particles are produced by a production method including a second step of stirring and surface-treating with a stirring device having no stirring blade ,
The fine particles are metal oxide fine particles,
The binder for an electrophotographic toner, wherein the binder resin precursor includes an amino resin, an acrylic resin having a hydroxyl value of 30 mgKOH / g or more that can be crosslinked with the amino resin, and a silicone resin. .   The electrophotographic toner according to claim 1, wherein an average film thickness h of the coating layer of the coating particles is 1 μm or more, and a mass ratio of the coating particles to a carrier of the coating layer is 5 mass% or more. Career. 3. The carrier for electrophotographic toner according to claim 1 , wherein the amino resin is guanamine . The coating layer, electrophotographic toner carrier according to any one of claims 1 to 3, characterized in that it contains an aminosilane coupling agent. Wherein the metal oxide is alumina or electrophotographic toner carrier according to any one of claims 1 to 4, characterized in that titanium oxide. The electrophotographic toner of the carrier according to any one of claims 1 to 5, wherein the fine particles are conductive treated conductive fine particles surface. The toner carrier for electrophotography according to any one of claims 1 to 6 , wherein the volume average particle diameter is 20 to 65 µm. A method for producing a carrier for an electrophotographic toner having a volume resistance of 10 ¹¹ to 10 ¹⁵ Ω · cm, wherein the surface of a core material is coated with a coating layer containing at least a binder resin and fine particles.
A first step of coating the core material surface with a coating liquid containing the binder resin precursor, fine particles, and a solvent to form coated particles;
A second step of surface-treating the coated particles by stirring with a stirring device having no stirring blade;
The fine particles are metal oxide fine particles,
The precursor of the binder resin includes an amino resin, an acrylic resin having a hydroxyl value of 30 mgKOH / g or more, and a silicone resin, which can crosslink with the amino resin,
The average film thickness h of the coating layer of the coated particles coated with the coating liquid in the first step satisfies the relationship of the following formula (1) with the volume average particle diameter Dv in terms of the spherical diameter of the fine particles. A method for producing a carrier for an electrophotographic toner, comprising:
Dv / h ≦ 0.3 (1) The method for producing a carrier for an electrophotographic toner according to claim 8 , wherein the coating liquid in the first step satisfies the condition of the following formula (2).
| T ₆ h (%) − T ₀ h (%) | ≦ 30 (%)
... Formula (2)
However, in the above formula _{(2), T 0 h (} %) is to display the transmittance of light having a wavelength of 550nm in immediately after preparing the coating solution, _T 6 h (%) is, immediately after preparing the coating solution Represents the transmittance of light having a wavelength of 550 nm after standing for 6 hours. Developer for electrophotography, wherein the electrophotographic toner of the carrier according, to be composed of a toner for electrophotography to any one of claims 1 to 7. An electrostatic latent image forming step for forming an electrostatic latent image on the electrostatic latent image carrier, and development for developing the electrostatic latent image with the developer according to claim 10 to form a visible image. An image forming method comprising: a step, a transfer step of transferring the visible image onto a recording medium to form a transfer image, and a fixing step of fixing the transfer image transferred onto the recording medium.

Images