JP2010160325A - Toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, process cartridge and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development, an electrostatic charge image developer, a toner cartridge, a process cartridge and an image forming apparatus that suppresses generation of hot offsets that becomes a problem, when ensuring a fixable region. <P>SOLUTION: The toner for electrostatic charge image development contains (A) a binder resin, (B) a release agent and (C) an external additive having a primary particle diameter in the range from 50 nm to 500 nm, wherein the external additive (C) contains at least (C-1) fluorocarbon resin particles or (C-2) particles surface treated with a treating agent containing fluorine atoms, and the melt viscosity of the toner by a Koka flow tester at 90°C is in the range of1.0×10<SP>2</SP>to 1.0×10<SP>5</SP>Pa s. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner, an electrostatic charge image developer, a toner cartridge, a process cartridge, and an image forming apparatus.

  In electrophotography, generally, a latent image is electrically formed on the surface of a photoconductor (image carrier) using a photoconductive substance by various means, and the formed latent image is replaced with toner. After developing with a developer containing the developer, a developed image is formed, and then the developed image is transferred to a surface of a transfer medium such as paper via an intermediate transfer body as necessary, and then heated, pressurized, and heated and pressed. An image is formed through a plurality of steps of fixing by, for example. In addition, the toner remaining on the surface of the photoreceptor is cleaned by various methods as necessary, and is used again for development.

  Silica treated with a quaternary ammonium salt is used as an external additive of toner for the purpose of obtaining excellent image quality without occurrence of image defects, with excellent fluidity, casing resistance, chargeability and environmental stability of the toner. Has been proposed (see, for example, Patent Documents 1 and 2).

In addition, for the purpose of maintaining a good image even for long-term printing at a low printing rate and obtaining excellent fixability, it has been proposed to use fluororesin fine powder as an external additive for toner (for example, Patent Documents). 3).
Japanese Patent Laid-Open No. 5-6032 Japanese Patent Laid-Open No. 5-100491 JP 2008-139851 A

  An object of the present invention is to provide a toner for developing an electrostatic charge image in which the occurrence of hot offset is suppressed as compared with the case without this configuration.

The above problem is solved by the following means. That is,
The invention according to claim 1
(A) a binder resin, (B) a release agent, and (C) an external additive having a primary particle size in the range of 50 nm to 500 nm, wherein the (C) external additive is at least (C-1 1) a fluororesin particle, or (C-2) a particle surface-treated with a fluorine atom-containing treatment agent, and the elevated flow tester melt viscosity at 90 ° C. of the toner is 1.0 × 10 ² Pa · s or more. An electrostatic charge developing toner having a range of 0 × 10 ⁵ Pa · s or less.

The invention according to claim 2
The surface coverage of the toner with the (C-1) fluororesin particles or (C-2) particles treated with a fluorine atom-containing treatment agent is in the range of 0.5% to 2.5%. Item 2. The electrostatic charge developing toner according to Item 1.

The invention according to claim 3
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1.

The invention according to claim 4
A toner cartridge in which the toner for developing an electrostatic charge image according to claim 1 is contained.

The invention according to claim 5
A process cartridge comprising at least a developer holder and containing the electrostatic charge image developer according to claim 3.

The invention according to claim 6
An image carrier,
Developing means for developing the electrostatic image formed on the image carrier as a toner image with a developer;
Transfer means for transferring a toner image formed on the image carrier onto the transfer target;
Fixing means for fixing the toner image transferred onto the transfer material;
Have
An image forming apparatus, wherein the developer is the electrostatic charge image developer according to claim 3.

According to the first aspect of the present invention, the occurrence of hot offset is suppressed compared to the case where this configuration is not provided.
According to the second aspect of the present invention, the occurrence of hot offset is suppressed as compared with the case where the surface coverage by the specific external additive is not taken into consideration.
According to the third aspect of the present invention, an image in which the occurrence of hot offset is suppressed can be obtained compared to the case where the present configuration is not provided.
According to the fourth aspect of the present invention, an image in which the occurrence of hot offset is suppressed can be obtained as compared with the case where this configuration is not provided.
According to the fifth aspect of the present invention, an image in which the occurrence of hot offset is suppressed can be obtained as compared with the case where this configuration is not provided.
According to the sixth aspect of the present invention, an image in which the occurrence of hot offset is suppressed can be obtained as compared with the case where this configuration is not provided.

Hereinafter, embodiments of the present invention will be described in detail.
<Toner for electrostatic image development>
The electrostatic image developing toner according to the embodiment (hereinafter sometimes referred to as “toner”) includes at least (A) a binder resin, (B) a release agent, and (C) in a range of 50 nm to 500 nm. Including an external additive having a primary particle diameter (hereinafter sometimes referred to as “specific external additive”), and (C-1) fluororesin particles as the external additive (C-1) or (C-2) In addition, the toner has an elevated flow tester melt viscosity at 90 ° C. of 1.0 × 10 ² Pa · s or more and 1.0 × 10 ⁵ Pa · s or less. It is characterized by that.

The toner according to the embodiment has the above-described configuration, so that the melt viscosity is in the above range, and at least (C-1) fluororesin particles or (C-2) fluorine atoms are contained as an external additive to the toner particles. Generation of hot offset is suppressed by including particles surface-treated with a treatment agent. In particular, hot offset at low temperature fixing at 200 ° C. or lower is suppressed.
Hot offset is a phenomenon in which toner is fused to a fixing member in a molten state. After being fused to a fixing member that is usually in the form of a roll and making one round of the roll, the fused toner adheres to the paper or the like and is recognized.

  Here, conventionally, in order to improve image strength and paper rubbing stains, a technique for causing the fluororesin fine powder to exist on the surface of the printing surface has been proposed. However, it uses a fluororesin fine powder having a relatively large average particle diameter of about 500 nm to 1 μm in order to impart slipperiness, and the abundance cannot be increased compared to the toner that forms an image. The occurrence of hot offset cannot be suppressed.

In a fixing mechanism generally referred to as “oilless fixing”, the wax contained in the toner melts during fixing and oozes out between the fixing member and the image surface, thereby suppressing the breakage of the toner layer. However, when a tertiary color typified by process black is output at a high density, the image surface temperature tends to cause sufficient melting of the toner, and the toner viscosity at the time of fixing tends to increase.
Furthermore, the fluororesin fine powder has a low affinity with the wax. Therefore, when the viscosity of the toner is high, the supply of the wax to the fixing member is suppressed, so that hot offset is likely to occur.

  In recent years, there are high market demands for energy saving and high speed, and development of low-temperature fixing toner is being promoted. However, in high-speed machines, there is a wide range of heat applied to the toner during fixing, so it is necessary to take a wide fixing temperature range, and it is necessary to reduce the melt viscosity together with the lower melting temperature of the toner. This lowers the problem that hot offset is likely to occur.

On the other hand, in this embodiment, it discovered that generation | occurrence | production of a hot offset was suppressed based on having discovered the following knowledge.
1) The external additive having a primary particle size in the range of 50 nm or more and 500 nm or less is included in the toner, 2) (C-1) fluorine resin particles or (C-2) fluorine atom containing as this external additive 3) The elevated flow tester melt viscosity at 90 ° C. of the toner is in the range of 1.0 × 10 ² Pa · s to 1.0 × 10 ⁵ Pa · s. point.

  That is, fluororesin particles having a primary particle diameter in the range of 50 nm or more and 500 nm or less, or particles surface-treated with a fluorine atom-containing treatment agent are included as external additives, and the melt viscosity is within the range of this embodiment. By using the toner, the fixing area is expanded and the occurrence of hot offset is suppressed. This makes it easy to achieve energy saving, high speed, versatility of paper, and colorization by fixing especially in a low temperature region.

  Hereinafter, a specific configuration of the toner will be described in detail.

(Toner particles)
The toner particles include (A) a binder resin, (B) a release agent, and (C) a specific external additive, and further include other additives as necessary. The structure of the toner particles is not particularly limited, and may be a single layer structure. For example, a core layer including a binder resin and a colorant or a release agent, and a core layer including the binder resin are covered. A so-called core-shell structure having a shell layer may be employed.

(A) Binder Resin As the binder resin, various resins such as an amorphous polyester resin and a crystalline polyester resin may be used as well as an amorphous resin typified by a vinyl resin.

  Examples of vinyl binder resins include vinyl styrenes such as styrene and parachlorostyrene, vinyl naphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. Esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-methyl chloroacrylate, methacryl Methylene aliphatic carboxylic acid esters such as methyl acid, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, for example vinyl such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether Monomers such as N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone and the like, monomers having an N-containing polar group, methacrylic acid, acrylic acid, cinnamic acid, Homopolymers and copolymers of vinyl monomers such as vinyl carboxylic acids such as carboxyethyl acrylate and / or various polyesters, and various waxes are also used.

  In the case of vinyl monomers, emulsion polymerization can be performed using an ionic surfactant or the like to prepare a resin particle dispersion. In the case of other resins, the resin is oily and has a relatively high solubility in water. If it is soluble in a small solvent, dissolve the resin in those solvents, disperse it in water with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte, and then heat or reduce the solvent. Is evaporated to obtain a resin particle dispersion.

As the crystalline resin, a crystalline polyester resin is preferable, and an aliphatic crystalline polyester resin having an appropriate melting temperature is more preferable. Hereinafter, a crystalline polyester resin will be described as an example.
Some crystalline aliphatic polyesters, such as polycaprolactone, progress through ring-opening polymerization, but others are synthesized from an acid (dicarboxylic acid) component and an alcohol (diol) component. In the present embodiment, the “acid-derived constituent component” refers to a constituent portion that was an acid component before the synthesis of the polyester resin, and the “alcohol-derived constituent component” refers to an alcohol component before the synthesis of the polyester resin. Refers to the component that was present.

When the polyester resin is not crystalline, that is, non-crystalline, it may be difficult to maintain toner blocking resistance and image storage stability while ensuring good low-temperature fixability.
In the present embodiment, “crystalline polyester resin” means that the half-value width of the endothermic peak observed in differential scanning calorimetry (DSC) is 6 ° C. or less, and other polyester resins are It means an amorphous polyester resin.
In the present embodiment, the term “polyester resin” refers to a polymer in which other components are copolymerized with a polyester main chain in addition to a resin having a pure polyester structure. A polymer is also meant.

-Acid-derived constituent component The acid-derived constituent component is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear carboxylic acid.
For example, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid Acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof And acid anhydrides, but are not limited thereto.

As the acid-derived constituent component, in addition to the above-mentioned aliphatic dicarboxylic acid-derived constituent component, constituent components such as a dicarboxylic acid-derived constituent component having a double bond and a dicarboxylic acid-derived constituent component having a sulfonic acid group are included. Is preferred.
The component derived from a dicarboxylic acid having a double bond is derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a double bond, in addition to a component derived from a dicarboxylic acid having a double bond. Components are also included. The dicarboxylic acid-derived constituent component having a sulfonic acid group is derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a sulfonic acid group, in addition to a constituent component derived from a dicarboxylic acid having a sulfonic acid group. Components are also included.

The dicarboxylic acid having a double bond is preferably used in order to prevent hot offset at the time of fixing since the entire resin can be crosslinked using the double bond. Examples of the dicarboxylic acid include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, fumaric acid, maleic acid and the like are preferable in terms of cost.
The dicarboxylic acid having a sulfonic acid group is effective in improving the dispersion of a coloring material such as a pigment.

  Further, when the toner base particles are prepared by emulsifying or suspending the entire resin in water, if there are sulfonic acid groups, they are emulsified or suspended without using a surfactant as described later. Examples of the dicarboxylic acid having a sulfone group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, 5-sulfoisophthalic acid sodium salt is preferable in terms of cost.

Content of acid-derived components other than aliphatic dicarboxylic acid-derived components (dicarboxylic acid-derived components having double bonds and / or dicarboxylic acid-derived components having sulfonic acid groups) in the acid-derived components Is preferably from 1 component mol% to 20 component mol%, more preferably from 2 component mol% to 10 component mol%.
When the content is less than 1 constituent mol%, pigment dispersion may not be good, the emulsified particle diameter may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, when it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the melting temperature is lowered, and the storage stability of the image may be deteriorated.

  In the present embodiment, “constituent mol%” refers to a percentage when each constituent component (acid-derived constituent component, alcohol-derived constituent component) in the polyester resin is 1 unit (mol).

-Alcohol-derived components-
The alcohol component is preferably an aliphatic dicarboxylic acid, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, 1,12-undecanediol, 1,13-tridecanediol, 1,14-tetradecanediol 1,18-octadecanediol, 1,20-eicosanediol, and the like, but are not limited thereto.

  When the alcohol-derived constituent component is an aliphatic diol-derived constituent component, the content of the aliphatic diol-derived constituent component is 80 constituent mol% or more, and other components are included as necessary. Furthermore, when the alcohol-derived constituent component is an aliphatic diol-derived constituent component, the content of the aliphatic diol-derived constituent component is preferably 90 constituent mol% or more.

When the content of the aliphatic diol-derived constituent component is less than 80 constituent mol%, the crystallinity of the polyester resin is lowered and the melting temperature is lowered, so that toner blocking resistance, image storage stability and low-temperature fixability are deteriorated. Resulting in.
Other components included as necessary include diol-derived components having double bonds and diol-derived components having sulfonic acid groups.
Examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol, and the like.
Examples of the diol having a sulfonic acid group include 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, and 2-sulfo-1,4-butanediol sodium. Examples include salts.

  When adding an alcohol-derived component other than these linear aliphatic diol-derived components, that is, when adding a diol-derived component having a double bond and / or a diol-derived component having a sulfonic acid group, The content of the diol-derived constituent component having a double bond and / or the diol-derived constituent component having a sulfonic acid group in the alcohol-derived constituent component is preferably from 1 constituent mol% to 20 constituent mol%, and preferably from 2 constituent mol% to 10 constituent mol%. It is more preferably less than mol%.

When the content of the alcohol-derived constituent component other than the aliphatic diol-derived constituent component is less than 1 constituent mol% with respect to the total alcohol-derived constituent component, the pigment dispersion is not good or the emulsion particle size is increased. In some cases, it is difficult to adjust the toner diameter by aggregation.
On the other hand, when it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the melting temperature is lowered, and the storage stability of the image may be deteriorated.

  The melting temperature of the binder resin of the toner is preferably 50 ° C. or higher and 120 ° C. or lower, and more preferably 60 ° C. or higher and 110 ° C. or lower. If the melting temperature is lower than 50 ° C., the storage stability of the toner and the storage stability of the toner image after fixing may become a problem. On the other hand, if the temperature is higher than 120 ° C., sufficient low-temperature fixing may not be obtained as compared with conventional toners.

  In the present embodiment, a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001) (hereinafter referred to as “DSC”) is used to measure the melting temperature of the crystalline resin at room temperature. It is determined as the melting peak temperature of the input compensated differential scanning calorimetry shown in JIS K-7121 when measurement is performed at a temperature rising rate of 10 ° C. per minute (for example, 25 ° C., the same applies hereinafter) to 150 ° C. The crystalline resin may show a plurality of melting peaks, but in this embodiment, the maximum peak is regarded as the melting temperature.

  The method for producing the polyester resin is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. For example, direct polycondensation, transesterification method, etc. Produced separately for different types. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

The polyester resin can be produced at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower, and the reaction system is reduced in pressure as necessary, and reacted while removing water and alcohol generated during condensation.
When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If there is a monomer with poor compatibility in the copolymerization reaction, the monomer with poor compatibility and the monomer and the acid or alcohol to be polycondensed may be condensed in advance before polycondensation with the main component. .

  Catalysts used in the production of the polyester resin include alkali metal compounds such as sodium and lithium, alkaline earth metal compounds such as magnesium and calcium, metal compounds such as zinc, manganese, antimony, titanium, tin, zirconium and germanium, Examples include phosphorous acid compounds, phosphoric acid compounds, and amine compounds. Specific examples include sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, and zinc stearate. , Zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributy Antimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenylphos Examples thereof include compounds such as phyto, tris (2,4-di-t-butylphenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, and triphenylamine.

  When a toner is prepared using an emulsion polymerization aggregation method described later, the binder resin is used as a resin particle dispersion containing resin particles obtained by emulsifying and dispersing the binder resin in an aqueous medium.

The average particle diameter of the resin particles is usually 1 μm or less, and preferably 0.01 μm or more and 1 μm or less. When the average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner may be broadened, or free particles may be generated, which may easily lead to a decrease in performance and reliability.
On the other hand, when the average particle size is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toners becomes good, and the variation in performance and reliability is advantageous. In addition, the said average particle diameter is measured, for example using a laser diffraction type particle size distribution measuring apparatus (the Horiba make, LA-700).

Examples of the dispersion medium in the resin particle dispersion include an aqueous medium and an organic solvent.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together. In the present embodiment, it is preferable to add and mix a surfactant in the aqueous medium. Although it does not specifically limit as surfactant, For example, anionic surfactants, such as sulfate ester type, sulfonate type, phosphate ester type, soap type; amine salt type, quaternary ammonium salt type, etc. Nonionic surfactants such as polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based, and the like.
Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together.

Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like. Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. Among these, ionic surfactants such as anionic surfactants and cationic surfactants are preferable.
Examples of the organic solvent include ethyl acetate and toluene, which are selected according to the binder resin.

  When the resin particles are homopolymers or copolymers (vinyl resins) of vinyl monomers such as esters having the vinyl group, the vinyl nitriles, the vinyl ethers, the vinyl ketones, By subjecting the vinyl monomer to emulsion polymerization or seed polymerization in an ionic surfactant, resin particles made of a homopolymer or copolymer (vinyl resin) of the vinyl monomer are converted into an ionic interface. A dispersion is prepared by dispersing in an active agent.

  When the resin particle is a resin other than the homopolymer or copolymer of the vinyl monomer, if the resin is dissolved in an oily solvent having low solubility in water, the resin is added to the resin. Dissolving in an oily solvent, this solution is dispersed in water together with an ionic surfactant and polymer electrolyte using a disperser such as a homogenizer, and then the oily solvent is evaporated by heating or decompression, A dispersion is prepared by dispersing resin particles made of resin other than vinyl resin in an ionic surfactant.

  On the other hand, when the resin particles are a crystalline polyester and an amorphous polyester resin, some or all of the functional groups that have self-water dispersibility and can be hydrophilic, containing functional groups that can become anionic by neutralization Is neutralized with a base to form a stable aqueous dispersion under the action of an aqueous medium. In the crystalline polyester and the amorphous polyester resin, the functional group that can become a hydrophilic group by neutralization is an acidic group such as a carboxyl group or a sulfone group, and examples of the neutralizing agent include sodium hydroxide, potassium hydroxide, Examples thereof include inorganic bases such as lithium hydroxide, calcium hydroxide, sodium carbonate and ammonia, and organic bases such as diethylamine, triethylamine and isopropylamine.

  In addition, when using a polyester resin that does not disperse in water as a binder resin, that is, does not have self-water dispersibility, the resin solution and / or an aqueous medium mixed therewith can be used in the same manner as the release agent described later. It is easy to disperse with polymer electrolytes such as ionic surfactants, polymer acids, polymer bases, etc., heat above the melting temperature and apply a strong shearing force, or treat with a pressure discharge type disperser To 1 μm or less. When this ionic surfactant or polymer electrolyte is used, the concentration in the aqueous medium is suitably about 0.5% by mass or more and 5% by mass or less.

  The volume average particle diameter of the resin particles in the resin particle dispersion thus obtained is measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

<(B) Release agent>
Next, the release agent will be described.

  One or more release agents are used in the toner of the present embodiment, and specific examples thereof include, for example, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene, silicones that exhibit a softening point by heating, oleic acid amide, Fatty acid amides such as erucic acid amide, ricinoleic acid amide, stearic acid amide, plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, montan wax , Ozokerite, ceresin, paraffin wax, microcrystalline wax, microcrystalline wax, Fischer-Tropsch wax and other mineral-based and petroleum-based waxes, and modified products thereof.

  These mold release agents are dispersed in water together with ionic surfactants, polymer electrolytes such as polymer acids and polymer bases, heated above the melting temperature, and have a strong shearing ability and pressure discharge. A release agent dispersion containing release agent particles having a volume average particle size of 1 μm or less is prepared by dispersing in a particle form using a mold dispersing machine (Gorin homogenizer, manufactured by Gorin).

It is desirable to add these release agents in the range of 5% by mass or more and 25% by mass or less with respect to the total weight of the toner constituting solids, in order to ensure the releasability of the fixed image in the oilless fixing system.
The particle size of the obtained release agent particle dispersion was measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.). In addition, when using a release agent, after the resin particles, colorant particles and release agent particles are agglomerated, it is possible to add a resin particle dispersion to adhere the resin particles to the surface of the agglomerated particles. It is desirable from the viewpoint of securing the property.

<(C) External additive having a primary particle diameter in the range of 50 nm to 500 nm>
The toner according to the exemplary embodiment includes (C) an external additive having a primary particle diameter in the range of 50 nm to 500 nm, and includes (C-1) fluororesin particles or (C-2) a fluorine atom-containing treatment agent. And at least one kind of particles surface-treated with.

<(C-1) Fluororesin Particle>
The fluororesin used for the fluororesin particles is polytetrafluoroethylene, a copolymer of tetrafluoroethylene and perfluoroalkoxyethylene, polyvinylidene fluoride, polyvinyl fluoride, or polychlorotrifluoroethylene. Preferred fluororesins are Polytetrafluoroethylene.

<(C-2) Particles Surface-treated with Fluorine Atom-Containing Treatment Agent>
The specific external additive used in the present embodiment may be particles surface-treated with a fluorine atom-containing treatment agent.
The fluorine atom-containing treatment agent is a particle obtained by surface-treating inorganic particles or organic particles described later with a fluorine atom-containing coupling agent.

Typical specific examples of the fluorine atom-containing coupling agent are shown in (1) to (10) below, but are not limited to these compounds.
_{(1) CF 3 CH 2 CH} 2 Si (OCH 3) 3
(2) CF ₃ CH ₂ SiCl ₃
(3) CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCl ₃
(4) CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(5) CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃
(6) CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(7) CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH ₃ Cl ₂
(8) CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
(9) (CH ₃ ) ₃ SiOSO ₂ CF ₃
(10) CF ₃ CON (CH ₃ ) SiCH ₃

  The treatment amount of the fluorine atom-containing treatment agent varies depending on the kind of inorganic particles or organic particles, and cannot be specified unconditionally. The range is preferably 0.1 parts by mass or less and more preferably 0.1 parts by mass or more and 30 parts by mass or less.

Examples of the inorganic _{particles, SiO 2, TiO 2, Al} 2 O 3, CuO, ZnO, SnO 2, CeO 2, Fe 2 O 3, MgO, BaO, CaO, K 2 O, Na 2 O, ZrO 2, CaO _{· SiO 2, K 2 O ·} (TiO 2) n, Al 2 O 3 · 2SiO 2, CaCO 3, MgCO 3, BaSO 4, inorganic oxide particles of MgSO ₄ and the like.

Organic particles include polyolefin resins such as polyethylene, polypropylene; polyvinyl and polyvinylidene resins such as polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether and Examples include polyvinyl ketone; vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; straight silicone resin composed of organosiloxane bond or a modified product thereof; polyester; A cured resin particle can be obtained by simultaneously using a crosslinking component such as divinylbenzene together with the resin formation.
Examples of thermosetting resin particles include phenol resin; amino resin such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin; epoxy resin.
Of these particles, preferred are SiO ₂ , TiO ₂ , and Al ₂ O ₃ .

  The particles that are surface-treated with the fluorine atom-containing coupling agent may have been previously hydrophobized. Examples of the hydrophobizing agent used for the hydrophobizing treatment of particles include alkylchlorosilanes such as methyltrichlorosilane, octyltrichlorosilane, and dimethyldichlorosilane, alkylmethoxysilanes such as dimethyldimethoxysilane and octyltrimethoxysilane, and hexamethyl. Examples include disilazane and silylating agents, silicone oil, titanate-based, aluminum-based coupling agents, and the like.

  As a surface treatment method of the particles with the fluorine atom-containing coupling agent, the fluorine atom-containing coupling agent is dissolved in an appropriate solvent such as alcohol or other organic solvent or water, and added to the particles therein, After dispersion, it is common to remove the solvent and cure as necessary. Specifically, it is desirable to carry out using a device such as a kneader, spray dryer, thermal processor or fluidized bed. .

The primary particle diameter (volume average particle diameter) of the specific external additive is desirably 50 nm or more and 500 nm or less, more preferably 50 nm or more and 300 nm or less, and further preferably 50 nm or more and 200 nm or less.
Within this range, the adhesion to the base toner is good.
Two or more different primary particle diameters may be used.

  The primary particle diameter (volume average particle diameter) of the specific external additive was measured and calculated as follows. First, the volume and number of individual external additive particles with respect to the particle size range (channel) obtained by dividing the particle size distribution of the external additive measured using Coulter Multisizer II (manufactured by Beckman-Coulter) as a measuring instrument. The cumulative distribution was drawn from the small diameter side, and the particle size at 50% cumulative was taken as the primary particle size (volume average particle size).

In this embodiment, the adhesion state of the specific external additive to the toner particle surface may be merely mechanical adhesion or may be loosely fixed to the surface. An example of the fixing method is a manufacturing method using a Henschel mixer.
Further, the entire surface of the toner particles may be coated or a part thereof may be coated. The specific external additive may be partially agglomerated and coated, but is preferably coated in a single-layer particle state. In that case, the surface coverage of the toner particle surface by the specific external additive is preferably 0.5% or more and 2.5% or less. Furthermore, 1.0% or more and 2.0% or less are preferable. If the surface coverage is less than this range, sufficient effects of the specific external additive cannot be expected, and if it exceeds this range, a problem occurs in hot offset.

<External additives other than specific external additives>
In the present embodiment, external additives other than the specific external additive may be included as necessary. The external additive other than the specific external additive is not particularly limited. For example, SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO _{, BaO, CaO, K 2 O} , Na 2 O, ZrO 2, CaO · SiO 2, K 2 O · (TiO 2) n, Al 2 O 3 · 2SiO 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4 Inorganic oxide particles such as

  Of the inorganic oxide particles, silica particles and titania particles are particularly desirable. In addition, it is desirable that the surface of the inorganic oxide particles is previously hydrophobized. This hydrophobization treatment improves the powder fluidity of the toner, and is more effective for improving the environmental dependency of charging and carrier contamination.

Further, as external additives other than the specific external additives, polyolefin resins such as polyethylene, polypropylene; polyvinyl and polyvinylidene resins such as polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, Examples thereof include polyvinyl carbazole, polyvinyl ether and polyvinyl ketone; vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; straight silicone resin composed of an organosiloxane bond or a modified product thereof; polyester; A cured resin particle can be obtained by simultaneously using a crosslinking component such as divinylbenzene together with the resin formation.
Examples of thermosetting resins include phenol resins; amino resins such as urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins; epoxy resins, and the like.

The toner for developing an electrostatic charge image of the exemplary embodiment is an image forming apparatus described later, that is, a surface resistivity and a volume resistivity of 10 ⁹ Ω / cm ² to 10 ¹³ Ω / cm ² and 10 ⁷ Ω · cm to 10 ^13. It is preferably used for an image forming apparatus having an intermediate transfer member of Ω · cm. By being used in such an apparatus, the toner effect of the present invention is exhibited better.

  The toner according to the exemplary embodiment may include a colorant, an additive (internal additive), and the like.

-Colorant-
As the colorant, a known colorant may be used. For example, the following colorant is used.
Examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.
Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, hansa yellow, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow NCG. .

  Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK.

  Red pigments include Bengala, Cadmium Red, Red Plum, Mercury Sulfide, Watch Young Red, Permanent Red 4R, Risor Red, Brilliantamine 3B, Brilliantamine 6B, Daypon Oil Red, Pyrazolone Red, Rhodamine B Lake, Lake Red C Naphthol red such as Rose Bengal, Eoxin Red, Alizarin Lake, Pigment Red 146, 147, 184, 185, 155, 238, and 269.

  Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, indanthrene blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Such as rate.

Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.
Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.
Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

  These colorants are used alone or in combination. In the case of producing a toner by using an emulsion polymerization aggregation method described later, these colorants are used as a colorant dispersion liquid in which colorant particles are dispersed. For example, a dispersion of colorant particles is prepared using a media type dispersing machine such as a rotary shearing homogenizer, a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersing machine, or the like. In addition, these colorants may be dispersed in an aqueous system by a homogenizer using a polar surfactant.

The colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner.
The colorant is added in the range of 4% by mass or more and 15% by mass or less based on the total weight of the toner constituent solids. When using a magnetic material as the black colorant, it is added in an amount of 12% by mass to 240% by mass, unlike other colorants.
The blending amount of the colorant is a necessary amount for securing the color developability at the time of fixing. Further, the central diameter (median diameter) of the colorant particles in the toner is set to 100 nm or more and 330 nm or less to ensure OHP transparency and color development. The center diameter of the colorant particles is measured by, for example, a laser diffraction particle size distribution measuring device (LA-700, manufactured by Horiba, Ltd.).

-Additives-
For the toner particles, a known internal additive may be used as necessary.
For example, when used as a magnetic toner, magnetic powder may be included. Specifically, a material that is magnetized in a magnetic field is used, but a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite is used.
When obtaining toner in the aqueous phase, it is necessary to pay attention to the water phase transferability of the magnetic material, and it is preferable to modify the surface of the magnetic material in advance, for example, to perform a hydrophobic treatment or the like.

Also, magnetic materials such as ferrite, magnetite, reduced iron, cobalt, nickel, manganese and other metals, alloys, and compounds containing these metals are used as internal additives, and quaternary ammonium salt compounds, nigrosine-based as charge control agents. Various commonly used charge control agents such as dyes composed of complexes of compounds, aluminum, iron, chromium, and triphenylmethane pigments may be used. However, when the toner is prepared by using the emulsion polymerization aggregation method, a material that is difficult to dissolve in water is preferable from the viewpoint of controlling ionic strength that affects aggregation and temporary stability and reducing wastewater contamination.
Further, a known lubricant or the like may be added to improve the cleaning characteristics. It is preferable to use a fatty acid metal salt such as resin particles or zinc stearate in combination.

-Melt viscosity characteristics of toner-
The melt viscosity of the toner in this embodiment is in the range of 1.0 × 10 ² Pa · s to 1.0 × 10 ⁵ Pa · s, as measured by an elevated flow tester at 90 ° C. The range of 0.0 × 10 ² Pa · s to 1.0 × 10 ⁴ Pa · s is preferable, and the range of 1.0 × 10 ² Pa · s to 8.0 × 10 ³ Pa · s is more preferable.
If the melt viscosity at 90 ° C. is within this range, the occurrence of hot offset is suppressed without inhibiting the seepage of the wax.

In the present embodiment, “melt viscosity” means an elevated flow tester melt viscosity obtained by the following measurement method.
Elevated flow tester measurement conditions: An elevated flow tester (CFT-500 manufactured by Shimadzu Corporation) is used to measure the melt viscosity of the toner, and 1.2 g of a sample is formed into a cylindrical shape with a sampler and measured under the following conditions.
Die (nozzle) diameter 0.5mm, thickness 1.0mm
Extrusion load 10kgf / cm ²
Plunger cross section 1.0cm ²
Initial setting temperature 50 ℃
Preheat time 300sec
The temperature was raised at a constant rate of 2 ° C./min.
The outflow amount at each temperature is measured in increments of 2 ° C., and the respective viscosities (Pa · s) at 90 ° C. and 180 ° C. are obtained.

  The toner having melt viscosity according to an embodiment of the present invention includes (1) a chemical structure of the binder resin, (2) a content of the binder resin contained in the toner, and (3) a release agent contained in the toner. It can be obtained by the amount, (4) the melting temperature of the release agent, etc., but greatly changes other properties required for the toner. By adding the specific external additive of the present embodiment, the melt viscosity of the toner is set within the range of the melt viscosity of the present embodiment, which is a preferable mode.

-Toner particle characteristics-
The volume average particle size of the toner particles is preferably in the range of 3 μm to 9 μm, and more preferably in the range of 3 μm to 8 μm. When the volume average particle diameter of the toner particles exceeds 9 μm, the ratio of coarse particles increases, and the reproducibility and gradation of fine lines and fine dots of the image obtained through the fixing process are lowered. On the other hand, if the volume average particle size of the toner particles is less than 3 μm, the powder fluidity, developability, or transferability of the toner deteriorates, and the cleaning properties of the toner remaining on the surface of the image carrier deteriorate. Various problems occur in other processes due to the deterioration of characteristics.

  As the particle size distribution index of the toner particles, the volume average particle size distribution index GSDv is preferably 1.30 or less, and the ratio GSDv / GSDp to the number average particle size distribution index GSDp is 0.95 or more. More preferred. When the volume distribution index GSDv exceeds 1.30, the resolution decreases, and when the ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp is less than 0.95, a decrease in chargeability occurs. At the same time, it may scatter and cause image defects such as fog.

The volume average particle size and the particle size distribution index were measured and calculated as follows. First, with respect to the divided particle size range (channel) of the toner particle size distribution measured using a Coulter Multisizer II (manufactured by Beckman-Coulter) as a measuring device, the volume and number of individual toner particles from the small diameter side. A cumulative distribution is drawn, and the particle size at 16% cumulative is defined as volume average particle size D16v and number average particle size D16p. The particle size at 50% cumulative is defined as volume average particle size D50v (this value is defined as volume average particle size). Defined as D50p). The particle diameters with a cumulative 84% are defined as volume average particle diameters D84v and D84p. Using these, the volume average particle size distribution index GSDv is defined as (D84v / D16v) ^1/2 and the number average particle size distribution index GSDp is defined as (D84p / D16p) ^1/2 .

Furthermore, the shape factor SF1 of the toner particles is preferably in the range of 110 to 140.
Here, the shape factor SF1 is obtained by the following equation.
SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, ML represents the absolute maximum length of the toner particles, and A represents the projected area of the toner particles.

  The SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and is calculated as follows, for example. That is, the optical microscope image of the toner spread on the surface of the slide glass is taken into a Luzex image analyzer through a video camera, the maximum length and the projected area of 100 toner particles are obtained, and the average value is obtained by the above formula. Is obtained.

(Toner production method)-
The toner according to the exemplary embodiment may be produced by either a kneading pulverization method or a wet method, and is not particularly limited. For example, in the kneading and pulverizing method, first, the toner components are mixed, and then the above materials are melt-kneaded using a kneader, an extruder, or the like. Thereafter, the melt-kneaded product is coarsely pulverized and then finely pulverized by a jet mill or the like, and toner particles having a target particle diameter are obtained by an air classifier. Further, an external additive (including a specific external additive) is externally added to complete the final toner.

  In addition, as a wet manufacturing method, in particular, after adding one or more kinds of aggregating agent to a raw material dispersion containing one or more kinds of raw material particles, the one or more kinds of raw material particles are aggregated to form aggregated particles. A production method (so-called emulsion polymerization aggregation method) including an agglomerated particle forming step and a fusing step of fusing the agglomerated particles by heating is suitably employed.

  Here, as raw material particles in the wet manufacturing method, at least resin particles (constituting a binder resin) are used, and colorant particles, release agent particles, and the like are used as necessary. When a polyester resin is used as the binder resin for the toner, a resin particle containing a polyester resin is used. Therefore, when two or more types of raw material particles are used, a raw material dispersion is prepared by mixing a dispersion containing each type of raw material particles.

  Further, when preparing a toner having a so-called core-shell structure, for example, a resin particle dispersion in which resin particles are dispersed and one or more kinds of aggregating agents are added to the raw material dispersion after the aggregate particle formation step. Then, after performing the coating layer forming step of forming the coating layer by attaching the resin particles to the surface of the aggregated particles, the fusion step is performed.

Here, in the production of the toner, when the process involving the aggregation of the raw material particles is performed once (that is, when the aggregated particle forming process is performed), the aggregation including the Al element as the aggregating agent used in the aggregated particle forming process is performed. An agent is used.
Further, in the production of toner, when the process involving aggregation of raw material particles is performed twice or more (for example, when the aggregated particle forming process and the coating layer forming process are performed), the aggregation used in at least one of the processes As the agent, an aggregating agent containing Al element is used.

The resin particles used in the aggregated particle forming step and the coating layer forming step are preferably resin particles containing a polyester resin. Thereby, a toner containing a polyester resin is produced.
Next, each step such as the aggregated particle forming step will be described in more detail.

-Aggregated particle formation process-
In the agglomerated particle forming step, in addition to the resin particle dispersion, a colorant dispersion is usually added, and other dispersion added as necessary (for example, a release agent dispersion in which a release agent is dispersed) Etc.) is further added to the raw material dispersion obtained by mixing, and heated to form aggregated particles in which these particles are aggregated. When the resin particles are a crystalline resin such as crystalline polyester, the aggregated particles are obtained by aggregating these particles by heating at a temperature equal to or lower than the melting temperature of the crystalline resin. Form.

Aggregated particles are formed by adding a flocculant at room temperature under stirring with a rotary shearing homogenizer to make the pH of the raw material dispersion acidic.
The aggregating agent used in the aggregated particle forming step is preferably a surfactant having a polarity opposite to that of the surfactant used as the dispersing agent added to the raw material dispersion, that is, an inorganic metal salt or a divalent or higher-valent metal complex. Use. In particular, the use of a metal complex is particularly preferable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

  Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. The inorganic metal salt polymer is more suitable.

When the toner is manufactured in the case where the step of using the flocculant is only the step of forming the aggregated particles, the flocculant containing Al element is used as the flocculant in this step. Moreover, when the process using an aggregating agent is an agglomerated particle forming process and a coating layer forming process, an aggregating agent containing an Al element as an aggregating agent may be used in both processes or one of the processes.
Here, as the aggregating agent containing Al element, those listed above such as polyaluminum chloride are used.

  In order to stop the agglomeration reaction in the agglomerated particle formation step and the coating layer formation step before the fusion step, in the conventional emulsion polymerization aggregation method, after adding the aggregating agent, an alkaline solution such as sodium hydroxide is added. The pH of the raw material dispersion is adjusted from the acidic side to the alkaline side (pH = 6.5 or more and 8.5 or less). Then, subsequent processes such as a fusion process are performed.

-Coating layer formation process-
After the aggregated particle forming step, the coating layer forming step may be performed if necessary. In the coating layer forming step, the coating layer is formed by attaching resin particles for forming a coating layer to the surface of the aggregated particles formed through the above-described aggregated particle forming step. Thereby, a toner having a so-called core / shell structure is obtained.

  The coating layer is usually formed by additionally adding a resin particle dispersion containing amorphous resin particles to the raw material dispersion in which aggregated particles (core particles) are formed in the aggregated particle forming step.

  A surfactant is used for emulsion polymerization of the binder resin, pigment dispersion, resin particle dispersion, release agent dispersion, particle aggregation, and aggregation particle stabilization. Specifically, sulfate surfactants, sulfonates, phosphates, soaps and other anionic surfactants, amine salts, quaternary ammonium salts and other cationic surfactants, polyethylene glycols, It is also effective to use nonionic surfactants such as alkylphenol ethylene oxide adducts and polyhydric alcohols as the dispersing means, and as a dispersion means, general use such as a ball mill, sand mill, dyno mill having a rotating shear homogenizer or media Use something specific.

-Fusion process-
In the agglomeration step performed after the aggregated particle forming step or the aggregated particle forming step and the coating layer forming step, the pH of the suspension containing the aggregated particles formed through these steps is 6.5 or more and 10 or less. By making it into the range, the progress of aggregation is stopped. When using the second (Al) 1 / (Al) 2 value control method, the pH of the suspension is selected within the above range, but the second (Al) 1 / (Al) 2 When using the value control method, the pH of the suspension is adjusted within the range of 9 or more and 10 or less.
Then, after the progress of aggregation is stopped, the aggregated particles are fused by heating. When a crystalline resin is used as the binder resin, the aggregated particles are fused by heating at a temperature equal to or higher than the melting temperature of the binder resin.

-Cleaning, drying process, etc.-
After completing the coalesced particle fusion step, desired toner particles are obtained through an arbitrary washing step, solid-liquid separation step, and drying step. In consideration of charging properties, the washing step may be replaced with ion exchange water. desirable. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  Then, the final toner is completed by externally adding the various external additives (including specific external additives) described above to the toner particles after drying.

<Electrostatic image developer>
Next, the electrostatic charge image developer of this embodiment will be described.
The electrostatic image developer of this embodiment is not particularly limited except that it contains the toner of this embodiment, and has a component composition according to the purpose. The developer of this embodiment becomes a one-component developer when the toner is used alone, and becomes a two-component developer when the toner and the carrier are used in combination.

Specific examples of the carrier include the following resin-coated carriers. Examples of the core material of the carrier include ordinary iron powder, ferrite, and magnetite molding, and the volume average particle size is in the range of about 30 μm to 200 μm.
The carrier core material preferably has a volume resistivity of 1 × 107.5 Ωcm to 1 × 109.5 Ωcm. If the volume resistivity is less than 1 × 107.5 Ω · cm, when the toner concentration in the developer is reduced by repeated copying, charge may be injected into the carrier and the carrier itself may be developed. On the other hand, if the volume resistivity is higher than 1 × 109.5 Ω · cm, the image quality such as the outstanding edge effect and pseudo contour may be adversely affected. The core material is not particularly limited as long as the above conditions are satisfied. For example, magnetic metals such as iron, steel, nickel, and cobalt, alloys of these with manganese, chromium, rare earth, and magnetic materials such as ferrite and magnetite. An oxide etc. are mentioned. Among these, ferrite, particularly alloys with manganese, lithium, strontium, magnesium and the like are preferable from the viewpoint of core surface properties and core material resistance.

  As coating resin, polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid copolymer, organosiloxane bond Straight silicone resin or modified product thereof, fluororesin, polyester, polycarbonate, phenol resin, urea-formaldehyde resin, melamine resin, silicone resin, benzoguanamine resin, urea resin, polyamide resin and other amino resins, epoxy resin, etc. However, it is not limited to these. These may be used individually by 1 type and may use 2 or more types together.

  Moreover, it is preferable that at least resin particles and conductive particles are dispersed in the resin coating layer (coating film).

  Examples of the resin particles include thermoplastic resin particles and thermosetting resin particles. Among these, thermosetting resins are preferable from the viewpoint of relatively easily increasing the hardness, and resin particles made of nitrogen-containing resin containing N atoms are preferable from the viewpoint of imparting negative chargeability to the toner. In addition, these resin particles may be used individually by 1 type, and may use 2 or more types together. The average particle size of the resin particles is preferably about 0.1 μm to 2 μm, and more preferably 0.2 μm to 1 μm. If the average particle size of the resin particles is less than 0.1 μm, the dispersibility of the resin particles in the coating film is very poor. On the other hand, if the average particle size exceeds 2 μm, the resin particles easily fall off from the coating film. It may not be effective. As conductive particles, metal particles such as gold, silver and copper, carbon black particles, semiconductive oxide particles such as titanium oxide and zinc oxide, titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate Examples thereof include particles whose surface such as powder is covered with tin oxide, carbon black, metal or the like. These may be used individually by 1 type and may use 2 or more types together. Among these, carbon black particles are preferable from the viewpoints of production stability, cost, conductivity, and the like. The type of carbon black is not particularly limited, but carbon black having a DBP oil absorption of about 50 ml / 100 g or more and 250 ml / 100 g or less is preferable because of excellent production stability.

  Examples of the method for forming the resin coating layer on the surface of the core material include an immersion method in which the coating film-forming liquid containing the coating resin is immersed, a spray method in which the coating film forming liquid is sprayed on the surface of the carrier core material, and a carrier. Examples thereof include a kneader coater method in which the core material is mixed with a coating film forming liquid in a state where the core material is floated by flowing air, and the solvent is removed.

  The amount of the resin coating formed by the above method is used by coating an amount of 0.5% by mass or more and 10% by mass or less with respect to the carrier core material. The mixing ratio (mass ratio) of the toner and the carrier is preferably in the range of toner: carrier = 1: 100 to 30: 100, and more preferably in the range of 3: 100 to 20: 100.

[Image forming apparatus]
The image forming apparatus of the present embodiment is not particularly limited as long as it can form a fixed image of a toner image on a recording medium using the developer according to the present embodiment. A charging unit that charges the surface of the electrostatic latent image holding member, an electrostatic latent image forming unit that forms an electrostatic latent image on the surface of the electrostatic latent image holding member, and a development arranged to face the electrostatic latent image holding member A developing means for developing the electrostatic latent image into a toner image with a developer, and a transfer means for transferring the toner image formed on the surface of the electrostatic latent image holding body to the surface of the recording medium. And an image forming apparatus including a fixing unit that fixes the toner image transferred to the recording medium.

  Image formation in the image forming apparatus of this embodiment is performed, for example, as follows when an electrophotographic photosensitive member is used as the electrostatic latent image holding member. First, the surface of the electrophotographic photosensitive member is charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic charge image. Next, the toner is attached to the electrostatic latent image in contact with or in proximity to a developing roll having a developer layer formed on the surface, thereby forming a toner image on the electrophotographic photosensitive member. The formed toner image is transferred onto the surface of a recording medium such as paper using a corotron charger or the like. Further, the toner image transferred to the surface of the recording medium is fixed by a fixing device, and an image is formed on the recording medium.

  As the electrophotographic photoreceptor, generally, an inorganic photoreceptor such as amorphous silicon or selenium, or an organic photoreceptor using polysilane, phthalocyanine or the like as a charge generation material or a charge transport material is used. In particular, as an electrophotographic photosensitive member, from the viewpoint of abrasion resistance, an amorphous silicon photosensitive member is used for an inorganic photosensitive member, and a resin having a crosslinked structure such as a melamine resin, a phenol resin, or a silicone resin on the outermost layer if an organic photosensitive member is used. A photoreceptor having a so-called overcoat layer having a layer is desirable.

  The fixing device is not particularly limited as long as fixing is performed by heating and pressing, and a hot roll fixing device, an oven fixing device, and the like are preferably used.

  As the heat roll fixing device, a heating roll type fixing device is generally used in which a pair of fixing rolls are pressed against each other. As a pair of fixing rolls, a heating roll and a pressure roll are provided facing each other, and a nip is formed by pressure contact. The heating roll has a metal hollow core with a heater lamp inside, and a surface layer made of an oil- and heat-resistant elastic body layer (elastic layer) and a fluororesin, etc. are sequentially formed. Accordingly, an oil- and heat-resistant elastic body layer and a surface layer are sequentially formed on a metal hollow core metal core having a heater lamp inside. An unfixed toner image is fixed by passing a recording medium on which an unfixed toner image is formed through a nip region formed by the heating roll and the pressure roll.

  Hereinafter, the image forming apparatus according to the present embodiment will be described. FIG. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus, but is not limited thereto. The main parts shown in the figure will be described.

  The image forming apparatus shown in FIG. 1 is a quadruple tandem color image forming apparatus. The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter simply referred to as “units”) 10Y, 10M, 10C, and 10K are juxtaposed in the horizontal direction at a distance from each other. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the main body of the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a driving roller 22 and a support roller 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other from the left to the right in the drawing. It is designed to travel in the direction toward 10K. The support roller 24 is urged away from the drive roller 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around both. Further, an intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the driving roller 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K includes yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The four colors of toner are supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K described above have the same configuration, here, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction. 10Y will be described as a representative. Note that the second to fourth units are denoted by reference numerals with magenta (M), cyan (C), and black (K) instead of yellow (Y) in the same parts as the first unit 10Y. The description of 10M, 10C, and 10K is omitted.

The first unit 10Y has a photoreceptor 1Y that functions as an image holding member. Around the photoreceptor 1Y, a charging roller 2Y for charging the surface of the photoreceptor 1Y to a constant potential, and the charged surface is exposed by a laser beam 3Y based on the color-separated image signal to form an electrostatic image. An exposure device 3; a developing device (developing means) 4Y for supplying the charged toner to the electrostatic image and developing the electrostatic image; a primary transfer roller 5Y (primary) for transferring the developed toner image onto the intermediate transfer belt 20; A transfer unit) and a photoconductor cleaning device (cleaning unit) 6Y for removing toner remaining on the surface of the photoconductor 1Y after the primary transfer with a cleaning blade.
The primary transfer roller 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described. First, prior to the operation, the surface of the photoreceptor 1Y is charged to a potential of about −600V to −800V by the charging roller 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate. This photosensitive layer usually has a high resistance (a resistance equivalent to that of a general resin), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic charge image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y flows. On the other hand, this is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic charge image formed on the photoreceptor 1Y in this way is rotated to the developing position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is visualized (developed image) by the developing device 4Y.

  For example, yellow toner is accommodated in the developing device 4Y. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged charge on the photoreceptor 1Y, and a developer roll (developer holder). Is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run, and the toner image developed on the photoreceptor 1Y is conveyed to the primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a primary transfer bias is applied to the primary transfer roller 5Y, and an electrostatic force from the photoreceptor 1Y toward the primary transfer roller 5Y acts on the toner image. Then, the toner image on the photoreceptor 1Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time is a (+) polarity opposite to the polarity (−) of the toner, and is controlled to about +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rollers 5M, 5C, and 5K after the second unit 10M is also controlled according to the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner.

  The intermediate transfer belt 20 onto which the four color toner images have been transferred through the first to fourth units is arranged on the image transfer surface side of the intermediate transfer belt 20 and the support roller 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roller (secondary transfer means) 26 is connected to a secondary transfer portion. On the other hand, the recording medium P is fed to the gap where the secondary transfer roller 26 and the intermediate transfer belt 20 are in pressure contact with each other via the supply mechanism, and the secondary transfer bias is applied to the support roller 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording medium P is applied to the toner image, so The toner image is transferred onto the recording medium P. The secondary transfer bias at this time is determined according to the resistance detected by a resistance detection means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

Thereafter, the recording medium P is sent to a fixing device (fixing means) 28, the toner image is heated, and the color-superposed toner image is melted and fixed on the recording medium P. The recording medium P on which the color image has been fixed is unloaded to the discharge unit, and a series of color image forming operations is completed.
The image forming apparatus exemplified above is configured to transfer the toner image to the recording medium P via the intermediate transfer belt 20, but is not limited to this configuration, and the toner image is directly transferred from the photoconductor. It may be a structure that is transferred to a recording sheet.

[Process cartridge]
FIG. 2 is a schematic configuration diagram illustrating an example of a process cartridge according to the present embodiment. The process cartridge shown in FIG. 2 includes a photosensitive member 107, a charging roller 108, a developing device 111, and a unit provided with a photosensitive member cleaning device (cleaning means) 113, an opening 118 for exposure, and a discharge exposure. It is combined with and integrated with a housing 119 provided with an opening 117 and a mounting rail 116.
The process cartridge is detachable from the main body of the image forming apparatus including the transfer device 112, the fixing device 115, and other components not shown, and forms an image together with the main body of the image forming apparatus. It constitutes a device. P is a recording medium.

  The process cartridge shown in FIG. 2 includes a photoreceptor 107, a charging device 108, a developing device 111, and a cleaning device (cleaning means) 113. These devices are selectively combined. Specifically, for example, in the process cartridge of the present embodiment, in addition to the developing device 111, at least one selected from the group consisting of a photoconductor 107, a charging device 108, and a cleaning device (cleaning means) 113 is used. Provide seeds.

[Toner cartridge]
Next, the toner cartridge of this embodiment will be described. The toner cartridge according to the present embodiment is detachably mounted on the image forming apparatus, and at least the toner cartridge that stores toner to be supplied to the developing unit provided in the image forming apparatus is described above. It is a toner according to the exemplary embodiment. It should be noted that at least the toner may be stored in the toner cartridge of the present embodiment, and for example, a developer may be stored depending on the mechanism of the image forming apparatus.

  Therefore, in an image forming apparatus having a toner cartridge detachable configuration, the storability can be maintained even in a toner cartridge whose container is miniaturized by using the toner cartridge containing the toner of the present embodiment. It is possible to achieve low temperature fixing while maintaining high image quality.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a detachable configuration of the toner cartridges 8Y, 8M, 8C, and 8K. The developing devices 4Y, 4M, 4C, and 4K are each developing device (color). And a toner supply pipe (not shown). Further, when the toner stored in the toner cartridge becomes low, the toner cartridge is replaced.

  Hereinafter, the present embodiment will be specifically described by way of examples. However, the present embodiment is not limited to these examples. In the following description, “part” and “%” all mean “part by mass” and “mass%” unless otherwise specified.

Example 1
-Preparation of non-crystalline polyester resin (A1) and non-crystalline resin particle dispersion (a1)-
In a heat-dried two-necked flask, 15 mol parts of polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (2,2) -2,2-bis (4 -Hydroxyphenyl) propane 85 mol part, terephthalic acid 10 mol part, fumaric acid 67 mol part, n-dodecenyl succinic acid 3 mol part, trimellitic acid 20 mol part, and these acid components (terephthalic acid, n After adding 0.05 mol part of dibutyltin oxide to the total number of moles of dodecenyl succinic acid, trimellitic acid and fumaric acid), introducing nitrogen gas into the container and maintaining the inert atmosphere to raise the temperature The copolycondensation reaction is carried out at 150 ° C. to 230 ° C. for 12 to 20 hours, and then gradually reduced in pressure at 210 ° C. to 250 ° C. to combine the amorphous polyester resin (A1). It was. This resin had a weight average molecular weight Mw of 65000 and a glass transition temperature Tg of 65 ° C.

  3000 parts of the obtained non-crystalline polyester resin, 10000 parts of ion-exchanged water, and 90 parts of surfactant sodium dodecylbenzenesulfonate were charged into an emulsification tank of a high-temperature and high-pressure emulsifier (Cabitron CD1010, slit: 0.4 mm). Then, after heating and melting at 130 ° C., it was dispersed at 110 ° C. at a flow rate of 3 L / m at 10,000 rpm for 30 minutes, passed through a cooling tank, and then a non-crystalline resin particle dispersion (high temperature / high pressure emulsifier (Cabitron CD1010 slit 0 .4 mm) was recovered to obtain an amorphous resin particle dispersion (a1).

-Preparation of crystalline polyester resin (B1) and crystalline resin particle dispersion (b1)-
Into a heat-dried three-necked flask, 45 mol parts of 1,9-nonanediol, 55 mol parts of dodecanedicarboxylic acid and 0.05 mol parts of dibutyltin oxide as a catalyst were added, and the air in the container was then decompressed. Was placed in an inert atmosphere with nitrogen gas, and stirred at 180 ° C. for 2 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 5 hours. When it became a viscous state, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (B1) was synthesized. This resin had a weight average molecular weight Mw of 25000 and a melting temperature Tm of 73 ° C.
Thereafter, a crystalline resin particle dispersion (b1) was obtained using a high-temperature, high-pressure emulsification apparatus (Cabitron CD1010, slit: 0.4 mm) under the same conditions as in the preparation of the amorphous resin dispersion (A1).

-Preparation of colorant particle dispersion (1)-
-Cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)): 1000 parts-Anionic surfactant (sodium lauryl sulfate, manufactured by Wako Pure Chemical Industries): 150 parts-Ion-exchanged water: 4000 parts

  A colorant particle dispersion obtained by mixing and dissolving the above and dispersing the colorant (cyan pigment) particles by dispersing for 1 hour using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). Was prepared. The volume average particle size of the colorant (cyan pigment) particles in the colorant particle dispersion was 0.15 μm, and the colorant particle concentration was 20%.

-Preparation of release agent particle dispersion (1)-
・ Fatty acid amide wax (Nippon Seika, Neutron D): 100 parts ・ Anionic surfactant (manufactured by NOF Corporation, Newlex R): 2 parts ・ Ion-exchanged water: 300 parts The above ingredients are heated to 95 ° C. Then, after dispersing using a homogenizer (manufactured by IKA, Ultra Tarrax T50), the dispersion is performed using a pressure discharge type gorin homogenizer (Gorin) to disperse the release agent particles having a volume average particle size of 200 nm. A release agent particle dispersion (1) (release agent concentration: 20% by mass) was prepared.

[Production of toner]
-Production of toner base particles A-
Amorphous resin particle dispersion (a1): 280 parts Crystalline resin particle dispersion (b1): 120 parts Colorant particle dispersion (1): 50 parts Release agent particle dispersion (1): 60 parts Aluminum sulfate (manufactured by Wako Pure Chemical Industries): 5 parts Surfactant aqueous solution: 10 parts 0.3M nitric acid aqueous solution: 50 parts Ion exchange water: 500 parts

  The above components were placed in a round stainless steel flask and dispersed using a homogenizer (IKA, Ultra Tarrax T50), then heated to 42 ° C. in a heating oil bath and held for 30 minutes. The temperature of the heating oil bath is raised and maintained at 58 ° C. for 60 minutes, and when it is confirmed that aggregated particles having an average particle diameter of about 5.2 μm are formed, an additional amorphous resin particle dispersion (A1): After adding 100 parts, the mixture was further held for 30 minutes.

  Subsequently, a 1N aqueous sodium hydroxide solution was gently added until pH 7.2 was reached, and then the mixture was heated to 83 ° C. while maintaining stirring and maintained for 3 hours. Thereafter, the reaction product was filtered, washed with ion-exchanged water, and then dried using a vacuum dryer to obtain toner mother particles A.

-Preparation of toner base particles B-
Non-crystalline resin particle dispersion (a1): 340 parts Crystalline resin particle dispersion (b1): 160 parts Colorant particle dispersion (1): 50 parts Release agent particle dispersion (1): 60 parts Aluminum sulfate (manufactured by Wako Pure Chemical Industries): 5 parts Surfactant aqueous solution: 10 parts 0.3 M nitric acid aqueous solution: 50 parts Ion exchange water: 500 parts The above components are contained in a round stainless steel flask. Then, after being dispersed using a homogenizer (manufactured by IKA, Ultra Turrax T50), heated to 42 ° C. in a heating oil bath and held for 30 minutes, then the temperature of the heating oil bath was further raised to 58 ° C. At the stage where it was confirmed that aggregated particles having an average particle diameter of about 5.2 μm were formed, and after adding 100 parts of additional amorphous resin particle dispersion (a1), Hold for 30 minutes.
Subsequently, a 1N aqueous sodium hydroxide solution was gently added until pH 7.2 was reached, and then the mixture was heated to 85 ° C. while maintaining stirring and maintained for 4.5 hours. Thereafter, the reaction product was filtered, washed with ion-exchanged water, and then dried using a vacuum dryer to obtain toner particles B.

-Preparation of toner base particles C-
Amorphous resin particle dispersion (a1): 225 parts Crystalline resin particle dispersion (b1): 175 parts Colorant particle dispersion (1): 50 parts Release agent particle dispersion (1): 60 parts Aluminum sulfate (manufactured by Wako Pure Chemical Industries): 5 parts Surfactant aqueous solution: 10 parts 0.3 M nitric acid aqueous solution: 50 parts Ion exchange water: 500 parts The above components are contained in a round stainless steel flask. Then, after being dispersed using a homogenizer (manufactured by IKA, Ultra Turrax T50), heated to 42 ° C. in a heating oil bath and held for 30 minutes, then the temperature of the heating oil bath was further raised to 58 ° C. At the stage where it was confirmed that aggregated particles having an average particle diameter of about 5.2 μm were formed, and after adding 100 parts of additional amorphous resin particle dispersion (a1), Hold for 30 minutes.
Subsequently, a 1N aqueous sodium hydroxide solution was gently added until pH 7.2 was reached, and then the mixture was heated to 80 ° C. while maintaining stirring and maintained for 2 hours. Thereafter, the reaction product was filtered, washed with ion-exchanged water, and then dried using a vacuum dryer to obtain toner base particles C.

-Preparation of toner base particle D: (St-Ac toner)-
<Preparation of resin particle dispersion>
-Styrene: 296 parts-n-butyl acrylate: 104 parts-Acrylic acid: 6 parts-Dodecanethiol: 10 parts-Divinyl adipate: 1.6 parts (above, manufactured by Wako Pure Chemical Industries, Ltd.)
12 parts of nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 8 parts Is added to a solution dissolved in 610 parts of ion-exchanged water, dispersed in a flask, emulsified, and slowly mixed for 10 minutes, while ion-exchanged water in which 8 parts of ammonium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved. 50 parts were added and nitrogen substitution was performed at 0.1 liter / min for 20 minutes. Thereafter, the contents in the flask were heated with an oil bath until the contents reached 70 ° C., and the emulsion polymerization was continued for 5 hours. The average particle size (number basis) was 200 nm, and the solid content concentration was 40% by mass. A resin fine particle dispersion was prepared. When a portion of the dispersion was left in an oven at 100 ° C. to remove moisture, DSC (differential scanning calorimeter) measurement was performed. As a result, the glass transition temperature was 53.8 ° C. and the weight average molecular weight was 33,000.

-Resin particle dispersion: 320 parts-Colorant dispersion: 80 parts-Release agent dispersion: 96 parts-Polyaluminum hydroxide (Pho2S manufactured by Asada Chemical Co., Ltd.): 0.8 parts-Ion exchange water: 1270 parts The above components were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA). In order to aggregate the particles, the inside of the flask was heated to 42 ° C. with stirring in a heating oil bath and held for 30 minutes, and then the temperature of the heating oil bath was further raised and held at 58 ° C. for 60 minutes.
Thereafter, in order to control the shape of the aggregate particles, a 1N sodium hydroxide aqueous solution is added to the slurry containing the aggregate particles to adjust the pH of the system to 7.2, and then the stainless steel flask is sealed. The mixture was heated to 83 ° C. with continuous stirring using a magnetic seal and held for 6 hours. Thereafter, the reaction product was filtered, washed with ion-exchanged water, and then dried using a vacuum dryer to obtain toner mother particles D.

-Production of toner base particles E-
Non-crystalline resin particle dispersion (a1): 150 parts Crystalline resin particle dispersion (b1): 250 parts Colorant particle dispersion (1): 50 parts Release agent particle dispersion (1): 60 parts Aluminum sulfate (manufactured by Wako Pure Chemical Industries): 5 parts Surfactant aqueous solution: 10 parts 0.3 M nitric acid aqueous solution: 50 parts Ion exchange water: 500 parts The above components are contained in a round stainless steel flask. Then, after being dispersed using a homogenizer (manufactured by IKA, Ultra Tarrax T50), heated to 42 ° C. in a heating oil bath and held for 30 minutes, then the temperature of the heating oil bath was further raised to 56 ° C. At the stage where it was confirmed that aggregated particles having an average particle diameter of about 5.2 μm were formed, and after adding 100 parts of additional amorphous resin particle dispersion (a1), Hold for 30 minutes.
Subsequently, a 1N aqueous sodium hydroxide solution was gently added until pH 7.2 was reached, and then the mixture was heated to 80 ° C. while maintaining stirring and maintained for 3 hours. Thereafter, the reaction product was filtered, washed with ion-exchanged water, and then dried using a vacuum dryer to obtain toner base particles E.

  100 parts of the toner base particles A, 0.11 part of polytetrafluoroethylene particles (particles having a particle diameter of 300 nm obtained by an emulsion polymerization method), and a rutile type oxidation having a volume average particle diameter of 20 nm hydrophobized with decylsilane. The toner of Example 1 was obtained by mixing 0.8 part of titanium and 1.0 part of silicon oxide treated with silicone oil and having a volume average particle size of 40 nm with a Henschel mixer under the following conditions.

(Creation of silica particles surface-treated with a fluorine atom-containing treatment agent)
Preparation of Particles Used in Example 5 After dissolving 2.0 g of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) _{3 in} a mixed solvent consisting of 95 parts of methanol and 5 parts of water, the average particle diameter After adding 10 g of 50 nm titania (EC-300: manufactured by Titanium Kogyo Co., Ltd.), ultrasonically dispersing, vaporizing methanol with an evaporator and drying, heat treating with a dryer set at 120 ° C., and grinding with a pin mill Thus, particles used in Example 5 were prepared.

Preparation of Particles Used in Comparative Example 4 After dissolving 2.0 g of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) _{3 in} a mixed solvent consisting of 95 parts of methanol and 5 parts of water, the average particle diameter 10 g of 35 nm titania (MT500B: manufactured by Teica) was added, and after ultrasonic dispersion, methanol was stripped off with an evaporator, dried, further heat-treated with a dryer set at 120 ° C., and pulverized with a pin mill. The particles used in 4 were prepared.

[Examples 2 to 8, Comparative Examples 1 to 4]
A toner was produced in the same manner as in Example 1 except that the external additive and the binder resin were changed according to Table 1. The surface coverage of the toner by the specific external additive was evaluated by the following measuring method, and the results are shown in Table 1.

  However, the specific external additive used in Example 4 is 500 nm PTFE particles obtained by the emulsion polymerization method, and the specific external additive used in Comparative Example 3 is 1000 nm PTFE obtained by the emulsion polymerization method. Particles.

(Toner surface coverage with specific external additives)
The surface coverage is obtained by scanning electron S-4700 (manufactured by Hitachi, Ltd.), observing 50 visual fields with a magnification of 3000 times, and then using the area analysis tool of image processing analysis software WinROOF (manufactured by Mitani Corporation) for the observed image. It is calculated using.

  In Table 1, the amount of the specific external additive added represents the content of the specific external additive relative to the whole toner in terms of mass.

[Evaluation]
A carrier was prepared as follows. 1,000 parts of Mn—Mg ferrite (volume average particle size: 50 μm, manufactured by Powder Tech Co., Ltd., shape factor SF1: 120) were added to a kneader, and a perfluorooctylmethyl acrylate-methyl methacrylate copolymer (polymerization ratio: 20 / 80, Tg: 72 ° C., weight average molecular weight: 72,000, manufactured by Soken Chemical Co., Ltd.) 150 parts dissolved in 700 parts of toluene, mixed at room temperature for 20 minutes, then heated to 70 ° C. under reduced pressure After drying, it was taken out to obtain a coat carrier. Furthermore, the obtained coated carrier was sieved with a mesh having an opening of 75 μm, and coarse powder was removed to obtain a carrier. The shape factor SF1 of the carrier was 122.

The above carrier and each of the obtained toners were combined in a V blender at a mass ratio of 95: 5 and stirred for 20 minutes to prepare a developer.
And it evaluated by the following method using the obtained developing agent. The results are summarized in Table 2.

(Elevated flow tester melt viscosity)
The melt viscosity of each toner at 90 ° C. was measured according to the method and conditions described above.

(Evaluation of hot offset)
Evaluation was carried out under an environment of 20 ° C./50% RH using a Fuji Xerox DocuPrint C3360 modified machine (modified so as to freely control the fixing pressure / temperature). The obtained developer was set in each engine of Y / M / C, output 1,000 sheets at 5% image density of each developer while maintaining the fixing temperature at 160 ° C. and the toner concentration at 7%, and then evaluated. went.
Thereafter, the developing amount of each developer was measured, and the toner concentration was controlled so that the developing amount was in the range of 4.5 ± 0.5 g / m ² . Thereafter, 100 images of 10 cm × 10 cm patches superimposed on each engine (image density Cin 80% of each image) were output continuously, and hot offset evaluation was performed.
At this time, the fixing pressure was 10 N / cm ² . However, in Example 8 was 28N / cm ^2.
Evaluation was also made at a fixing temperature of 220 ° C.

The hot offset was determined according to the following evaluation criteria and shown in Table 2.
○: No offset can be confirmed visually Δ: The diameter of one offset is 1 mm or less and the number of occurrences per sheet is 5 or less ×: The size of the offset is greater than 1 mm, or the number of occurrences per sheet is 5 More than

(Development amount)
An image having a 2 cm × 5 cm solid patch with 2 locations (6 locations in total) for each engine was output, and the development amount was measured.

  From the above results, Examples 1 to 8 include the specific external additive according to the embodiment of the present invention as the external additive, and the elevated flow tester melt viscosity at 90 ° C. is within the range of the embodiment of the present invention. It can be seen that in both cases, the hot offset hardly occurred even at a fixing temperature of 160 ° C. or 220 ° C., and good results were obtained. On the other hand, hot offset occurred in Comparative Example 1 and Comparative Example 2 in which the elevated flow tester melt viscosity was outside the range of the embodiment of the present invention. Also in Comparative Example 3 and Comparative Example 4 in which the particle diameter of the specific external additive was outside the range of the embodiment of the present invention, a hot offset occurred and a good image could not be obtained.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge which concerns on this embodiment.

1Y, 1M, 1C, 1K Photoconductor 2Y, 2M, 2C, 2K Charging roller 3Y, 3M, 3C, 3K Laser beam 3 Exposure device 4Y, 4M, 4C, 4K Developing device 5Y, 5M, 5C, 5K Primary transfer Rollers 6Y, 6M, 6C, 6K Cleaning devices 8Y, 8M, 8C, 7K Toner cartridges 10Y, 10M, 10C, 10K Image forming unit 20 Intermediate transfer belt 22 Drive roller 24 Support roller 26 Secondary transfer roller 28 Fixing device 30 Intermediate transfer Body cleaning device 107 Photoconductor 108 Charging roller 108 Charging device 111 Developing device 112 Transfer device 115 Fixing device 116 Mounting rail 117 Opening 118 Opening 119 Housing

Claims (6)

(A) a binder resin, (B) a release agent, and (C) an external additive having a primary particle size in the range of 50 nm to 500 nm, wherein the (C) external additive is at least (C-1 1) a fluororesin particle, or (C-2) a particle surface-treated with a fluorine atom-containing treatment agent, and the elevated flow tester melt viscosity at 90 ° C. of the toner is 1.0 × 10 ² Pa · s or more. An electrostatic charge developing toner having a range of 0 × 10 ⁵ Pa · s or less.   The surface coverage of the toner with the (C-1) fluororesin particles or (C-2) particles treated with a fluorine atom-containing treatment agent is in the range of 0.5% to 2.5%. Item 2. The electrostatic charge developing toner according to Item 1.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1.   A toner cartridge in which the toner for developing an electrostatic charge image according to claim 1 is contained.   A process cartridge comprising at least a developer holder and containing the electrostatic charge image developer according to claim 3. An image carrier,
Developing means for developing the electrostatic image formed on the image carrier as a toner image with a developer;
Transfer means for transferring a toner image formed on the image carrier onto the transfer target;
Fixing means for fixing the toner image transferred onto the transfer material;
Have
An image forming apparatus, wherein the developer is the electrostatic charge image developer according to claim 3.

Images