JP5151493B2 - Toner for developing electrostatic image, two-component developer, image forming method and image forming apparatus - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image, a two-component developer using the toner, an image forming method, and an image forming apparatus.

In an electrophotographic apparatus or an electrostatic recording apparatus, a toner is attached to an electrostatic latent image formed on a photosensitive member, transferred to a transfer material, and then the toner is fixed to the transfer material by heat. Is forming. Also, full-color image formation is generally performed by using four color toners of black, yellow, magenta, and cyan. Each color is developed and each toner layer superimposed on the transfer material is heated simultaneously. Then, a full color image is obtained by fixing. However, for users who are familiar with printing, images in full-color copiers are not yet satisfactory, and there is a demand for higher image quality that satisfies photography and high resolution and high resolution.

  Conventionally, an electric or magnetic latent image is visualized with toner. It is known to use a toner having a small particle size and a narrow particle size distribution for improving the image quality of an electrophotographic image. Such toner is generally colored particles in which a binder, a charge control agent, and other additives are contained in a binder resin, and the production methods are roughly classified into a pulverization method and a polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventing agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner.

According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, a composition obtained by melt mixing must be capable of being easily pulverized and classified by an apparatus. From this requirement, the melt-mixed composition must be made sufficiently brittle. Therefore, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, the particle size There is a disadvantage that the fine powder of 5 μm or less and the coarse powder of 20 μm or more must be removed by classification, resulting in a very low yield. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. The non-uniform dispersion of the additive adversely affects toner fluidity, developability, durability, image quality, and the like.

  In recent years, in order to overcome these problems in the pulverization method, for example, Patent Document 1 discloses an invention of a suspension polymerization method, and Patent Document 2 associates resin fine particles obtained by an emulsion polymerization method with an irregular shape. An invention of a method for obtaining toner particles is disclosed. All of these polymerized toners are more spherical than particles of pulverized toner, and are expected to have a uniform composition, so they have excellent image reproducibility. A new problem has arisen in that the presence of external additives such as imparting agents tends to change on the surface of the particles.

  This is because the surface of the toner is smooth and the packing property is high, so the contact point of the toner increases, and the external additive is easily embedded in the toner at the contact point between the toner and the toner or each member. It is believed that. As a solution to these problems, a technique of mixing resin particles having a relatively large particle diameter with particles has been found.

Patent Document 3 discloses an invention of a method in which not only high-molecular weight resin fine particles are contained in toner particles but also the resin fine particles are unevenly distributed on the surface of the toner particles, thereby improving offset resistance. Yes. However, the invention described in this document has an increase in the minimum fixing temperature, the low-temperature fixability, that is, the energy-saving fixability is not sufficient, and the high molecular weight resin component forms part of the toner particles. Since there was no change in the shape of the particles, it was insufficient to prevent the external additive from being buried.
Japanese Patent Laid-Open No. 9-43909 Japanese Patent No. 2537503 JP 2000-292978 A

  The present invention has been made in view of the above-mentioned conventional problems, and although it is a spherical toner, it can prevent the external additive from being buried easily or under a low-stress load, has little fluctuation in image density, and can be used over time. An object of the present invention is to provide a toner capable of obtaining excellent image quality while maintaining cleaning properties and transferability, and to provide a two-component developer, an image forming method, and an image forming apparatus using the obtained toner. To do.

  In order to solve the above problems, the invention according to claim 1 is a toner obtained by mixing base particles containing at least a colorant and a resin, and hard fine particles, and the surface of the base particles includes the toner. It is a toner for developing an electrostatic image having a projecting portion composed of organic resin fine particles having a composition different from that of the resin constituting the main component of the base particles.

  According to a second aspect of the present invention, in the electrostatic charge image developing toner according to the first aspect, the protruding portions are scattered on the surface of the base particle.

  According to a third aspect of the present invention, in the electrostatic image developing toner according to the first or second aspect, the organic resin fine particles have a particle diameter of 1/5 or less of an average particle diameter of the toner, and are hemispherical. It is characterized in that a convex portion having a shape is formed.

  According to a fourth aspect of the present invention, there is provided the electrostatic image developing toner according to any one of the first to third aspects, wherein the toner removes oil droplets of an organic solvent in which a toner composition containing a prepolymer is dissolved. It is characterized by comprising particles dispersed in and formed by at least one of an extension reaction or a crosslinking reaction.

  According to a fifth aspect of the present invention, in the electrostatic image developing toner according to any one of the first to fourth aspects, the resin contains at least a polyester resin.

  According to a sixth aspect of the present invention, in the electrostatic image developing toner according to any one of the first to fifth aspects, an organic solvent in which the protruding portion dissolves a toner composition containing a prepolymer is used as the organic resin fine particles. In addition to the aqueous medium containing the organic solvent, the organic resin fine particles are supported on the surface of the oil droplets when forming the oil droplets of the organic solvent, and are formed by performing at least one of an extension reaction or a crosslinking reaction. To do.

  According to a seventh aspect of the present invention, in the electrostatic image developing toner according to any one of the first to sixth aspects, an average circularity E of the toner particles is 0.90 to 0.99. And

  According to an eighth aspect of the invention, in the electrostatic image developing toner according to any one of the first to seventh aspects, the toner has a circularity SF-1 value of 100 to 150 and a circularity SF-2 value. Is 100 to 140.

  The invention according to claim 9 is the electrostatic image developing toner according to any one of claims 1 to 8, wherein the volume average particle diameter Dv of the toner particles is 2 to 7 μm, and the volume average particle diameter Dv is The ratio Dv / Dn of the number average particle diameter Dn is 1.25 or less.

  A tenth aspect of the present invention is a two-component developer including the carrier according to any one of the first to ninth aspects and a carrier made of magnetic particles.

  The invention according to claim 11 and claims 12 to 13 develops the electrostatic image on the electrostatic image carrier with a developer to form a toner image, and transfers the toner image to the surface of the electrostatic image carrier via a transfer material. 11. An image forming method and an image forming apparatus for bringing a toner image into contact with each other and electrostatically transferring the toner image onto the transfer material, wherein the developer is the two-component developer according to claim 10. To do.

  According to the present invention, a toner having a hemispherical protrusion on the surface of the base particle, although it is a spherical toner, prevents the external additive from being buried easily and under a low stress load, and changes in image density. Therefore, it is possible to provide a toner, a two-component developer, an image forming method, and an image forming apparatus that have low image quality, maintain cleanability and transferability over time and have excellent image quality.

The toner, two-component developer, image forming method, and image forming apparatus of the present invention will be described below in detail with reference to the drawings.
The toner of the present invention is a toner characterized in that a partial protrusion is provided on the toner particle surface. This is because the surface of the toner particles is dotted with protrusions made of a resin component having a composition different from that of the constituent resin of the toner base particles. With this protrusion, it is possible to prevent the external additive from being rapidly buried during the use of the toner. These protrusions are preferably scattered and firmly adhered to the surface of the base particles, and are preferably not present in a state of being detached from toner particles such as externally added fine particles.

  The closer the toner shape is to a spherical shape, the more easily an external additive such as silica that is a fluidity imparting agent of the toner is embedded in the toner surface due to a low stress load. This is because the toner surface is subjected to stress such as friction while the toner is used, and the external additive is buried in the toner. In such a spherical toner, the entire surface of the particles is uniformly subjected to stress due to contact with each member, for example, a carrier, a stirring member, a regulating blade, etc., and the external additive is buried quickly and uniformly and flows from the initial use of the toner. There is a disadvantage that the property is remarkably easily changed.

  On the other hand, in the case of irregularly shaped particles such as pulverized toner, the toner and the particle surface of each member do not contact as uniformly as spherical particles, so the change in fluidity is relatively gentle, but the adhesion of particles There are many problems in terms of image quality due to non-uniformity. Therefore, the toner shape is preferably approximately spherical, but by providing a protruding portion on the surface of the particle, the rapid and uniform embedding of the external additive is suppressed, and the change in the toner fluidity is suppressed. It is possible to maintain excellent image quality.

  The protrusions on the toner surface are preferably organic resin fine particles having a composition different from that of the resin as the main component. This is because the protrusions themselves can be prevented from being buried in the particles when the toner is used, and the protrusions can be easily formed in various polymerization toner manufacturing methods. Typically, it is preferable to use a base resin whose main component is polyester and other resin composition represented by styrene acryl, particularly a thermoplastic resin that can be used as a binder resin for the toner, for the protrusion.

  As a result, the external additive can be prevented from being buried without affecting the fixing property of the toner. For example, a suspension polymerization method in which a monomer containing at least a colorant, a charge control agent, a release agent and the like of each toner composition is suspended in an aqueous medium, and the monomer is polymerized to form particles. It is preferable to form toner particles by mixing organic resin fine particles or raw materials thereof in advance in a monomer or dispersion medium.

  If the particles are formed by aggregating and coalescing at least particles of resin, colorant, release agent, etc. in an aqueous medium, the organic resin fine particles are agglomerated at the same time, or later in the agglomeration operation and coalescence operation. By coexisting organic resin fine particles or raw materials thereof, deposition on the toner surface layer can be performed.

When a resin composition and a composition such as a colorant and a release agent are dissolved or melted and suspended in an aqueous medium and granulated, organic resin fine particles or raw materials thereof are present in the resin composition. Or in an aqueous medium, and the organic resin fine particles may be present on the toner surface in the granulation step.

Preferably, at least a colorant, a prepolymer containing a release agent, and a prepolymer reactive with the prepolymer are dissolved or dispersed in a non-aqueous organic solvent, and the solution or dispersion is dissolved in an aqueous medium. In the granulation method in which the molecular weight is controlled by the reaction between prepolymers in the suspension, the organic resin fine particles or their raw materials are present in a non-aqueous solvent and granulated, or in the aqueous medium. The method of making it exist and making it adhere to the particle | grain surface is used preferably. In this method, organic resin fine particles or raw materials thereof are present in a non-aqueous solvent or an aqueous medium, and are deposited at the oil-water interface when a suspended state is formed.

The protrusion is preferably substantially hemispherical. This is because the corresponding shape can be easily formed by semi-embedding other fine particle components on the surface of the toner particles.

Further, the size of the protrusions is preferably a particle diameter of 1/5 or less of the average particle diameter of the toner. When the protrusion is too large relative to the toner size, the uniformity of the image quality is inferior compared to the spherical toner.

As a method for producing the toner particles of the present invention, various polymerization methods can be preferably used. In particular, since the main component is polyester and a substantially spherical shape can be easily obtained, oil droplets of an organic solvent in which a toner composition containing a prepolymer is dissolved are dispersed in an aqueous medium, and at least one of an elongation reaction or a crosslinking reaction is performed. A method of forming by reaction is preferably used. In this method, a polyester component, which is a main component of toner, is dissolved in an organic solvent, and this is dispersed in an aqueous medium to form droplets, and toner particles are formed from the droplets.

By containing a resin fine particle component having a composition different from that of the polyester in the aqueous medium,
It is possible to deposit resin fine particles in a protruding shape on the surface of the oil droplet. When the resin fine particles in such an aqueous medium are made into polyester fine particles, the polyester component and the fine particles in the droplets are completely united, and it becomes difficult to generate protrusions. For this reason, in the present invention, the protrusion can be formed on the toner surface by providing the protrusion component with a composition different from that of the polyester or a difference in compatibility with the polyester.

Further, in the present invention, the toner is obtained by externally adding a hard fine powder. As the hard fine powder in the present invention, external additives conventionally used for the purpose of imparting fluidity and chargeability can be used. For example, in addition to the oxide fine particles, inorganic fine particles and hydrophobized inorganic particles can be used together. In particular, the hydrophobized primary particles have an average particle diameter of 1 to 100 nm, more preferably 5 nm to 70 nm. It is more desirable to contain at least one kind.

Further, the hydrophobic treated primary particles include at least one kind of small inorganic particle having an average particle diameter of 20 nm or less and at least one large fine particle of 30 nm or more.
It is more desirable to include the type.

The inorganic fine particles preferably have a specific surface area by the BET method of 20 to 500 m ² / g. The volume specific resistance Rl of one large particle component of at least two kinds of fine particles is larger than the volume specific resistance Rs of the small particle component, and the volume resistivity is 10 to 17 [Lo].
gΩcm] is preferable.

Rs should be relatively small as compared with Rl, but in order not to prevent the occurrence of the previous charge, the volume resistivity is preferably 7 to 14 [Log Ωcm].

Any known one that satisfies the above conditions can be used. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate)
, Metal oxides (titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers, and the like may be contained.

Particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. As silica fine particles, HDKH 2000, HDK H 2000
/ 4, HDK H 2050EP, HVK21, HDK H 1303 (Hoechst)
And R972, R974, RX200, RY200, R202, R805, and R812 (Nippon Aerosil). As titania fine particles, P-25 (Nippon Aerosil)
And STT-30, STT-65C-S (above Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT-600B, MT-150A (above Taker). Particularly, the hydrophobized titanium oxide fine particles include T-805 (Nippon Aerosil), STT-30A, STT-65S-S (above Titanium Industry), TAF-500.
T, TAF-1500T (above Fuji Titanium Industry), MT-100S, MT-100T (above Takeka), IT-S (Ishihara Sangyo), etc.

In order to obtain hydrophobized oxide fine particles, silica fine particles, titania fine particles, and alumina fine particles, these hydrophilic fine particles are treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. It can be obtained by processing. Also, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles can be suitably used.

Examples of silicone oils that can be used include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino acid. Modified silicone oil, epoxy modified silicone oil, epoxy / polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, acrylic, methacryl modified silicone oil, α-methylstyrene modified silicone oil, etc. can be used. .

Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, quartz sand, clay, mica, and silica ash. Examples thereof include stone, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Of these, silica and titanium dioxide are particularly preferred.

The amount of inorganic fine particles added may be 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the toner.

The average particle size of the primary particles of the inorganic fine particles is 100 nm or less, preferably 3 nm or more and 70 nm.
It is as follows. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor is undesirably damaged.

In addition, as hard fine powder, polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, and heavy polymers such as silicone, benzoguanamine and nylon are used. Examples of the polymer particles include a condensation system and a thermosetting resin.

When polymer fine particles are used as a fluidizing agent, such a fluidizing agent performs surface treatment,
The hydrophobicity can be increased, and deterioration of flow characteristics and charging characteristics can be prevented even under high humidity.
For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

A cleaning property improving agent for removing the developer after transfer remaining on the photosensitive member or the primary transfer medium can also be included in the resin fine particles. Examples of such fine particles include zinc stearate, calcium stearate, stearic acid, and the like. Examples include fatty acid metal salts such as polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

Further, as these fine powders, resin fine particles such as emulsion polymer particles can be used. In the present invention, resin fine particles can be contained as required.

On the other hand, the resin fine particles used have a glass transition point (Tg) of 40 to 100 ° C., more preferably a weight average molecular weight of 9000 to 200,000. As described above, the glass transition point (Tg) or the weight average molecular weight. When at least one of these is the lower limit of 40 ° C. and less than 9,000, the storage stability of the toner deteriorates and blocking occurs during storage and in the developing machine. In addition, when at least one of the upper limit values of 100 ° C. and 200,000 is exceeded,
Adhesiveness with paper, which is a medium to which resin fine particles are fixed, is inhibited, and the minimum fixing temperature is increased.

More preferably, the residual ratio with respect to the toner particles is 0.5 to 5.0 wt%. When the residual ratio is less than 0.5 wt%, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the residual amount is 5.0 wt% or more, the resin fine particles are not present. The exudation of the wax is obstructed, the effect of releasing the wax is not obtained, and the occurrence of offset is observed.

The residual ratio of the resin fine particles of the resin fine particles to the toner particles can be measured by analyzing with a pyrolysis gas chromatograph mass spectrometer and calculating from the peak area. As a detector,
A mass spectrometer is preferable, but there is no particular limitation.

The resin fine particles may be any resin that can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin Resin, phenolic resin, melamine resin,
Examples include urea resins, aniline resins, ionomer resins, and polycarbonate resins.

As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained. The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, for example, styrene-
(Meth) acrylic acid ester resin, styrene-butadiene copolymer, (meth) acrylic acid-acrylic acid ester polymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid A copolymer etc. are mentioned.

It is important that the toner in the present invention has a specific shape and shape distribution, and the average circularity E is preferably 0.90 to 0.99. A toner having an irregular shape of 0.90 or less, which is too far from a spherical shape, does not provide satisfactory transferability and high-quality images free from dust. 0
. If it exceeds 99, it becomes a perfect sphere, which is not preferable because of poor cleaning properties.

As a method for measuring the shape, an optical detection band method is used in which a suspension containing toner particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. Can do. The average circularity E is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle.

In order for the toner to form a high-definition image having an appropriate density and reproducibility, the average circularity E is 0.
. More preferably, it is 94-0.99.

From the viewpoint of ease of cleaning, it is more preferable that the average circularity E is 0.94 to 0.99, and the number of particles having a circularity of less than 0.94 is 10% or less.

As an apparatus for measuring the average circularity E, a flow type particle image analyzer FPIA-21 is used.
The average circularity E can be measured by 00 (manufactured by Toa Medical Electronics).

As a specific measuring method, 100 to 150 ml of water from which impure solids in the container have been removed in advance.
A surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant in the range of 0.1 to 0
. Add 5 ml and add about 0.1 to 0.5 g of the sample to be measured. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. It is done.

(Circularity SF-1, SF-2)
The shape factors SF-1 and SF-2, which are the circularity used in the present invention, are obtained by randomly sampling 300 SEM images of toner obtained by measurement with a FE-SEM (S-4200) manufactured by Hitachi, Ltd. The image information was introduced into an image analysis apparatus (Luzex AP) manufactured by Nireco through an interface and analyzed, and the values obtained from the following equations were defined as SF-1 and SF-2. The values of SF-1 and SF-2 are preferably values obtained by Luzex, but are not particularly limited to the FE-SEM device and the image analysis device as long as similar analysis results can be obtained.

SF-1 = (L2 / A) × (π / 4) × 100
SF-2 = (P2 / A) × (1 / 4π) × 100
Here, the absolute maximum length of the toner is L, the projected area of the toner is A, and the maximum peripheral length of the toner is P. In the case of a true sphere, all become 100, and from a spherical shape to an indefinite shape as the value becomes larger than 100. In particular, SF-1 represents the shape of the entire toner (such as an ellipse or a sphere), and SF-2 is a shape factor indicating the degree of unevenness on the surface.

(Volume average particle diameter, Dv / Dn (volume average particle diameter / number average particle diameter ratio))
The volume average particle diameter (Dv) of the toner of the present invention is more preferably 2 to 7 μm, and the number average particle diameter (
Dn) is a dry toner having a ratio (Dv / Dn) of 1.25 or less, preferably 1.10 to 1.25, and is excellent in all of heat-resistant storage stability, low-temperature fixability, and hot offset resistance. When used in a full-color copying machine, etc., it has excellent image glossiness. Furthermore, in a two-component developer, even if the toner balance is maintained over a long period of time, the fluctuation of the toner particle diameter in the developer is reduced, and the developing device Good and stable developability can be obtained even with long-term stirring.

Further, when the toner is used as a one-component developer, the fluctuation of the toner particle diameter is reduced even if the balance of the toner is performed. At the same time, there is no filming of the toner on the developing roller and no fusion of the toner to a member such as a blade for thinning the toner, and it is good and stable even in long-term use (stirring) of the developing device. Developability and image were obtained. In particular, when using inorganic fine particles surface-treated with at least both a fluorine-containing compound and a silicon-containing compound as a fluidizing agent, the particle size distribution is more preferable because the margin for filming is reduced due to the influence of fluorine groups. .

In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced, When used as an agent, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.

Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention.

On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. The same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.

(resin)
In the present invention, a polyester resin can be used as the resin, and a modified polyester resin can be used as the polyester resin. For example, a polyester prepolymer having an isocyanate group can be used. Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group further reacted with a polyisocyanate (3). Can be mentioned.

Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

As the polyol (1), a diol (1-1) and a trivalent or higher polyol (1-2)
And (1-1) alone or a mixture of (1-1) and a small amount of (1-2) is preferable.

The diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-
Propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,
6-hexanediol); alkylene ether glycol (diethylene glycol,
Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol (1,
4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (
Bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols; alkylene oxides of the above bisphenols (ethylene oxide,
And propylene oxide, butylene oxide, etc.). Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred.

Examples of the dicarboxylic acid (2-1) include alkylene dicarboxylic acids (succinic acid, adipic acid,
Alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.)
Etc. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like).

In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

The ratio of the polyol (1) to the polycarboxylic acid (2) is such that the hydroxyl group [OH] and the carboxyl group [
The equivalent ratio [OH] / [COOH] of COOH] is usually 2/1 to 1/1, preferably 1.5.
/ 1-1 / 1, more preferably 1.3 / 1 to 1.02 / 1.

Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); aromatic aliphatic diisocyanates (α, α, α)
', Α'-tetramethylxylylene diisocyanate); isocyanurates; those obtained by blocking the polyisocyanate with a phenol derivative, oxime, caprolactam, etc .; and combinations of two or more of these.

The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. [NCO]
If / [OH] exceeds 5, the low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.
8 to 2.5. If it is less than 1 per molecule, the molecular weight of the modified polyester after crosslinking and / or elongation becomes low, and the hot offset resistance deteriorates.

(Crosslinking agent and extender)
In the present invention, amines can be used as a crosslinking agent and / or an extender. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino groups B1 to B5 blocked (B6) etc. are mentioned.

Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like.

Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.

Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.

Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.

  Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.

Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

Furthermore, if necessary, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for crosslinking and / or elongation. Stoppers include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) and their blocked (
Ketimine compound).

The ratio of the amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of the isocyanate groups [NCO] in the prepolymer (A) having an isocyanate group and the amino groups [NHx] in the amines (B).
Usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1
. 2/1 to 1 / 1.2. If [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

As the polyester resin in the present invention, it is important not only to use the modified polyester (A) alone, but also to contain the unmodified polyester (C) as a toner binder component together with the (A). By using (C) in combination, the low-temperature fixability and the glossiness when used in a full-color apparatus are improved.

Examples of (C) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (A), and preferred ones are also the same as (A). Also,
(C) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, for example, may be modified with a urethane bond.

It is preferable that (A) and (C) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (A) and (C) preferably have similar compositions. When (A) is contained, the weight ratio of (A) to (C) is usually 5/95 to 75/25,
The ratio is preferably 10/90 to 25/75, more preferably 12/88 to 25/75, and particularly preferably 12/88 to 22/78. If the weight ratio of (A) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

The peak molecular weight of (C) is usually 1000 to 30000, preferably 1500 to 1000.
0, more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate.

The hydroxyl value of (C) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

The acid value of (C) is usually from 0.5 to 40, preferably from 5 to 35. By having an acid value, it tends to be negatively charged. Further, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.

In the present invention, the glass transition point (Tg) of the toner is usually 40 to 70 ° C., preferably 45.
~ 55 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient.

Due to the coexistence of the crosslinked and / or elongated polyester resin, the toner for developing an electrostatic charge image of the present invention exhibits good storage stability even when the glass transition point is low, as compared with known polyester-based toners.

The storage elastic modulus of the toner is 10,000 dyne / cm at a measurement frequency of 20 Hz.
^The temperature (TG ′) to be ² is usually 100 ° C. or more, preferably 110 to 200 ° C. 10
If it is less than 0 ° C., the resistance to hot offset deteriorates.

As the viscosity of the toner, the temperature (Tη) at which the measurement frequency is 20 Hz becomes 1000 poise.
) Is usually 180 ° C. or lower, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, from the viewpoint of achieving both low-temperature fixability and hot offset resistance, TG
'Is preferably higher than Tη. In other words, the difference between TG ′ and Tη (TG′−Tη) is 0 ° C.
(0 [deg.]) Or more is preferable. More preferably, 10 [deg. ], More preferably 20 [deg. That's it. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is 0 to 100 [deg. ] Is preferable. More preferably, it is 10-90 [deg. ], Particularly preferably 20 to 80 [de
g. ].

(Coloring agent)
As the colorant of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G
), Cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartra Gin Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FR , FRLL, F4RH), Fast Scarlet VD, Belcan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux BL 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thio Indigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone orange, Oil orange, Cobalt blue, Cerulean blue, Alkaline blue lake, Pi Cock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide , Zinc white, litbon and mixtures thereof can be used.

The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

The colorant used in the present invention can also be used as a master batch combined with a resin.

As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrenic copolymer such as acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane,
Polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. Can be used.

The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin.

In addition, a so-called flushing method, which is a wet method of colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
Further, a wax may be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax,
Sazol wax and the like); carbonyl group-containing wax and the like. Of these, carbonyl group-containing waxes are preferred.

Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (
Trimellitic acid tristearyl, distearyl maleate, etc.); polyalkanoic acid amide (such as ethylenediamine dibehenyl amide); polyalkylamide (such as trimellitic acid tristearyl amide); and dialkyl ketone (such as distearyl ketone) It is done. Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.

The melting point of the wax used in the present invention is usually 40 to 160 ° C., preferably 50 to
120 degreeC, More preferably, it is 60-90 degreeC.

A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature.

Moreover, the melt viscosity of wax is 5-100 as a measured value in temperature 20 degreeC higher than melting | fusing point.
0 cps is preferable, and more preferably 10 to 100 cps. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability.

The wax content in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.
It is.

(Charge control agent)
Further, a charge control agent can be contained in order to control the charge amount of the toner.

As a method for supporting the charge amount component, the base toner and a compound such as a charge amount control agent are agitated and mixed to physically adhere the compound to the surface of the toner base particles, or heating or mechanical impact. Examples thereof include a method of immobilizing on the toner surface using force, or a method of chemically reacting and immobilizing the functional group on the toner surface and the charge controllable compound.

As the charge amount control agent here, all known ones can be used, for example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments,
Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts and salicylic acid derivatives Metal salts, etc.

Specifically, Bontron 03, a nigrosine dye, Bontron P, a quaternary ammonium salt
-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82
, Salicylic acid-based metal complex E-84, phenol-based condensate E-89 (manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (
As mentioned above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP20
38, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nihon Kalit) Manufactured by the same company), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

(Manufacture of toner)
The toner in the present invention can be produced by the following method.

First, the toner binder comprises the polyol (1) and the polycarboxylic acid (2).
Heat to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxy titanate, dibutyltin oxide, etc., and distill off the water produced while reducing the pressure as necessary to obtain a polyester having a hydroxyl group. Subsequently, this and polyisocyanate (3
) To obtain a prepolymer (A) having an isocyanate group.

The toner of the present invention can be produced in an aqueous medium.
The aqueous phase used in the present invention is used by adding resin fine particles in advance. The aqueous phase may be water alone or a solvent miscible with water can be used in combination.

Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

The toner particles are obtained by forming a dispersion composed of a polyester prepolymer (A) having an isocyanate group dissolved or dispersed in an organic solvent in an aqueous phase and reacting with amines (B).

As a method for stably forming a dispersion comprising a polyester prepolymer (A) in an aqueous phase, a composition of a toner raw material comprising a polyester prepolymer (A) dissolved or dispersed in an organic solvent in an aqueous phase is added. And a method of dispersing by applying a shearing force.

A polyester prepolymer (A) dissolved or dispersed in an organic solvent and another toner composition (hereinafter referred to as toner raw material), a colorant masterbatch, a release agent, a charge control agent,
Unmodified polyester resin or the like may be mixed when the dispersion is formed in the aqueous phase, but after the toner raw material is mixed in advance and dissolved or dispersed in an organic solvent, the mixture is then added to the aqueous phase. In addition, it is more preferable to disperse.

In the present invention, toner raw materials other than the resin such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in the aqueous phase, but after the particles are formed. , May be added. For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method. The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied.

In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperature is polyester prepolymer (A)
It is preferable in that the dispersion made of is low in viscosity and easy to disperse.

The amount of the aqueous phase used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts of the toner composition containing the polyester prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. 200
If it exceeds 0 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed.
It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino acids as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in the aqueous phase Amine salt types such as alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, and quaternary ammonium such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride Nonionic surfactants such as salt-type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-di Amphoteric surfactants such as chill ammonium betaine.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount.

Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (C _6- C ₁₁₎ oxy] -1-alkyl (C ₃ ~C ₄₎ sulfonate, sodium 3- [omega - fluoroalkanoyl (C ₆ ~C ₈₎ -N- ethylamino] -1-sodium sulfonic acid, fluoroalkyl (C ₁₁ ~C ₂₀₎ carboxylic acids and metal salts thereof, perfluoroalkyl carboxylic acids (C ₇
-C ₁₃₎ and their metal salts, perfluoroalkyl (C ₄ -C ₁₂₎ sulfonic acids and metal salts thereof, perfluorooctane sulfonic acid diethanolamide, N- propyl-N-(2-hydroxyethyl) perfluorooctane sulfonamide , perfluoroalkyl (C ₆ -C _1
0 ) Sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C ₆ -C
_{10)-N-ethylsulfonyl} glycine salts, and monoperfluoroalkyl (C ₆ ~C ₁₆₎ ethyl phosphates.

Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), Megafuck F-110, F
-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306
A, 501, 201, 204 (manufactured by Tochem Products), Footage F-100
F-150 (manufactured by Neos).

In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C6 to C10) sulfonamidopropyltrimethylammonium salt which right the fluoroalkyl group, Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade name Surflon S-1
21 (manufactured by Asahi Glass Co., Ltd.), Florard FC-135 (manufactured by Sumitomo 3M Company), Unidyne DS-20
2 (Daikin Kogyo Co., Ltd.), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.),
Extop EF-132 (manufactured by Tochem Products), Footgent-300 (manufactured by Neos) and the like can be mentioned.

Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.

Further, the dispersed droplets may be stabilized by a polymer protective colloid.
For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid,
Acids such as itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or (meth) acrylic monomers containing hydroxyl groups such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, Acrylic acid-β-hydroxypropyl,
Methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxypropyl, acrylic acid-3-chloro-2-hydroxypropyl,
Methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylolacrylamide,
N-methylol methacrylamide, ethers with vinyl alcohol or vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and a carboxyl group, such as vinyl acetate , Vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, nitrogen such as vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine Homopolymers or copolymers such as those having atoms or heterocycles thereof, polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamino Polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester, etc. Celluloses such as ethylene, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation.

When a dispersant is used, the dispersant may remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after at least one reaction of elongation or crosslinking reaction.

The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there.

The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. .

(Carrier for two components)
When the toner of the present invention is used in a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 100 parts by weight of the carrier.
-10 parts by weight is preferred.

As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used.

Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins.

Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle size is larger than 1 μm,
It becomes difficult to control the electrical resistance.

The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier, or a non-magnetic toner.

(Intermediate transfer member)
The toner of the present invention can be preferably used in an image forming apparatus using an intermediate transfer member.
An embodiment of the intermediate transfer member will be described below.

FIG. 1 is a schematic configuration diagram of a copying machine according to the present embodiment. Photosensitive drum (image carrier)
A charging roller 20 as a charging device and an exposure device 30 are provided around the photosensitive member 10.
, A cleaning device 60 having a cleaning blade, and a static elimination lamp 7 as a static elimination device
0, a developing device 40, and an intermediate transfer member 50 as an intermediate transfer member are provided.

The intermediate transfer member 50 is suspended by a plurality of suspension rollers 51 and is configured to run endlessly in the direction of the arrow by a driving unit such as a motor (not shown). This suspension roller 5
Part of 1 also serves as a transfer bias roller for supplying a transfer bias to the intermediate transfer member, and a predetermined transfer bias voltage is applied from a power source (not shown).

A cleaning device 90 having a cleaning blade for the intermediate transfer member 50 is also provided.

Further, a transfer roller 80 is provided as a transfer means for transferring the developed image onto the transfer paper 100 as the final transfer material, facing the intermediate transfer member 50, and the transfer roller 80 is transferred by a power supply device (not shown). Supplied. Around the intermediate transfer member 50, a corona charger 52 as a charge applying unit is provided.

The developing device 40 includes a developing belt 41 as a developer carrying member, a black (hereinafter referred to as Bk) developing unit 45K provided around the developing belt 41, and a yellow (hereinafter referred to as Y).
Developing unit 45Y, magenta (hereinafter referred to as magenta) developing unit 45M, cyan (
(Hereinafter referred to as C) and a developing unit 45C.

Further, the developing belt 41 is stretched between a plurality of belt rollers, and is configured to run endlessly in a direction indicated by an arrow by a driving unit such as a motor (not shown). Moves at approximately the same speed as 10. Since the configuration of each developing unit is common, the following description will be given only for the Bk developing unit 45K, and the other developing units 45Y, 45M.
45C, the portions corresponding to those in the Bk developing unit 45K in the figure are denoted by Y, M, and C after the numbers given to those in the unit, and description thereof is omitted.

The developing unit 45K is disposed so that a developing tank 42Bk containing a high-viscosity, high-concentration liquid developer containing toner particles and a carrier liquid component and a lower part are immersed in the liquid developer in the developing tank 42Bk. And a coating roller 44Bk that thins the developer pumped from the pumping roller 43Bk and applies it to the developing belt 41. The application roller 44Bk has conductivity, and a predetermined bias is applied from a power source (not shown).

In addition to the apparatus configuration as shown in FIG. 1, the apparatus configuration of the copying machine according to the present embodiment is an apparatus configuration in which development units 45 for each color are provided around the photoconductor 10 as shown in FIG. It may be.

Next, the operation of the copying machine will be described. In FIG. 1, the photosensitive member 10 is uniformly charged by the charging roller 20 while being driven to rotate in the direction of the arrow, and then the reflected light from the original is imaged and projected by an optical system (not shown) by the exposure device 30 on the photosensitive member 10. An electrostatic latent image is formed on the surface. This electrostatic latent image is developed by the developing device 40 to form a toner image as a visible image. Development belt 41
The upper developer thin layer is peeled off from the belt 41 in a thin layer state by contact with the photoreceptor in the development region, and moves to a portion on the photoreceptor 10 where a latent image is formed.

The toner image developed by the developing device 40 is transferred to the surface of the intermediate transfer member 50 at the contact portion (primary transfer region) between the photosensitive member 10 and the intermediate transfer member 50 moving at a constant speed (primary transfer). Transcription). When transferring three or four colors to be superimposed, this process is repeated for each color to form a color image on the intermediate transfer member 50.

The corona charger 52 for applying an electric charge to the superimposed toner image on the intermediate transfer member is provided at a contact facing portion between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is installed on the downstream side and on the upstream side of the contact facing portion between the intermediate transfer member 50 and the transfer paper 100.

The corona charger 52 gives the toner image a true charge having the same polarity as the charge polarity of the toner particles forming the toner image, and is sufficient for good transfer to the transfer paper 100. Charge is applied to the toner image.

The toner image is charged by the corona charger 52, and then transferred to the transfer paper 100 conveyed in the direction of the arrow from a paper supply unit (not shown) by a transfer bias from the transfer roller 80 (two). Next transfer).

Thereafter, the transfer paper 100 onto which the toner image is transferred is transferred to the photosensitive member 10 by a separation device (not shown).
And is discharged from the apparatus after a fixing process is performed by a fixing apparatus (not shown).

On the other hand, after the transfer, the untransferred toner is collected and removed by the cleaning device 60, and the residual charge is discharged by the discharging lamp 70 in preparation for the next charging.

As described above, the static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably from several Ωcm to 10 ³ Ωcm. When the volume resistance is set to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means hardly remains on the intermediate transfer member. Transfer unevenness can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

The material of the intermediate transfer member is not particularly limited, and all known materials can be used. An example is shown below. (1) A material having a high Young's modulus (tensile modulus) is used as a single layer belt,
PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT (polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ET
FE / PAT, PC / PAT blend material, carbon black dispersed thermosetting polyimide, etc. These single-layer belts with high Young's modulus have a small amount of deformation with respect to stress during image formation,
In particular, there is an advantage that registration is unlikely to occur during color image formation.

(2) A belt having a two- or three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery thereof. Therefore, the line image has a performance capable of preventing the line image from being lost.

(3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the width of the belt is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .

Conventionally, fluororesin, polycarbonate resin, polyimide resin, and the like have been used for the intermediate transfer belt. However, in recent years, an elastic belt in which the entire belt layer or a part of the belt is used as an elastic member has been used. The transfer of a color image using a resin belt has the following problems. A color image is usually formed with four colored toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet)
The cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has a high hardness and does not deform according to the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely to occur.

Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a paper with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. 2 to increase adhesion
When the transfer pressure at the next transfer portion is increased, the condensing power of the toner layer is increased, and the above-described character void is generated.

The elastic belt is used for the following purposes. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, the elastic belt deforms following local irregularities,
Without excessively increasing the transfer pressure with respect to the toner layer, it is possible to obtain a transfer image with excellent uniformity even on a paper having poor flatness with good adhesion and no missing characters.

The elastic belt resin is polycarbonate, fluororesin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer. Polymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer and styrene-phenyl acrylate copolymer), styrene-methacrylic acid ester copolymer (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer) Coalesce etc.), styrene-α-chloroacryl Styrenic resin (monopolymer or copolymer containing styrene or styrene-substituted product), methyl methacrylate resin, butyl methacrylate resin, acrylic resin, such as methyl phosphate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer Ethyl acid resin, butyl acrylate resin, modified acrylic resin (silicone modified acrylic resin, vinyl chloride resin modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate Polymer, rosin-modified maleic resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polyurethane resin, silicone resin, ketone resin, Len - ethyl acrylate copolymer, may be used xylene resin and polyvinyl butyral resin, polyamide resin, one kind or two kinds or more selected from the group consisting of modified polyphenylene oxide resin. However, it is a matter of course that the material is not limited to the above materials.

Elastic rubber and elastomer include butyl rubber, fluorine rubber, acrylic rubber, EP
DM, NBR, acrylonitrile-butadiene-styrene rubber natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-
Propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, silicone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, hydrogen Use one or more selected from the group consisting of nitrile rubber, thermoplastic elastomer (for example, polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, polyurea, polyester, fluororesin) can do.
However, it is a matter of course that the material is not limited to the above materials.

There is no particular limitation on the conductive agent for adjusting the resistance value. For example, carbon black, graphite,
Conductivity such as metal powders such as aluminum and nickel, tin oxide, titanium oxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), indium oxide-tin oxide composite oxide (ITO) The conductive metal oxide and the conductive metal oxide may be coated with insulating fine particles such as barium sulfate, magnesium silicate, and calcium carbonate. Of course, the conductive agent is not limited thereto.

Surface layer materials and surface layers are required to prevent contamination of the photoreceptor with elastic materials and to reduce surface friction resistance to the transfer belt surface to reduce toner adhesion and improve cleaning and secondary transfer properties. . For example, one type or two of polyurethane, polyester, epoxy resin, etc.
Materials that use more than one type to reduce surface energy and improve lubricity, such as fluororesins, fluorine compounds, fluorocarbons, titanium dioxide, silicon carbide powders, one or more types, or particle sizes Different types can be dispersed and used. Further, it is also possible to use a material such as a fluorine-based rubber material in which a surface is reduced by forming a fluorine-rich layer on the surface by heat treatment. The method for manufacturing the belt is not limited.

Centrifugal molding method in which material is poured into a rotating cylindrical mold to form a belt, spray coating method in which liquid paint is sprayed to form a film, dipping method in which a cylindrical mold is dipped in a solution of the material, and inner mold There is a casting method to be injected into the outer mold, a method in which a compound is wound around a cylindrical mold and vulcanization polishing is performed, but this is not restrictive, and a belt is manufactured by combining a plurality of manufacturing methods. Is common.

As a method for preventing the elastic belt from stretching, there are a method of forming a rubber layer in the core resin layer having a small elongation, a method of putting a material for preventing the elongation into the core layer, and the like.

Materials constituting the core layer for preventing elongation include, for example, natural fibers such as cotton and silk, polyester fibers, nylon fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, 1 selected from the group consisting of synthetic fibers such as polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers and phenol fibers, inorganic fibers such as carbon fibers, glass fibers and boron fibers, and metal fibers such as iron fibers and copper fibers.
By using seeds or two or more kinds, a woven or thread-like one can be produced. Of course, the material is not limited to the above.

The yarn may be twisted in any manner, such as one or a plurality of filaments twisted, a single twisted yarn, various twisted yarns, a double yarn or the like. Further, for example, fibers of a material selected from the above material group may be blended. Of course, the yarn can be used after being subjected to an appropriate conductive treatment.

On the other hand, the woven fabric can be any woven fabric such as knitted fabric, and of course, a woven fabric that is interwoven can also be used, and naturally conductive treatment can be applied.

The production method for providing the core layer is not particularly limited, for example, a method of providing a woven fabric woven in a cylindrical shape on a mold and the like, and providing a coating layer thereon, the woven fabric woven in a cylindrical shape is a liquid rubber And a method of providing a coating layer on one side or both sides of the core layer, and a method of winding a thread spirally around a mold at an arbitrary pitch and providing a coating layer thereon.

The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur in the surface layer. In addition, it is not preferable that the thickness is too large (approximately 1 mm or more) because the amount of expansion and contraction increases and the image is stretched.

(Tandem type color image forming device)
The toner of the present invention can also be used in a tandem color image forming apparatus. An example of an embodiment of a tandem type color image forming apparatus will be described. The tandem type electrophotographic apparatus has a structure shown in FIG.
As shown in FIG. 4, a direct transfer system in which an image on each photoconductor 1 is sequentially transferred to a sheet s conveyed by a sheet conveying belt 3 by a transfer device 2, and as shown in FIG. Indirect transfer system in which the image on the intermediate transfer body 4 is once transferred sequentially to the intermediate transfer body 4 by the primary transfer apparatus 2 and then transferred onto the sheet s by the secondary transfer apparatus 5. . The transfer device 5 is a transfer conveyance belt, but there is also a roller-shaped method.

Comparing the direct transfer type and the indirect transfer type, the former arranges the sheet feeding device 6 on the upstream side of the tandem image forming apparatus T on which the photoconductors 1 are arranged, and the fixing device 7 on the downstream side. There is a drawback in that the size increases in the sheet conveying direction.

On the other hand, the latter can set the secondary transfer position relatively freely. Paper feeder 6
, And the fixing device 7 can be disposed so as to overlap the tandem image forming apparatus T, and there is an advantage that downsizing is possible.

In the former, in order not to increase the size in the sheet conveying direction, the fixing device 7 is disposed close to the tandem type image forming apparatus T. For this reason, the fixing device 7 cannot be disposed with a sufficient margin that allows the sheet s to bend, and an impact when the leading edge of the sheet s enters the fixing device 7 (particularly with a thick sheet) or fixing. There is a drawback that the fixing device 7 tends to affect image formation on the upstream side due to the difference in speed between the sheet conveyance speed when passing through the apparatus 7 and the sheet conveyance speed by the transfer conveyance belt.

On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that the sheet s can be bent, so that the fixing device 7 can hardly affect the image formation.

In view of the above, recently, an indirect transfer type of tandem type electrophotographic apparatus has attracted attention.

In this type of color electrophotographic apparatus, as shown in FIG.
The transfer residual toner remaining on the surface is removed by the photoconductor cleaning device 8 to clean the surface of the photoconductor 1 to prepare for image formation again. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

FIG. 5 shows an embodiment of the present invention, which is a tandem indirect transfer type electrophotographic apparatus. In the figure, reference numeral 150 is a copying machine main body, 200 is a paper feed table on which it is placed, 300
Is a scanner mounted on the copying apparatus main body 150, and 400 is an automatic document feeder (ADF) mounted on the scanner.

The copying apparatus main body 150 is provided with an endless belt-shaped intermediate transfer member 50 at the center. And
As shown in FIG. 5, in the illustrated example, it is wound around three support rollers 14, 15, 16 and can be rotated and conveyed clockwise in the figure. In this illustrated example, an intermediate transfer body cleaning device 17 that removes residual toner remaining on the intermediate transfer body 50 after image transfer is provided to the left of the second support roller 15 among the three. Among the three, the first support roller 14 and the second support roller 15
On the intermediate transfer member 50 stretched between them, four image forming units 18 of yellow, cyan, magenta, and black are arranged side by side along the conveying direction.
Configure 0.

An exposure device 21 is further provided on the tandem image forming apparatus 120 as shown in FIG. On the other hand, on the side opposite to the tandem image forming apparatus 120 with the intermediate transfer member 50 interposed therebetween, 2
A next transfer device 22 is provided. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23, and is pressed against the third support roller 16 via the intermediate transfer body 10. The image on the intermediate transfer member 50 is transferred to a sheet.

A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt. The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveying function together.

In the illustrated example, a sheet reversing device 28 for reversing the sheet so as to record an image on both sides of the sheet is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 120 described above. Is provided.

Now, when making a copy using this color electrophotographic apparatus, the automatic document feeder 4
A document is set on the 00 document table 130. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it. When a start switch (not shown) is pressed, the automatic document feeder 4
When the document is set to 00, after the document is transported and moved onto the contact glass 32, when the document is set on the other contact glass 32, the scanner 300 is immediately driven, and the first traveling body 33 is driven. And the 2nd traveling body 34 is drive | worked. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34, and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.

When a start switch (not shown) is pressed, the support rollers 14, 1 are driven by a drive motor (not shown).
One of 5 and 16 is rotationally driven, the other two support rollers are driven to rotate, and the intermediate transfer member 50 is rotated and conveyed. At the same time, each photoconductor 10 is rotated by rotating the photoconductor 10 by each image forming means 18.
Monochrome images of black, yellow, magenta, and cyan are formed on the top, respectively. And
Along with the conveyance of the intermediate transfer member 50, these single color images are sequentially transferred to form a composite color image on the intermediate transfer member 50.

On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 142 of the paper feed table 200 is selectively rotated, and a sheet is fed out from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and the separation roller 145. Are separated one by one into the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped.

Alternatively, the sheet feeding roller is rotated to feed out the sheet on the manual feed tray 51, and the separation roller 5
8 is separated one by one and put into the manual feed path 53, and abutted against the registration roller 49 and stopped.

Then, the registration roller 4 is synchronized with the synthesized color image on the intermediate transfer member 50.
9 is rotated, the sheet is fed between the intermediate transfer member 50 and the secondary transfer device 22, and transferred by the secondary transfer device 22 to record a color image on the sheet.

The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge roller. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.

On the other hand, the intermediate transfer member 50 after image transfer is removed by the intermediate transfer member cleaning device 17 to remove residual toner remaining on the intermediate transfer member 50 after image transfer, and is prepared for re-image formation by the tandem image forming device 120.

Here, the registration roller 49 is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.

Now, in the tandem image forming apparatus 120 described above, the individual image forming means 18 includes, for example, a charging device 160, around a drum-shaped photoconductor 10, as shown in FIG.
A developing device 61, a primary transfer device 62, a photoreceptor cleaning device 63, a charge removal device 64, and the like are provided.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
Hereinafter, a part shows a weight part.

(Production Example 1)
~ Synthesis of organic fine particle emulsion ~
In a reaction vessel equipped with a stirrer and a thermometer, water 683 parts, sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries)
When 11 parts, 166 parts of methacrylic acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and an aqueous dispersion of vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). [Fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 58 ° C., and the weight average molecular weight was 130,000.

-Adjustment of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7): Sanyo Kasei Kogyo Co., Ltd., and 90 parts of ethyl acetate were mixed and stirred. A liquid was obtained. To this, 10 parts of styrene butyl acrylate fine particles having a weight average diameter of 110 nm (weight average molecular weight 120,000) prepared by the soap-free emulsion polymerization method as resin fine particles A for forming protrusions were added, and this was stirred with a homogenizer.
Distributed. The obtained liquid was filtered through a stainless mesh having an opening of 28 μm to remove coarse substances. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct 5
29 parts, 208 parts of terephthalic acid, 46 parts of adipic acid, and 2 parts of dibutyltin oxide were reacted at 230 ° C. for 7 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10-15 mmHg. Add 44 parts of trimellitic acid, react at 180 ° C and normal pressure for 3 hours,
Low molecular weight polyester 1] was obtained. [Low molecular polyester 1] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, Tg of 43 ° C., and an acid value of 25.

~ Synthesis of intermediate polyester ~
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 2-mole adduct 8
1 part, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 7 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10-15 mmHg [intermediate polyester 1 ] Was obtained. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.

Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe.
To give [Prepolymer 1]. The free isocyanate of [Prepolymer 1] was 1.53% by weight.

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

~ Synthesis of master batch (MB) ~
1200 parts of water, 540 parts of carbon black (Printex35 Dexa) [DBP
Oil absorption = 42 ml / 100 mg, pH = 9.5], 1200 parts of polyester resin are added and mixed with a Henschel mixer (made by Mitsui Mining Co., Ltd.), and the mixture is 110 ° C. using two rolls.
The mixture was kneaded for 1 hour, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

~ Preparation of oil phase ~
378 parts of [low molecular weight polyester 1], 100 parts of carnauba wax, and 947 parts of ethyl acetate were charged in a container equipped with a stirring bar and a thermometer, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Then, it cooled to 30 degreeC in 1 hour. Then in the container [Masterbatch 1] 5
00 parts and 500 parts of ethyl acetate were added and mixed for 1 hour to obtain [Material Solution 1].
[Raw material solution 1] Transfer 1324 parts to a container, and further hydrophobic silica fine particles (12 nm) 2
1 part, and using a bead mill (Ultra Visco Mill, manufactured by IMEX), liquid feeding speed 1k
g / hr, disk peripheral speed 6 m / sec, filled with 80% by volume of 0.5 mm zirconia beads, 3
Carbon black and wax were dispersed under the pass conditions. Next, 1324 parts of a 65% ethyl acetate solution of [Low molecular polyester 1] was added, and the mixture was subjected to two passes using a bead mill under the above conditions.
[Pigment / wax dispersion 1] was obtained. Solid content concentration of [Pigment / Wax Dispersion 1] (130
C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
[Pigment / Wax Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, add 1200 parts of [Aqueous Phase 1] to the container, and rotate with a TK homomixer at a rotational speed of 1
The mixture was mixed at 3,000 rpm for 25 minutes to obtain [Emulsified slurry 1].
[Emulsion slurry 1] was charged into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 40 ° C. for 24 hours to obtain [Dispersion slurry 1].

~ Washing⇒Drying ~
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): Add 100 parts of ion-exchanged water to the filter cake and mix with a TK homomixer (rotation speed: 1)
Then filtered at 2,000 rpm for 10 minutes.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes) and then filtered.
(4): 100 parts of ion exchange water is added to the filter cake of (3), and the solid content of the cake is 0.1 wt.
% Aqueous solution in which a fluorine-based surfactant was dissolved was added, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes) and then filtered.
(5): Add 300 parts of ion-exchanged water to the filter cake of (4) and mix with a TK homomixer (
The filter is filtered twice after the rotation of 12,000 rpm for 10 minutes [Filter cake 1]
Got.
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer. Opening 75μm after that
Sieve with a mesh [Particle 1 having a protrusion on the toner base particle surface] was obtained.

(Production Examples 2 to 5)
In Production Example 1, particles 2 to 5 having projections on the surface of the toner base particles were obtained in the same manner as in Production Example 1 except that the projection-forming resin fine particles A added to the aqueous phase were changed as shown in Table 1.

(Production Example 6)
Toner base particles 6 were obtained in the same manner as in Production Example 1 except that the protrusion-forming resin fine particles A added to the aqueous phase were not used.

(Carrier production)
・ Core material Mn ferrite particles (weight average diameter: 35 μm) 5000 parts ・ Coating material Toluene 200 parts Silicone resin SR2400 (made by Toray Dow Corning Silicone, nonvolatile content 50%
)
200 parts Aminosilane SH6020 (manufactured by Toray Dow Corning Silicone) 7 parts Carbon black 4 parts The above coating material is dispersed with a stirrer for 10 minutes to prepare a coating liquid, and this coating liquid and core material are rotated in the fluidized bed. The coating liquid was applied to the core material by applying the coating liquid while forming a swirling flow provided with a disk and stirring blades. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to obtain a carrier.

(Mixing of external additives)
To 100 parts of the particles obtained in the production example, 1.5 parts of hydrophobic silica particles having a particle diameter of 12 nm and 0.75 parts of hydrophobic titanium oxide fine particles having a particle diameter of 16 nm are mixed as external additives,
Each toner particle was obtained. The external additive was mixed with a Henschel mixer.

(Removal of coarse particles)
The amount of coarse particles in the toner was controlled by the following steps. The mesh used was a stainless steel wire or twill mesh according to JIS standards. The particle diameter and the circularity were measured as follows.

A flow type particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics Co., Ltd. was used. For the measurement, fine dust is removed through a filter, and 10 ml of water having 10 or less particles in a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) in 10 ⁻³ cm ³ water.
A nonionic surfactant (preferably, Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto. Further, 5 mg of a measurement sample was added, and 2 UH-50 made by an ultrasonic dispersing device STM was used.
After dispersion treatment for 1 minute under the conditions of 0 kHz and 50 W / 10 cm ³ , dispersion treatment is further performed for a total of 5 minutes, and the particle concentration of the measurement sample is 4000 to 8000 pieces / 10 ⁻³ cm ³ (particles in the equivalent circle diameter range of measurement). The sample dispersion was used as a target). Using this sample dispersion, the particle size distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is measured.

The sample dispersion liquid is passed through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to perform measurement using an optical path that crosses and passes through the thickness of the flow cell, the strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain particle images. Each particle is photographed as a two-dimensional image having a certain range parallel to the flow cell. From the area of the two-dimensional image of each photographed particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter.

By using the sample dispersion liquid having the above concentration, the equivalent circle diameter of 1200 or more particles can be measured in about 1 minute, and the number based on the equivalent circle diameter distribution and the particles having the prescribed equivalent circle diameter Ratio (number%) can be measured. The results (frequency% and cumulative%) are as shown in Table 1,
The range of 0.06 to 400 μm can be obtained by dividing the range into 226 channels (divided into 30 channels per octave). In actual measurement, the equivalent circle diameter is 0.60 μm or more and 15
The particles are measured in the range of less than 9.21 μm.

Similarly, let Dv be the volume average particle diameter obtained from the measuring device.

As described above, toners A to F were obtained using the particles 1 to 5 having protrusions on the surface of the toner base particles and the toner base particles 6 for comparison not using the protrusion forming resin fine particles A.

<Evaluation of two-component developer>
7 parts by weight of each toner obtained in Table 1 and 100 parts by weight of the carrier obtained in the carrier production example are uniformly mixed and charged using a type of tumbler mixer in which the container is moved while being rotated and stirred. Thus, a developer was prepared.
This developer was loaded into IPSIO Color 2500 manufactured by Ricoh, and an image was output.
The image was output in the same manner after the initial image and the toner supply mechanism were stopped and 3000 blank images were output. The image was evaluated as follows for the initial image and the image after 3000 sheets were passed.
The toner used and the evaluation results are shown in Table 2.

(1) Image density 0.3 ± 0.1 mg / c, which is the amount of adhesion on plain paper transfer paper (Ricoh type 6200)
After outputting a solid image at an adhesion amount of m ² , the image density was measured by X-Rite (manufactured by X-Rite). An image density of 1.4 or higher was evaluated as ◯, and an image density lower than that as X.

(2) Cleanability Transfer residual toner on the photoconductor that has passed the cleaning process after outputting 1,000 sheets of a 95% image area ratio chart is transferred to white paper with Scotch tape (manufactured by Sumitomo 3M Limited), and the Macbeth reflection density Measured with a total of RD514 type, and the difference from the blank is less than 0.005.
~ 0.010, ◯, 0.011-0.02 △, more than 0.02 ×
As evaluated.

(3) Transfer loss The image density is adjusted as appropriate so that the adhesion amount is 0.4 ± 0.1 mg / cm ² , and the entire area of the A4 image is 1 cm × 1 cm so that the image area ratio is 25%. Image formation was performed using an image chart in which solid images were distributed. The power of the main body was turned off during image formation, and images on the photoreceptor and the intermediate transfer member were visually observed. Twenty solid images of 1 cm × 1 cm were observed, and the spot-like transfer omission portions having a diameter of 0.5 mm or more were counted. 0 to 1 ◎ 2 to 10
Evaluations were made by placing a circle on ◯, a triangle on 10-20, and a bet on more than 20.

(4) Unevenness of transfer Image formation was performed using an image chart in which a solid image of 1 cm × 1 cm was distributed on a 2 × 2 600 dpi A4 whole image. In the course of image formation, the main body was turned off, and images on the photosensitive member and the intermediate transfer member were visually observed in four stages.

From the above table, it can be seen that particles having resin fine particles supported on the particle surface and having a projection shape have good image characteristics and very little deterioration over time.

FIG. 1 is a schematic configuration diagram of a copying machine provided with an intermediate transfer member used in the present invention. FIG. 2 is a schematic configuration diagram showing another embodiment of a copying machine provided with an intermediate transfer member. FIG. 3 is a schematic configuration diagram illustrating an embodiment of a tandem color image forming apparatus. FIG. 4 is a schematic configuration diagram illustrating an example of an embodiment of a tandem type color image forming apparatus including an intermediate transfer member. FIG. 5 is a schematic configuration diagram showing the entire tandem color image forming apparatus of FIG. 6 is a partial detail view of the tandem color image forming apparatus of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 3 Sheet conveyance belt 4 Intermediate transfer body 7 Fixing device 8 Photoconductor cleaning device 10 Photoconductor 18 Image forming means 20 Charging roller 30 Exposure device 40 Development device 41 Development belt 45 Development unit 50 Intermediate transfer body 80 Transfer roller 90 Cleaning apparatus

Claims (7)

A toner obtained by externally adding hard fine particles to base particles containing at least a colorant and a resin,
On the surface of the base particles, there are protrusions made of organic resin fine particles having a composition different from that of the resin constituting the main component of the base particles,
The resin constituting the main component of the base particles is a polyester resin,
The organic resin fine particles contain a vinyl resin,
The organic resin fine particles have a weight average diameter of 520 nm to 710 nm,
Ri volume average particle diameter Dv is 5.6μm~7μm der of the toner,
The protruding portion adds an organic solvent in which a toner composition containing a prepolymer is dissolved to the aqueous medium containing the organic resin fine particles, and causes the organic resin fine particles to be supported on the surface of the oil droplets when forming the oil droplets of the organic solvent. , elongation reaction and cross-linking at least one reaction is formed by performing a toner for developing electrostatic images, wherein Rukoto reaction.   The electrostatic image developing toner according to claim 1, wherein the protruding portions are scattered on the surface of the base particle. 3. The toner for developing an electrostatic charge image according to claim 1, wherein an average circularity E of the toner is 0.90 to 0.99. A two-component developer comprising a carrier comprising the toner according to claim 1 and magnetic particles. The electrostatic image on the electrostatic image carrier is developed with a developer to form a toner image, and a transfer means is brought into contact with the surface of the electrostatic image carrier via a transfer material, and the toner image is placed on the transfer material. An image forming method for electrostatic transfer, wherein the developer is the two-component developer according to claim 4. The electrostatic image on the electrostatic image carrier is developed with a developer to form a toner image, and a transfer means is brought into contact with the surface of the electrostatic image carrier via a transfer material, and the toner image is placed on the transfer material. An image forming apparatus having electrostatic transfer means, wherein the developer is the two-component developer according to claim 4. The image forming apparatus according to claim 6, wherein the image forming apparatus is a tandem indirect transfer color image forming apparatus.