JP4332383B2 - Toner, image forming method, process cartridge, and developing unit - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, or a toner jet recording method, an image forming method using the toner, a process cartridge and a developing unit used therefor.

  Conventionally, many methods are known as electrophotographic methods. Generally, a photoconductive substance is used to form an electric latent image on an image carrier (photosensitive member) by various means, and then, The latent image is developed with toner to be visualized, and if necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat / pressure to obtain a copy. Is.

  As a method for visualizing an electric latent image, a magnetic two-component developing method comprising a magnetic toner and a carrier, a non-magnetic two-component developing method comprising a non-magnetic toner and a carrier, and a non-magnetic toner using an external additive particle alone are not used. In general, a magnetic one-component development system and a magnetic one-component development system using a magnetic toner are widely used.

  On the other hand, in the electrophotographic industry, the image resolution of printers and the like has been increased to 1200, 2400 dpi. Accordingly, the development method of the printer apparatus is also required to have higher definition. Also, copying machines are becoming more sophisticated and digitized, and as with printers, higher resolution and higher definition are required.

  Further, in recent years, as copiers and printers using electrophotography have been widely used, including in homes, etc., there is an increasing demand for making copy machines or printers inexpensive and small.

  In response to the above requirements, it has been required to enable a design with simpler components. As a result, the image forming apparatus has higher functionality required for members used in various respects. The same applies to the functionality required of the toner, and if the improvement in toner performance cannot be achieved, a more excellent image forming apparatus is no longer realized. In particular, there is a strict requirement for maintaining the image quality of the initial image and obtaining a stable image in any environment, and improvement of charging performance is an indispensable issue in improving toner performance.

  Either the two-component development method, in which the charge amount is determined by frictional charging between the toner and the carrier, or the one-component development method, in which the charge amount is determined only by the friction between the developer carrier and the charge imparting material, There are still problems to improve such as maintaining the charge amount, charge speed, and charge value.

  Especially when used for a long period of time, the two-component development method is greatly affected by the contamination of the carrier with the toner, and the one-component development method is greatly affected by the contamination of the regulating member with the toner. Maintenance is a major issue.

As a means for solving the above problems, a charge control agent has been added to stabilize the charging of the toner. As charge control agents, for example, monoazo dye metal complex salts, salicylic acid, naphthoic acid, dicarboxylic acid metal complex salts, and copper phthalocyanine pigments are known. However, since these charge control agents are colored, there is a problem that the hue changes when used in color toners. In addition, since such a charge control agent has poor compatibility with the binder resin or poor storage stability, the charge control agent on the toner surface, which is greatly involved in charging, is easily dissociated, and toner charge Variation and sleeve contamination are likely to occur. In particular, it is difficult to maintain the charging ability of the toner in a long-term use, and the influence of environmental factors becomes large in the charging performance of the toner in each environment, and the charge variation is likely to occur. Furthermore, since many of these contain heavy metals such as chromium, they have recently become a problem from the viewpoint of safety.

  Therefore, a method using a resin charge control agent as a charge control agent having improved compatibility with the binder resin, transparency of the toner fixed image, and safety has been proposed (for example, see Patent Documents 1, 2, and 3). ). Since these resin charge control agents have good compatibility with the binder resin, they are excellent in stable chargeability and transparency. However, toners using these resin charge control agents have the disadvantage that the charge amount and charge speed are inferior compared to toners using charge control agents such as azo dye metal complex salts. In addition, the chargeability is improved by increasing the amount of the resin charge control agent added, but the compatibility with the binder resin is lowered and there is a problem that the toner fixability (offset resistance / low temperature fixability) is adversely affected. .

  Further, toners using these resin charge control agents have a broad charge distribution, and unevenness occurs in development and transfer, which causes problems such as fogging, insufficient density, and insufficient solid image uniformity. In recent years, the demand for printers has expanded, and devices have become smaller, faster, and lower in cost. As a result, higher reliability and longer life have been demanded for the devices. However, conventional resin charge control agents cannot maintain the charge control effect, and there is a problem that the charge performance of the toner is lowered.

  Therefore, in this resin charge control agent, a method in which sulfur element is contained and a predetermined metal is contained in the toner, and an aromatic monomer having a sulfonate group, a perfluoroalkyl group, and an electron withdrawing group are contained in the resin charge control agent. There has been proposed a method of containing a predetermined amount (see, for example, Patent Documents 4 and 5).

In the method in which a sulfur atom is contained in the resin charge control agent and a predetermined metal is contained in the toner, the resin charge control agent is more uniformly distributed in the toner, and the effect of moisture is reduced, thereby stabilizing the chargeability. In addition, since the dispersion of the colorant is also improved, a part of the wax adhering to the surface of the colorant particle is scattered in the binder resin, and the fixing property is improved. In a method in which a predetermined amount of an aromatic monomer having a sulfonate group, a perfluoroalkyl group, or an electron withdrawing group is contained in the resin charge control agent, these resin charge control agents have a high charge amount and a sharp charge distribution over a long period of time. can get. However, toners using these methods are insufficient in fixing properties to cope with the speeding up of the apparatus, the initial density of the image is low in a low temperature and low humidity environment, and the uniformity of the solid image is also insufficient. The problem occurs. Further, in a low-temperature and low-humidity environment, the charge distribution is macroscopically sharp during the development process, but microscopically, a toner with a high charge amount tends to be present in a part, and therefore, on the developing sleeve or The toner layer formed on the latent image carrier is likely to be uneven, and the behavior of the toner at the time of transfer is likely to be non-uniform, causing a problem that image unevenness is likely to occur particularly in a halftone image.
JP 63-184762 A JP-A-3-56974 JP-A-6-230609 JP 11-218965 A JP 2002-108019 A

  An object of the present invention is a toner that solves the above-described problems, that is, has excellent fixability at a low temperature and causes problems such as fogging, blurring, and density reduction even in long-term use in a high-temperature and high-humidity environment. It is an object of the present invention to provide a toner in which a sufficient image density can be obtained from the initial stage even in a low-temperature and low-humidity environment, the uniformity of a solid image is good, and image unevenness does not occur in a halftone image. Another object of the present invention is to provide an image forming method, a process cartridge, and a developing unit using the toner.

  As a result of intensive studies, the present inventors have made the toner particles contain a resin and a wax containing sulfur atoms, and externally added at least silica fine powder and titanium oxide fine powder to the toner particles. The inventors have found that the chargeability and fluidity of the toner can be controlled by controlling the next particle size within an appropriate range, and the present invention has been achieved.

That is, the present invention is obtained through a granulation step in an aqueous medium containing at least a binder resin, a condensation resin, a colorant, a resin containing a sulfur atom having an acid value of 10 to 30 mg KOH / g, and a wax. Hydrophobized anatase type having 0.10 to 3.00 parts by mass of silica fine powder externally added to the toner particles and a primary particle size of 35 to 500 nm with respect to 100 parts by mass of the obtained toner particles The toner having at least 0.01 to 1.00 parts by mass of titanium oxide fine powder, wherein the acid value AV1 of the condensation resin and the acid value AV2 of the resin containing sulfur atoms satisfy the relationship AV1 <AV2. met and a toner, wherein the said titanium oxide fine powder in the toner particle surfaces and number liberation ratio of the silica fine powder is from 0.10 to 25.00%, respectively.

  The present invention also provides an image forming method, a process cartridge, and a developing unit using the toner.

  The toner of the present invention controls the chargeability and fluidity of the toner, and is free from fogging, blurring, and density reduction even when used for a long time in a high temperature and high humidity environment. Prevents the occurrence of problems such as toner scattering, toner fusing and fixing to the developing sleeve and regulating member, and anti-offset properties, and has good solid image uniformity, cleanability, and anti-offset properties, and sufficient density from the beginning. In addition, the image has excellent fixability at low temperatures.

  Further, by using the toner, it is possible to provide an image forming method, a process cartridge, and a developing unit that can obtain a good image even in each environment.

The present invention was obtained through a granulating step in an aqueous medium containing at least a binder resin, a condensation resin, a colorant, a resin containing a sulfur atom having an acid value of 10 to 30 mgKOH / g, and a wax. 0.10 to 3.00 parts by mass of silica fine powder externally added to the toner particles , and a hydrophobized anatase type titanium oxide having a primary particle size of 35 to 500 nm with respect to 100 parts by mass of the toner particles a toner containing at least 0.01 to 1.00 parts by weight of fine powder, and the condensation resin having an acid value AV1 and the sulfur atom-containing resin having an acid value AV2 is, Shi satisfy the relationship AV1 <AV2 The toner is characterized in that the number free rate of the titanium oxide fine powder and the silica fine powder on the toner particle surface is 0.10 to 25.00%, respectively .

  With the above configuration, it has excellent fixability at low temperature, and there is no fogging, blurring or density reduction in long-term use under high temperature and high humidity environment, and insufficient initial image density under low temperature and low humidity environment Further, it is possible to prevent occurrence of toner problems such as insufficient uniformity of a solid image and image unevenness in a halftone image. Details will be described below.

The toner of the present invention contains a sulfur atom-containing resin so that it has sufficient charging performance in each environment, and the toner surface has a silica fine powder and a primary particle size controlled to be hydrophobized and oxidized. By attaching titanium fine powder, it is possible to optimize the fluidity and charging ability of the toner, and the toner layer can be uniformly formed on the developing sleeve and the latent image carrier. As a result, sufficient image uniformity can be obtained, and a sufficient image density can be obtained from the beginning in each environment.

  Even though the toner has sufficient charging performance regardless of the environment due to the resin containing sulfur atoms, the fluidity of the toner is insufficient by itself, and the charge distribution is not sufficiently sharpened. Therefore, it is necessary to adjust the fluidity. In this case, generally, a method of attaching inorganic fine powder, organic fine powder or the like to the toner surface is conceivable. However, organic fine powders are preferable because they are poor in environmental stability and durability in long-term use and easily cause member contamination. Among inorganic fine powders, taking environmental stability into consideration, a combination of silica fine powder and titanium oxide fine powder is good, and the primary particle diameter of titanium oxide fine powder is 35 to 500 nm and is hydrophobized. It is preferable.

  If only silica fine powder is added externally, there is a strong tendency to agglomerate electrostatically, so it is difficult to sufficiently sharpen the charge distribution of the toner, which is particularly affected in low temperature and low humidity environments. It is large, and problems are likely to occur in terms of initial image density and image unevenness.

  On the other hand, the fluidity of the titanium oxide fine powder alone is too high, so that appropriate triboelectric charging is difficult, and in addition, the rapid rise of charging is insufficient. Furthermore, when the primary particle diameter of the titanium oxide fine powder is less than 35 nm, it is likely to be embedded in the toner in the course of long-term use. On the other hand, when the primary particle size of the titanium oxide fine powder is 500 nm or more, it is easy to be detached from the toner surface, and it becomes difficult to maintain the fluidity and charging performance of the toner for a long period of time. The primary particle size of the titanium oxide fine powder is preferably 35 to 250 nm, and more preferably 45 to 100 nm. When the primary particle diameter of the titanium oxide fine powder is 35 nm or more, the developer can be stored in the developer unit in the developing unit even after use for a long period of time due to the fluidity imparting effect and the spacer effect that have a small electrostatic influence. Not packed inside. As a result, sufficient fluidity can be maintained even after being left for a long period of time, and the toner layer on the developing sleeve and the latent image carrier is maintained with respect to the layer thickness and uniformity even during long-term use. Thus, an image having a sufficiently excellent image quality with respect to density, image unevenness, cleaning property and fixing property can be obtained.

  In addition, since the titanium oxide fine powder is hydrophobized, the influence of environmental fluctuations can be suppressed, and by adjusting the degree of hydrophobicity, contamination of components can also be suppressed. The degree is preferably 30 to 95%, more preferably 45 to 80%.

  Since the toner has the above-described configuration, the toner layer is uniformly formed on the developing sleeve and the latent image carrier and is transferred evenly in the cleaning property. It is also possible to suppress the occurrence of poor cleaning due to the occurrence of many local portions. Further, the fixing property is also transferred uniformly, so that the toner layer of the unfixed image is uniform in the fixing process, and the heat and pressure of the fixing device are applied uniformly. An image having fixability can be obtained.

A resin containing a sulfur atom (hereinafter also referred to as “sulfur atom-containing resin”) preferably has a certain acid value. In general, in combination with a colorant that often has basicity, the acid of the sulfur atom-containing resin and the base of the colorant are distributed so that the charge leak sites of the pigment are covered with the sulfur atom-containing resin. As a result, the toner has excellent chargeability. At this time, it is preferable that the sulfur atom-containing resin is a resin containing a SO ₃ X (X = H, alkali metal) group because the effect is great and the charging ability of the sulfur atom-containing resin itself is also excellent.

The resin containing a sulfur atom is more preferably a resin containing a SO ₃ X (wherein X represents H or an alkali metal) group. Examples of the alkali metal X in the formula include sodium and potassium.

Examples of the monomer containing a sulfur atom used for producing a sulfur atom-containing resin include styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid , vinyl Examples include sulfonic acid, methacrylsulfonic acid, or maleic acid amide derivatives, maleimide derivatives, styrene derivatives, sodium styrenesulfonate, sodium 2-acrylamido-2-methylpropanesulfonate, and sodium methacrylsulfonate having the following structure. Preferred is (meth) acrylamide containing a sulfonic acid group.

  The sulfur atom-containing resin according to the present invention may be a homopolymer of the above monomer, but is preferably a copolymer of the above monomer and another monomer. As other monomers that form a copolymer with the above monomers, polymerizable monomers such as vinyl aromatic hydrocarbons and (meth) acrylic acid esters are preferably used. More specifically, monofunctional polymerizable monomers and polyfunctional polymerizable monomers exemplified below can be used.

Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2 -Ethylhexyl acrylate, n- octyl acrylate, n- nonyl acrylate, cyclohexyl accession relays preparative, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, acrylic acid esters such as 2-benzoyloxy ethyl acrylate; methyl Methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, benzyl methacrylate, diethyl phosphate Ethyl methacrylate,
Methacrylic acid esters such as dibutyl phosphate ethyl methacrylate; Methylene aliphatic monocarboxylic acid esters; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; Vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl Vinyl ethers such as ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3- Butylene glycol dimethacrylate, 1, - hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetra- methacrylates, divinyl benzene, divinyl naphthalene, divinyl ether.

  The sulfur atom-containing resin preferably contains 0.01 to 20% by mass of a unit derived from a monomer having a sulfur atom, more preferably 0.05 to 10% by mass, and still more preferably 0.1 to 7%. It is preferable to contain by mass. When the amount is less than 0.01% by mass, the effect of adding the sulfur atom-containing resin is not sufficiently obtained. When the amount exceeds 20% by mass, the compatibility with the binder resin deteriorates when the toner is formed. This is not desirable for controlling the shape of the toner. Further, it is not desirable because impurities are likely to remain because moisture and counter ions are easily retained due to an increase in hygroscopicity during production. In the present invention, when the ions contained in water and the ions contained in the sulfur atom-containing resin have a charge of sulfur atoms or the sulfur atom-containing resin contains a sulfonic acid group or the like, Counter ions are easily held by the sulfonic acid group.

  The sulfur atom-containing resin preferably contains 0.01 to 10% by mass of a monomer unit having an aromatic group having no ionic or nonionic electron donating group or electron withdrawing group as a substituent in the side chain. More preferably, the content of 0.10 to 5.0% by mass is preferable because the dispersion state in the toner becomes better. In particular, in the case of acrylic acid ester and methacrylic acid ester monomer units, the effect is great.

The sulfur atom-containing resin has the following structure.
A (SO ₃ ⁻ ) n · mY ^{k +}
(In the formula, A represents a polymer site derived from the polymerizable monomer, Y ⁺ represents a counter ion, k is a valence of the counter ion, m and n are integers, and n = k × m.)

  Counter ions are preferably hydrogen ions, sodium ions, potassium ions, calcium ions, and ammonium ions, and more preferably hydrogen ions.

  The acid value of the sulfur atom-containing resin is preferably 3 to 80 mgKOH / g, more preferably 5 to 40 mgKOH / g, and still more preferably 10 to 30 mgKOH / g. When the acid value is less than 3 mgKOH / g, it is difficult to obtain a sufficient charge control action, and the environmental stability tends to be inferior. Conversely, when the acid value exceeds 80 mgKOH / g, when toner particles are produced by suspension polymerization using a composition containing such a resin, the toner particles have an irregular shape. The degree of circularity is reduced, and the release agent contained therein appears on the surface of the toner particles and tends to cause a decrease in developability.

  The sulfur atom-containing resin is preferably contained in an amount of 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the binder resin. When the content of the sulfur atom-containing resin is less than 0.01 parts by mass, it is difficult to obtain sufficient charge control action. When the content exceeds 15 parts by mass, toner particles are produced by suspension polymerization. Has a tendency to decrease the granulation property and cause a decrease in developability and transferability.

  Furthermore, in the present invention, it is preferable to contain a unit derived from a monomer having 0.001 to 3 parts by mass of a sulfur atom per 100 parts by mass of the binder resin, and further 0.005 to 2 parts by mass. Parts, particularly 0.01 to 1.5 parts by weight.

  The content of the sulfur atom-containing resin in the toner can be measured using capillary electrophoresis or the like.

  The weight average molecular weight (Mw) of the sulfur atom-containing resin is preferably 500 to 100,000. More preferably, it is 1000-70000, More preferably, it is 5000-50000. When the weight average molecular weight (Mw) is less than 500, component contamination is likely to occur, and when the weight average molecular weight (Mw) exceeds 100,000, it takes time to dissolve in the monomer and is compatible. The toner is not uniformly dispersed in the toner due to the lowering of the toner, the effect on the chargeability of the toner is not sufficiently obtained, the effect of improving the dispersibility of the pigment is reduced, and the coloring power of the toner tends to be reduced. is there.

  The volatile content of the sulfur atom-containing resin is preferably 0.01 to 2.0% by mass. In order to reduce the volatile content to less than 0.01% by mass, the volatile content removal process performed after the polymerization reaction or after the washing process after the polymerization reaction becomes complicated, and the volatile content exceeds 2.0% by mass. Becomes inferior with respect to charging under high temperature and high humidity, especially charging after standing. The volatile matter is the proportion of mass that decreases when heated at a high temperature (135 ° C.) for 1 hour.

  The residual monomer amount of the sulfur atom-containing resin is 1000 ppm or less, preferably 500 ppm or less. When the residual monomer amount is 1000 ppm or more, it is not desirable because it is contaminated with various members during image formation, resulting in a decrease in developability.

The residual monomer amount can be measured by a gas chromatography method (GC method) described below. GC-17A (manufactured by Shimadzu Corporation) is used for measurement of the amount of residual monomer by gas chromatography (GC method). As a sample, 1 μl of a solution previously dissolved in toluene at a concentration of 1% by mass is injected into a GC apparatus equipped with an on-column injector. As the column, 0.5 mm diameter × 10 m long Ultra Alloy-1 (HT) is used. The column is initially 40 ° C. to 40 ° C./min. The temperature was increased to 200 ° C. at a temperature increase rate of 15 ° C./min. At 350 ° C. and then 7 ° C./min. The temperature is raised to 450 ° C. at a temperature raising speed of As the carrier gas, He gas is allowed to flow under a pressure condition of 50 kPa. The compound species is identified by separately injecting the monomer of the raw material of the sulfur atom-containing resin and comparing the same outflow times, or by introducing the gasification component into mass spectrometry. The amount of residual monomer is calculated by determining the ratio of the peak area to the total peak area of the chromatogram.

The melt index value (MI value; g / 10 min.) Of the sulfur atom-containing resin is preferably 0.1 to 100, and more preferably 0.2 to 80. When the MI value is less than 0.1, it becomes difficult to dissolve the sulfur atom-containing resin in the monomer constituting the binder resin of the toner when the toner is prepared by the polymerization method, and the toner is prepared by the pulverization method. In doing so, the compatibility of the sulfur atom-containing resin with the binder resin becomes poor. Therefore, when a toner is produced by a polymerization method, the monomer system becomes non-uniform, and as a result, it becomes difficult to obtain a toner having a good particle size distribution. When the MI value exceeds 100, the toner becomes inferior in blocking resistance when converted to toner, and tends to reduce durability.
The measuring method of MI value is performed based on the A method of JIS standard K7210, and converts a measured value into a 10 minute value.

  When obtaining the above physical properties, if extraction of the sulfur atom-containing resin from the toner is required, the extraction method is not particularly limited, and any method can be handled.

  Furthermore, it is desirable that the glass transition temperature (Tg) of the sulfur atom-containing resin is 50 to 100 ° C, more preferably 50 to 80 ° C. This is because if the glass transition temperature is 100 ° C. or higher, the toner fixability is lowered, and if it is lower than 50 ° C., the storage stability is poor, and it is not desirable because it easily causes member contamination in the image forming process.

  The method for producing the sulfur atom-containing resin includes bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, ionic polymerization, etc., but solution polymerization is preferable from the viewpoint of operability. In order to satisfy the physical properties (acid value, molecular weight, volatile content, melt index, glass transition temperature, etc.) of the sulfur atom-containing resin, the monomer composition, initiator amount, reaction temperature, washing conditions, and drying conditions are used in production. Can be prepared by adjusting.

  The binder resin used in the toner of the present invention is not particularly limited, and a resin generally used as a binder resin for toner can be used. Specifically, homopolymers of styrene such as polyester resin, polystyrene, polyvinyltoluene and the like, and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic Acid methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer Polymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, Styrene-vinylmethylke Copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc .; polymethyl methacrylate, polybutyl methacrylate , Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, epoxy resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, paraffin wax, And carnauba wax. These can be used alone or in combination.

  Further, the wax used in the toner of the present invention may contain only one type of wax in the toner, but preferably contains at least waxes having different wax endothermic peak temperatures in DSC measurement, and each endothermic peak. The temperature difference is desirably 3 ° C. or more. In addition, it is desirable that waxes having different endothermic peak temperatures are contained in an amount of 10% by mass or more of the total wax content. The reason for this is that, by optimizing the content of waxes having different wax endothermic peak temperatures, the presence of the wax having the lower wax endothermic peak temperature allows rapid formation of the release layer during fixing, and the wax. Since the total content of the toner is sufficient, it is not necessary to make the wax excessively present while having excellent fixing properties and offset resistance, so that the component contamination is caused by the wax present in the toner, particularly in the vicinity of the toner surface. It is less likely to be caused, and it is possible to achieve both developability and fixability, which is desirable.

  The wax preferably has a weight average molecular weight (Mw) of 350 to 4000 and a number average molecular weight (Mn) of 200 to 4000, more preferably Mw of 400 to 3500 and Mn of 250 to 3500. When Mw is less than 350 and Mn is less than 200, the blocking resistance of the toner tends to decrease. When Mw exceeds 4000 and Mn exceeds 4000, the crystallinity of the wax itself increases, and OHP The transparency of the fixed image tends to be lowered.

The molecular weight and molecular weight distribution of the wax are measured by GPC under the following conditions.
(GPC measurement conditions) Apparatus: GPC-150C (Waters)
Column: GMH-MT 30 cm 2 series (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow rate: 1.0 ml / min.
Sample: 0.4 ml injection of 0.15% sample A molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived | led-out from the Mark-Houwink viscosity formula.

  At least one of the waxes used in the present invention has a melting point (temperature corresponding to the maximum endothermic peak of the DSC endothermic curve in the temperature range of 20 to 200 ° C.) of 30 to 120 ° C., preferably 50 to 110 ° C., more preferably 50 What is -80 degreeC is good. A solid wax that is solid at room temperature is preferable, and a solid wax having a melting point of 50 to 80 ° C. is particularly preferable in terms of toner blocking resistance, durability of a large number of sheets, low-temperature fixability, and offset resistance.

  Examples of waxes include polymethylene waxes such as paraffin wax, polyolefin wax, microcrystalline wax, and Fischer-Tropsch wax, amide waxes, higher fatty acids, long chain alcohols, ester waxes, ketone waxes, and derivatives such as these graft compounds and block compounds. Can be mentioned. Among these, those having a sharp maximum endothermic peak in the DSC endothermic curve from which low molecular weight components have been removed are preferred.

  The wax preferably used includes at least one linear alkyl alcohol having 15 to 100 carbon atoms, linear fatty acid, linear acid amide, linear ester or montan derivative. Those from which impurities such as liquid fatty acids have been previously removed from these waxes are also preferred.

  Further, the wax preferably used is preferably a solid ester wax in order to improve the translucency of the fixed image. An ester wax having 1 to 6 ester groups is preferable, and an ester wax having 1 to 4 ester groups is more preferable.

  As ester wax, Preferably, what is shown by the following general formula (I)-(V) is mentioned.

(In the formula, a and b are integers of 0 to 4 and a + b is 4. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms. M and n are integers of 0 to 40. Yes, m and n are not 0 at the same time.)

(In the formula, a and b are integers of 0 to 3, a + b is 1 to _3. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms. R ₃ is a hydrogen atom or a carbon number. Is an organic group of 1 or more, k is an integer of 1 to 3, and a + b + k = 4, m and n are integers of 0 to 40, and m and n are not 0 at the same time.)

(In the formula, R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may be the same or different. R ₂ is an organic group having 1 to 40 carbon atoms. Is shown.)

(In the formula, R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may or may not be the same. R ₂ represents an organic group having 1 to 40 carbon atoms. Show.)

(In the formula, a is an integer of 0 to 4, b is an integer of 1 to 4, and a + b is 4. R ₁ is an organic group having 1 to 40 carbon atoms. (It is an integer of 40, and m and n are not 0 at the same time.)

  Specifically, examples of the ester wax having 1 to 6 ester groups include the following. The wax used in the toner of the present invention contains 50% by mass or more of the wax represented by the structural formulas (No. 1 to No. 12) exemplified below.

  Furthermore, an ester wax containing 50 to 95% by mass (based on wax) of an ester compound having the same total carbon number is preferable. The content of the ester compound having the same total carbon number can be measured by a gas chromatography method (GC method) described below.

GC-17A (manufactured by Shimadzu Corporation) is used for measuring the content of ester compounds having the same carbon number by gas chromatography (GC method). As a sample, 1 μl of a solution previously dissolved in toluene at a concentration of 1% by mass is injected into a GC apparatus equipped with an on-column injector. As the column, 0.5 mm diameter × 10 m long Ultra Alloy-1 (HT) is used. The column is initially 40 ° C. and 40 ° C./min. The temperature was increased to 200 ° C. at a temperature increase rate of 15 ° C./min. At 350 ° C. and then 7 ° C./min. The temperature is raised to 450 ° C. at a temperature raising speed of As the carrier gas, He gas is allowed to flow under a pressure condition of 50 kPa. The identification of the compound species is performed by separately injecting alkanes with known carbon numbers and comparing the same outflow times or by introducing gasification components into mass spectrometry. The ester compound content is calculated by determining the ratio of the peak area to the total peak area of the chromatogram.

  When an ester wax having an ester compound having the above structural formula is used as the wax, a toner having good transparency and excellent fixability can be obtained.

  In particular, when a toner is produced using this wax and a sulfur atom-containing resin, the wax is well dispersed in the toner particles, the charge amount is large, and the speed to reach an appropriate charge value is high. Furthermore, an excellent toner with little variation in triboelectric charge amount can be obtained in the durability of a large number of sheets.

  When the toner is produced by the polymerization method, the wax is preferably blended in an amount of 1 to 40 parts by mass (more preferably 10 to 30 parts by mass) with respect to 100 parts by mass of the polymerizable monomer. Is preferably contained in an amount of 1 to 40 parts by weight (more preferably 10 to 30 parts by weight) of wax per 100 parts by weight of the binder resin.

  When the toner is produced by the melt-kneading pulverization method, the wax is preferably contained in the toner in an amount of 1 to 10 parts by weight, more preferably 1 to 5 parts by weight per 100 parts by weight of the binder resin.

  Compared with the dry toner manufacturing method, compared to the dry toner manufacturing method, the toner manufacturing by the polymerization method is easier to encapsulate a large amount of wax by the polar resin contained in the toner compared with the dry toner manufacturing method by the melt kneading pulverization method. Therefore, the effect of preventing offset at the time of fixing is further improved.

  If the added amount of wax is less than the lower limit, the effect of preventing offset tends to be lowered. When the upper limit is exceeded, the anti-blocking effect is lowered and the anti-offset effect is easily adversely affected, the toner latent image carrier is fused, and the toner developing sleeve is fused. The toner is produced by a polymerization method. In some cases, a toner having a wide particle size distribution tends to be generated.

The wax used in the present invention preferably has a melt viscosity at 135 ° C. of 1 to 300 cPs, more preferably a wax having 3 to 50 cPs. When the melt viscosity is lower than 1 cPs, when the toner layer is thinly coated on the developing sleeve with a coating blade or the like by the non-magnetic one-component developing method, the sleeve is liable to be contaminated by mechanical shearing force . In the two-component development method, when an electrostatic image is developed using a carrier and toner, the toner is easily damaged due to the shearing force between the toner and the carrier, and the external additive is buried and the toner is easily crushed. If the melt viscosity exceeds 300 cPs, the viscosity of the polymerizable monomer composition becomes high when a toner is produced using a polymerization method, and it is difficult to obtain a toner having a fine particle size with a sharp particle size distribution. It becomes.

  The melt viscosity of the wax can be measured using a cone plate rotor (PK-1) with VP-500 manufactured by HAAKE.

  Further, the penetration of the wax is 14 or less, preferably 4 or less, more preferably 3 or less. When the penetration exceeds 14, filming is likely to occur on the surface of the latent image carrier. In addition, the measurement of penetration is according to JIS-K2235.

  When the above physical properties are required, when the wax needs to be extracted from the toner, the extraction method is not particularly limited, and any method can be used.

  As an example of a method for extracting wax from toner, a predetermined amount of toner is subjected to Soxhlet extraction with toluene, and after removing the solvent from the obtained toluene-soluble component, a chloroform-insoluble component is obtained.

  Thereafter, identification analysis is performed by IR method or the like.

  In addition, quantitative analysis is performed by DSC or the like.

  In the toner of the present invention, a condensation resin may be added in addition to the binder resin. By adding a condensation resin, in the case of a polymerization method toner, it is possible to improve granulation property, environmental stability of charge amount, developability and transferability. Further, the condensation resin is preferably localized on the surface of the particles of the polymerizable monomer composition. The condensation resin preferably has a weight average molecular weight (Mw) of 6,000 to 100,000, more preferably 6,500 to 85,000, still more preferably 6,500 to 45,000.

  When the weight-average molecular weight of the condensation resin is less than 6,000, the external additive on the toner surface tends to be buried due to durability in continuous image output, and transferability is likely to be lowered. On the contrary, when the weight average molecular weight exceeds 100,000, it takes a lot of time to dissolve the condensation resin in the polymerizable monomer. Furthermore, the viscosity of the polymerizable monomer composition increases, and it becomes difficult to obtain a toner having a small particle size and a uniform particle size distribution.

  The condensation resin preferably has a number average molecular weight (Mn) of 3,000 to 80,000, more preferably 3,500 to 60,000, still more preferably 3,500 to 12,000. The condensation resin has a main peak value (Mp) of molecular weight distribution in gel permeation chromatogram (GPC) in the region of molecular weight 4,500 to 40,000, more preferably in the region of molecular weight 6,000 to 30,000. It should be present. More preferably, it is a region having a molecular weight of 6,000 to 20,000. If it is outside the above range, the same tendency as when the weight average molecular weight is too high is shown.

  The condensation resin has a Mw / Mn of 1.2 to 3.0, more preferably 1.5 to 2.5. When Mw / Mn is less than 1.2, the durability and offset resistance of a large number of toners are reduced, and when it exceeds 3.0, in terms of low-temperature fixability, it is more than the range. Slightly inferior.

  The condensation resin has a glass transition point (Tg) of 50 to 100 ° C, preferably 50 to 95 ° C. More preferably, 55-90 degreeC is good. When the glass transition point is lower than 50 ° C., the blocking resistance of the toner is lowered. When the glass transition point exceeds 100 ° C., the low-temperature offset resistance of the toner tends to decrease. Tg represents a value obtained by the midpoint method.

The acid value of the condensation resin is 0.1 to 35 mgKOH / g, preferably 3 to 35 mgKOH / g, more preferably 4 to 35 mgKOH / g, and further preferably 5 to 30 mgKOH / g.
It is. When the acid value is less than 0.1 mgKOH / g, the toner charge amount rises slowly and fogging tends to occur. When the acid value exceeds 35 mgKOH / g, the triboelectric charging characteristics of the toner after being left under high temperature and high humidity are likely to vary, and the image density is likely to vary during continuous image output. Furthermore, if the acid value of the condensation resin exceeds 35 mgKOH / g, the affinity between the condensation resin polymers becomes stronger, making it difficult for the condensation resin to dissolve in the polymerizable monomer and uniform polymerization. It takes time to prepare the functional monomer composition.

  The hydroxyl value of the condensation resin is 0.2 to 50 mgKOH / g, preferably 5 to 50 mgKOH / g, more preferably 7 to 45 mgKOH / g. When the hydroxyl value is less than 0.2 mg KOH / g, the condensation resin is less likely to be localized on the surface of the polymerizable monomer composition particles in the aqueous medium. When the hydroxyl value exceeds 50 mgKOH / g, the charge amount characteristic of the toner after standing under high temperature and high humidity tends to be slightly lower than that within the optimum range, and the image density varies during continuous image output. It's easy to do. The extraction of the condensation resin is not particularly limited, and any method can be handled.

  In the present invention, the acid value of the condensation resin (hereinafter also referred to as “AV1”) and the acid value of the sulfur atom-containing resin (hereinafter also referred to as “AV2”) satisfy the relationship AV1 <AV2. Preferably it is. In this case, since the proportion of the sulfur atom-containing resin unevenly distributed on the outermost surface of the droplet is increased in the aqueous medium in the granulation step during the production of the toner particles by the wet method, the sulfur atom is used as the charging ability of the toner. This is preferable because the charging performance of the contained resin can be effectively exhibited.

  The condensation resin is preferably used in an amount of 0.1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the binder resin.

  The molecular weight and molecular weight distribution by GPC of the sulfur atom-containing resin and the condensation resin are measured by the following method.

The column is stabilized in a 40 ° C. heat chamber, and THF (tetrahydrofuran) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml per minute, and 100 μl of a THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko is used, and it is appropriate to use at least about 10 standard polystyrene samples. is there. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, a combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko, Examples include combinations of TSKgel G1000H (H XL), G2000H (H XL), G3000H (H XL), G4000H (H XL), G5000H (H XL), G6000H (H XL), G7000H (H XL), and TSKguardcolumn.

  Samples for measurement of molecular weight and molecular weight distribution by GPC are prepared as follows.

  Place the sample in tetrahydrofuran (THF), let stand for several hours, and then shake well to mix well with THF (until the sample is no longer united) and let stand for more than 12 hours. At this time, the standing time in THF is set to be 24 hours or longer. Thereafter, a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysori Disc H-25-5 manufactured by Tosoh Corporation, Excro Disc 25CR manufactured by Gelman Science Japan Co., Ltd., etc.) can be used. A sample of GPC is used. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

  The glass transition point of the sulfur atom-containing resin and the condensation resin is determined by DSC measurement.

  In DSC measurement, from the measurement principle, it is preferable to measure with a differential scanning calorimeter of high accuracy internal heat type input compensation type. For example, DSC-7 manufactured by Perkin Elmer can be used.

  The measurement method is performed according to ASTM D3418-82. The measurement was performed once after raising and lowering the temperature and taking a previous history, and then measuring the temperature at 10 ° C./min. Then, the DSC curve measured when the temperature is raised is used.

  The acid values of the sulfur atom-containing resin and the condensation resin are determined as follows. Basic operation conforms to JIS-K0070.

  The number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids and the like contained in 1 g of a sample is referred to as an acid value and is measured as follows.

(1) Reagent preparation (a) Solvent preparation As a sample solvent, an ethyl ether-ethyl alcohol mixture (1 + 1 or 2 + 1) or a benzene-ethyl alcohol mixture (1 + 1 or 2 + 1) is used. These solutions are neutralized with 0.1 mol / liter potassium hydroxide ethyl alcohol solution using phenolphthalein as an indicator immediately before use.

(B) Preparation of phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%). (C) Preparation of 0.1 mol / L Potassium Hydroxide-Ethyl Alcohol Solution Dissolve 7.0 g of potassium hydroxide in as little water as possible and add ethyl alcohol (95 v / v%) to make 1 liter. Filter after standing for days. The standardization is performed according to JIS-K8006 (basic matters concerning titration during the reagent content test).

(2) Operation Weigh correctly 1 to 20 g of sample, add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well until the sample is completely dissolved. In the case of a solid sample, dissolve it by heating on a water bath. After cooling, this was titrated with a 0.1 mol / liter potassium hydroxide-ethyl alcohol solution, and the neutralization end point was reached when the indicator continued to light red for 30 seconds.

(3) Calculation The acid value is calculated by the following formula.
A = B × f × 5.611 / S
(In the formula, A; acid value (mgKOH / g),
B: Amount used of 0.1 mol / L potassium hydroxide ethanol solution,
f; Factor of 0.1 mol / L potassium hydroxide ethanol solution,
S: Sample (g). )
The hydroxyl value of the sulfur atom-containing resin and the condensation resin is determined as follows. Basic operation conforms to JIS-K0070.

  When 1 g of a sample is acetylated by a prescribed method, the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group is referred to as a hydroxyl value, and the test is performed by the following reagents, operations and calculation formulas.

(1) Preparation of reagent (a) Preparation of acetylating reagent Add 25 ml of acetic anhydride to a 100 ml volumetric flask, add pyridine to make a total volume of 100 ml, and shake well. (In some cases, pyridine may be added). The acetylating reagent should be kept in brown bottles away from moisture, carbon dioxide and acid vapors.

(B) Preparation of phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%). (C) Preparation of 0.2 mol / L Potassium Hydroxide-Ethyl Alcohol Solution Dissolve 35 g of potassium hydroxide in as little water as possible and add ethyl alcohol (95 v / v%) to 1 liter to make 2-3 days. Filter after standing. The orientation is performed according to JIS-K8006.

(2) Operation 0.5 to 20 g of a sample is correctly weighed in a round bottom flask, and 5 ml of an acetylating reagent is correctly added thereto. Put a small funnel over the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at 95-100 ° C. and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, a cardboard disk with a round hole in it is put on the base of the neck of the flask. After 1 hour, the flask is removed from the bath, and after cooling, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride. To complete further decomposition, the flask was again heated in a glycerin bath for 10 minutes, allowed to cool, then the funnel and flask wall were washed with 5 ml of ethyl alcohol, and 0.2 mol / liter of phenolphthalein solution was used as an indicator. Titrate with potassium hydroxide ethyl alcohol solution. A blank test is performed in parallel with the main test. In some cases, a KOH-THF solution may be used as an indicator.

(3) Calculation The hydroxyl value is calculated by the following formula.
A = [(B−C) × f × 28.05 / S} + D
(Wherein, A: hydroxyl value (mgKOH / g),
B: Amount of use of 0.5 mol / L potassium hydroxide ethanol solution in the blank test (ml),
C: Amount used (0.5 ml) of 0.5 mol / L potassium hydroxide ethanol solution of this test,
f; factor of 0.5 mol / L potassium hydroxide ethanol solution,
S: Sample (g)
D: Acid value (mgKOH / g). )
As the condensation resin used in the toner of the present invention, resins such as polyester, polycarbonate, phenol resin, epoxy resin, polyamide, and cellulose can be used. More preferably, polyester is desired due to the variety of materials.

  Examples of methods for producing polyester waxes used as condensation resins and ester waxes used as waxes include synthesis methods based on oxidation reactions, synthesis from carboxylic acids and derivatives thereof, ester group introduction reactions represented by Michael nonreaction, Examples include a method utilizing a dehydration condensation reaction from an acid compound and an alcohol compound, a reaction from an acid halide and an alcohol compound, and a transesterification reaction. The catalyst may be a general acidic or alkaline catalyst used in the esterification reaction, such as zinc acetate or a titanium compound. Thereafter, it may be highly purified by a recrystallization method, a distillation method or the like.

  A particularly preferred production method is a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound because of the diversity of raw materials and the ease of reaction.

The composition of the polyester when polyester is used as the condensation resin will be described below.

  It is preferable that 45-55 mol% of polyester is an alcohol component and 55-45 mol% is an acid component in all the components.

  As alcohol components, ethyl glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexane Diol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivative represented by the following general formula (1)

(In the formula, R represents an ethylene or propylene group, x and y each represents an integer of 1 or more, and the average value of x + y represents 2 to 10), or a diol represented by the following general formula (2) Kind.

(In the formula, R ′ represents —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) —, —CH ₂ C (CH ₃ ) ₂ —).

  Divalent carboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, diphenyl-P · P′-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylmethane Benzenedicarboxylic acids such as -P · P'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, 1,2-diphenoxyethane-P · P'-dicarboxylic acid, or anhydrides thereof; succinic acid, adipic acid, Succinic acid substituted with alkyl dicarboxylic acids or their anhydrides such as sebacic acid, azelaic acid, glutaric acid, cyclohexanedicarboxylic acid, triethylenedicarboxylic acid, malonic acid and the like, and further an alkyl group or alkenyl group having 6 to 18 carbon atoms, or Its anhydrides; unsaturated dimers such as fumaric acid, maleic acid, citraconic acid, itaconic acid Carboxylic acid or its anhydride.

  A particularly preferred alcohol component is a bisphenol derivative represented by the general formula (1), and an acid component is phthalic acid, terephthalic acid, isophthalic acid or an anhydride thereof, succinic acid, n-dodecenyl succinic acid, or an anhydride thereof. And dicarboxylic acids such as fumaric acid, maleic acid and maleic anhydride.

  The condensation resin can be obtained by synthesizing from a divalent dicarboxylic acid and a divalent diol. However, in some cases, the polycarboxylic acid or polyol having a valence of 3 or more is not adversely affected by the present invention. A small amount may be used.

Trivalent or higher polycarboxylic acids include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid Acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,3-dicarboxyl-2-methyl-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2 , 7,8-octanetetracarboxylic acid and their anhydrides.

  Examples of the trivalent or higher polyol include sulfitol, 1,2,3,6-hexanetetol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-methanetriol. Glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.

  The toner of the present invention may use a charge control agent.

  Examples of the charge control agent for controlling the toner to be negatively charged include the following substances. For example, organometallic compounds, chelate compounds, monoazo metal compounds, acetylacetone metal compounds, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, quaternary ammonium salts, calixarene, silicon compounds, nonmetal carboxylic acid compounds And derivatives thereof.

  In addition, as a charge control agent for controlling the toner to be positively charged, there are the following substances. For example, modified products of nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and phosphonium salts that are analogs thereof Onium salts and their lake pigments, triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, Ferrocyanide, etc.), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyl Diorgano tin borate such as Zuboreto; can be used in combination singly or two or more kinds. Among these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.

  The charge control agent may be contained in an amount of 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin in the toner.

  The toner of the present invention contains a colorant. As the black colorant, carbon black, a magnetic material, and a color toned to black using a yellow / magenta / cyan colorant shown below are used.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used as pigments. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110,111,117,123,128,129,138,139,147,148,150,166,168,169,177,179,180,181,183,185,191: 1,191,192,193 199 is preferably used. Examples of the dye system include C.I. l. Solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. Disperse Yellow 42.64.2011.211.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, C.I. I. Pigment Bio Red 19 is particularly preferable.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, and 66 are particularly preferably used.

  These colorants can be used alone or in combination, and further in a solid solution state. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  In the present invention, when a toner is obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and water phase transferability of the colorant. Preferably, surface modification of the colorant, for example, hydrophobic treatment with a substance that does not inhibit polymerization is performed. In particular, since dyes and carbon black often have polymerization inhibiting properties, care must be taken when using them. A preferred method for surface-treating the colorant includes a method in which a polymerizable monomer is polymerized in the presence of these colorants in advance, and the resulting polymer containing the colorant is added to the monomer composition. It is preferable to add. In addition to carbon black, the carbon black may be grafted with a substance that reacts with the surface functional group of the carbon black, such as polyorganosiloxane.

  Further, when the toner of the present invention contains a magnetic material and is used as a magnetic toner, the magnetic material contained in the magnetic toner in the present invention includes iron oxides such as magnetite, hematite, and ferrite; iron, cobalt, nickel, and the like. Metals or alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof. Can be mentioned.

  The magnetic material used in the present invention is more preferably a surface-modified magnetic material. When used in a polymerization toner, the magnetic material is subjected to a hydrophobizing treatment with a surface modifier that is a substance that does not inhibit polymerization. Is preferred. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.

  These magnetic materials preferably have a primary particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount to be contained in the toner is 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

The magnetic properties under application of 796 kA / m (10 k Oersted) are coercive force (Hc) of 1.59 to 23.9 kA / m (20 to 300 Oersted), saturation magnetization (σs) of 50 to 200 emu / g, and residual magnetization. A magnetic material of (σr) ^{2 to} 20 Am ² / kg (emu / g) is preferable.

The toner particles of the present invention preferably have an average circularity of 0.960 or more and less than 0.995, more preferably 0.965 or more and less than 0.990. Further, it is preferable that the circularity standard deviation is in a range of less than 0.05. When the average circularity of the toner particles is less than 0.960 and the standard deviation of the circularity is 0.05 or more, the transfer efficiency is lowered because the shape of the toner particles is not uniform, and the heat and pressure during fixing are uniform. Therefore, the melting of the binder resin and the wax becomes non-uniform, so that the fixability is inferior particularly in a low temperature region.

  Further, since the shape is not uniform even during development, the charging property of the toner is not uniform, and the fluidity is also not uniform, so the uniformity of fog, solid image and halftone image is also not uniform. It is not preferable because it is sufficient.

  When the average circularity is 0.995 or more, when removing the toner remaining on the image carrier after the transfer, the fluidity of the toner is too good, and the gap between the cleaning means and the latent image carrier or intermediate transfer member. Since it is easy to slip through, there is a problem that cleaning failure occurs. Further, in fixing, particularly in pressure fixing, it is difficult to be destroyed by pressure, and fixing failure tends to occur. Further, it is not preferable even during development because it is difficult to regulate the toner layer with a regulating member.

  The weight average particle size of the toner of the present invention is preferably from 3.0 to 9.0 μm. If the weight average particle size is less than 3.0 μm, slip-through is likely to occur, and it is not desirable in terms of cleaning properties, and if it is 9.0 μm or more, it is not desirable because it is insufficient for obtaining a high-resolution image.

  The weight average particle diameter of the toner can be measured by various methods such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Corp.). In the present invention, Coulter Counter TA-II type (Coulter Corp.) is used. The interface for outputting the number distribution and the volume distribution (manufactured by Nikka) and the PC9801 personal computer (manufactured by NEC) are connected, and 1% NaCl aqueous solution is prepared using first-grade sodium chloride as the electrolyte. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toners of 2 μm or more are measured using the Coulter counter TA-II with a 100 μm aperture as an aperture. The volume distribution and the number distribution are calculated. Then, a volume-based weight average particle diameter (D4: the median value of each channel is a representative value of the channel) obtained from the volume distribution according to the present invention is obtained.

The average circularity and the circularity standard deviation are measured in a circle-based equivalent diameter-circularity scattergram based on the number of toner particles measured by a flow type particle image measuring apparatus. In the present invention, “FPIA-1000 type” is used. ”(Manufactured by Toa Medical Electronics Co., Ltd.), and calculation is performed using the following formula.
Circularity = circular length having the same projected area as the particle image / peripheral length average circularity of the projected particle image = total circularity of each particle / total number of particles circularity standard deviation = {Σ (circularity of each particle− Average circularity) ² / total number of particles} ^1/2

  Here, the “particle projected area” is an area of a binarized toner particle image. As a specific measurement method, 10 ml of ion-exchanged water from which impure solids and the like are previously removed is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, and then further measurement is performed. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “UH-50 type” (manufactured by SMT Co., Ltd.) equipped with a titanium alloy chip having a diameter of 5 mm as a vibrator is subjected to a dispersion treatment for 5 minutes, and a measurement dispersion liquid And In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more.

  To measure the shape of the toner, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner particle concentration during measurement is 3000 to 10,000 particles / μl, and 1000 or more toner particles are measured To do. After the measurement, the circularity of the toner is obtained using this data.

  As a method of controlling the shape factor (circularity, circularity standard deviation) of the toner particles of the present invention, for example, the toner particles produced by the pulverization method are controlled by controlling the spheroidizing treatment conditions. And a method of producing a toner by controlling polymerization conditions when producing toner particles by a polymerization method such as emulsion polymerization, suspension polymerization, dispersion polymerization or the like.

  The method for spheroidizing toner particles produced by the pulverization method is as follows. First, binder resin, wax, colorant, charge control agent, etc. are uniformly dispersed using a pressure kneader, an extruder or a media dispersing machine, and then collided with a target under a mechanical or jet stream to obtain a desired toner. Finely pulverize to particle size. Thereafter, the toner particles are spheroidized by a hot water bath method, a hot air flow method, a mechanical impact method, or the like, and further, a particle size distribution is adjusted through a classification step. The shape factor of the toner particles can be adjusted by appropriately controlling the processing conditions such as the processing temperature, processing time, and processing energy when performing the spheroidization processing. In particular, in the method of mechanically spheroidizing the toner particles produced by the pulverization method, not only the shape factor is adjusted, but also the result is that the binder resin covers the wax exposed on the toner particle surface by mechanical impact. As a result, the wax is distributed in the vicinity of the toner surface, and the effect of contributing to both the fixing property and the developing property is also seen.

  The method for producing spherical toner particles by the polymerization method is as follows. First, wax, colorant, charge control agent, polymerization initiator and other additives are added to the polymerizable monomer constituting the binder resin and the monomer constituting the sulfur atom-containing resin, and the homogenizer / ultrasonic dispersion is added. The monomer composition uniformly dissolved or dispersed by a machine or the like is dispersed by a homomixer or the like in an aqueous phase containing a dispersion stabilizer. The granulation is stopped when the droplets made of the monomer composition have the desired toner particle size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. Polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. Further, for the purpose of obtaining a predetermined molecular weight distribution, the temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers, by-products, etc., in the latter half of the reaction or after the completion of the reaction. A part of the aqueous medium may be distilled off. After completion of the reaction, the produced toner particles are recovered by washing and filtration and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer composition.

  When producing toner particles by the polymerization method, the shape factor of the toner particles can be adjusted by controlling the type and amount of the dispersion stabilizer, the stirring conditions, the pH and polymerization conditions of the aqueous layer, and the molecular weight of the additive. it can.

The toner of the present invention preferably has a melt index (MI) in the range of 5.0 to 30.0 g / 10 minutes, more preferably 5.0 to 25.0 g / 10 minutes. A toner having an MI in the above range exhibits excellent developability and fixability. When the MI of the toner is less than 5.0, it is necessary to make the pressure and heating from the fixing roller necessary for fixing high and high pressure, which is disadvantageous from the viewpoint of simplifying the fixing method and reducing power consumption. Furthermore, since organic and inorganic fine powders and the like adhering to the toner surface are likely to be released from the toner surface during long-term use, it is not preferable because it easily causes member contamination. Moreover, when it exceeds 30.0, since internal cohesion force falls, offset resistance deteriorates and is not desirable. In addition, organic and inorganic fine powders adhering to the toner surface during long-term use tend to be buried in the toner, causing a decrease in fluidity, which is not preferable in terms of image uniformity, density, and member contamination. .

Here, the melt index is measured by a manual cutting method under the following measurement conditions using an apparatus described in Japanese Industrial Standard thermoplastic flow test method JIS K7210. At this time, the measured value is converted into a 10-minute value.
Measurement temperature: 135 ° C
Load: 1.20kg
Sample filling amount: 5-10 g
In the toner of the present invention, at least silica fine powder and titanium oxide fine powder are externally added to toner particles.

  The primary particle size of the titanium oxide fine powder externally added to the toner particles is 35 to 500 nm, preferably 35 to 250 nm, and more preferably 45 to 100 nm. If the titanium oxide fine powder is less than 35 nm, the titanium oxide fine powder tends to be embedded in the toner in the course of long-term use, and if it exceeds 500 nm, it tends to be detached from the toner surface. It becomes difficult to maintain the performance for a long time. Accordingly, it is desirable that the thickness is 500 nm or less because it is more difficult to detach from the toner surface.

  At least silica fine powder and titanium oxide fine powder are externally added to the toner particles, the primary particle diameter of the titanium oxide fine powder is 35 to 500 nm, and the following effects can be obtained. . By externally adding the silica fine powder to the toner particles, the charging performance and fluidity of the toner can be improved, and the titanium oxide fine powder that hardly causes electrostatic aggregation compared to the silica fine powder is added to the toner particles. By adding, stable fluidity can be obtained, whereby the toner can be uniformly charged and a uniform toner layer can be formed in image formation. In particular, by subjecting the titanium oxide fine powder to a hydrophobic treatment, it becomes possible to protect the titanium oxide fine powder having high hygroscopicity from the influence of environmental fluctuations. Furthermore, in a low-temperature and low-humidity environment, the silica fine powder alone is partially overcharged, resulting in problems that the toner charge distribution becomes non-uniform and the toner layer cannot be formed uniformly due to electrostatic aggregation. By adding the titanium oxide fine powder together, it is possible to impart fluidity to the toner while suppressing electrostatic factors, and it is possible to uniformly charge the toner and form the toner layer uniformly. It becomes.

  In particular, a toner containing a sulfur atom-containing resin is partially overcharged due to the high chargeability of the sulfur atom-containing resin, but externally adding the silica fine powder and titanium oxide fine powder to the toner particles. Thus, the toner can be uniformly charged, and a uniform image can be obtained without impairing the charging ability of the sulfur atom-containing resin regardless of the environment. Moreover, the toner of the present invention has high charging ability and environmental stability by containing a sulfur atom-containing resin even in long-term use, and the primary particle size of the titanium oxide fine powder is 35 to 500 nm. Since it has fluidity and durability and the silica fine powder is externally added to it, the toner is charged quickly, so that a good image can be obtained even after initial and long-term standing regardless of the environment. . Furthermore, since the toner is supplied uniformly and the toner layer is uniformly formed on the developing sleeve, the stress applied to the member is also uniform, and a large amount of stress is partially applied to the developing sleeve and the regulating member. Problems such as toner fusing and sticking, contamination of the developing sleeve, regulating member, latent image carrier and charging member due to the release of inorganic fine powder adhering to the toner surface, and toner scattering A good image can be obtained without this.

The titanium oxide fine powder can be used with a degree of hydrophobicity of 30 to 95%, preferably 45 to 80%. If the degree of hydrophobicity of the titanium oxide fine powder is less than 30%, moisture adsorption is not sufficiently suppressed, and if it is 95% or more, it tends to agglomerate electrostatically in a low-temperature and low-humidity environment, resulting in stable fluidity. This is undesirable because it is difficult to maintain.

  The degree of hydrophobicity is measured by a methanol titration test as follows.

  The methanol titration test is a test for confirming the degree of hydrophobicity of the titanium oxide fine powder having a hydrophobized surface.

  0.2 g of titanium oxide fine powder is added to 50 ml of water in a 250 ml Erlenmeyer flask. Methanol is titrated from the burette until the entire titanium oxide fine powder is wet. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed by suspending the total amount of titanium oxide fine powder in the liquid, and the degree of hydrophobicity is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

  As the titanium oxide fine powder used in the present invention, one produced by a general production method can be used. The content of the titanium oxide fine powder is 0.01 to 100 parts by mass of the toner particles. To 3.00 parts by mass, more preferably 0.01 to 1.00 parts by mass, still more preferably 0.05 to 0.50 parts by mass, and particularly preferably 0.05 to 0.20 parts by mass. And good. If the content is less than 0.01 parts by mass, the effect is small, and if it exceeds 3.00 parts by mass, the fluidity of the toner is high.

  As the silica fine powder used in the present invention, those prepared by a general production method can be used, but those that have been subjected to a hydrophobic treatment are preferred. The content of the fine silica powder is preferably 0.10 to 3.00 parts by mass, more preferably 0.30 to 2.00 parts by mass, and still more preferably 0.50 to 100 parts by mass of the toner particles. The amount is preferably 2.00 parts by mass, particularly preferably 0.80 to 1.70 parts by mass. If the content is less than 0.10 parts by mass, the effect is small, and if it exceeds 3.00 parts by mass, the fluidity of the toner is high.

  The primary particle size of the silica fine powder is desirably 5 to 120 nm, more preferably 5 to 60 nm, and still more preferably 5 to 30 nm. When the primary particle size is less than 5 nm, the silica fine powder is likely to be embedded in the toner surface during long-term use, and when it exceeds 120 nm, the toner chargeability is poor.

  A conventionally known method is used as a hydrophobizing method for the titanium oxide fine powder and the silica fine powder. For example, specifically, the titanium oxide fine powder is preliminarily heated to 100 to 150 ° C. under vacuum and stored in a desiccator to remove water. For example, a method (solvent wet processing method) in which dehydrated titanium oxide fine powder and a silane coupling agent are reacted in toluene to hydrophobize the OH groups on the surface of the titanium oxide fine powder. In addition, a solvent dry spray method, an aqueous emulsion treatment method, an aqueous hydrolysis method and the like can be mentioned.

  The following silane coupling agents, titanium coupling agents, silicone oils and the like can be used as hydrophobic treatment agents for hydrophobizing inorganic fine powders such as titanium oxide fine powder and silica fine powder.

Examples of the silane coupling agent include hexamethyldisilazane, methyltrimethoxysilane, octyltrimethoxysilane, isobutyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aniline. Linopropyltrimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, γ-glycidoxypropyltrimethoxysilane,
Aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, monobutylaminopropyltrimethoxysilane, dioctylamino Propyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ-propylbenzylamine, γ-anilinopropyl Examples include trimethoxysilane. Octyltrimethoxysilane, isobutyltrimethoxysilane or vinyltriacetoxysilane is preferable, and octyltrimethoxysilane is more preferable.

  Examples of the titanium coupling agent include bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, tetrabutyl titanate, and tetraoctyl titanate.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, alkyl modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil, and the like. Particularly preferred is chlorophenyl silicone oil.

  The silicone oil preferably has a viscosity of 50 to 1000 centistokes (cSt) at a temperature of 25 ° C. More preferably, it is 100-200 centistokes. If it is less than 50 centistokes, part of it is exerted by the application of heat, and the charging characteristics tend to deteriorate. When it exceeds 1000 centistokes, handling becomes difficult in terms of processing work. A known technique can be used as a method for treating the silicone oil.

  For example, silica fine powder and silicone oil are mixed using a mixer. Silicone oil is sprayed into the silica fine powder using a sprayer. Or the method of mixing a silica fine powder after dissolving silicone oil in a solvent is mentioned. The processing method is not limited to this.

  There is no problem even if a method using an oil such as silicone oil is used as a method for hydrophobizing the titanium oxide fine powder, but a method using a coupling agent such as a silane coupling agent or a titanium coupling agent is preferred. Further, as a method for hydrophobizing the silica fine powder, there is no problem even if a method using a coupling agent is used, but a method using a processing method using oil such as silicone oil is preferable. This is because the titanium oxide fine powder needs to maintain the degree of hydrophobicity even after long-term use, and therefore a coupling agent is used to perform the hydrophobic treatment firmly by chemical bonds that do not peel off due to stress. This is because it is preferable. As for silica fine powder, since it has high chargeability from the beginning, excessive hydrophobization treatment tends to cause electrostatic aggregation, especially in low-temperature and low-humidity environments. It is preferable because the chargeability can be easily adjusted.

  Hydrophobic treatment of these inorganic fine powders, especially surface treatment with silicone oil, can also cause the adhesion strength to the toner to be weakened. Therefore, such hydrophobization treatment can be performed only by controlling the chargeability of the inorganic fine powder. In addition, it can be used for adjusting the adhesion strength of the inorganic fine powder to the toner particle surface.

The number release rates of the titanium oxide fine powder and the silica fine powder in the toner are each 0.10 to 25.00%, preferably 0.10 to 15.00%. The reason for this is that if it is less than 0.10%, the fluidity of the toner particles is extremely lowered, the toner spikes on the developing sleeve tend to be rough, and the halftone image or the like is not smooth and uneven in the circumferential direction. It tends to occur. When used for a long period of time, it is not desirable because fog increases especially under high temperature and high humidity. Generally, embedding of external additives is likely to occur due to stress of a regulating member or the like under a high temperature environment, and the fluidity of toner particles is inferior to that in the initial stage in long-term use, and the above problem is considered to occur. Further, if it is 30.00% or more, member contamination is generated by the fine titanium oxide powder and silica fine powder which are liberated, which is not desirable.

  Below, the number release rate of titanium oxide fine powder and silica fine powder is demonstrated.

The number release rate of fine titanium oxide powder and fine silica powder was measured by a particle analyzer (PT1000: manufactured by Yokogawa Electric Corporation). Using the particle analyzer, 65-68 in the paper of Japan Hardcopy 97. Measure according to the principle described on the page. Specifically, the particle analyzer introduces fine particles such as toner one by one into a high-temperature non-thermal equilibrium plasma having an electron density of 5 × 10 ¹³ cm ^{−3, an} excitation temperature of 3,300 K, and a high electron temperature exceeding 20,000 K. The element, the number of particles, and the particle size of the emitted light can be known from the emission spectrum of the fine particles accompanying this excitation.

  Among them, the “number release rate” is the simultaneous emission of carbon atoms, which are constituent elements of the binder resin in the toner particles, and emission of Ti atoms derived from titanium oxide fine powder and Si atoms derived from silica fine powder. It is defined that it is obtained from the following formulas (1) and (2).

(1) Number release rate of fine titanium oxide powder (%)
= 100 × (Number of light emission of only Ti atom / Number of light emission of only Ti atom emitted simultaneously with carbon atom + Number of light emission of only Ti atom)

(2) Number release rate of silica fine powder (%)
= 100 × (Number of times of light emission of only Si atoms / number of times of light emission of Si atoms emitted simultaneously with carbon atoms + number of times of light emission of only Si atoms)

  Here, simultaneous emission of carbon atoms, Ti atoms and Si atoms means simultaneous emission of Ti atoms and Si atoms emitted within 2.6 msec from the emission of carbon atoms, and subsequent emission of Ti atoms and Si atoms. The light emission is the light emission of only Ti atoms and Si atoms. In the present invention, since the titanium oxide fine powder and the silica fine powder are externally attached to the toner particle surface, the fact that carbon atoms, Ti atoms and Si atoms emit light simultaneously means that the titanium oxide fine powder and silica are on the toner particle surface. This means that fine powder is attached, and light emission of only Ti atoms and Si atoms can be paraphrased as meaning that titanium oxide fine powder and silica fine powder are separated from the toner particle surface. .

  As a specific measurement method, helium gas containing 0.1% oxygen is used, and measurement is performed in an environment of 60% humidity at 23 ° C., and carbon atoms are measured in channel 4 (measurement wavelength 247.860 nm, K factor is the main body. Recommended value), Si atom in channel 2 (measurement wavelength 288.160 nm, K factor is the recommended value for the main unit) Ti atom (measurement wavelength 232.232 nm, K factor is the recommended value for the main unit) is measured in channel 3, and one scan Then, sampling is performed so that the number of light emission of carbon atoms is 1000 ± 200, and scanning is repeated until the total number of light emission of carbon atoms reaches 10,000 or more, and the light emission number is integrated. Based on this data, the number release rates of the titanium oxide fine powder and the silica fine powder are calculated using the above formulas (1) and (2). The measurement of the emission intensity of the titanium oxide fine powder and the silica fine powder according to the present invention is not particularly limited as long as a channel recommended in PT1000 is selected.

In measuring the number release rate of titanium oxide fine powder and silica fine powder, when the toner particles of the present invention are color toner particles (yellow toner particles, magenta toner particles, cyan toner particles and black toner particles), carbon The measurement is carried out with a setting of a low third root voltage value of an arbitrary channel for measuring atoms (4 channels are used in the present invention).

  The reason is as follows. In the particle analyzer according to the present invention (PT1000: manufactured by Yokogawa Electric Corporation), a signal proportional to the number of atoms (mass) of the element is detected, but an equivalent particle size display (when light emission of an element is obtained) , Assuming a true spherical particle made of only that element), and taking the third root of the detected voltage. Although this is defined as the cube root voltage, since the cube root of the number of atoms is proportional to the particle size, the cube root voltage is proportional to the particle size. Therefore, when the color toner particles according to the present invention have the same cube root voltage portion as that of the one-component toner particles using a magnetic material, the emission intensity of carbon atoms in the toner particles is determined by the binder resin component, the colorant. The color toner particles become larger due to the influence of the components, etc., and the same cube root voltage value as that of the one-component toner particles cannot show the particle size distribution up to the small particle size portion. In measuring the number release rate, the cube root voltage value must be set low.

  For this reason, when measuring color toner particles in the present invention, the third root voltage of carbon atoms is set to Low Voltage (1.8 V), and the number free rate of titanium oxide fine powder and silica fine powder is determined. taking measurement.

  In calculating the number free ratio according to the present invention, the noise level is set to 1.5V for the 1st to 3rd channels and 1.3V for the 4th channel.

  As a method for adjusting the number release rate of the silica fine powder and the titanium oxide fine powder, in addition to the adjustment method based on the addition amount and viscosity of the silicone oil at the time of the hydrophobization treatment described above, there are external methods for external addition to the toner particles. A method based on an addition method or external addition conditions is also possible. For example, a Henschel mixer, a ball mill, a coffee mill, or the like can be used as the external addition means, and adjustment can be made by optimizing conditions appropriately.

  The titanium oxide fine powder can be used in either anatase type or rutile type, but is preferably anatase type titanium oxide fine powder. The reason for this is that the rutile type titanium oxide fine powder has a needle-like fine powder shape, which makes it difficult to uniformly adhere to the toner when it is externally added. Therefore, in the long-term use, some of the toner is likely to be liberated from the toner surface, which is not desirable in terms of maintaining the fluidity and chargeability of the toner for a long time. In this regard, anatase-type titanium oxide fine powder is desirable because the fine powder shape is almost spherical.

The volume resistance value of the titanium oxide fine powder is 1.0 × 10 ^{3 to} 1.0 × 10 ¹⁵ Ω · cm, preferably 1.0 × 10 ^{3 to} 1.0 × 10 ¹⁵ Ω · cm, more preferably 1. It is desirable to be 0 × 10 ^{4 to} 1.0 × 10 ¹⁴ Ω · cm. The reason for this is that if the volume resistance value of the titanium oxide fine powder is less than 1.0 × 10 ² Ω · cm, the charge of the charged toner tends to leak, which is not desirable. Exceeding 1.0 × 10 ¹⁵ Ω · cm is not desirable because it tends to be affected by environmental fluctuations, particularly in low temperature and low humidity environments.

  Here, the volume resistance value in the method of measuring the static resistance of the titanium oxide fine powder is measured as follows using the cell A shown in FIG.

A cell A is filled with fine titanium oxide powder 7, electrodes 1 and 2 are arranged in contact with the filled fine titanium oxide powder 7, and a voltage is applied from the constant voltage device 6 between the electrodes. Is obtained by monitoring the voltage with the voltmeter 5 and measuring the current flowing at that time with the ammeter 4.
In addition, 3 is an insulator and 8 is a guide ring.

The measurement conditions were as follows: the contact area between the electrodes 1 and 2 of the filled titanium oxide fine powder 7 in an environment of 23 ° C. and 65% S = 0.283 cm ² , thickness d = 1.0 mm, and the load of the upper electrode 2 of 120 g / cm ² and an applied voltage of 400V.

  A method for measuring the primary particle diameter of fine powder (titanium oxide fine powder, silica fine powder, magnetic material, etc.) other than the toner in the present invention will be described below.

  The primary particle size is determined by observing the fine powder with a transmission electron microscope, measuring the particle size of 100 particles of 0.001 μm or more in the field of view, and obtaining the average particle size. The 100 fine powders in the field of view are qualitatively determined by XMA (photoelectron spectroscopy), and the particle size is measured to determine the average particle size.

  In the toner of the present invention, various inorganic and organic additives can be used for the purpose of imparting various properties in addition to the above-mentioned titanium oxide fine powder and silica fine powder, and these are externally added to the toner particles. Can be obtained. The additive to be used preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles from the viewpoint of durability when added to the toner. The particle size of the additive means the average particle size obtained by observing the surface of the toner particles with a scanning electron microscope. As additives for the purpose of imparting these characteristics, for example, the following are used, but are not particularly limited.

1) Fluidity imparting agent: metal oxide (silicon oxide, aluminum oxide, etc.), carbon black, carbon fluoride, etc. Each of them is more preferably hydrophobized.

2) Abrasives: metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, barium sulfate, etc.) , Calcium carbonate, etc.).

3) Lubricant: Fluorine-based resin powder (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salt (zinc stearate, calcium stearate, etc.) and the like are preferable.
4) Charge controllable particles: metal oxides (tin oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black and the like are preferable.

  These additives are used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner. These additives may be used alone or in combination.

Next, the method for producing toner particles of the present invention will be described.
Examples of the method for producing the toner particles of the present invention include the following methods. A method of directly producing toner particles using the suspension polymerization method described in JP-B-36-10231, JP-A-59-53856, and JP-A-59-61842; emulsion polymerization method typified by a soap-free polymerization method for generating a toner particle by direct polymerization in the presence of a water-soluble polymerization initiator soluble; interfacial polymerization method such as microcapsule production method, the method according to in calling sit u polymerization A method based on a coacervation method; at least one kind of fine particles disclosed in JP-A-62-106473 and JP-A-63-186253 are aggregated to obtain toner particles having a desired particle size. A method by a combined method; a method by a dispersion polymerization method characterized by monodispersion; a method by an emulsion dispersion method in which toner particles are obtained in water after dissolving necessary resins in a water-insoluble organic solvent The toner components are kneaded and uniformly dispersed using a pressure kneader, extruder, media disperser, etc., then cooled, and the kneaded product is allowed to collide with the target under mechanical or jet airflow to obtain the desired toner particle size. A pulverization method in which toner particles are produced by further finely pulverizing and then passing through a classification step to produce toner particles; a method of obtaining toner particles by subjecting the toner particles obtained by the pulverization method to spheroidization by heating or the like in a solvent.

  Of these, the production of toner particles by suspension polymerization, association polymerization, or emulsion dispersion is preferred.

  More preferably, a suspension polymerization method capable of easily obtaining toner particles having a small particle diameter is desired. Further, a seed polymerization method in which a monomer is further adsorbed to the obtained polymer particles and then polymerized using a polymerization initiator can be suitably used in the present invention. At this time, it is also possible to use a compound having polarity dispersed or dissolved in the monomer to be adsorbed.

  When suspension polymerization is used as a method for producing toner particles, the toner particles can be produced directly by the following production method. A monomer in which a wax, a colorant, a sulfur atom-containing resin, a polymerization initiator, a crosslinking agent, other additives, etc. are added to a polymerizable monomer and dissolved or dispersed uniformly by a homogenizer, an ultrasonic disperser or the like. The composition is dispersed in an aqueous medium having a dispersion stabilizer by a normal stirrer, homomixer, or homogenizer. Preferably, the monomer composition is granulated by adjusting the stirring speed and time so that the droplets of the monomer composition have a desired toner particle size. Thereafter, stirring may be carried out to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. The polymerization is carried out at a polymerization temperature of 40 ° C. or higher, usually 50 to 95 ° C., preferably 55 to 85 ° C. The temperature may be raised in the latter half of the polymerization reaction, and the pH may be changed as necessary. Further, in order to remove unreacted polymerizable monomers, by-products and the like that cause odor during fixing, a part of the aqueous medium may be distilled off in the latter half of the reaction or after the completion of the reaction. After completion of the reaction, the produced toner particles are collected by washing and filtration and dried.

  The pH in the aqueous medium during granulation is not particularly limited, but preferably 4.5 to 13.0, more preferably 4.5 to 12.0, and particularly preferably 4.5 to 11.0. Most preferably, it is 4.5-7.5. When the pH is less than 4.5, a part of the dispersion stabilizer dissolves, making it difficult to stabilize the dispersion, and granulation may not be possible. On the other hand, when the pH exceeds 13.0, components added to the toner particles may be decomposed, and sufficient charging ability may not be exhibited. When granulation is carried out in the acidic region, it is possible to suppress an excessive content of metal derived from the dispersion stabilizer in the toner particles, which is desirable.

  The toner particles are preferably washed with an acid having a pH of 3 or less, more preferably 1.5 or less. By washing the toner particles with an acid, the dispersion stabilizer present on the surface of the toner particles can be reduced. The acid used for washing is not particularly limited, and inorganic acids such as hydrochloric acid and sulfuric acid can be used.

  Examples of the dispersion stabilizer used in the present invention include magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, and metasilicic acid. Examples include calcium, calcium sulfate, barium sulfate, and hydroxyapatide.

  Further, as the dispersion stabilizer, those containing at least any of magnesium, calcium, barium, zinc, aluminum and phosphorus are used, but preferably contain any of magnesium, calcium, aluminum and phosphorus. It is hoped that

Organic compounds in the dispersion stabilizer, such as polyvinyl alcohol, gelatin, methylation cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, may be used in combination with starch.

  These dispersion stabilizers are preferably used in an amount of 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Furthermore, you may use together 0.001-0.1 mass% surfactant for refinement | miniaturization of these dispersion stabilizers. Specifically, commercially available nonionic, anionic and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like are preferably used.

  In the present invention, when toner particles are obtained by suspension polymerization, the polymerizable monomer used is styrene, such as styrene, o (m-, p-)-methylstyrene, m (p-)-ethylstyrene, or the like. Monomer; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic (Meth) acrylate monomers such as stearyl acid, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate; butadiene, Preferably used are ene-based monomers such as isoprene, cyclohexene, (meth) acrylonitrile, and acrylamide. That. These are monomers alone or generally such that the theoretical glass transition temperature (Tg) described in the publication polymer handbook 2nd edition III-Pl39-192 (John Wiley & Sons) is 40-80 ° C. Are preferably mixed and used as appropriate. When the theoretical glass transition temperature is less than 40 ° C., there are problems in terms of the storage stability of the toner and the durability stability of the toner. On the other hand, when it exceeds 80 ° C., the fixing point is increased, which is not preferable.

  In addition, in the method of obtaining toner particles using the suspension polymerization method, it is particularly preferable to add a polar resin at the same time from the viewpoint of performing the polymerization reaction of the polymerization monomer without hindrance. Examples of polar resins used in the present invention include copolymers of styrene and (meth) acrylic acid, copolymers of styrene and unsaturated carboxylic acid esters, nitrile monomers such as acrylonitrile, and vinyl chloride. Polymers such as halogen monomers, unsaturated carboxylic acids such as acrylic acid or methacrylic acid, other unsaturated dibasic acids and unsaturated dibasic acid anhydrides, nitro monomers, or these monomers and styrene A copolymer with a monomer or the like, a maleic acid copolymer, a polyester resin, an epoxy resin, or the like is preferably used. The polar resin is particularly preferably one containing no unsaturated group capable of reacting with the monomer in the molecule. The addition amount of these polar resins is preferably 0.1 to 10% by mass of the polymerizable monomer.

  As the polymerizable monomer used when the toner of the present invention is produced by a polymerization method, a vinyl polymerizable monomer capable of radical polymerization may be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2 -Ethylhexyl acrylate, acrylic polymerizable monomers such as n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate , N-nonyl methacrylate, diethyl phosphate ethyl methacrylate Methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl Examples include vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3- Butylene glycol dimethacrylate, 1, - hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinyl naphthalene, divinyl ether.

  In the present invention, the above monofunctional polymerizable monomers may be used alone or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers may be used in combination. Can do. The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

  As the polymerization initiator used in the polymerization of the polymerizable monomer described above, an oil-soluble initiator and / or a water-soluble initiator is used. For example, as the oil-soluble initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) Azo compounds such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide Oxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide Side, t- butyl hydroperoxide, di -t- butyl peroxide, peroxide initiators such as cumene peroxide.

  Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloric acid Examples thereof include salts, azobis (isobutylamidine) hydrochloride, 2,2′-azobisisobutyronitrile sodium sulfonate, ferrous sulfate and hydrogen peroxide.

  In the present invention, in order to control the polymerization degree of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor or the like can be further added and used.

  Moreover, in this invention, it can also be set as resin which has bridge | crosslinking using a crosslinking agent. As the crosslinking agent, a compound having two or more polymerizable double bonds can be used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline and divinyl ether , Divinyl sulfide, divinylsulfone, and other divinyl compounds; and compounds having three or more vinyl groups. These are used alone or as a mixture.

  The toner of the present invention is obtained by externally adding silica fine powder and titanium oxide fine powder and, if necessary, various additives to the toner particles. The toner of the present invention thus obtained can be used as a toner for a one-component developer, and can also be used as a toner for a two-component developer having a carrier.

  In the case of a magnetic toner containing a magnetic material in the toner used as a one-component developer, there is a method of conveying and charging the magnetic toner using a magnet built in the developing sleeve. In the case of using a non-magnetic toner that does not contain a magnetic material, there is a method in which a blade or a roller is used to forcibly frictionally charge with a developing sleeve, and the toner is deposited on the developing sleeve and conveyed.

  When used as a two-component developer, the toner of the present invention and a carrier are mixed and used as a developer. As a carrier, it is comprised by the atom single or composite ferrite state which consists of iron, copper, zinc, nickel, cobalt, manganese, and a chromium element. The carrier has a spherical shape, a flat shape, or an indeterminate shape, and any of them can be used. Furthermore, it is preferable to control the fine structure of the carrier surface state (for example, surface unevenness). In general, a method is used in which carrier core particles are generated in advance by firing and granulating the inorganic oxide, and then coating with a resin. From the viewpoint of reducing the load on the toner of the carrier, a method of obtaining a low density dispersion carrier by kneading and classifying the inorganic oxide and the resin, and further, a kneaded product of the inorganic oxide and the monomer directly It is also possible to utilize a method in which a spherical carrier is obtained by suspension polymerization in an aqueous medium.

  A coated carrier in which the surface of the carrier is coated with a resin is particularly preferable. As the method, a method in which a resin is dissolved or suspended in a solvent and a solution or suspension is applied and adhered to a carrier, or a method in which resin powder and a carrier are simply mixed and adhered is applicable.

  The coating material on the carrier surface varies depending on the toner material. For example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin, polyacid, polyvinyl butyral, amino An acrylate resin etc. are mentioned. These may be used alone or in combination.

The magnetic properties of the carrier are as follows. The magnetization intensity (σ1000) at 79.6 kA / m (1 k Oersted) after magnetic saturation is preferably 3000 to 30000 kA / m ² . Furthermore, in order to achieve high image quality, it is preferably 10,000 to 25000 kA / m ² . When it is larger than 30000 kA / m ^2, it becomes difficult to obtain a high-quality toner image. On the other hand, if it is less than 3000 kA / m ² , the magnetic binding force is also reduced, and carrier adhesion is likely to occur.

When a two-component developer is prepared by mixing the toner of the present invention and a carrier, the mixing ratio is usually 2 to 15% by mass, preferably 4 to 13% by mass as the toner concentration in the developer. Results.

  The toner of the present invention is preferably a non-magnetic one-component toner because it has a particularly great effect on developability. This is because, in the case of the non-magnetic one-component developing method, unlike the two-component developing method, the charging performance of the toner itself is greatly affected because there is no help from a carrier or the like when charging the toner.

  Furthermore, the non-magnetic one-component development method is more desirable for reducing the size and weight of the image forming apparatus as compared with the magnetic one-component development method and the two-component development method. Furthermore, the toner of the present invention is effective in the nonmagnetic one-component non-contact development method, but more preferably, it is more effective when used in the nonmagnetic one-component contact development method. This is because in the case of contact development, the effect of using the toner of the present invention is great because it is easily affected by coating unevenness caused by the chargeability and fluidity of the toner coated on the developing sleeve. Further, contact development is desirable in terms of toner scattering.

  In the one-component development method, when the latent image carrier and the developing sleeve have a distance, electric lines of force concentrate on the edge of the electrostatic latent image on the latent image carrier, and the toner is developed along the electric lines of force. Therefore, contact development is desirable because the image quality is likely to be deteriorated due to the edge effect in which the toner is biased and developed at the edge portion of the image.

  Next, the toner of the present invention can be applied to, for example, the following image forming method, process cartridge, and developing unit. Details will be described below.

  First, FIG. 1 shows a specific example of an image forming method and a process cartridge in a non-magnetic one-component contact developing system applied as the present invention using the toner of the present invention. In FIG. 1, the developing unit 13 is located in a developer container 23 containing a nonmagnetic toner 17 as a one-component developer, and an opening extending in the longitudinal direction in the developer container 23. A photosensitive drum 10 and a developing sleeve 14 disposed opposite to each other, and the electrostatic latent image on the latent image carrier 10 is developed and visualized. The latent image carrier contact charging member 11 is in contact with the latent image carrier 10. The bias of the latent image carrier contact charging member 11 is applied by a power source 12.

  The developing sleeve 14 is provided horizontally with the substantially right half-periphery surface shown in the drawing through the opening into the developer container 23 and the left substantially half-periphery surface exposed outside the developer container 23. The surface exposed to the outside of the developer container 23 is in contact with the latent image carrier 10 located on the left side of the developing unit 13 as shown in FIG.

The developing sleeve 14 is rotationally driven in the direction of the arrow B, and the surface thereof has appropriate irregularities for increasing the probability of rubbing with the nonmagnetic toner 17 and for carrying the nonmagnetic toner 17 well. Yes. In the case where the developing sleeve 14 is used by contacting the latent image carrier 10 as shown in FIG. 1, as an example, the NBR base layer is coated with ether urethane on the surface, and the developing sleeve 14 has a diameter of 16 mm and a surface roughness Rz. An elastic roller having a size of ³ to 10 μm and a volume resistance value of 10 ⁴ to 10 ⁸ Ω · cm can be used. The peripheral speed of the latent image carrier 10 is 50 to 170 mm / s, and the peripheral speed of the developing sleeve 14 is rotated at a peripheral speed of 1 to 2 times the peripheral speed of the latent image carrier 10.

Above the developing sleeve 14, a metal plate such as SUS, a rubber material such as urethane or silicone, a metal thin plate of SUS or phosphor bronze having spring elasticity is used as a base, and a rubber is provided on the contact surface side with the developing sleeve 14. A regulating member 16 made of a material bonded or the like is supported by the regulating member support sheet metal 24 and is provided so that the vicinity of the free end side is in contact with the outer peripheral surface of the developing sleeve 14 by surface contact. The contact direction is a so-called counter direction in which the tip side is located upstream of the rotation direction of the developing sleeve 14 with respect to the contact portion. As an example of the regulating member 16, a plate-like urethane rubber having a thickness of 1.0 mm is bonded to the regulating member support metal plate 24, and the contact pressure (linear pressure) against the developing sleeve 14 is appropriately set. . 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. The regulating member 16 having a rubber material or the like bonded to the abutting surface is desirable in terms of adhesion to the toner, and can suppress the fusion and fixing of the toner to the regulating member in long-term use. Further, the restricting member 16 can also be in contact with the developing sleeve 14 by edge contact in which the tip is contacted. 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 developing sleeve at the contact point with the developing sleeve to be 40 degrees or less.

  The elastic roller 15 is in contact with the contact portion of the regulating member 16 with the surface of the developing sleeve 14 on the upstream side in the rotation direction of the developing sleeve 14 and is rotatably supported. As this structure, a foamed skeleton-like sponge structure or a fur brush structure in which fibers such as rayon or nylon are planted on the core metal is used for supplying the non-magnetic toner 17 to the developing sleeve 14 and stripping off the undeveloped toner. It is preferable from the point. As an example of the elastic roller, an elastic roller 15 having a diameter of 12 mm in which a polyurethane foam is provided on the core metal 15a is used. As the contact width of the elastic roller 15 with respect to the developing sleeve 14, 1 to 8 mm is effective, and it is preferable that the developing sleeve 14 has a relative speed at the contact portion.

  The charging roller 29 is not essential for the process cartridge of the present invention, but is preferably installed. The charging roller 29 is an elastic body such as NBR or silicone rubber, and is attached to the suppression member 30. The contact load of the charging roller 29 on the developing sleeve 14 by the suppressing member 30 is set to 0.49 to 4.9N. By contact of the charging roller 29, the toner layer on the developing sleeve 14 is finely packed and uniformly coated. The longitudinal positional relationship between the regulating member 16 and the charging roller 29 is preferably arranged so that the charging roller 29 can reliably cover the entire contact area of the regulating member 16 on the developing sleeve 14.

  In addition, for the driving of the charging roller 29, a driven or the same peripheral speed is indispensable with the developing sleeve 14, and if a peripheral speed difference occurs between the charging roller 29 and the developing sleeve 14, the toner coat becomes non-uniform, Unevenness occurs on the image, which is not preferable.

  A bias of the charging roller 29 is applied by a power source 27 between the developing sleeve 14 and the latent image carrier 10 in a direct current (27 in FIG. 1), and the nonmagnetic toner 17 on the developing sleeve 14 is applied from the charging roller 29. The charge is applied by discharge.

  The bias of the charging roller 29 is a bias equal to or higher than the discharge start voltage having the same polarity as the non-magnetic toner, and is set so that a potential difference of 1000 to 2000 V is generated with respect to the developing sleeve 14.

  After being charged by the charging roller 29, the toner layer formed as a thin layer on the developing sleeve 14 is uniformly conveyed to a developing unit that is a portion facing the latent image carrier 10.

  In this developing unit, the toner layer formed on the developing sleeve 14 is formed into a latent image carrier by a DC bias applied between the developing sleeve 14 and the latent image carrier 10 by the power source 27 shown in FIG. The electrostatic latent image on image 10 is developed as a toner image.

  In the present invention, the following members are used as members constituting the image forming apparatus shown in FIG.

As the elastic roller that can be used as the developing sleeve, an elastic layer, preferably a layer having a relatively high resistance is provided on a conductive substrate. As the elastic layer of the roller, rubber or sponge such as chloroprene rubber, isoprene rubber, EPDM rubber, polyurethane rubber, epoxy rubber, butyl rubber, silicone rubber, styrene-butadiene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester thermoplastic elastomer It can be formed of a thermoplastic elastomer such as ethylene-vinyl acetate thermoplastic elastomer. The developing sleeve preferably has a volume resistance of 10 ³ Ω · cm to 10 ⁹ Ω · cm.

The developing sleeve is preferably in the form of a roller having two or more layers on a core metal, and each layer is formed of rubber or the like having a different composition. A desirable developing sleeve can be obtained by controlling the conductivity (volume resistance value) of each layer.
The volume resistance value (Rv) of each layer is measured as follows. That is, a sheet of a material for forming each layer is prepared, a 10 mm square electrode is drawn with a silver paste on the outer surface of the sheet (with a guard electrode), a counter electrode is provided on the opposite side of the sheet, and the electric resistance between the electrodes Measure. A DC voltage of 100 V is applied between the electrodes.

  Examples of means for controlling conductivity include a method of dispersing conductive particles such as carbon, aluminum, nickel, and titanium oxide, and a method of using ionic conductivity by containing a quaternary ammonium salt, lithium perchlorate, or the like. .

  Examples of relatively high resistance layers include tetrafluoroethylene perfluoroalkyl vinyl ether copolymers, fluorine resins such as polyvinylidene fluoride, silicone resins such as methyl silicone, methyl phenyl silicone, and silicone acrylic, and nylon-6. , Nylon-12, nylon-46, polyamide resins such as aramids, polyester resins such as PET, polyolefin resins such as PE and PP, epoxy resins, vinyl chloride resins, polyurethane resins, polycarbonate resins, Melamine resins, styrene resins, acrylic resins such as polymethacrylates, polyacetal resins, vinyl acetate resins, phenol resins and the like can be used to adjust the resistance as appropriate.

As the developing sleeve used in the present invention, those having an Asker C hardness of 30 to 60 ° and a developing sleeve surface roughness Rz of 3 to 10 μm do not cause a large stress on the toner and cause poor regulation. This is desirable because a sufficient image density can be obtained.
The Asker C hardness is measured under the condition of a load of 500 g using an Asker hardness meter C type manufactured by Kobunshi Keiki Co., Ltd.
The surface roughness (Rz) is measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom) according to the method described in JIS B 0601.

  Further, a bias may be applied to the charged toner that is regulated by the developing sleeve and the regulating member and further in contact with the developing sleeve. This not only increases the charging of the toner but also makes it uniform, which is desirable because it improves the image quality including fogging and blurring.

As the charging auxiliary roller, a rubber or sponge material with appropriately adjusted resistance such as chloroprene rubber, isoprene rubber, EPDM rubber, polyurethane rubber, epoxy rubber, butyl rubber, silicone rubber, etc. is preferably used, and its volume resistance value is preferably 10 ⁴ Ω · cm or more and 10 ⁹ Ω · cm or less.

The latent image carrier used in the present invention has a photosensitive layer, and the photosensitive layer has a single layer or a laminated structure.
In the case of a single layer structure, the photosensitive layer contains both a charge generating material that generates carriers and a charge transport material that transports carriers. In the case of a laminated structure, a charge generation layer containing a charge generation material that generates carriers and a charge transport layer containing a charge transport material that transports carriers are stacked to form a photosensitive layer. The surface layer may be formed by either a charge generation layer or a charge transport layer.

  In the case of a single layer structure, the photosensitive layer preferably has a thickness of 5 to 100 μm, and more preferably 10 to 60 μm. Further, the charge generation material and the charge transport material are preferably contained in an amount of 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total mass of the photosensitive layer. In the case of a single layer structure, the photosensitive layer contains a binder resin described later in addition to the charge generation material and the charge transport material, and may contain an ultraviolet absorber, an antioxidant, other additives and the like as necessary. it can.

  In the photosensitive layer in the case of a laminated structure, the thickness of the charge generation layer is preferably 0.001 to 6 μm, and more preferably 0.01 to 2 μm. The content of the charge generation material is preferably 10 to 100% by mass, and more preferably 40 to 100% by mass with respect to the total mass of the charge generation layer. The charge generation layer may be composed only of a charge generation material. In other cases, the charge generation layer may contain a binder resin or the like. The thickness of the charge transport layer is preferably 5 to 100 μm, and more preferably 5 to 19 μm. The content of the charge transport material is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. The charge transport layer contains a binder resin in addition to the charge transport material, and can optionally contain other additives in the same manner as the photosensitive layer having a single layer structure.

  Examples of charge generating materials used in the present invention include phthalocyanine pigments, polycyclic quinone pigments, azo pigments, perylene pigments, indigo pigments, quinacridone pigments, azulenium salt dyes, squarylium dyes, cyanine dyes, pyrylium dyes, thiopyrylium dyes, xanthene dyes. Quinoneimine dye, triphenylmethane dye, styryl dye, selenium, selenium-tellurium, amorphous silicon, and hardened cadmium.

  Examples of the charge transport material used in the present invention include pyrene compounds, carbazole compounds, hydrazone compounds, N, N-dialkylaniline compounds, diphenylamine compounds, triphenylamine compounds, triphenylmethane compounds, pyrazoline compounds, styryl compounds, and stilbene compounds. Is mentioned.

  As binder resin used for the photosensitive layer, polyester, polyurethane, polyarylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamideimide, polysulfone, polyallyl ether, polyacetal, phenol resin, acrylic resin, silicone resin, Examples thereof include an epoxy resin, a urea resin, an allyl resin, an alkyd resin, and a butyral resin. Furthermore, reactive epoxy, (meth) acrylic monomers and oligomers can also be used after being mixed and cured.

  In the latent image carrier used in the present invention, a protective layer may be laminated on the photosensitive layer. The thickness of the protective layer is preferably 0.01 to 20 μm, and more preferably 0.1 to 10 μm. The protective layer usually has a structure in which a charge generation material or a charge transport material, a metal and its oxide, nitride, salt, alloy, and a conductive material such as carbon are dispersed in a binder resin. Examples of the binder resin, charge generating material, and charge transporting material used for the protective layer include the same materials as those used for the photosensitive layer.

The conductive support used for the latent image carrier used in the present invention is composed of metals such as iron, copper, nickel, aluminum, titanium, tin, antimony, indium, lead, zinc, gold and silver; alloys; A conductive material such as carbon; or a conductive resin can be used. There are cylindrical, belt-like and sheet-like shapes. Moreover, although the said electroconductive material may be shape-processed, you may apply | coat as a coating material or may vapor-deposit. Note that the conductive support used in the latent image carrier shown in FIG. 1 is cylindrical.

  In addition, an undercoat layer may be provided between the conductive support and the photosensitive layer. The undercoat layer is mainly composed of a binder resin, but may contain the conductive material or an acceptor compound such as dimethyl terephthalate, a benzoquinone compound, or trinitrofluorenone. The binder resin that forms the undercoat layer is polyester, polyurethane, polyarylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamideimide, polysulfone, polyallyl ether, polyacetal, phenol resin, acrylic resin, silicone Examples thereof include resins, epoxy resins, urea resins, allyl resins, alkyd resins, and butyral resins.

  Further, as described above, a conductive layer may be provided between the conductive support and the photosensitive layer. When the photoreceptor has both the undercoat layer and the conductive layer, the conductive support, the conductive layer, the undercoat layer, and the photosensitive layer are usually laminated in this order. The conductive layer generally has a configuration in which the conductive material is dispersed in a binder resin similar to that used in the undercoat layer.

  As a method for producing the latent image carrier used in the present invention, a method of laminating an undercoat layer, a photosensitive layer, a protective layer and the like on a conductive support by vapor deposition or coating is usually used. For coating, a bar coater, knife coater, roll coater, attritor, spray, dip coating, electrostatic coating, powder coating and the like are used. In addition, in order to form the undercoat layer, the photosensitive layer, the protective layer, and the like by a coating method, a solution in which each component is dissolved and dispersed in an organic solvent, a dispersion, or the like is applied by the above method. After that, the solvent may be removed by drying or the like. Alternatively, when a reaction-curable binder resin is used, a solution, a dispersion, or the like obtained by dissolving and dispersing the constituent components of each layer in a resin raw material component and an appropriate organic solvent added as necessary After the coating, for example, the resin raw material may be reacted and cured by heat or light, and the solvent may be removed by drying or the like as necessary.

  It is desirable to have at least a charge generation layer on the conductive substrate of the latent image carrier and a charge transport layer on the charge generation layer, and a protective layer of 19 μm or less on the charge generation layer. This is because if the thickness of the protective layer formed on the charge generation layer is larger than 19 μm, the sensitivity is lowered and the formed film is difficult to be uniform. Moreover, the problem that the residual amount of the solvent used on manufacture tends to increase also arises.

  As the latent image carrier contact charging member, a roller, a blade, a brush, or the like is used. In the case of a roller or a blade, a metal such as iron, copper, and stainless steel, a carbon dispersion resin, a metal or metal oxide dispersion resin, or the like is used as the conductive substrate, and a bar shape, a plate shape, or the like can be used. For example, as a configuration in which the roller as the latent image carrier contact charging member is an elastic roller, a structure in which an elastic layer, a conductive layer, and a resistance layer are provided on a conductive substrate is used. Elastic layers include chloroprene rubber, isoprene rubber, EPDM rubber, polyurethane rubber, epoxy rubber, butyl rubber and other rubber or sponge, styrene-butadiene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester thermoplastic elastomer, ethylene-vinegar. It can be formed of a thermoplastic elastomer such as a thermoplastic elastomer.

The conductive layer has a volume resistance of 10 ⁷ Ω · cm or less, preferably 10 ⁶ Ω · cm or less. For the conductive layer, for example, a metal deposition film such as aluminum, indium, nickel, copper, iron, etc .; conductive particles such as carbon, aluminum, nickel, titanium oxide, urethane, polyester, vinyl acetate-vinyl chloride copolymer, poly Conductive particle-dispersed resin dispersed in a resin such as methyl methacrylate; conductive resins such as quaternary ammonium salt-containing polymethyl methacrylate, polyvinyl aniline, polyvinyl pyrrole, polydiacetylene, and polyethyleneimine are used.

The resistance layer is, for example, a layer having a volume resistance value of 10 ⁶ to 10 ¹² Ω · cm, and a semiconductive resin, a conductive particle-dispersed insulating resin, or the like can be used. As the semiconductive resin, resins such as ethyl cellulose, nitrocellulose, methoxymethylated nylon, ethoxymethylated nylon, copolymerized nylon, polyvinyl hydrin, and casein are used. As conductive particle dispersion insulating resin, conductive particles such as carbon, aluminum, indium oxide and titanium oxide are dispersed in a small amount in insulating resin such as urethane, polyester, vinyl acetate-vinyl chloride copolymer and polymethyl methacrylate. And the like.

As the latent image carrier contact charging member, a brush whose resistance is adjusted by dispersing a conductive material in commonly used fibers is used. As the fiber, generally known fiber can be used, and examples thereof include nylon, acrylic, rayon, polycarbonate, polyester and the like. As the conductive material, generally known conductive materials can also be used, and metals such as copper, nickel, iron, aluminum, gold, and silver, or iron oxide, zinc oxide, tin oxide, antimony oxide, and titanium oxide. And metal oxides such as carbon black, and conductive powders such as carbon black. These conductive powders may be subjected to surface treatment for the purpose of hydrophobization and resistance adjustment, if necessary. In use, it is selected in consideration of dispersibility with fibers and productivity. As the shape of the brush, the fiber thickness is 1 to 20 denier (fiber diameter of about 10 to 500 μm), the brush fiber length is 1 to 15 mm, and the brush density is 10,000 to 300,000 per square inch (1 Those of about 1.5 × 10 ^{7 to} 4.5 × 10 ⁸ per square meter are preferably used.

  In the image forming method of the present invention, it is desirable that the latent image carrier contact charging member is a roller because of excellent charging uniformity.

  As described above, the case where the toner of the present invention is applied to an image forming method, a developing unit, and a process cartridge having a developing unit that is detachable from the main body of the image forming apparatus has been described. You may apply to the developing unit of the structure which replenishes. An image forming apparatus comprising at least the developing unit, and forming all or some of the latent image carrier, a cleaning blade as a cleaning unit, a waste toner container, and a charging unit as a charging unit as necessary. You may apply to the process cartridge which can be attached or detached from a main body.

  Further, when the image forming method includes a step of cleaning a toner remaining on the latent image carrier without being transferred by, for example, placing a blade-shaped cleaning member as a cleaning unit in pressure contact with the latent image carrier, It is desirable to add a charge eliminating step for discharging the surface of the latent image carrier in order to facilitate cleaning in the previous stage of the cleaning step.

  Further, an image forming method by non-magnetic one-component non-contact development using a non-magnetic one-component developer and a developing unit will be described based on a schematic configuration diagram shown in FIG.

The developing unit 170 carries a developer container 171 containing a non-magnetic one-component developer 176 as a non-magnetic toner, and a one-component non-magnetic developer 176 contained in the developer container 171, and in the developing area. A developing sleeve 172 for conveying, a supply roller 173 for supplying a one-component non-magnetic developer onto the developing sleeve, a developer layer thickness regulating member 174 for regulating the developer layer thickness on the developing sleeve, and development A stirring member 175 for stirring the one-component nonmagnetic developer 176 in the agent container 171 is provided.

  Reference numeral 169 denotes a latent image carrier for carrying an electrostatic latent image, and the latent image is formed by an electrophotographic process means or electrostatic recording means (not shown). The developing sleeve 172 is made of a nonmagnetic material made of aluminum or stainless steel. The developing sleeve may be a rough tube of aluminum or stainless steel as it is, but preferably the surface of the developing sleeve is blown uniformly with glass beads, the surface is mirror-finished, or the surface is coated with a resin. Good. In particular, the method of coating the surface of the developing sleeve with a resin is easy to adjust the surface roughness and conductivity of the developing sleeve or to impart lubricity to the surface of the developing sleeve by dispersing various particles in the resin. Therefore, it is preferably used.

  The resin used to coat the surface of the developing sleeve and the various particles added to the resin are not particularly limited. Examples of the resin include stainless steel resin, vinyl resin, polyethersulfone resin, polycarbonate resin, and polyphenylene. Thermoplastic resins such as oxide resin, polyamide resin, fluororesin, fiber resin, acrylic resin, epoxy resin, polyester resin, alkyd resin, phenol resin, melamine resin, polyurethane resin, urea resin, silicone resin, polyimide resin, etc. The heat or photo-curable resin is preferably used.

  Various particles to be added include PMMA (polymethyl methacrylate), acrylic resin, polybutadiene resin, polystyrene resin, polyethylene, polypropylene, polybutadiene, or a copolymer thereof, benzoguanamine resin, phenol resin, polyamide resin, nylon, fluorine-based. Resin, silicone resin, epoxy resin, polyester resin resin particles; furnace black, lamp black, thermal black, acetylene black, channel black, etc. carbon black; titanium oxide, tin oxide, zinc oxide, molybdenum oxide, potassium titanate Metal oxides such as antimony oxide and indium oxide; metals such as aluminum, copper, silver and nickel; inorganic fillers such as graphite, metal fibers and carbon fibers are preferably used

  The one-component nonmagnetic developer 176 is stored in the developer container 171 and is supplied onto the developing sleeve 172 by the supply roller 173. The supply roller 173 is made of a foam material such as polyurethane foam, and rotates relative to the developing sleeve 172 in a forward or reverse direction with a non-zero relative speed, and with the developer supplied, the developer after development on the developing sleeve 172 ( Undeveloped developer) is also removed. The one-component nonmagnetic developer supplied onto the developing sleeve 172 is uniformly and thinly applied by the developer layer thickness regulating member 174.

  It is effective that the contact pressure between the developer layer thickness regulating member 174 and the developing sleeve is 0.3 to 25 kg / m, preferably 0.5 to 12 kg / m as the linear pressure in the developing sleeve bus line direction. When the contact pressure is less than 0.3 kg / m, it is difficult to uniformly apply the one-component nonmagnetic developer, and the charge amount distribution of the one-component nonmagnetic developer becomes broad, which causes fogging and scattering. When the contact pressure exceeds 25 kg / m, a large pressure is applied to the one-component nonmagnetic developer, and the one-component nonmagnetic developer is deteriorated. Absent. Further, it is not preferable because a large torque is required to drive the developing sleeve. That is, by adjusting the contact pressure to 0.3 to 25 kg / m, it becomes possible to effectively loosen the aggregation of the one-component nonmagnetic developer using the toner of the present invention. It becomes possible to instantly raise the charge amount of the non-magnetic developer.

Materials for the developer layer thickness regulating member include rubber elastic bodies such as silicone rubber, urethane rubber and NBR; elastomers such as polyethylene terephthalate and polyamide; stainless steel, steel,
Metal elastic bodies such as phosphor bronze can be used, and composites thereof can also be used. Preferably, a material obtained by injection-molding rubber materials such as urethane and silicone and various elastomers such as polyamide elastomer on a thin metal plate of SUS or phosphor bronze having spring elasticity is preferable.

  In this non-magnetic one-component development system, in a system in which a one-component non-magnetic developer is thinly coated on a developing sleeve by a developer layer thickness regulating member, in order to obtain a sufficient image density, one on the developing sleeve is used. It is preferable to make the layer thickness of the component nonmagnetic developer smaller than the facing gap α between the developing sleeve and the latent image carrier, and to apply an alternating voltage to this gap. That is, the bias power source shown in FIG. 4 is used to apply an alternating voltage or a developing bias in which a DC voltage is superimposed on the alternating voltage between the developing sleeve 172 and the latent image carrier 169, so that the latent image carrier on the latent image carrier. This makes it easy to move the one-component non-magnetic developer to the surface, and a higher quality image can be obtained.

  In the present invention, the gap α between the latent image carrier and the developer carrier is set to 50 to 500 μm, for example, and the layer thickness of the developer carried on the developing sleeve is set to 40 to 400 μm, for example. It is preferable.

  The developing sleeve is rotated at a peripheral speed of 100 to 200% with respect to the latent image carrier. The alternating voltage of the developing bias to be applied is 0.1 kV or more, preferably 0.2 to 3.0 kV, more preferably 0.3 to 2.0 kV, peak to peak. The frequency of the alternating voltage is 1.0 to 5.0 kHz, preferably 1.0 to 3.0 kHz, more preferably 1.5 to 3.0 kHz. As the waveform of the alternating voltage, a waveform such as a rectangular wave, a sine wave, a sawtooth wave or a triangular wave can be applied. Furthermore, positive and reverse voltages and asymmetrical alternating voltages with different times can be used. It is also preferable to superimpose a DC voltage.

  Next, an image forming method and a developing unit using a two-component developer composed of the toner of the present invention as a nonmagnetic toner and a carrier will be described with reference to a schematic configuration diagram shown in FIG.

  The development unit 120 carries a developer container 126 that contains a two-component developer 128, a developer sleeve 121 that carries the two-component developer 128 contained in the developer container 126, and transports it to the development area. A developer layer thickness regulating member 127 for regulating the layer thickness of the developer formed on the sleeve 121 is provided.

  The developing sleeve 121 includes a magnet 123 as a magnetic field generating means in a nonmagnetic sleeve base 122.

The inside of the developer container 126 is divided into a developing chamber (first chamber) R ₁ and an agitating chamber (second chamber) R ₂ by a partition wall 130, and a toner storage chamber above the agitating chamber R _{2 with} a partition wall 130 therebetween. R ₃ is formed. A developer 128 is stored in the developing chamber R ₁ and the stirring chamber R ₂ , and a replenishing toner (nonmagnetic toner) 129 is stored in the toner storage chamber R ₃ . The toner storage chamber R ₃ is provided with a supply port 131, and an amount of supply toner 129 corresponding to the toner consumed through the supply port 131 is dropped and supplied into the stirring chamber R ₂ .

The developing chamber R ₁ is provided with conveying screw 124, the developer 128 in the developing chamber R ₁ by the driving rotation of the conveying screw 124 is conveyed toward the longitudinal direction of the developing sleeve 121. Similarly, a transport screw 125 is provided in the storage chamber R ₂ , and the toner that has fallen into the stirring chamber R ₂ from the replenishing port 131 by the rotation of the transport screw 125 is transported along the longitudinal direction of the developing sleeve 121. .

  The developer 128 is a two-component developer having a nonmagnetic toner and a carrier.

  An opening is provided in a portion of the developer container 126 close to the latent image carrier 119, the developing sleeve 121 protrudes from the opening, and a gap is formed between the developing sleeve 121 and the latent image carrier 119. Is provided. A power supply 132 for applying a developing bias is arranged on the developing sleeve 121 made of a nonmagnetic material.

As described above, the magnet 123 fixed to the sleeve base 122 includes the developing magnetic pole S ₁ , the magnetic pole N ₃ located downstream thereof, and the magnetic poles N ₂ , S ₂ , and N ₁ for conveying the developer 128. Have. The magnet 123 is disposed in the sleeve base 122 so that the developing magnetic pole S ₁ faces the latent image carrier 119. The developing magnetic pole S ₁ forms a magnetic field in the vicinity of the developing portion between the developing sleeve 121 and the latent image carrier 119, and a magnetic brush is formed by the magnetic field.

  The developer layer thickness regulating member 127 that is disposed above the developing sleeve 121 and regulates the layer thickness of the developer 128 on the developing sleeve 121 is made of a nonmagnetic material such as aluminum or SUS316. The distance A between the end of the developer layer thickness regulating member 127 and the surface of the developing sleeve 121 is 300 to 1000 μm, preferably 400 to 900 μm. If the distance A is smaller than 300 μm, the carrier tends to have unevenness in the thickness of the developer, that is, the developer layer thickness, and the developer necessary for good development cannot be applied, and there are many unevennesses of low density. There is a problem that only a toner image can be obtained. In order to prevent uneven application (so-called restriction member clogging) due to unnecessary particles mixed in the developer, 400 μm or more is preferable. When the distance A is greater than 1000 μm, the amount of developer applied onto the developing sleeve 121 increases, the predetermined developer layer thickness cannot be regulated, the carrier adheres to the latent image carrier 119, and the developer does not move. There is a problem that the developer regulating force by the circulating, non-magnetic developer layer and the developer layer thickness regulating member 127 is weakened, and toner tribo is insufficient and fogging easily occurs.

In the development using the two-component developing unit 120, a magnetic brush composed of toner and a carrier is in contact with a latent image carrier (for example, a photosensitive drum) 119 while applying an alternating voltage. Develop with. This by the magnetic brush and the latent image bearing member is in contact, after the transfer, the transfer residual toner carried on the latent image bearing member, are incorporated into the magnetic brush is collected into the developing chamber R _1. The distance (S-D distance) B between the developing sleeve 121 and the latent image carrier 119 is preferably 100 to 1000 μm in terms of preventing carrier adhesion and improving dot reproducibility. If it is narrower than 100 μm, the supply of the developer tends to be insufficient, and the image density becomes low. If it exceeds 1000 μm, the magnetic lines from the magnetic pole S ₁ spread and the density of the magnetic brush decreases, resulting in inferior dot reproducibility, The restraining force is weakened and carrier adhesion tends to occur.

  The voltage between the peaks of the alternating voltage is preferably 500 to 5000 V, and the frequency is 500 to 10000 Hz, preferably 500 to 3000 Hz, which can be appropriately selected and used for each process. In this case, the waveform can be selected from a triangular wave, a rectangular wave, a sine wave, or a waveform with a changed duty ratio. In addition, when the voltage between the peaks of the applied voltage is lower than 500 V, it is difficult to obtain a sufficient image density, and the fog toner in the non-image area may not be recovered well. When the voltage between the peaks of the applied voltage exceeds 5000 V, the electrostatic image may be disturbed via the magnetic brush, and the image quality may be deteriorated.

  By using a two-component developer having a well-charged toner, the fog removal voltage (Vback) can be lowered and the primary charge of the latent image carrier can be lowered. Life can be extended. Vback is 150 V or less, more preferably 100 V or less, although it depends on the developing method.

  The contrast potential is preferably 200 V to 500 V so that a sufficient image density is obtained.

  If the frequency is lower than 500 Hz, it is related to the process speed, but charge injection into the carrier occurs, so that there are cases where the image quality is degraded by disturbing the carrier adhesion or the latent image. When the frequency exceeds 10,000 Hz, the toner cannot follow the electric field and the image quality is liable to deteriorate.

  In order to achieve a sufficient image density, excellent dot reproducibility, and development without carrier adhesion, the contact width (development nip) C of the magnetic brush on the developing sleeve 121 with the latent image carrier 119 is preferably 3 ˜8 mm. If the contact width C is smaller than 3 mm, it is difficult to satisfactorily satisfy a sufficient image density and dot reproducibility. If the contact width C is larger than 8 mm, developer packing occurs and the operation of the machine is stopped, or the carrier adheres. It becomes difficult to hold down enough. As a method of adjusting the contact width, the contact width is appropriately adjusted by adjusting the distance A between the developer layer thickness regulating member 127 and the developing sleeve 121 or by adjusting the distance B between the developing sleeve 121 and the latent image carrier 119. adjust.

  In the development method using the above two-component developer, the transfer residual toner remaining on the latent image carrier after the transfer is developed between the transfer part in the transfer process and the charging part in the charging process, and in the charging part and the development process. It is possible to perform a simultaneous development cleaning system in which a simultaneous development cleaning that is recovered by the development unit in the development process is performed without providing a cleaning unit that comes into contact with the surface of the latent image carrier.

  In the simultaneous development cleaning system, the developing unit, the transfer unit, and the charging unit are positioned in this order with respect to the moving direction of the latent image carrier, and between the transfer unit and the charging unit and between the charging unit and the developing unit. In the meantime, there is no cleaning means for removing the transfer residual toner present on the surface of the latent image carrier in contact with the surface of the latent image carrier.

  The image forming method using the simultaneous development cleaning method will be described by taking as an example reversal development in which development is performed with the charged polarity of the toner and the charged polarity of the electrostatic latent image of the latent image carrier being the same polarity in the developing step. When a negatively chargeable latent image carrier and negatively chargeable toner are used, in the transfer process, an image visualized by a transfer member having a positive polarity is transferred to a transfer material. Depending on the relationship between the thickness, resistance, and dielectric constant) and the image area, the charging polarity of the residual toner varies from positive to negative. However, the negatively charged charging member for charging the negatively chargeable latent image carrier is uniform even if the transfer residual toner as well as the surface of the latent image carrier is shifted to the positive polarity in the transfer process. The charging polarity can be aligned to the negative side. Therefore, even when toner that is negatively charged uniformly at the time of development is present on the surface of the latent image carrier, when reversal development is used as the developing method, the residual toner that is negatively charged is It remains in the bright portion potential portion to be developed and does not remain in the dark portion potential where the toner should not be developed, and is attracted toward the magnetic brush or the developing sleeve due to the development electric field and does not remain.

  Next, the fixing method and fixing means used in the image forming method of the present invention will be described.

  The toner of the present invention is heat-fixed to a transfer material such as plain paper or an overhead projector (OHP) transparent sheet by contact heat fixing means.

  As the contact heating fixing means, a heating and pressure roller fixing device, or a fixed and supported heating body, and a pressing member that is in pressure contact with the heating body and closely contacts the transfer material to the heating body through a thin film. And surf fixing means for heating and fixing the toner.

Therefore, in order to shorten the standby time and reduce the power consumption, a surf fixing method using a film having a small heat capacity is desirable. As shown in FIG. 3, the heating or fixing device using the surf fixing method includes a pressure roller 36. The pressure roller 36 is provided with a cored bar. The pressure roller 36 is rotatable.

  Hereafter, the evaluation method of the evaluation item in the Example of this invention is shown. In addition, although the evaluation method of the magenta toner is shown as an example, the same evaluation method is used when evaluating a colored toner other than the magenta toner.

<Evaluation method>
(Fog)
The fog was measured using an LBP-2710 (manufactured by Canon Inc.) commercially available as an image forming apparatus with a process speed modified to 200 mm / s as follows. The product toner is extracted from the commercially available magenta cartridge of the apparatus, the interior is cleaned by air blow, and 300 g of the toner obtained in this example is filled, and the product toner is extracted from the other cyan, yellow, and black cartridges. Then, it was inserted into each station, and a durability test was conducted at a printing rate of 2% in a high temperature and high humidity environment (30 ° C., 80% RH) and a low temperature and low humidity environment (15 ° C., 10% RH). After printing 7000 sheets of durability from the beginning, leave it in each environment for 2 days, and then change the fog amount of the first image sample from Tokyo Denshoku's REFLECT.
It measured using METER MODELTC-6DS and computed from following formula (3). The smaller the value, the less fog. A fogging amount of 2% or less was regarded as no practical problem. As a transfer material used for the durability test, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
(3) Fog amount (%) = (Whiteness before printing out) − (Whiteness of non-image forming portion (white background portion) of recording material after printing)

(Dropping off)
The flaking was measured as follows using a process speed of LBP-2710 (manufactured by Canon Inc.) modified to 200 mm / s in a hot and humid environment (30 ° C., 80% RH). . The product toner is extracted from the commercially available magenta cartridge of the apparatus, the inside is cleaned by air blow, and 300 g of the toner obtained in this example is filled. For other cyan, yellow, and black cartridges, the product toner is used. Unplug, insert into each station, perform a durability test at a printing rate of 2%, print 5000 sheets of durability from the beginning, leave it in a hot and humid environment for 2 days, and then visually check the first image sample evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. The evaluation criteria are as follows.
A: Not generated at all B: One present on the image C: Two to three present on the image, but no practical problem D: Generated, practically problematic

(Density reduction)
The decrease in image density was measured as follows using a commercially available LBP-2710 (manufactured by Canon Inc.) modified to 200 mm / s in a hot and humid environment (30 ° C., 80% RH). did. The product toner is extracted from the commercially available magenta cartridge, the interior is cleaned by air blow, 300 g of the toner obtained in this embodiment is filled, and the product toner is extracted from other cyan, yellow, and black cartridges. Then, insert it into each station, perform a durability test at a printing rate of 2%, and use the REFLECT METER MODELTC-6DS made by Tokyo Denshoku Co., Ltd. for the 5000th image sample from the beginning compared to the initial image. Then, the concentration was measured, and the concentration difference was evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. The evaluation criteria are as follows.
A: No decrease in density B: A decrease in density of 0.01
C: Concentration decrease is 0.02
D: Density decrease is 0.03 or more

(Solid image uniformity)
The solid image uniformity is as follows using a process speed of LBP-2710 (manufactured by Canon Inc.) modified to 200 mm / s in a low temperature and low humidity environment (15 ° C., 10% RH). It was measured. The product toner is extracted from the commercially available magenta cartridge, the interior is cleaned by air blow, 300 g of the toner obtained in this embodiment is filled, and the product toner is extracted from other cyan, yellow, and black cartridges. Then, after inserting into each station, the endurance test was performed by continuous printing at a printing rate of 2%, and immediately after printing the 10th and 10000th images, one full-surface solid chart was printed respectively, and image evaluation Went. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. The evaluation criteria for the image samples are as follows.
A: The toner is uniformly transferred and colored on the entire surface. B: A portion having a low density partially exists after 70 mm from the image leading edge. C: The toner is not transferred to the paper after 70 mm from the image leading edge. There is an exposed part of the skin

(Halftone image unevenness)
Halftone image unevenness is as follows using a process speed of LBP-2710 (manufactured by Canon Inc.) modified to 200 mm / s in a low temperature and low humidity environment (15 ° C., 10% RH). It was measured. The product toner is extracted from the commercially available magenta cartridge, the interior is cleaned by air blow, 300 g of the toner obtained in this embodiment is filled, and the product toner is extracted from other cyan, yellow, and black cartridges. Then, it was inserted into each station, and 1000 sheets were printed continuously at a printing rate of 2%, and the subsequent halftone image was evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.

As an evaluation image, an image having a 15% density halftone image printed on the entire surface was used. The image samples were evaluated as follows.
A: There is no unevenness on the image. B: There is slight unevenness on the image, but there is no practical problem. C: There is unevenness on the image, and there is a practical problem.

(Initial image density)
The initial image density was measured in a low-temperature and low-humidity environment (15 ° C., 10% RH) using a commercially available LBP-2710 (manufactured by Canon Inc.) modified to 200 mm / s as follows. did. The product toner is extracted from the commercially available magenta cartridge of the apparatus, the inside is cleaned by air blow, and 300 g of the toner obtained in this example is filled. For other cyan, yellow, and black cartridges, the product toner is used. Unplug, insert into each station, perform endurance test with continuous printing at a printing rate of 2%, before the endurance test and immediately after printing the 10th, 100th, and 500th images, respectively One full-surface solid chart was printed, and the image density of each image was measured. The density of the image sample was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. When the image density is 1.20 or more, there is no practical problem. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. The evaluation criteria are as follows.
A: Concentration 1.25 or more B: Concentration 1.20 or more C: Concentration 1.15 or more D: Concentration 1.10 or more E: Concentration less than 1.10

(Filming)
Filming was measured in a low-temperature and low-humidity environment (15 ° C., 10% RH) using a commercially available LBP-2710 (manufactured by Canon Inc.) modified to 200 mm / s as follows. . The product toner is extracted from the commercially available magenta cartridge of the apparatus, the inside is cleaned by air blow, and 300 g of the toner obtained in this example is filled. For other cyan, yellow, and black cartridges, the product toner is used. The sample was pulled out and inserted into each station, and a durability test was performed by continuous printing at a printing rate of 2%. The 2000th durability image sample from the initial stage was visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. The evaluation criteria are as follows.
A: Not generated at all B: Slightly generated but practically no problem C: Slightly generated but practically no problem D: Generated and practically problematic

(Toner scattering)
Toner scattering was measured in a low-temperature and low-humidity environment (15 ° C., 10% RH) using a commercially available LBP-2710 (manufactured by Canon Inc.) modified to 200 mm / s as follows. . The product toner is extracted from the commercially available magenta cartridge of the apparatus, the inside is cleaned by air blow, and 300 g of the toner obtained in this example is filled. For other cyan, yellow, and black cartridges, the product toner is used. It was pulled out and inserted into each station, and a durability test was performed at a printing rate of 2%. After printing 5000 sheets, the cartridge was taken out of the machine and visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. The evaluation criteria are as follows.
A: Not generated at all B: Slightly generated but practically no problem C: Slightly generated but practically no problem D: Generated and practically problematic

(Toner fusion and adhesion)
To fuse and fix the toner to the developing sleeve and the regulating member, the process speed of a commercially available LBP-2710 (manufactured by Canon Inc.) was modified to 200 mm / s in a low temperature and low humidity environment (15 ° C., 10% RH). It measured as follows using the thing. The product toner is extracted from the commercially available magenta cartridge of the apparatus, the inside is cleaned by air blow, and 300 g of the toner obtained in this example is filled. For other cyan, yellow, and black cartridges, the product toner is used. The sample was pulled out and inserted into each station, and a durability test was performed at a printing rate of 2%. The image sample of the 10,000th durability from the beginning was visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. The evaluation criteria are as follows.
A: Not generated at all B: Slightly generated, but no practical problem C: Generated, practical problem

(Cleanability)
The cleaning property is a commercially available LBP-271 in a low temperature and low humidity environment (15 ° C., 10% RH).
Measurement was performed as follows using a process speed of 0 (manufactured by Canon Inc.) modified to 200 mm / s. The product toner is extracted from the commercially available magenta cartridge, the interior is cleaned by air blow, 300 g of the toner obtained in this embodiment is filled, and the product toner is extracted from other cyan, yellow, and black cartridges. Then, it was inserted into each station, and 10,000 sheets were continuously printed out at a printing rate of 2%, and the cleaning property and image quality were visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. The evaluation criteria are as follows.
A: Good cleaning B: Poor (Blade elasticity decreased and toner slipped, black horizontal streaks slightly occurred in the image, but there is no practical problem)
C: Poor (the elasticity of the blade is reduced and the toner slips through, causing slight black horizontal streaks in the image, which is problematic in practice)

(Fixability)
Fixability was measured as follows using a LBP-2710 (manufactured by Canon Inc.) modified to 200 mm / s in a low temperature and low humidity environment (15 ° C., 10% RH). . The product toner is extracted from the commercially available magenta cartridge of the apparatus, the inside is cleaned by air blow, and 300 g of the toner obtained in this example is filled. For other cyan, yellow, and black cartridges, the product toner is used. Unplug and insert into each station, the machine and toner-filled cartridges become familiar with the environment (after leaving in that environment for 24 hours), and after turning on the power, the 200 μm wide horizontal line pattern (width 200 μ, An interval of 200 μm was printed out, and the 50th printed image was used for evaluation of the fixing property. The fixing property was evaluated by rubbing the image with Sylbon paper at a load of 100 g for 5 reciprocations, and the peeling of the image was evaluated by the average reduction rate (%) of reflection density.

For the evaluation, bond paper having a surface smoothness of 10 sec or less was used. The evaluation criteria are shown below.
A: Density reduction rate less than 10% B: Density reduction rate of 10% or more and less than 20% C: Density reduction rate of 20% or more Fixation failure has occurred in the previous evaluation image

(Offset resistance)
Offset resistance was measured as follows using a commercially available LBP-2710 (manufactured by Canon Inc.) modified to 200 mm / s in a low temperature and low humidity environment (15 ° C., 10% RH). did. The product toner is extracted from the commercially available magenta cartridge of the apparatus, the inside is cleaned by air blow, and 300 g of the toner obtained in this example is filled. For other cyan, yellow, and black cartridges, the product toner is used. Unplug, insert into each station, print out 50 full-color images immediately after turning on the power from the state in which the device and the cartridge filled with toner have been adapted to the environment (after leaving in that environment for 24 hours) The image samples were evaluated.

For the evaluation, an OHP film (CG3700, manufactured by Sumitomo 3M Limited) was used. The evaluation criteria are shown below.
A: No offset occurred at all B: Offset occurred very slightly, but there was no practical problem (and within 2 sheets)
C: Offset occurs and is problematic in practical use Hereinafter, the present invention will be described in detail with reference to examples, but this does not limit the present invention. In the following examples, “parts” in the blending amount represents “parts by mass”.

<Manufacture of sulfur atom-containing resin>
(Production of sulfur atom-containing resin 1)
In a 2 L flask equipped with a stirrer, condenser, thermometer, nitrogen introduction tube, 100 parts of toluene, 300 parts of methanol, 470 parts of styrene, 40 parts of 2-acrylamido-2-methylpropanesulfonic acid, 70 parts of 2-ethylhexyl acrylate, Charge 20 parts of benzyl methacrylate and 10 parts of lauryl peroxide, stir and polymerize the solution at 65 ° C. for 10 hours under introduction of nitrogen, take out the contents from the flask, dry under reduced pressure at 40 ° C. for 96 hours, and crush in a hammer mill The coarsely crushed product was further dried under reduced pressure at 40 ° C. for 48 hours to obtain a sulfur atom-containing resin 1. The physical properties of the obtained sulfur atom-containing resin were Mw = 25000, volatile content 0.10%, Tg = 68 ° C., and residual monomer = 400 ppm.

  In addition, the acid value (AV2) of the obtained sulfur atom containing resin 1 was 20 mgKOH / g.

(Production of sulfur atom-containing resin 2)
In a 2 L flask equipped with a stirrer, condenser, thermometer, nitrogen introduction tube, 300 parts of toluene, 100 parts of methanol, 470 parts of styrene, 40 parts of 2-acrylamido-2-methylpropanesulfonic acid, 70 parts of 2-ethylhexyl acrylate, 20 parts of benzyl methacrylate and 12 parts of lauryl peroxide were charged, stirred and subjected to solution polymerization at 65 ° C. for 10 hours under introduction of nitrogen, the contents were taken out from the flask, dried under reduced pressure at 40 ° C., and roughly crushed with a hammer mill, The coarsely crushed product was further dried under reduced pressure at 40 ° C. for 48 hours to obtain a sulfur atom-containing resin 2. The physical properties of the obtained sulfur atom-containing resin 2 were Mw = 42000, volatile content 0.10%, Tg = 68 ° C., and residual monomer = 400 ppm.

  In addition, the acid value (AV2) of the obtained sulfur atom containing resin 2 was 18 mgKOH / g.

(Production of sulfur atom-containing resin 3)
In a 2 L flask equipped with a stirrer, condenser, thermometer, nitrogen introduction tube, 100 parts of toluene, 300 parts of methanol, 500 parts of styrene, 40 parts of 2-acrylamido-2-methylpropanesulfonic acid, 40 parts of 2-ethylhexyl methacrylate, Charge 20 parts of benzyl methacrylate and 12 parts of lauryl peroxide, stir, polymerize the solution at 65 ° C. for 10 hours under nitrogen introduction, take out the contents from the flask, dry under reduced pressure at 40 ° C., and crush in a hammer mill. The coarsely crushed product was further dried under reduced pressure at 40 ° C. for 48 hours to obtain a sulfur atom-containing resin 3. The physical properties of the obtained sulfur atom-containing resin 3 were Mw = 40000, volatile matter 0.10%, resin Tg = 86 ° C., and residual monomer = 400 ppm.

  In addition, the acid value (AV2) of the obtained sulfur atom containing resin 3 was 23 mgKOH / g.

<Production of hydrophobic titanium oxide fine powder>
(Production of hydrophobic titanium oxide fine powder 1)
Titanium oxide fine powder (KR-310, manufactured by Titanium Industry) was treated with 3 parts of a 200 centistoke chlorophenyl silicone oil emulsion in an aqueous system, filtered and dried to obtain hydrophobic titanium oxide fine powder 1. The primary particle size was 450 nm, the degree of hydrophobicity = 30%, the volume resistance value 1.5 × 10 ¹⁵ Ω · cm, and the rutile type.

(Production of hydrophobic titanium oxide fine powder 2)
Titanium oxide fine powder (KR-310, manufactured by Titanium Industry) was treated with 3 parts of a 200 centistoke chlorophenyl silicone oil emulsion in an aqueous system, then filtered, dried and classified to obtain hydrophobic titanium oxide fine powder 2. . The primary particle size was 550 nm, the degree of hydrophobicity = 30%, the volume resistance value 1.5 × 10 ¹⁵ Ω · cm, and the rutile type.

(Production of hydrophobic titanium oxide fine powder 3)
Titanium oxide fine powder (JA-1, manufactured by Teica) was treated with 10 parts of isobutyltrimethoxysilane in toluene, then filtered and dried to obtain hydrophobic titanium oxide fine powder 3. The primary particle size was 200 nm, the degree of hydrophobicity = 65%, the volume resistance value = 4.0 × 10 ¹¹ Ω · cm, and an anatase type.

(Production of hydrophobic titanium oxide fine powder 4)
Titanium oxide fine powder (JA-1, manufactured by Teica) was treated with 15 parts of octyltrimethoxysilane in toluene, then filtered and dried to obtain hydrophobic titanium oxide fine powder 4. The primary particle size was 200 nm, the degree of hydrophobicity = 75%, the volume resistance value = 6.0 × 10 ¹³ Ω · cm, and an anatase type.

(Production of hydrophobic titanium oxide fine powder 5)
Titanium oxide fine powder (JA-1, manufactured by Teica) was pulverized by a jet mill and then classified to obtain titanium oxide fine powder having a primary particle size of 80 nm. The titanium oxide fine powder was treated with 10 parts of isobutyltrimethoxysilane in an aqueous system, filtered and dried to obtain hydrophobic titanium oxide fine powder 5. The primary particle size was 80 nm, the degree of hydrophobicity = 55%, the volume resistance value = 2.5 × 10 ¹⁰ Ω · cm, and anatase type.

(Production of hydrophobic titanium oxide fine powder 6)
The hydrophobization treatment was performed in the same manner as the fine titanium oxide powder 5 except that the treatment was performed with 17 parts of octyltrimethoxysilane in toluene. The primary particle size was 80 nm, the degree of hydrophobicity = 75%, the volume resistivity = 3.5 × 10 ¹³ Ω · cm, and anatase type.

(Manufacture of hydrophobic titanium oxide fine powder 7)
The hydrophobization treatment was carried out in the same manner as in the production of the hydrophobic titanium oxide fine powder 5 except that it was treated with 12 parts of octyltrimethoxysilane in toluene. The primary particle size was 80 nm, the degree of hydrophobicity = 70%, the volume resistance value = 3.0 × 10 ¹² Ω · cm, and anatase type.

(Production of hydrophobic titanium oxide fine powder 8)
The hydrophobization treatment was performed in the same manner as in the production of the hydrophobic titanium oxide fine powder 5 except that the hydrophobization treatment was stirred and mixed with 7 parts of vinyltriacetoxysilane in an aqueous system. The primary particle size was 50 nm, the degree of hydrophobicity = 60%, the volume resistance value = 3.0 × 10 ¹¹ Ω · cm, and an anatase type.

(Production of hydrophobic titanium oxide fine powder 9)
The hydrophobizing treatment was carried out in the same manner as the production of the hydrophobic titanium oxide fine powder 5 except that the hydrophobizing treatment was performed by stirring and mixing with 8 parts of octyltrimethoxysilane in an aqueous system. The primary particle size was 50 nm, the degree of hydrophobicity = 65%, the volume resistance value = 4.0 × 10 ¹¹ Ω · cm, and anatase type.

[Example 1]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium (dispersion medium) was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 1 0.8 parts The above materials are put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin 8 parts (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15)
・ Wax No. 5 (melting point = 70 ° C) 20 parts polyethylene wax 5 parts (high wax 110P, Mitsui Chemicals, melting point = 109 ° C)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the obtained magenta colored toner particles, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 8 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 1 having an external additive was obtained. The physical properties of the obtained toner 1 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 2]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
・ Styrene 60 parts ・ Colorant (CI Pigment Blue 15: 3) 7 parts ・ Sulfur atom-containing resin 1 0.8 part The above materials were introduced into an attritor dispersing machine (Mitsui Miike Chemical Co., Ltd.), and A zirconia particle having a diameter of 2 mm was used and dispersed at 220 rpm for 5 hours to obtain a polymerizable monomer composition.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 (melting point = 70 ° C) 20 parts polyethylene wax 5 parts (high wax 110P, Mitsui Chemicals, melting point = 109 ° C)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain cyan colored toner particles.

  100 parts of the cyan colored toner particles obtained, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 8 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 2 having an external additive was obtained. The physical properties of the obtained toner 2 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 3]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
・ Styrene 60 parts ・ Colorant (CI Pigment Yellow 17) 7 parts ・ Sulfur atom-containing resin 1 0.8 parts The above materials were put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.), and diameter 2 mm The polymerizable monomer composition was obtained by dispersing the obtained zirconia particles at 220 rpm for 5 hours.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 (melting point = 70 ° C) 20 parts polyethylene wax 5 parts (high wax 110P, Mitsui Chemicals, melting point = 109 ° C)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain yellow colored toner particles.

  100 parts of the yellow colored toner particles obtained, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 8 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 3 having an external additive was obtained. The physical properties and the like of the obtained toner 3 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 4]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
・ Styrene 60 parts ・ Colorant (carbon black) 7 parts (REGAL 250R, manufactured by CABOT)
-Sulfur atom-containing resin 1 0.8 parts The above materials are put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 (melting point = 70 ° C) 20 parts polyethylene wax 5 parts (high wax 110P, Mitsui Chemicals, melting point = 109 ° C)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain black colored toner particles.

  100 parts of the black colored toner particles obtained, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 8 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 4 having an external additive was obtained. The physical properties of the obtained toner 4 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[ Reference Example 5]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . TK homomixer (
An aqueous medium containing a dispersion stabilizer was prepared by batch-feeding 10 parts of ion-exchanged water with 8 parts of calcium chloride dissolved in 10 parts of ion exchange water while stirring at 12,000 rpm.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 1 0.8 parts The above materials are put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 (melting point = 70 ° C) 20 parts polyethylene wax 5 parts (high wax 110P, Mitsui Chemicals, melting point = 109 ° C)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

100 parts of the obtained magenta colored toner particles, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 1 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 5 having an external additive was obtained. The physical properties of the obtained toner 5 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 6]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 1 0.8 parts The above materials are put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 20 parts polyethylene wax 5 parts (High Wax 110P, Mitsui Chemicals, melting point = 109 ° C)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

100 parts of the obtained magenta colored toner particles, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 3 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 6 having an external additive was obtained. The physical properties and the like of the obtained toner 6 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 7]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 1 0.8 parts The above materials are put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 20 parts polyethylene wax 5 parts (High Wax 110P, Mitsui Chemicals, melting point = 109 ° C)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the obtained magenta colored toner particles, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 4 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 7 having an external additive was obtained. The physical properties and the like of the obtained toner 7 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 8]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-0.8 part of sulfur element-containing resin 1 The above material is charged into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm for polymerization. A functional monomer composition was obtained.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 20 parts polyethylene wax 5 parts (High Wax 110P, Mitsui Chemicals, melting point = 109 ° C)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the obtained magenta colored toner particles, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 6 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 8 having an external additive was obtained. The physical properties and the like of the obtained toner 8 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 9]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 1 0.8 parts The above materials are put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 20 parts polyethylene wax 5 parts (High Wax 110P, Mitsui Chemicals, melting point = 109 ° C)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the obtained magenta colored toner particles, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 5 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 9 having an external additive was obtained. The properties of the obtained toner 9 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 10]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 20 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added and kept at 65 ° C. for 60 minutes while purging with N ₂ . TK homomixer (
An aqueous medium containing a dispersion stabilizer was prepared by batch-feeding an aqueous calcium chloride solution containing 12 parts of calcium chloride into 10 parts of ion-exchanged water while stirring at 12,000 rpm using a special machine chemical).
(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (CI Pigment Red 122 / CI Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 1 0.8 parts The above materials are put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
20 parts of styrene 20 parts of n-butyl acrylate Condensation resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8.5 parts 5 20 parts polyethylene wax 5 parts (High Wax 110P, Mitsui Chemicals, melting point = 109 ° C)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the obtained magenta colored toner particles, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 7 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 10 having an external additive was obtained. The physical properties and the like of the obtained toner 10 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 11]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (CI Pigment Red 122 / CI Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 1 0.8 parts The above materials are put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 20 parts polyethylene wax 5 parts (High Wax 110P, Mitsui Chemicals, melting point = 109 ° C)
・ Crosslinking agent (divinylbenzene) 0.4 parts

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the obtained magenta colored toner particles, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 9 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 11 having an external additive was obtained. The physical properties and the like of the obtained toner 11 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 12]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 1 0.8 parts The above materials are put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 20 parts polyethylene wax 5 parts (High Wax 110P, Mitsui Chemicals, melting point = 109 ° C)
・ Crosslinking agent (divinylbenzene) 0.4 parts

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the obtained magenta colored toner particles, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 7 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 12 having an external additive was obtained. The physical properties and the like of the obtained toner 12 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 14]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 1 0.8 parts The above materials are put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 20 parts polyethylene wax 5 parts (High Wax 110P, Mitsui Chemicals, melting point = 109 ° C)
・ Crosslinking agent (divinylbenzene) 0.1 part

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the obtained magenta colored toner particles, 1.0 part of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 7 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 14 having an external additive was obtained. The physical properties and the like of the obtained toner 14 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Example 15]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 2 0.8 part The above material is put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
Styrene 20 parts n-butyl acrylate 20 parts Condensed resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts 5 20 parts polyethylene wax 5 parts (High Wax 110P, Mitsui Chemicals, melting point = 109 ° C)
・ Crosslinking agent (divinylbenzene) 0.1 part

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the obtained magenta colored toner particles, 1.3 parts of silica fine powder (RY200, manufactured by Nippon Aerosil Co., Ltd.) and 0.2 part of hydrophobic titanium oxide fine powder 7 are mixed in a coffee mill, and external additives are added. Toner 15 having the following properties was obtained: The physical properties and the like of the obtained toner 15 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Comparative Example 1]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 3 0.8 part The above material is put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
20 parts of styrene 20 parts of n-butyl acrylate Condensation resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts Polyethylene wax 20 parts (high wax 100P, Mitsui Chemical)
・ 0.5 parts of crosslinking agent (divinylbenzene)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the obtained magenta colored toner particles and 1.2 parts of silica fine powder (RX200, manufactured by Nippon Aerosil Co., Ltd.) were mixed in a coffee mill to obtain toner 16 having an external additive. The physical properties and the like of the obtained toner 16 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Comparative Example 2]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-Sulfur atom-containing resin 3 0.8 part The above material is put into an attritor disperser (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 2 mm. A mass composition was obtained.

The following components were added to the polymerizable monomer composition.
・ Styrene 20 parts ・ N-butyl acrylate 20 parts ・ Condensation resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts ・ Fischer-Tropsch wax 20 parts
(Sasol H1, Schumann Sasol)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the obtained magenta colored toner particles and 0.2 part of the hydrophobic titanium oxide fine powder 2 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner 17 having an external additive. The physical properties and the like of the obtained toner 17 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[Comparative Example 3]
(Dispersion medium)
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system containing a dispersion stabilizer. A medium was prepared.

(Polymerizable monomer composition)
-Styrene 60 parts-Colorant 7 parts (C.I. Pigment Red 122 / C.I. Pigment Red 57 = 1/1)
-0.5 parts of azo metal complex (Bontron S-34: manufactured by Orient Chemical Co., Ltd.)
The above materials were put into an attritor dispersing machine (Mitsui Miike Chemical Co., Ltd.), and further dispersed using 220 nm zirconia particles at 220 rpm to obtain a polymerizable monomer composition.

The following components were added to the polymerizable monomer composition.
・ Styrene 20 parts ・ N-butyl acrylate 20 parts ・ Condensation resin (saturated polyester (isophthalic acid-propylene oxide modified bisphenol A), Mw = 10000, AV1 = 15) 8 parts ・ Fischer-Tropsch wax 20 parts
(Sasol H1, Schumann Sasol)

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 2.5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(toner)
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, and granulated by stirring at 10000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is pressure filtered and washed with more than 2000 parts of ion exchange water. The obtained cake is returned to 1000 parts of ion-exchanged water again and washed again with stirring for 2 hours in a state in which 10% hydrochloric acid is added to make pH = 1 or less. The emulsion was filtered under pressure in the same manner as described above, further washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored toner particles.

  100 parts of the magenta colored toner particles obtained, 1.0 part of silica fine powder (RX200, manufactured by Nippon Aerosil Co., Ltd.), and 0.2 part of hydrophobic titanium oxide fine powder 1 were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). By mixing, a toner 18 having an external additive was obtained. The physical properties of the obtained toner 18 are shown in Table 1. The evaluation results are shown in Tables 2 and 3.

FIG. 3 is a schematic view of a developing unit that performs nonmagnetic one-component contact development using the toner of the present invention. It is explanatory drawing of the apparatus used for the measurement of the volume resistance value of a titanium oxide fine powder. 1 is a schematic view of a fixing device. FIG. 3 is a schematic view of a developing unit that performs non-magnetic one-component non-contact development using the toner of the present invention. FIG. 3 is a schematic view of a developing unit that performs two-component development using the toner (nonmagnetic toner) of the present invention.

Explanation of symbols

A Cell 1 Lower electrode 2 Upper electrode 3 Insulator 4 Ammeter 5 Voltmeter 6 Constant voltage device 7 Fine powder of titanium oxide 8 Guide ring 10 Latent image carrier (photosensitive drum)
11 Latent image carrier contact charging member (elastic roller)
DESCRIPTION OF SYMBOLS 12 Power supply 13 Developing unit 14 Developing sleeve 15 Elastic roller 16 Restriction member 17 Toner 24 Restriction member support sheet metal 25 Stirring means 26 Toner leakage prevention member 27 Power supply 29 Charging roller (pressure contact elastic member)
30 suppression member 31 heater base 32 heating element 33 temperature detection element 34 holder 35 film 36 pressure roller 37 film drive roll 38 tension roll 39 toner P transfer paper 119 photosensitive drum 120 developing device 121 developing sleeve 122 sleeve base 123 magnet 124 conveying screw 125 Conveying screw 126 Developer container 127 Developer layer thickness regulating member 128 Two-component developer 129 Replenishing toner (non-magnetic toner)
130 Partition 131 Supply port 132 Power supply R1 Development chamber (first chamber)
R2 stirring chamber (second chamber)
R3 Toner storage A Distance between developer regulating member and developing sleeve B Distance between developing sleeve and photosensitive drum C Contact width of magnetic brush on developing sleeve with photosensitive drum 169 Latent image carrier 170 Developing unit 171 Developer container 172 Development sleeve 173 Supply roller 174 Developer layer thickness regulating member 175 Stirring member 176 Non-magnetic one-component developer

Claims (22)

100 masses of toner particles obtained through a granulation step in an aqueous medium containing at least a binder resin, a condensation resin, a colorant, a resin containing a sulfur atom having an acid value of 10 to 30 mg KOH / g, and a wax to parts, from 0.10 to 3.00 parts by weight of silica fine powder is externally added to the toner particles, and a primary particle size of 35~500nm hydrophobized anatase type titanium oxide fine powder 0 A toner having at least 0.01 to 1.00 parts by mass ,
Said condensation resin having an acid value AV1 and the sulfur atom-containing resin having an acid value AV2 is, meets the relationship AV1 <AV2,
The toner according to claim 1, wherein the number free rate of the titanium oxide fine powder and the silica fine powder on the toner particle surface is 0.10 to 25.00%, respectively .   The toner according to claim 1, wherein the wax contains waxes having different wax endothermic peak temperatures in DSC measurement, and a difference in each endothermic peak temperature is 3 ° C. or more.   The toner according to claim 1, wherein the toner is a non-magnetic one-component toner.   The toner according to claim 1, wherein the titanium oxide fine powder has a primary particle size of 35 to 250 nm.   The toner according to claim 1, wherein the titanium oxide fine powder has a primary particle size of 45 to 100 nm. Resin containing the sulfur atom, SO ₃ X (wherein, X is H,. An alkali metal) toner according to any one of claims 1 to 5, characterized in that a resin containing a group .   The toner according to claim 1, wherein the titanium oxide fine powder has a hydrophobicity of 45 to 80%. The toner according to claim 1, wherein the titanium oxide fine powder has a volume resistance value of 1.0 × 10 ^{3 to} 1.0 × 10 ¹⁵ Ω · cm. The toner according to claim 1, wherein the titanium oxide fine powder has a volume resistance value of 1.0 × 10 ^{4 to} 1.0 × 10 ¹⁴ Ω · cm.   The toner according to claim 1, wherein the toner particles have an average circularity of 0.960 to 0.995.   The toner according to claim 1, wherein the wax contains at least an ester wax having 1 to 6 ester groups.   The toner according to claim 1, wherein the wax contains a wax having a wax endothermic peak temperature of 30 to 120 ° C. in DSC measurement.   The toner according to claim 1, wherein the silica fine powder is at least oil-treated.   The toner according to claim 1, wherein the toner has a melt index of 5.0 to 30.0. A developing sleeve that supplies toner to the developing sleeve by a toner supplying member, forms a toner layer by a regulating member for forming a thin toner layer on the developing sleeve, and develops the toner image in a non-contact or contact manner with the latent image carrier. In an image forming method for forming a toner image on a latent image carrier,
The toner was obtained through a granulation step in an aqueous medium containing at least a binder resin, a condensation resin, a colorant, a resin containing a sulfur atom having an acid value of 10 to 30 mg KOH / g, and a wax. 0.10 to 3.00 parts by mass of silica fine powder externally added to the toner particles , and a hydrophobized anatase type titanium oxide having a primary particle size of 35 to 500 nm with respect to 100 parts by mass of the toner particles A toner having at least 0.01 to 1.00 parts by mass of fine powder,
Said condensation resin having an acid value AV1 and the sulfur atom-containing resin having an acid value AV2 is, meets the relationship AV1 <AV2,
An image forming method, wherein the toner particles have a number free rate of the titanium oxide fine powder and the silica fine powder on the surface of the toner particles of 0.10 to 25.00%, respectively .   The image forming method according to claim 15, wherein the toner according to claim 2 is used as the toner. The toner is transferred to an electrostatic latent image formed on the latent image carrier to form a toner image, and the toner image is transferred to a transfer material to form an image. A process cartridge,
One or two or more selected from the latent image carrier, a charging unit for charging the latent image carrier, and a cleaning unit,
The toner is transferred to the electrostatic latent image formed on the latent image carrier and is supported integrally with a developing unit that forms and develops a toner image,
The developing means is obtained through a granulating step in an aqueous medium containing at least a binder resin, a condensation resin, a colorant, a resin containing a sulfur atom having an acid value of 10 to 30 mgKOH / g, and a wax. 100 parts by mass of the toner particles, 0.10 to 3.00 parts by mass of silica fine powder externally added to the toner particles , and a hydrophobized anatase type oxidation having a primary particle size of 35 to 500 nm A toner having at least 0.01 to 1.00 parts by mass of titanium fine powder,
Said condensation resin having an acid value AV1 and the sulfur atom-containing resin having an acid value AV2 is, meets the relationship AV1 <AV2,
A process cartridge comprising a toner in which the number free rate of the titanium oxide fine powder and the silica fine powder on the toner particle surface is 0.10 to 25.00%, respectively .   18. The process cartridge according to claim 17, wherein the latent image carrier is negatively charged by a charging member that contacts the latent image carrier, and the toner is a negatively chargeable toner.   The process cartridge according to claim 17 or 18, wherein the toner is the toner according to any one of claims 2 to 14. A developer container for containing toner, a developing sleeve provided in an opening of the developer container, and a nip formed with the developing sleeve to regulate a layer thickness of the toner carried on the developing sleeve. And a developing unit having a regulating member for frictionally charging the toner and a toner supply member for supplying toner to the developing sleeve,
The developing unit is obtained through a granulating step in an aqueous medium containing at least a binder resin, a condensation resin, a colorant, a resin containing a sulfur atom having an acid value of 10 to 30 mg KOH / g, and a wax. 100 parts by mass of the toner particles, 0.10 to 3.00 parts by mass of silica fine powder externally added to the toner particles , and a hydrophobized anatase type oxidation having a primary particle size of 35 to 500 nm A toner having at least 0.01 to 1.00 parts by mass of titanium fine powder,
Said condensation resin having an acid value AV1 and the sulfur atom-containing resin having an acid value AV2 is, meets the relationship AV1 <AV2,
A developing unit comprising a toner in which the number free rate of the titanium oxide fine powder and the silica fine powder on the toner particle surface is 0.10 to 25.00%, respectively .   21. The toner according to claim 20, wherein the toner is a negatively chargeable toner, and the developing sleeve develops the toner in non-contact or contact with the latent image carrier to form a toner image on the photosensitive member. Development unit.   The developing unit according to claim 20 or 21, wherein the toner is the toner according to any one of claims 2 to 14.