JP5645580B2 - toner - Google Patents

Description

  The present invention relates to a toner used in a recording method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method, and a toner jet method.

  In order to achieve low-temperature fixing, a toner that can be fixed to a transfer material with a small amount of heat is required, such as lowering the molecular weight and glass transition temperature (Tg) of the binder resin used in the toner, and lowering the melting point of the wax. Considered. However, when these methods are used, the stress resistance of the toner tends to decrease, and the deterioration of the toner is promoted particularly in the development process. For this reason, when a large number of printouts are performed, the chargeability and fluidity of the toner are remarkably reduced, and a phenomenon such as fogging and a decrease in image density occurs, thereby degrading the image quality.

  In order to solve these problems, a method for controlling the size and shape of the wax-dispersed particles present in the toner is disclosed (see Patent Document 1). This toner is characterized in that the shape of the wax-dispersed particles in the toner particles is a spherical shape or a shape close thereto, and the size of the wax-dispersed particles is uniform. However, this method can solve the above-mentioned problem in printing a large number of sheets to some extent, but it is not yet a sufficient level for further low-temperature fixing. In addition, a method for flattening the shape of the wax-dispersed particles is disclosed (see Patent Document 2). In this case, detachment of the wax component from the toner particles can be greatly suppressed, and the occurrence of carrier spent can be prevented in the two-component development. However, since the shape of the wax-dispersed particles is flat, the wax tends to be exposed on the toner surface layer when stress is applied to the toner for a long period of time. Therefore, when a large number of printouts are performed, image quality such as fogging is deteriorated.

  Furthermore, it has been found that conventional toners including the above toner may cause contamination of the fixing member peripheral member due to the wax component in the toner particles when a large number of printouts are repeated over a long period of time. . If the contamination of the fixing device peripheral member deteriorates, an image defect may occur in the fixing process.

  As described above, there is a need for a toner that can achieve both low-temperature fixability and stress resistance, and can prevent contamination of peripheral members of the fixing device.

JP 2006-337902 A JP 2001-142248 A

  An object of the present invention is to provide a toner that has improved low-temperature fixability, can provide an image with stable developability even when a large number of printouts are made, and can prevent in-machine contamination of fixing device peripheral members and the like. There is to do.

The present invention relates to a toner having toner particles containing a binder resin, a colorant, and a hydrocarbon wax, wherein the hydrocarbon wax has a melting point of 80 ° C. or higher and 120 ° C. or lower, and the hydrocarbon wax is heated and desorbed. In the GC / MS analysis of the component heated and desorbed at 200 ° C. for 10 minutes with an apparatus, the amount of volatile components detected after the peak detection time of hexadecane is 1100 ppm or less in terms of hexadecane, and a transmission electron microscope (TEM) In the cross-sectional observation of the toner particles using (1), the hydrocarbon wax dispersion particles observed in the cross-section of the toner particles have a particle concentration with a shape factor SF-1 of 1.5 or less and a particle concentration of A number% and a shape factor SF. -1 is a particle concentration of 3.0 or more and B number%,
30 ≦ A ≦ 75
2 ≦ B ≦ 20
Thus, the present invention relates to a toner characterized in that the hydrocarbon wax is dispersed in the toner particles.

  According to the present invention, it is possible to obtain a toner that can achieve both low-temperature fixability and stress resistance and can suppress in-machine contamination of a fixing member peripheral member and the like.

It is a system diagram of one embodiment incorporating a stirring device in a circulation line. It is an expanded sectional view of one embodiment of a stirring device. FIG. 2 is a schematic cross-sectional view of a developing device and a toner hopper. 1 is a schematic sectional view of an image forming apparatus. It is a system diagram of one embodiment incorporating a stirring device into a circulation line. It is a figure of one Embodiment of a stirring apparatus. It is an expanded sectional view of one embodiment of a stirring device. It is an expanded sectional view of one embodiment of a stirring device. It is a perspective view of the stator of a stirring apparatus. It is a perspective view of the rotor of a stirring apparatus.

  The toner of the present invention contains a hydrocarbon wax. The hydrocarbon wax has low compatibility with the binder resin used for the toner, and is hardly compatible with the binder resin. Therefore, it is possible to exhibit high performance when controlling the shape of the wax dispersion particles in the toner particles.

  The hydrocarbon wax used in the toner of the present invention has a melting point of 80 ° C. or higher and 120 ° C. or lower. If the melting point of the hydrocarbon wax is within the above range, the melting point of the toner can be improved because the melting point is relatively higher than that of the wax used in the conventional toner. Further, the blocking resistance is good when the toner is left at a relatively high temperature of about 50 ° C. However, use of a wax having a high melting point generally tends to be disadvantageous for low-temperature fixability. The toner of the present invention has a great point that even if a wax having a high melting point is used, the shape of the wax-dispersed particles in the toner particles can be made specific to exhibit good performance with respect to low-temperature fixability. It is a feature.

  In the present invention, the endothermic peak top of the wax is defined as the melting point of the wax. The endothermic peak top of the wax is measured by differential scanning calorimetry. More specifically, the measurement is performed according to ASTM D 3417-99, and measurement is performed using DSC-7 manufactured by PerkinElmer, DSC2920 manufactured by TA Instruments, and Q1000 manufactured by TA Instruments. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. An aluminum pan is used as a measurement sample, and an empty pan is set for control and measured. In the present invention, the modulated mode is used and measurement is performed under the following conditions, and the melting point of the wax is obtained from the DSC curve at the time of temperature increase. When there are a plurality of endothermic peaks, the one having the highest endothermic peak is adopted.

<Modulated mode measurement conditions>
• Equilibrate at 20 ° C for 1 minute.
-Apply a modulation of 1.5 ° C / min and raise the temperature to 180 ° C at 2 ° C / min.
• Equilibrate at 180 ° C for 10 minutes.
In the present invention, in the cross section of the toner particles observed using a transmission electron microscope (TEM), carbonization in the cross section is performed. When the proportion of particles having a shape factor SF-1 of hydrogen wax dispersed particles of 1.5 or less is A number% and the proportion of particles having a shape factor SF-1 of 3.0 or more is B number%,
30 ≦ A ≦ 75
2 ≦ B ≦ 20
It is important that the hydrocarbon wax is dispersed in the toner particles.

  In the toner particle cross section, moderately present particles having SF-1 of 1.5 or less and particles having SF-1 of 3.0 or more exhibit high performance with respect to low-temperature fixability. it can. In addition, as a result of printing out a large number of sheets, a stable charging property can be exhibited even with respect to stress applied to the toner.

  In the toner particle cross section, particles having SF-1 of 1.5 or less have a true sphere shape or a shape close thereto, and therefore exist stably in the toner particles. For this reason, the effect of suppressing the exposure of the wax to the toner surface layer is high even with respect to the stress applied to the toner, and stable chargeability can be maintained. However, the fixing process tends to be disadvantageous because the oozing of wax (bleedability) at low temperature fixing is weakened. On the other hand, when the wax dispersed particles are flat dispersed particles having an SF-1 of 3.0 or more, the wax tends to ooze out due to the characteristic shape of the wax, which is disadvantageous for stress resistance. It is. However, at the time of fixing, flat particles are more easily exposed on the surface of toner particles when subjected to pressure, and the bleedability of wax is high. That is, the present inventors consider that it is important that the wax-dispersed particles having different shapes are present appropriately in order to achieve both the fixing property and the stress resistance at a high level.

  In the present invention, the values of A and B are 30 ≦ A ≦ 75 and 2 ≦ B ≦ 20, more preferably 30 ≦ A ≦ 60 and 5 ≦ B ≦ 20. When the value of A is less than 30, the charging stability in the printout of a large number of sheets cannot be maintained, and when it exceeds 75, it is disadvantageous for low-temperature fixability. On the other hand, when the value of B is less than 2, it is disadvantageous for low-temperature fixability, and when it exceeds 20, the stress resistance deteriorates. In order to achieve both the fixing property and the stress resistance, A + B is preferably 80 or more.

  In order to properly set A and B, the following methods can be mentioned. Moreover, it is good also considering A and B as an appropriate range by using these methods together.

1. The wax is pulverized by a conventionally known mechanical method.
For example, when pulverizing wax using a pulverizer, the shape of the wax is controlled by adjusting the pulverization method, pulverization strength, and the like. Thereafter, the wax thus pulverized is added to the toner.

2. The wax is mixed with a solvent or monomer, and wet pulverized by a mechanical method.
When the toner is produced by a pulverization method or an emulsion aggregation method, after dissolving the wax in a solvent in which the wax is soluble, the solvent is removed by desolvation or the like to obtain a desired wax shape and used. When a toner is produced by a suspension polymerization method or a wet granulation method, it is dissolved in the same manner as other raw materials, and a wax is precipitated in a polymerization step or a solvent removal step to obtain a desired wax shape.

3. The wax is mixed with a solvent or a monomer, heat-treated, and then cooled to obtain a crystalline product.
For example, when the toner is produced by suspension polymerization, if the wax is insoluble in the monomer, the temperature is raised above the melting point of the wax in the monomer solution to dissolve the wax once at a high temperature and then cooled. A wax crystal is obtained. In the case of this method, the shape of the wax can be controlled by the cooling rate.

  A and B are measured as follows. Toner particles dispersed in a water-soluble resin are put into a cryomicrotome (ULTRACUT N FC4E manufactured by Reichert). The apparatus is cooled to −80 ° C. with liquid nitrogen, and the water-soluble resin in which the toner particles are dispersed is frozen. The frozen water-soluble resin is trimmed by a glass knife so that the cutting surface shape is about 0.1 mm wide and about 0.2 mm long. Next, an ultra-thin section (thickness setting: 70 nm) of toner containing a water-soluble resin is prepared using a diamond knife, and is moved onto a TEM observation grid mesh using an eyelash probe. After returning the ultra-thin slice of the toner particles containing the water-soluble resin to room temperature, the water-soluble resin is dissolved in pure water to obtain an observation sample of a transmission electron microscope (TEM). The sample is observed with a transmission electron microscope H-7500 (manufactured by Hitachi, Ltd.) at an acceleration voltage of 100 kV, and an enlarged photograph of the cross section of the toner particles is taken. The magnification of the magnified photograph is 1000 times, and arbitrarily select five images having 10 to 20 toner particles in one field of view. SF-1 is calculated by the following method for all wax dispersed particles present in five arbitrarily selected images, and the values of A and B are obtained. SF-1 indicating the shape factor is analyzed by introducing the above image into an image analysis apparatus (Luzex III) manufactured by Nireco through an interface, and the value obtained from the following equation is defined as the shape factor SF-1. . The shape factor SF-1 indicates the degree of roundness of the particles.

(Where MXLNG indicates the absolute maximum length of the particle, and AREA indicates the projected area of the particle.)
In addition, when the wax dispersed particles are flat, they appear flat or round depending on how the toner cross section is cut. However, if the measurement is performed by the above method, the values of A and B can be calculated with high accuracy.

  The inventors of the present invention heated the hydrocarbon wax contained in the toner at a temperature of 200 ° C. for 10 minutes with a heat desorption device, and in the GC / MS analysis of the desorbed component, after the peak detection time of hexadecane (16 carbon atoms). The amount of volatile components detected was analyzed. And if the amount of volatile components was 1100 ppm or less in hexadecane conversion, it discovered that the suppression effect of in-machine contamination was acquired. The reason for determining the analysis conditions as described above is that the toner is generally fixed at a temperature of about 200 ° C., and if heated for 10 minutes, volatile components contained in the hydrocarbon wax are sufficiently generated. This is because the analysis is considered to correspond to a monitor of the volatility of the wax in the fixing temperature range. The reason for paying attention to the amount of volatile components detected after the peak detection time of hexadecane (16 carbon atoms) is that the volatile components have a relatively high boiling point, and such volatile components are included in the configuration of the image forming apparatus. It is because it is easy to precipitate by contacting with a member. In-machine contamination occurs due to the accumulation of such precipitates, so the volatile component is considered to be a component that contributes to in-machine contamination. When the amount of the volatile component exceeds 1100 ppm, the in-flight contamination cannot be sufficiently suppressed. The amount of the volatile component can be controlled by selecting a wax type, adjusting a wax production method, and purification conditions.

<Measurement of Wax Volatile Component Concentration Using Heat Desorption Device>
(Device to be used)
Thermal desorption device: Manufacturer: PerkinElmer, TurboMatrixATD
GC / MS: Manufacturer: Thermo Fisher Scientific, TRACE DSQ
(Heat desorption equipment conditions)
Tube temperature: 200 ° C
Transfer temperature: 300 ° C
Valve temperature: 300 ° C
Column pressure: 150 kPa
Inlet split: 25 ml / min
Outlet split: 10 ml / min
Secondary adsorption tube material: TenaxTA
Holding time: 10 min
Secondary adsorption tube temperature during desorption: -30 ° C
Secondary adsorption tube desorption temperature: 300 ° C
(GC / MS conditions)
Column: Ultra Alloy (Metal Column) UT-5 (Inner Diameter 0.25 mm, Liquid Phase 0.25 μm, Length 30 m)
Column heating conditions: 60 ° C. (3 min), 350 ° C. (20.0 ° C./min), 350 ° C. (10 min)
Note that the transfer line of the heat desorption device and the GC column are directly connected, and the GC inlet is not used (production of an internal standard glass tube)
A glass tube for a heat desorption apparatus in which 10 mg of TenaxTA adsorbent is sandwiched between glass wools in advance is prepared, and a glass tube that has been conditioned at 300 ° C. for 3 hours in a state of flowing an inert atmosphere gas is prepared. Thereafter, 5 uL of a methanol solution of 100 ppm of deuterated hexadecane (hexadecane D34) is adsorbed on TenaxTA to obtain a glass tube containing an internal standard.

(Measurement of wax)
About 1 mg of the weighed wax is wrapped in aluminum foil previously baked out at 300 ° C. and placed in a dedicated tube prepared in (Preparation of glass tube with internal standard). The sample is covered with a Teflon cap for a heat desorption apparatus and set in the apparatus. This sample is measured under the above conditions, and the total peak area of the internal standard peak and the peak after deuterated hexadecane is calculated.

(analysis)
Of the peaks obtained by the above operation, all peaks after the retention time of hexadecane (excluding the deuterated hexadecane peak which is an internal standard) are integrated, and the total value of all peaks is calculated. At this time, a noise peak different from the peak is not added to the integrated value.
Formula 1 ... concentration of volatile component of wax (mg / kg) = (A1 / B1 × 0.0005 * ¹ × 0.77 * ² ) / C1 × 1000000
* 1 Volume of deuterated hexadecane in 5 μL of methanol solution (μL)
* 2 ... Density of hexadecane (mg / μL)
A1 ... Total peak area after deuterated hexadecane B1 ... Peak area of deuterated hexadecane (internal standard) C1 ... Weight of wax weighed (mg)
The value obtained above is defined as the amount of volatile component detected after the peak detection time of hexadecane in the GC / MS analysis of the component desorbed by heating the wax at 200 ° C. for 10 minutes with a heat desorption apparatus.

  As the hydrocarbon wax used in the present invention, the following can be used. A polyolefin obtained by purifying a low molecular weight by-product obtained at the time of polymerizing a high molecular weight polyolefin; a polyolefin polymerized using a catalyst such as a Ziegler catalyst or a metallocene catalyst; a paraffin wax, a Fischer-Tropsch wax; Synthetic hydrocarbon waxes synthesized by the hydrocol method or the age method; synthetic waxes using a compound having one carbon atom as a monomer; hydrocarbon waxes having functional groups such as hydroxyl groups and carboxyl groups; hydrocarbon waxes and functional groups Mention may be made of mixtures with hydrocarbon waxes. In addition, these waxes have a sharp molecular weight distribution using techniques such as the press sweating method, solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method, and melt liquid crystal deposition method, and low molecular weight solid fatty acids. , Low molecular weight solid alcohol, low molecular weight solid compound, and other impurities are used. Among them, those preferably used are paraffin wax, Fischer-Tropsch wax, microcrystalline wax, polyethylene synthesized using a metallocene catalyst, low molecular weight by-product distillation purified product obtained during polyethylene polymerization, synthesized using a metallocene catalyst. It is a distillation purified product of low molecular weight by-products obtained during polymerization of polypropylene and polyethylene. Furthermore, as the wax used in the toner of the present invention, paraffin wax, Fischer-Tropsch wax, and microcrystalline wax are particularly preferably used particularly from the viewpoint of efficiently removing high boiling point volatile components. Among these, when Fischer-Tropsch wax is used, the effect of improving developability and transferability is further enhanced.

  By refining these waxes, waxes with a reduced amount of high-boiling volatile components can be obtained. Examples of the purification method include solvent extraction, vacuum distillation method, press sweating method, recrystallization method, vacuum distillation method, molecular distillation method, supercritical gas extraction method, and melt liquid crystal deposition method for raw materials and wax products. Among these, a purification method combining a vacuum distillation method and a molecular distillation method is most preferable. For example, distillation is performed by the following method. The wax as a raw material is distilled under reduced pressure, and the process of removing the initial distillation is repeated to separate the wax. Thereafter, molecular distillation is repeated on the collected wax to remove low molecular weight components.

  The content of the hydrocarbon wax component is preferably 4 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the binder resin of the toner. When the content of the hydrocarbon wax component is less than 4 parts by mass, a sufficient effect is not exhibited with respect to fixing properties. When the content exceeds 25 parts by mass, the wax component is exposed to the toner surface layer, which adversely affects the chargeability of the toner. And fog and image density decrease are likely to occur.

  In the present invention, in addition to the hydrocarbon wax, a polar wax such as an ester wax may be used in combination in order to supplement the release action and plasticization of the resin. As these polar waxes, the peak top temperature of the endothermic main peak is preferably 70 to 110 ° C. For example, the following wax can be mentioned. A wax such as carnauba wax and its derivatives, which includes oxides, block copolymers with vinyl monomers, and graft modified products. Other examples include alcohol waxes, fatty acid waxes, acid amide waxes, ester waxes, ketone waxes, hardened castor oil and derivatives thereof, plant waxes, animal waxes, and montan waxes. Among them, the wax polar wax preferably used is carnauba wax, linear alcohol wax, fatty acid wax, acid amide wax, ester wax, or a montan derivative. The content of these polar waxes can be used in a total amount of 1.0 to 20.0 parts by mass, preferably 1.0 to 15 parts in combination with the wax of the present invention, with respect to 100 parts by mass of the binder resin. It is effective to use at 0.0 part by mass.

  Examples of the binder resin used in the present invention include generally used styrene-acrylic copolymers, styrene-methacrylic copolymers, epoxy resins, styrene-butadiene copolymers, and the like. As the polymerizable monomer for obtaining the above resin, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Examples of the polymerizable monomer used in the binder resin include styrene; styrene monomers such as o- (m-, p-) methylstyrene and m- (p-) ethylstyrene; methyl acrylate and methacrylic acid. Methyl, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, Acetic acid such as behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate Le ester monomer or methacrylic acid ester monomer; butadiene, isoprene, cyclohexene, acrylonitrile, methacrylonitrile, acrylic acid amide, and such ene monomers methacrylic acid amide.

  These are used alone or by appropriately mixing monomers with reference to the theoretical glass transition temperature (Tg) described in Publication Polymer Handbook 2nd Edition III-p139 to 192 (manufactured by John Wiley & Sons).

  Further, it is preferable to add a low molecular weight polymer to the toner in order to obtain a preferable molecular weight distribution. The low molecular weight polymer can be added at the time of melt kneading with a binder resin or the like when the toner is produced by a pulverization method, and the polymerizable single monomer is produced when the toner is produced by a suspension polymerization method. It can be added to the body composition. As the low molecular weight polymer, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 2,000 to 5,000, and Mw / Mn is less than 4.5, preferably 3 Less than 0.0 is good. Examples of the low molecular weight polymer include low molecular weight polystyrene, low molecular weight styrene-acrylic acid ester copolymer, and low molecular weight styrene-acrylic copolymer. A polar resin such as a polyester resin or a polycarbonate resin can be used in combination with the above-described binder resin.

  In order to increase the mechanical strength of the toner particles and to control the molecular weight of the binder resin of the toner, a crosslinking agent may be used when the binder resin is synthesized. As a crosslinking agent, as a bifunctional crosslinking agent, divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 Each of diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Nippon Kayaku), and the above Those obtained by changing the acrylate dimethacrylate. Polyfunctional crosslinkers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxypolyethoxy Phenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate. The addition amount of these crosslinking agents is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the monomer.

  A polar resin is preferably added to the toner of the present invention. The polar resin means a resin having a polar group such as a carboxyl group, a hydroxyl group, and a sulfonic acid group. By using a polar resin, when a toner is directly produced by a suspension polymerization method or the like, a thin layer shell made of a polar resin can be formed on the surface of the toner particles according to the balance of polarity. Alternatively, a polar resin can be present so as to have a gradient from the toner particle surface toward the center. By adding a polar resin and making the toner particles have a core-shell structure, the durability and fixability of the toner can be improved. A preferable addition amount of the polar resin is 1 to 30 parts by mass with respect to 100 parts by mass of the binder resin. By setting the addition amount of the polar resin within the above range, the chargeability and stress resistance of the toner are improved.

  In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system. As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable. As the charge control agent for controlling the toner to be negatively charged, organometallic compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dye compounds. Examples thereof include carboxylic acid-based metal compounds. In addition, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, phenol derivatives such as bisphenol, and the like are also used. Further, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and the like are also used.

  Examples of the charge control agent for controlling the toner to be positively charged include nigrosine-modified products such as nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutyl. Quaternary ammonium salts such as ammonium tetrafluoroborate and onium salts such as phosphonium salts and analogs thereof and lake pigments thereof; triphenylmethane dyes and lake lake pigments (as rake agents include phosphotungstic acid, Phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide Diorganotin oxides such as id, dibutyltin tin borate, dioctyl tin borate, such as diorganotin tin borate such dicyclohexyl tin borate, and the like. These charge control agents can be contained alone or in combination of two or more.

  Among these charge control agents, metal-containing salicylic acid compounds are preferable, and the metal is particularly preferably aluminum or zirconium. A more preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound. A preferable blending amount of the charge control agent is 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. However, it is not essential to add a charge control agent to the toner of the present invention, and the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

  It is also a preferable form to use a resin-based charge control agent for toner mainly for charge control. As the resin charge control agent, a polymer having a sulfonic acid group, a sulfonic acid group salt or a sulfonic acid ester group in the side chain is preferably used. Among them, it is particularly preferable to use a polymer or copolymer of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group. When the toner is produced by a suspension polymerization method, by adding the above polymer, the stabilization of granulation promotes the core-shell structure of the toner particles in the polymerization stage rather than the basis. Therefore, it is possible to further improve both the durability and the fixing property of the toner. Examples of the monomer having a sulfonic acid group, a sulfonic acid group salt, or a sulfonic acid ester group include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamide-2-methylpropane sulfonic acid, and vinyl. There are sulfonic acid, methacrylsulfonic acid and their alkyl esters. The polymer containing a sulfonic acid group, a sulfonic acid group salt or a sulfonic acid ester group may be a homopolymer of the above monomer, but the copolymer of the above monomer with another monomer It does not matter if they are combined. As a monomer that forms a copolymer with the above monomer, there is a vinyl polymerizable monomer, and a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

The following are mentioned as a coloring agent used for this invention.
As the black colorant, carbon black, a magnetic material, and a toned color of each color using a yellow / magenta / cyan colorant shown below are used. In particular, since dyes and carbon black have many polymerization-inhibiting properties, care must be taken when using them.

  Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 214.

  Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19.

  Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner. The addition amount of the colorant is used by adding 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin.

  Furthermore, the toner of the present invention may be a magnetic toner containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. Magnetic materials include iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, Examples include alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof. The magnetic body is preferably a surface-modified magnetic body. When a magnetic toner is prepared by a polymerization method, it is preferable to apply a hydrophobic treatment with a surface modifier, which is a substance that does not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents. A magnetic material having a number average particle diameter of 2 μm or less, preferably 0.1 to 0.5 μm is used. The amount of the magnetic substance to be contained in the toner particles is 20 to 200 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin, preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin. .

  In order to improve the fluidity of the toner particles, a fluidity improver may be added to the toner particles. As a fluidity improver, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder; fatty acid metal salt such as zinc stearate, calcium stearate, lead stearate; titanium oxide powder, aluminum oxide powder, Metal oxide such as zinc oxide powder, or powder obtained by hydrophobizing the above metal oxide; and silica fine powder such as wet-process silica and dry-process silica, or silane coupling agent, titanium coupling agent, silicone A surface-treated silica fine powder that has been surface-treated with a treating agent such as oil is exemplified. The fluidity improver is preferably used in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the toner particles.

  As a toner production method, a conventionally known pulverization method, a dissolution suspension method in which a binder resin or other material is dissolved or dispersed in a solvent and the solvent is removed after granulation in an aqueous medium, or a conventionally known suspension method is used. A turbid polymerization method is mentioned. Among these, it is more preferable to produce by a suspension polymerization method in which the wax dispersed particles can be present in a good state in the toner particles.

  It is preferable to add a dispersion stabilizer to the aqueous medium used when the toner particles are produced by the suspension polymerization method. The following inorganic compounds used as dispersion stabilizers are calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, sulfuric acid. Examples include calcium, barium sulfate, bentonite, silica, and alumina. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, and starch. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Further, 0.001 to 0.1 parts by mass of a surfactant may be used for fine dispersion of these dispersion stabilizers. This is to promote the initial action of the dispersion stabilizer. Specific examples include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate. When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain finer particles, the inorganic compound may be generated and used in an aqueous medium. For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high stirring.

  As the polymerization initiator for polymerizing the polymerizable monomer, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. Further, when the polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 10,000 and 100,000 is usually obtained. A toner having excellent strength and melting characteristics can be obtained. As polymerization initiators, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), Azo or diazo polymerization initiators such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2-ethylhexano Ate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoylper Peroxide polymerization such as oxide and lauroyl peroxide Initiator, and the like. In order to control the degree of polymerization of the polymerizable monomer, a known chain transfer agent, polymerization inhibitor or the like can be further added and used.

  In the method for producing toner particles by suspension polymerization, before adding the polymerizable monomer composition to the aqueous medium, the same as the rotor in which ring-shaped protrusions having a plurality of slits are formed in multiple stages on concentric circles. It is preferable to have the process of processing the said polymerizable monomer composition using the stirring apparatus installed on the same axis | shaft so that the stator of the shape may maintain a fixed space | interval and may mutually mesh. By introducing the above-mentioned process at the time of producing the toner, the wax dispersed particles in the toner particles can maintain a good dispersed state as described above, and the toner performance can be further improved. FIG. 5 shows a system incorporating a mixing device comprising the rotor and stator described above, and FIG. 6 shows a side view of the main body of the mixing device. FIG. 7 is a view showing a cross section A-A ′ in FIG. 5, and FIG. 8 is a view showing a cross section B-B ′ in FIG. 6. 9 and 10 show a perspective view of the stator 221 and a perspective view of the rotor 225 of the mixing device, respectively.

  Hereinafter, the mixing apparatus will be specifically described. In FIG. 5, a coloring agent-containing monomer in which a coloring agent is dispersed in a polymerizable monomer and a resin-containing monomer in which a resin is dissolved in the polymerizable monomer are introduced into a holding tank 208. To prepare the solution. The charged preparation liquid is supplied from the inlet of the mixing device via the circulation pump 210, and in the mixing device, passes through the slits of the rotor 225 and the stator 221 provided in the casing 202, and in the centrifugal direction. To be discharged. When the preparation liquid passes through the mixing device, the preparation liquid is mixed by compression in the centrifugal direction caused by displacement of the slits of the rotor and the stator, impact by discharge, and impact by shear between the rotor and the stator. The shape of the rotor and the stator is a shape in which ring-shaped protrusions having a plurality of slits are formed in multiple stages on concentric circles, and are arranged on the same axis so as to mesh with each other at a constant interval. It is preferable. Since the rotor and the stator are arranged so as to mesh with each other, the short path is reduced and the preparation liquid can be sufficiently dispersed. In addition, since the rotor and the stator are alternately present in multiple stages in the concentric direction, a large amount of shear and impact are applied when the preparation liquid proceeds in the centrifugal direction, so that the dispersion level can be further increased. Since the holding tank 208 has a jacket structure, the processed product can be cooled and heated.

  The circumferential speed of the rotor and the stator is the circumferential speed of the maximum diameter of the rotor and the stator. When the peripheral speed of the rotor 225 is G (m / s), it is preferable that the prepared liquid is mixed by rotating at 20 ≦ G ≦ 60. More preferably, the circumferential speed G of the rotor is 30 ≦ G ≦ 40. If the circumferential speed G of the rotor is 20 ≦ G ≦ 60, the shock caused by the compression and discharge of the prepared liquid in the centrifugal direction caused by the displacement of the slits of the rotor and the stator and the impact caused by the shear between the rotor and the stator And a high degree of dispersion is achieved. As a result, the dispersion of the prepared liquid is extremely less uneven than in the past, and a uniform dispersion state can be achieved. When the circumferential speed G of the rotor is smaller than 20 m / s, the impact due to the compression and discharge in the centrifugal direction and the impact due to the shear between the rotor and the stator are reduced, and it is difficult to reach a desired dispersion level. In addition, with the passage of time, a preparation solution having poor dispersion stability in which the colorant particles aggregate is often generated. Further, when the circumferential speed G of the rotor is larger than 60 m / s, a large pressure loss occurs when discharging from the slits of the rotor and the stator, so that not only a sufficient flow rate cannot be secured but also solid matter such as a colorant. And the polymerizable monomer may be separated. As the above-mentioned mixing device, for example, Cavitron (manufactured by Eurotech) can be suitably used.

  In the method for producing toner particles, before adding the polymerizable monomer composition to the aqueous medium, a stirring device including a stirring blade that rotates at a high speed and a screen that rotates around the stirring blade at a high speed in a direction opposite to the stirring blade. It is also preferred to have a step of treating and using the polymerizable monomer composition. A system in which a stirrer is incorporated in a circulation path will be described with reference to FIG. 1 and 2, reference numeral 1 denotes a stirring blade that rotates at high speed, 2 denotes a screen that rotates around the stirring blade 1 in a direction opposite to that of the stirring blade 1, and 3 denotes a stirring chamber formed by the stirring blade 1 and the screen 2 3, 4 is a dispersion vessel, 5 is a discharge port provided on the screen 2, 6 is a jacket, 7 is a holding tank, 8 is a stirring blade, 9 is a circulation pump, 10 is a dispersion vessel inlet, 11 is a suction port, 12 is Exhaust port, 13 is a heat exchanger, 14 is a flow meter, 15 is a pressure regulating valve, 16 is a lower motor, 17 is an upper motor, 18 is a lid, 19 is a support cylinder, 20 is an upper rotating shaft, and 21 is a mechanical seal , 22 is an upper housing, 23 is a partition plate, 24 is a lower rotating shaft, 25 is a pressure gauge, and 26 is a thermometer.

  The stirring device of FIG. 2 will be described. The polymerizable monomer composition charged into the dispersion container 4 is formed in a minute gap between the inner wall of the screen 2 and the blade tip by the stirring blade 1 rotating at high speed inside the stirring chamber 3. The pigment that has undergone shearing force and re-agglomerated by pigment shock in the polymerizable monomer composition is redispersed. And since the stirring chamber 3 rotates in the direction opposite to the rotation direction of the stirring blade 1, the relative rotational speed of both can be increased, and the shearing force applied to the re-aggregated pigment can be increased. Thereby, it is possible to disperse the re-aggregated pigment to a higher degree than the conventional stirring device. Furthermore, since the discharge port 5 in the stirring chamber 3 rotates in the direction opposite to the rotation direction of the stirring blade 1, the fluid discharge position changes with the rotation, and the polymerizable monomer is changed in the dispersion container 4. The composition circulates well. In addition, since this flow is added to the discharge flow caused by the rotation of the stirring blade 1 that rotates with a small gap from the discharge port 5, a faster discharge flow can be obtained, and the entire circulation is further promoted. .

  Furthermore, by providing the inlet 10 at the upper part of the stirring blade 1 inside the stirring chamber 3, the polymerizable monomer composition rotates in the opposite direction at high speed immediately after the polymerizable monomer composition is discharged into the dispersion container 4 from the inlet 10. The agitating blade 1 and the screen 2 that are subjected to high-speed shearing can pass through the discharge port 5 from the inside of the agitating chamber 3. That is, the polymerizable monomer composition can be prevented from returning to the adjustment tank without passing through the discharge port 5 without being subjected to the high-speed shearing process (short pass), and the dispersion time can be shortened. Become. In addition, when the short path cannot be suppressed, the processing time increases, resulting in pigment overdispersion and overgrinding. As a result, the viscosity of the polymerizable monomer composition increases due to an increase in the surface area of the pigment. Resulting in. An increase in the viscosity of the polymerizable monomer composition deteriorates the granulation property in the next granulation step, and the particle size distribution becomes broad. Therefore, a short pass can be prevented and a decrease in granulation property can be suppressed by optimally designing the introduction port inside the stirring chamber. Further, the dispersion container 4 has a jacket structure, and by flowing a cooling medium in the jacket 6, it becomes possible to lower the temperature of the polymerizable monomer composition that has risen due to shear inside the dispersion container. .

  Next, the distributed system of FIG. 1 will be described. After the colorant-containing monomer and the resin are charged into the adjustment tank 7, the polymerizable monomer composition mixed by the stirring blade 8 laid on the adjustment tank 7 is introduced from the inlet 10 through the circulation pump 9. Supplied and introduced into the inlet 11. Next, the polymerizable monomer composition introduced from the suction port 11 passes through the above-described minute gap and is discharged from the discharge port 5. The discharged polymerizable monomer composition circulates in the dispersion container 4, is then discharged from the discharge port 12, and returns to the holding tank 7 via the heat exchanger 13. The circulation of supplying the polymerizable monomer composition returned to the holding tank 7 to the inlet 10 again is repeated. By repeating the circulation between the disperser and the adjusting tank 7, the pigment re-aggregated by the pigment shock in the polymerizable monomer composition is uniformly and efficiently redispersed. It is preferable that the portion of the heavy synthetic monomer composition that has been subjected to the high-speed shearing treatment to be discharged again into the adjustment tank is located in the heavy polymerization monomer composition in the adjustment tank. Since the heavy synthetic monomer composition subjected to the high-speed shearing treatment is returned to the heavy synthetic monomer composition in the adjustment tank, gas entrainment can be prevented. Incorporation of gas into the polysynthetic monomer composition is not preferred because it promotes the generation of cavitation during the high-speed shearing process in the stirring chamber 3 and decreases the dispersion efficiency. The heat exchanger 13 is not necessarily provided on the circulation line, and a coil-type heat exchange line may be installed in the dispersion vessel 4.

  The processing flow rate is measured by a flow meter 14 installed in the circulation path. Further, it is possible to apply a back pressure by the pressure adjusting valve 15. By applying the back pressure, it becomes possible to suppress the occurrence of cavitation due to the rotation of the stirring blade 1 and the screen 2, and it is possible to further apply a shearing force to the treatment liquid. As a result, the re-dispersion of the pigment in the polymerizable monomer composition can be efficiently performed. Therefore, in the present invention, a back pressure can be suitably applied. A particularly preferable back pressure is in the range of 50 kPa to 150 kPa. If it is 50 kPa or less, the back pressure is insufficient, and it is difficult to suppress the occurrence of cavitation, which is not preferable. In addition, at 150 kPa or more, the shearing force becomes very large, the temperature of the polymerizable monomer composition in the stirring chamber 3 is extremely increased, and the polymerizable monomer composition starts polymerization by heat. This is not preferable because the molecular weight of the toner cannot be obtained.

  Next, the conditions of the stirring blade 1 and the screen 2 for efficiently redispersing the pigment in the polymerizable monomer composition will be described in detail. Assuming that the peripheral speed of the stirring blade 1 is A (m / s) and the peripheral speed of the screen 2 is B (m / s), there are ranges where 25 ≦ A ≦ 40 and (A−10) ≦ B ≦ (A + 10). preferable. As the peripheral speed of the stirring blade 1 increases, the shearing force applied to the polymerizable monomer composition increases, and the redispersion efficiency of the pigment also improves.

  Similar to the stirring blade 1, the higher the peripheral speed of the screen 2, the greater the shearing force applied to the polymerizable monomer composition and the better the redispersion efficiency of the pigment. However, when the peripheral speed B (m / s) of the screen is relatively 10 or less relative to the peripheral speed A (m / s) of the stirring blade, the screen rotates in the reverse direction through a minute gap between the blade tip and the blade. This is not preferable because the shearing force with the screen 2 is insufficient. On the other hand, with the rotation of the stirring blade 1, the polymerizable monomer composition is discharged from the stirring blade 1 toward the discharge port 5 of the screen 2, and is discharged out of the stirring chamber as a high-pressure flow from the discharge port. The The pressure generated in the polymerizable monomer composition discharged outside the stirring chamber≈resistance≈shearing force increases as the peripheral speed of the screen 2 increases, and at the same time, the polymerizable monomer discharged from the discharge port 5 of the screen 2 increases. The discharge amount of the meter composition decreases. And when the peripheral speed B of the screen 2 is relatively 10 or more larger than the peripheral speed A of the stirring blade, the decrease in the discharge amount of the polymerizable monomer composition discharged from the discharge port 5 of the screen 2 is large. The ratio of the polymerizable monomer composition that is short-passed without passing through the discharge port 5 and discharged out of the stirring chamber increases. Therefore, when the number is 10 or more, a decrease in the redispersion rate due to an increase in the short path and a circulation flow inside the dispersion vessel 4 are reduced, and nonuniformity in the tank occurs, which is not preferable. From the above, the peripheral speed B (m / s) of the screen 2 is preferably in the range of (A−10) ≦ B ≦ (A + 10). As the above-mentioned disperser, for example, Creamics W motion (manufactured by M Technique Co., Ltd.) can be suitably used.

  An image forming method suitably used in the present invention will be described with reference to FIGS. FIG. 4 shows the configuration of the image forming apparatus used in the evaluation of the present embodiment. FIG. 4 is a sectional view of a tandem color LBP (color laser printer) using a transfer type electrophotographic process. In FIG. 4, the image forming apparatuses Y, M, C, and Bk are referred to as a unit a, a unit b, a unit c, and a unit d, respectively. The electrostatic adsorption conveyance belt 109a is stretched around a driving roller 109b, fixed rollers 109c and 109e, and a tension roller 109d. The electrostatic adsorption conveyance belt 109a is rotationally driven by the driving roller 109b in the direction of the arrow in the figure to adsorb and convey the recording medium S. To do. A toner image is formed on the photosensitive drum by the developing units 104a to 104d, and the electrostatic latent image is visualized. The formed four-color toner images are synchronized by a registration roller 108c that stops and re-transports the recording medium S conveyed by the paper feed roller 108b at a predetermined timing, so that the photosensitive drum and the electrostatic adsorption conveyance belt 109a are in contact with each other. The toner images are sequentially transferred to the recording medium S at the nip portion. The recording medium S to which the toner image has been transferred is separated from the surface of the electrostatic attraction / conveyance belt 109a by the driving roller 109b and sent to the fixing device 110. After the toner image is fixed by the fixing device 110, the recording medium S is discharged by the discharge roller 110c. It is discharged to the discharge tray 113.

  Next, a specific example of the image forming method using the non-magnetic one-component contact developing method will be described with reference to an enlarged view of the developing unit (FIG. 3). In FIG. 3, a developing unit 313 is located in a developer container 323 containing a nonmagnetic toner 317 as a one-component developer, and an opening extending in the longitudinal direction in the developer container 323, and a latent image carrier ( A photosensitive drum 310 and a toner carrier 314 disposed opposite to each other. The electrostatic latent image on the latent image carrier 310 is developed and visualized. The latent image carrier contact charging member 311 is in contact with the latent image carrier 310. The bias of the latent image carrier contact charging member 311 is applied by a power source 312.

  The toner carrying member 314 is horizontally provided with the substantially right half-peripheral surface shown in the drawing through the opening into the developer container 323 and the left substantially half-periphery surface exposed to the outside of the developer container 323. The surface exposed to the outside of the developer container 323 is in contact with the latent image carrier 310 located on the left side of the developing unit 313 in the drawing as shown in FIG.

  The toner carrier 314 is rotationally driven in the direction of arrow B, the peripheral speed of the latent image carrier 310 is 50 to 170 mm / s, and the peripheral speed of the toner carrier 314 is 1 to 2 with respect to the peripheral speed of the latent image carrier 310. It is rotating at twice the peripheral speed.

  Above the toner carrier 314, a metal plate such as SUS, a rubber material such as urethane or silicone, a metal thin plate made of SUS or phosphor bronze having spring elasticity, and a contact surface side to the toner carrier 314 A restricting member 316 made of a rubber material and the like is supported by the restricting member support metal plate 324 so that the vicinity of the free end is brought into contact with the outer peripheral surface of the toner carrier 314 by surface contact. The contact direction is a so-called counter direction in which the tip side with respect to the contact portion is located upstream of the rotation direction of the toner carrier 314. As an example of the regulating member 316, a plate-like urethane rubber having a thickness of 1.0 mm is bonded to the regulating member support metal plate 324, and the contact pressure (linear pressure) with respect to the toner carrier 314 is appropriately set. is there. The contact pressure is preferably 20 to 300 N / m. The measurement of the contact pressure is converted from a value obtained by inserting three metal thin plates with known friction coefficients into the contact portion and pulling out the central one with only a spring. It is preferable that the regulating member 316 is made by adhering a rubber material or the like on the abutting surface side because it has an adhesive property to the toner and can suppress the fusion and fixing of the toner to the regulating member during long-term use. In addition, the regulating member 316 can make the contact state with the toner carrier 314 an edge contact that makes the tip contact. In the case of edge contact, it is more desirable in terms of toner layer regulation to set the contact angle of the regulating member with respect to the tangent of the toner carrying body at the contact with the toner carrying body to be 40 degrees or less.

  The toner supply roller 315 is in contact with the contact portion of the regulating member 316 with the surface of the toner carrier 314 on the upstream side in the rotation direction of the toner carrier 314 and is rotatably supported. The contact width of the toner supply roller 315 with respect to the toner carrier 314 is preferably 1 to 8 mm, and it is preferable that the toner carrier 314 has a relative speed at the contact portion.

  The charging roller 329 is not essential for the image forming method of the present invention, but is preferably installed. The charging roller 329 is an elastic body such as NBR or silicone rubber, and is attached to the suppression member 330. The contact load of the charging roller 329 on the toner carrier 314 by the suppressing member 330 is set to 0.49 to 4.9N. By the contact of the charging roller 329, the toner layer on the toner carrier 314 is finely packed and uniformly coated. The longitudinal positional relationship between the regulating member 316 and the charging roller 329 is preferably arranged so that the charging roller 329 can reliably cover the entire contact area of the regulating member 316 on the toner carrier 314.

  In addition, for driving the charging roller 329, it is essential to follow or have the same peripheral speed with the toner carrier 314. If a peripheral speed difference occurs between the charging roller 329 and the toner carrier 314, the toner coat becomes uneven. This is not preferable because unevenness occurs on the image. The bias of the charging roller 329 is applied by a power source 327 between the toner carrier 314 and the latent image carrier 310 in a direct current, and the nonmagnetic toner 317 on the toner carrier 314 is charged by the discharge from the charging roller 329. Get granted. The bias of the charging roller 329 is equal to or higher than the discharge start voltage having the same polarity as that of the nonmagnetic toner, and is set so as to generate a potential difference of 1000 to 2000 V with respect to the toner carrier 314.

  After being charged by the charging roller 329, the toner layer formed as a thin layer on the toner carrier 314 is uniformly conveyed to the developing unit which is a portion facing the latent image carrier 310. In this developing unit, the toner layer formed on the toner carrier 314 is formed into a latent image by a DC bias applied between the toner carrier 314 and the latent image carrier 310 by the power source 327 shown in FIG. The electrostatic latent image on the carrier 310 is developed as a toner image.

  The present invention will be specifically described with reference to the following examples. Unless otherwise specified, all parts and% in the examples and comparative examples are based on mass.

(Toner Production Example 1)
[Creation of aqueous medium]
9 parts by mass of tricalcium phosphate and 11 parts by mass of 10% hydrochloric acid are added to 1300 parts by mass of ion-exchanged water heated to a temperature of 60 ° C., and TK-type homomixer (manufactured by Special Machine Industries) is used. The aqueous medium was prepared by stirring at 000 r / min.

[Preparation of wax dispersion]
20.0 parts by mass of styrene and 9.0 parts by mass of a hydrocarbon wax having a melting point at 111 ° C. (C105, manufactured by Schumann-Sazol) were mixed and wet-pulverized with a homogenizer for 30 minutes to obtain a wax dispersion.

[Create Toner]
The following materials were dissolved with a propeller type stirring device at 100 r / min to prepare a solution.

Styrene 49.0 parts by mass n-butyl acrylate 31.0 parts by mass sulfonic acid group-containing resin (acrylic base FCA-1001-NS, manufactured by Fujikura Kasei) 0.7 part by mass Polar resin (styrene-methyl methacrylate) -Methacrylic acid copolymer) 15.0 parts by mass (copolymerization ratio: styrene / methyl methacrylate / methacrylic acid = 95.85 / 2.50 / 1.65, Mp = 15800, Mw = 14000)
Next, the following materials were added to the solution.
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, negative charge control agent (Bontron E-88, manufactured by Orient Chemical Co., Ltd.) 0.7 parts by mass, the wax dispersion 29.0 parts by mass, and then the polysynthetic monomer composition Was heated to 60 ° C. and then treated with a Cavitron (manufactured by Eurotech) as a stirrer at a peripheral speed of the rotor of 35 (m / s) for 2 hours. The polymerizable monomer composition and 8.0 parts by mass of the polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) are charged into the aqueous medium, and a TK homomixer at a temperature of 60 ° C. Was stirred for 10 minutes at 15,000 r / min and granulated. Thereafter, the reaction was carried out at a temperature of 80 ° C. for 10 hours while moving to a propeller type stirring device and stirring at 100 r / min. After completion of the polymerization reaction, the resulting slurry containing the particles was cooled, washed with 10 times the amount of water as the slurry, filtered and dried, and then adjusted to a particle size by classification to obtain toner particles.

Hydrophobic silica fine powder (number average 1) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100 parts by mass of the toner particles. A toner (A) was obtained by mixing 2.0 parts by mass of a secondary particle size of 10 nm and a BET specific surface area of 170 m ^{2 /} g with a Henschel mixer (manufactured by Mitsui Miike) at 3,000 r / min for 15 minutes. With respect to the obtained toner, the wax content in the toner was measured and found to be 9 parts by mass with respect to 100 parts by mass of the binder resin.

(Toner Production Example 2)
In Toner Production Example 1, the polysynthetic monomer composition was heated to 60 ° C., and then the same as in Example 1 except that Creamix W Motion (M Technique) was used as a stirring device. Thus, toner (B) was obtained. The treatment conditions were as follows: the peripheral speed of the stirring blade 1 was 30 (m / s), the peripheral speed of the screen 2 was 30 (m / s), and the back pressure was 100 kPa for 2 hours.

(Toner Production Example 3)
A toner (C) was produced in the same manner as in Example 1 except that the wax was changed to a hydrocarbon wax having a melting point of 83 ° C. (Hi-Mic-1080, manufactured by Nippon Seiki Co., Ltd.). Obtained.

(Toner Production Example 4)
A toner (D) was obtained in the same manner as in Example 1 except that the wax was changed to a hydrocarbon wax having a melting point of 118 ° C. (410P, manufactured by Mitsui Petrochemical Co., Ltd.). .

(Toner Production Example 5)
In Example 1, a toner (E) was obtained in the same manner as in Example 1 except that the wet pulverization process in the adjustment step of the wax dispersion was 40 minutes.

(Toner Production Example 6)
In Example 1, a toner (F) was obtained in the same manner as in Example 1 except that the wet pulverization in the step of adjusting the wax dispersion was performed for 20 minutes.

(Toner Production Example 7)
A toner (G) was obtained in the same manner as in Example 1 except that the reaction temperature was changed to 78 ° C. in Example 1.

(Toner Production Example 8)
A toner (H) was obtained in the same manner as in Example 1 except that the reaction temperature was changed to 85 ° C. in Example 1.

(Toner Production Example 9)
The toner (I) was obtained in the same manner as in Example 1 except that the wet pulverization process in the wax dispersion liquid adjusting process in Example 1 was 20 minutes and the reaction temperature was changed to 85 ° C. It was.

(Toner Production Example 10)
In Example 1, the toner is manufactured in the same manner as in Example 1 except that the wet pulverization process in the adjustment step of the wax dispersion is 20 minutes and the reaction temperature is changed to 65 ° C. to obtain toner (J). It was.

(Toner Production Example 11)
A toner (K) is produced in the same manner as in Example 1 except that the wet pulverization process in the wax dispersion adjusting step is 1 hour and the reaction temperature is changed to 85 ° C. in Example 1. It was.

(Toner Production Example 12)
A toner (L) is produced in the same manner as in Example 1 except that the wet pulverization process in the wax dispersion adjusting step is 1 hour and the reaction temperature is changed to 65 ° C. in Example 1. It was.

(Toner Production Example 13)
Example 1 was the same as Example 1 except that the low molecular weight component of hydrocarbon wax (PW725, manufactured by Toyo Petrolite Co., Ltd.) having a melting point of 98 ° C. was changed to a wax cut by 30% by mass by distillation. Thus, toner (M) was obtained.

(Toner Production Example 14)
A toner (N) was produced in the same manner as in Example 1 except that the amount of wax added was changed to 5.0 parts by mass in Example 1. In this production example, as the wax is changed to 5.0 parts by mass, 25.0 parts by mass of the wax dispersion at the time of toner preparation is added.

(Toner Production Example 15)
A toner (O) was obtained in the same manner as in Example 1 except that the amount of wax added in Example 1 was changed to 24.0 parts by mass. In this production example, as the wax is changed to 24.0 parts by mass, 44.0 parts by mass of the wax dispersion at the time of toner preparation is added.

(Toner Production Example 16)
A toner (P) was obtained in the same manner as in Example 1, except that the stirring treatment of the polysynthetic monomer composition was not performed in Example 1.

(Toner Production Example 17)
A toner (Q) was obtained in the same manner as in Example 1 except that the amount of wax added was changed to 3.0 parts by mass in Example 1. In this production example, as the wax is changed to 3.0 parts by mass, 23.0 parts by mass of the wax dispersion at the time of toner preparation is added.

(Toner Production Example 18)
A toner (R) was obtained in the same manner as in Example 1 except that the amount of wax added in Example 1 was changed to 26.0 parts by mass. In this production example, as the wax is changed to 26.0 parts by mass, 46.0 parts by mass of the wax dispersion at the time of toner preparation is added.

(Toner Production Example 19)
In Toner Production Example 19, a toner was produced by the following dissolution suspension method.

[Creation of aqueous medium]
At room temperature, 9 parts by mass of tricalcium phosphate and 11 parts by mass of 10% hydrochloric acid are added to 1300 parts by mass of ion-exchanged water, and 10,000 r / min is used using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.). The aqueous medium was prepared by stirring at

[Preparation of wax dispersion]
20.0 parts by mass of ethyl acetate and 9.0 parts by mass of hydrocarbon wax (C105, manufactured by Schumann-Sazol) having a melting point at 111 ° C. were mixed, and wet-pulverized for 30 minutes with a homogenizer to obtain a wax dispersion. .

[Create Toner]
Moreover, the following material was melt | dissolved at 100 r / min with the propeller-type stirring apparatus, and the solution was prepared.
・ Ethyl acetate 300.0 parts by mass ・ Styrene-n-butyl acrylate copolymer 100.0 parts by mass (the copolymerization ratio is styrene / n-butyl acrylate = 70/30, Mp = 19000, Mw = 110000)
・ Sulphonic acid group-containing resin (acrylic base FCA-1001-NS, manufactured by Fujikura Kasei Co., Ltd.) 0.7 parts by mass Polar resin (styrene-methyl methacrylate-methacrylic acid copolymer) 15.0 parts by mass (copolymerization ratio is Styrene / methyl methacrylate / methacrylic acid = 95.85 / 2.50 / 1.65, Mp = 15800, Mw = 14000)
Next, the following materials were added to the solution.
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, negative charge control agent (Bontron E-88, manufactured by Orient Chemical Co., Ltd.) 0.7 parts by mass, the wax dispersion 29.0 parts by mass, and then the polysynthetic monomer composition Was heated to 60 ° C. and then treated with a Cavitron (manufactured by Eurotech) as shown in FIG. 5 at a rotor peripheral speed of 35 (m / s) for 2 hours. The polymerizable monomer composition was charged into the aqueous medium, and the mixture was granulated by stirring at 15,000 r / min for 10 minutes at a temperature of 60 ° C. using a TK homomixer. Thereafter, the mixture was transferred to a propeller type stirring apparatus and distilled at a temperature of 80 ° C. for 10 hours under reduced pressure while stirring at 100 r / min to remove ethyl acetate. The resulting slurry containing the particles was cooled, washed with 10 times the amount of water as the slurry, filtered and dried, and then the particle diameter was adjusted by classification to obtain toner particles.

Hydrophobic silica fine powder (number average 1) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100 parts by mass of the toner particles. A toner (S) was obtained by mixing 2.0 parts by mass of a secondary particle size of 10 nm and a BET specific surface area of 170 m ^{2 /} g with a Henschel mixer (manufactured by Mitsui Miike) at 3,000 r / min for 15 minutes.

(Toner Production Example 20)
In Toner Production Example 20, the toner was produced by the following pulverization method.

(Creation of wax dispersion particles)
20.0 parts by mass of ethyl acetate and 9.0 parts by mass of hydrocarbon wax having a melting point at 111 ° C. (C105, manufactured by Schumann-Sazol) were mixed, wet-pulverized with a homogenizer for 30 minutes, and then ethyl acetate by distillation under reduced pressure. Were removed to obtain wax-dispersed particles.

[Create Toner]
Styrene-n-butyl acrylate copolymer 100.0 parts by mass (copolymerization ratio is styrene / n-butyl acrylate = 70/30, Mp = 19000, Mw = 110000)
・ Sulphonic acid group-containing resin (acrylic base FCA-1001-NS, manufactured by Fujikura Kasei Co., Ltd.) 0.7 parts by mass Polar resin (styrene-methyl methacrylate-methacrylic acid copolymer) 15.0 parts by mass (copolymerization ratio is Styrene / methyl methacrylate / methacrylic acid = 95.85 / 2.50 / 1.65, Mp = 15800, Mw = 14000)
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, negative charge control agent (Bontron E-88, manufactured by Orient Chemical Co., Ltd.) 0.7 parts by mass Particles were obtained.

Hydrophobic silica fine powder (number average 1) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100 parts by mass of the toner particles. A toner (T) was obtained by mixing 2.0 parts by mass of a secondary particle size of 10 nm and a BET specific surface area of 170 m ^{2 /} g with a Henschel mixer (manufactured by Mitsui Miike) at 3,000 r / min for 15 minutes.

(Toner Production Example 21)
In Example 1, except that the low molecular weight component of hydrocarbon wax (PW725, manufactured by Toyo Petrolite Co., Ltd.) having a melting point at 98 ° C. was changed to wax cut by 27% by mass by distillation, the same as in Example 1. Thus, toner (a) was obtained.

(Toner Production Example 22)
In Example 1, a toner (b) was obtained in the same manner as in Example 1 except that the wet pulverization process in the adjustment step of the wax dispersion was performed for 2 hours.

(Toner Production Example 23)
A toner (c) was obtained in the same manner as in Example 1 except that the wet pulverization process in the wax dispersion liquid adjusting step was 10 minutes.

(Toner Production Example 24)
A toner (d) was obtained in the same manner as in Example 1 except that the reaction temperature was changed to 50 ° C. in Example 1.

(Toner Production Example 25)
In Example 1, except that the reaction temperature was changed to 90 ° C. A toner (e) was obtained in the same manner as in Example 1.

  Table 1 shows the A value, the B value, the wax content (analysis result) with respect to 100 parts by mass of the binder resin, and the total amount of wax volatile substances for the toners (A) to (T) and the toners (a) to (e). Show.

  Hereinafter, the evaluation method and evaluation criteria will be described.

<Evaluation of low-temperature fixability>
In a developer container of the Satera LBP 5800 (manufactured by Canon Inc.) which is a developing device of the one-component contact developing system shown in FIG. (Humidity 60% RH). At this time, the transfer paper was also left in the same manner. Thereafter, a developing device is mounted on the unit c in FIG. 4 in an environment of normal temperature and humidity (temperature 23.5 ° C., humidity 60% RH), and an unfixed image is processed at a process speed of 250 mm / s in the cyan monochrome mode. Output.

(Rubbing test)
A plain paper for copying machines (64 g / m ² paper) was used as a transfer material, and an unfixed solid image with a toner paste amount of 0.7 mg / cm ² was obtained. This was fixed at a process speed of 250 mm / s using a fixing machine of IRC3200 (manufactured by Canon Inc.). The fixing temperature was decreased by 5 ° C from 200 ° C to 130 ° C. The image was reciprocated five times with sylbon paper applied with a load of 4.9 kPa, and the temperature at which the density reduction rate was 20% or more was evaluated as the minimum fixing temperature.
A: The minimum fixing temperature is less than 145 ° C.
B: The minimum fixing temperature is 145 ° C. or higher and lower than 155 ° C.
C: The minimum fixing temperature is 155 ° C. or higher and lower than 165 ° C.
D: The minimum fixing temperature is 165 ° C. or higher.

(Burn test)
A plain paper for copying machines (105 g / m ² paper) was used as a transfer material, and an unfixed solid image having a toner paste amount of 0.7 mg / cm ² was obtained. This was fixed using a fixing machine of IRC3200 (manufactured by Canon Inc.) at a process speed of 250 mm / s and a fixing temperature of 190 ° C. Swelling is a phenomenon in which a part of an image is peeled off by a fixing roller during a fixing process because a sufficient amount of heat is not applied to toner particles. This level of blistering was evaluated visually.
A: Not generated B: Generated slightly C: Generated but no problem Level D: Generated significantly (bending test)
A plain paper for copying machines (64 g / m ² paper) was used as a transfer material, and an unfixed solid image with a toner paste amount of 0.7 mg / cm ² was obtained. This was fixed using a fixing machine of IRC3200 (manufactured by Canon Inc.) at a process speed of 250 mm / s and a fixing temperature of 190 ° C. Thereafter, the image portion is bent. The bending condition was that the bent portion was moved 5 times while applying a load of 4.9 kPa with a flat weight. Thereafter, the folded image portion was rubbed and rubbed 5 times with sylbon paper applied with a load of 4.9 kPa, and the density reduction rate of the image density before and after rubbing was measured.
A: The decrease in density is less than 5%.
B: The decrease in density is 5% or more and less than 10%.
C: Density decrease is 10% or more and less than 15%.
D: Density decrease is 15% or more.

<Evaluation on fusing member contamination and developability>
In the developing device of the one-component contact developing system shown in FIG. 3, a developer container is filled with 70 g of the toner described in the examples and comparative examples, and is in an environment of normal temperature and normal humidity (temperature 23.5 ° C., humidity 60% RH). Leave for 24 hours. At this time, the transfer paper was also left in the same manner. In this evaluation, Xerox 4200 (manufactured by Xerox Corporation) (75 g / m ² paper) was used as the transfer paper. Thereafter, the developing device was mounted on the unit c in FIG. 4 in an environment of normal temperature and normal humidity (temperature 23.5 ° C., humidity 60% RH). In the cyan monochrome mode, the process speed was 250 mm / s, and continuous output was performed on a chart with a printing ratio of 2%. The following evaluation was carried out at the time of initial (first sheet) / 5,000 sheets / 10,000 sheets for the evaluation of the fusing member member contamination and developability.

(Visual evaluation of fuser member contamination)
The contamination of the fixing device member was evaluated by directly checking the fixing device visually.
A: Not generated.
B: Slight contamination is seen.
C: Contamination has occurred but there is no problem.
D: Contamination is remarkable.

(Image density)
The image density was measured using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth). As a measurement method, a relative density with respect to an image of a white background portion having an original density of 0.00 was measured.
A: The image density is 1.40 or more.
B: The image density is 1.30 or more and less than 1.40.
C: The image density is 1.20 or more and less than 1.30.
D: The image density is 1.10 or more and less than 1.20.

(Fog)
The fog evaluation method outputs an image having a white background portion, and the whiteness (reflectance Ds (%)) of the white background portion of the printout image measured by “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku) and the transfer paper The fog density (%) (= Dr (%) − Ds (%)) was calculated from the difference in whiteness (average reflectance Dr (%)), and the image fog at the end of the durability evaluation was evaluated. An amberlite filter was used as the filter.

  A: The fog density is less than 0.5%.

  B: The fog density is 0.5% or more and less than 1.0%.

  C: The fog density is 1.0% or more and less than 1.5%.

  D: The fog density is 1.5% or more.

  Table 2 shows the results of evaluation of toners (A) to (T) and toners (a) to (e) by the above evaluation method. All of the toners (A) to (T) were evaluated (A to C) at or above a level at which there was no problem in use in all the evaluation items of low temperature fixability, fixing member contamination, and developability. On the other hand, toners (a) to (e) were evaluated at a level (D) that is not permitted in use in any of the above evaluation items.

DESCRIPTION OF SYMBOLS 1 Stirring blade 2 Screen 3 Stirring chamber 5 Discharge port 6 Jacket 7 Holding tank 8 Stirring blade 9 Circulation pump 10 Dispersion container inlet 11 Suction port 12 Discharge port 13 Heat exchanger 104 Developing part 108b Paper feed roller 108c Registration roller 109a Electrostatic adsorption Conveying belt 109b Drive roller 109c Fixed roller 109d Tension roller 109e Fixed roller 110 Fixing device 110c Discharge roller 113 Discharge tray 202 Casing 208 Holding tank 210 Circulation pump 221 Stator 225 Rotor 310 Latent image carrier 311 Latent image carrier contact charging member 313 Development unit 314 Toner carrier 316 Restriction member 317 Non-magnetic toner 323 Developer container 329 Charging roller

Claims (6)

A toner having toner particles containing a binder resin, a colorant and a hydrocarbon wax,
The melting point of the hydrocarbon wax is 80 ° C. or higher and 120 ° C. or lower,
In the GC / MS analysis of the component desorbed by heating the hydrocarbon wax at 200 ° C. for 10 minutes with a heat desorption apparatus, the amount of volatile components detected after the peak detection time of hexadecane is 1100 ppm or less in terms of hexadecane. ,
In the cross section of the toner particles observed using a transmission electron microscope (TEM), the ratio of the number of particles in which the shape factor SF-1 of the dispersed particles of the hydrocarbon wax in the cross section is 1.5 or less is A number. %, When the proportion of particles having a shape factor SF-1 of 3.0 or more is B number%,
30 ≦ A ≦ 75
2 ≦ B ≦ 20
The toner is characterized in that the hydrocarbon wax is dispersed in the toner particles. A and B are
30 ≦ A ≦ 60
5 ≦ B ≦ 20
The toner according to claim 1, wherein:   The toner according to claim 1, wherein a content of the hydrocarbon wax is 4 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the binder resin.   The toner particles are obtained by dispersing a polymerizable monomer composition containing a polymerizable monomer, the colorant and the hydrocarbon wax in an aqueous medium, granulating the polymerized monomer. 4. The toner according to claim 1, wherein the toner particles are obtained as described above.   When dispersing the polymerizable monomer composition in the aqueous medium, a stirring device provided with a stirring blade rotating at high speed and a screen rotating around the stirring blade at high speed in the direction opposite to the stirring blade is used. The toner according to claim 4, wherein the polymerizable monomer composition is treated.   When the polymerizable monomer composition is dispersed in the aqueous medium, a stator having a shape similar to a rotor in which ring-shaped protrusions having a plurality of slits are formed in multiple stages on a concentric circle are spaced apart from each other. 5. The toner according to claim 4, wherein the polymerizable monomer composition is treated using a stirring device installed coaxially so as to maintain the same and mesh with each other.