JP2002318474A - Toner and electrophotographic two-component developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner excellent in fluidity which does not cause increase in the contamination (fog) on a white base or decrease in the image density when the toner is repeatedly used for a copying machine, printer or the like. SOLUTION: In the toner prepared by mixing toner mother particles containing a binder resin, a coloring agent and a charge controlling agent with a fluidizing agent as an external additive, the charge controlling agent consists of a triphenylmethane dye and a quaternary ammonium salt, and the fluidizing agent consists of inorganic fine particles subjected to the surface treatment with silicone oil and inorganic fine particles subjected to the surface treatment with a silane coupling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic developer used for developing an electrostatic latent image in electrophotography, electrostatic recording, and electrostatic printing, and a method for producing the same.
More specifically, the present invention relates to an electrophotographic developer having excellent copy quality, durability and stability.

[0002]

2. Description of the Related Art Conventionally, a copy image or a recorded image (hereinafter, both images are combined) using an electrophotographic copying machine or a laser beam printer using an electrophotographic method, an electrostatic recording device using an electrostatic recording method, or the like. , Simply referred to as “copy image”). For example, in an electrophotographic copying machine or a laser beam printer using electrophotography, image formation is usually performed as follows. That is, first, an electrostatic latent image carrier made of a photosensitive drum such as amorphous silicon, selenium, and an organic semiconductor is charged positively or negatively by a charger, and then the charged electrostatic latent image carrier is slit-exposed. Alternatively, an electrostatic charge image is formed on the electrostatic latent image carrier by beam exposure. The formed electrostatic image is developed by a developer, the developed toner image is transferred to a transfer target such as paper, and the transferred toner image is fixed by a heat roll, a pressure roll, or the like to form a copy image. . As a method of developing the electrostatic charge image,
(A) a two-component dry developing method such as a magnetic brush method or a cascade method using a two-component dry developer containing carrier particles such as iron powder and glass powder and a toner containing a resin and a colorant as main components; There are (b) a one-component development method in which development is performed using only toner without using carrier particles, and (c) a liquid development method in which an insulating carrier liquid is used. In the two-component developing method, a non-magnetic two-component developing method using an insulating non-magnetic toner having carbon black in the toner as a black developer is generally used. The toner used in the two-component development method and the one-component development method is usually a binder resin,
Colored fine particles containing a colorant and a charge control agent as components and, if necessary, an additive called an external additive.

When these toner particles are repeatedly used in a copying machine, a printer, or the like, and are continuously copied, the background fouling (hereinafter, referred to as fog) on a white background, which is called fog, increases and the image density decreases. No symptoms occur. In addition, the components constituting the toner migrate to and adhere to the photosensitive drum, and are fixed by continuous copying, making cleaning impossible. As a result, the toner component adhering to the photoconductor drum is insulative, so that the adhering portion always retains electric charge, and the function of the organic photoconductor photoconductor is lost, causing image defects. In the case of normal development, this image defect is developed by toner because the charge of the photoreceptor is lost as a result of the loss of its function as an optical semiconductor, and the charge remains where it should be on the white background where the charge has fallen. In the case of the reversal development, the development is hindered where the toner in the portion where the charge has dropped should be developed, and white spots occur in the black background.

There is also a problem that aggregation and blocking occur due to a decrease in the fluidity of the toner. As a result, the supply from the toner container and the cartridge to the developing unit does not work properly. As an attempt to improve these drawbacks, conventionally, the type and amount of the colorant, the type and amount of the charge control agent, the type and amount of the external additive such as the fluidizing agent and the abrasive, the toner base particles and the toner In the case of the two-component developer, the selection and combination of materials such as the particle size distribution and resistance of the carrier and the selection of the coating agent have been improved. Is currently not available.

[0005]

SUMMARY OF THE INVENTION The present inventor has proposed a copying machine,
It does not cause an increase in fogging, a decrease in image density, the adhesion of toner components to the surface of the photoconductor drum, and filming does not occur when used repeatedly and continuously with a printer, etc. As a result of intensive studies to provide a toner with excellent fluidity, durability and stability that does not cause the occurrence, the use of two specific charge control agents and specific inorganic fine particles to be processed as a fluidizing agent The present invention has been found out that the above problems can be solved by the present invention.

[0006]

That is, the present invention relates to the following inventions (1) to (6). (1) In a toner obtained by mixing toner base particles containing a binder resin, a colorant and a charge control agent with a fluidizing agent as an external additive, the charge control agent is a triphenylmethane dye and A toner characterized in that the fluidizing agent is inorganic fine particles whose surface is treated with a silane coupling agent and inorganic fine particles whose surface is treated with silicone oil. (2) The toner according to (1), wherein the inorganic fine particles are silica. (3) The specific surface area of the colorant by the BET method is 25 to 100.
m2 / g. (1) or (2). (4) The toner according to any one of (1) to (3), wherein the colorant is carbon black. (5) The peripheral speed of the toner base particles and the fluidizing agent is 10 to 30 m /
sec. The toner according to any one of (1) to (4), wherein the toner is mixed. (6) A two-component developer for electrophotography, comprising the toner and the carrier according to any one of (1) to (5).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As the type of the colorant used in the present invention, any of dyes and pigments conventionally used as a colorant for a toner can be used. Examples of such known dyes and pigments include, for example, carbon black, aniline blue (CI No. 50405), chaconil blue (CI No. Azess Blue 3), and chrome yellow (CI No. 14090), Ultramarine Blue (CI No. 77103), Methylene Blue Chloride (CI No. 52015), Phthalocyanine Blue (CI. No. 74160), Dupont Oil Red (CI. No. 26015) ), Quinoline yellow (CI No. 47005), malachite green oxalate (CI. No. 4200), lamp black (CI. No. 77266), rose bengal (CI. 45435). And mixtures thereof. These colorants are usually added in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 20 parts by weight, based on 100 parts by weight of the binder resin. When the magnetic powder functions as a colorant in the magnetic toner,
A coloring agent may be used if necessary. As a coloring agent,
For example, carbon black, copper phthalocyanine, iron black and the like are used.

In the use of the colorant of the present invention, any of the above-mentioned types can be used, and the specific surface area by the BET method is 25 to 100 m ² / g, preferably 3 to 100 m ² / g.
The desired effect can be found in the case of 0 to 85 m ² / g. The specific surface area of the colorant by the BET method is 1
Use of more than 00 m ² / g increases fog,
In some cases, toner scattering in the machine tends to increase, and the quality of a copied image may be degraded. This is because it becomes difficult to uniformly disperse the colorant in the toner base particles, and the uneven distribution of the colorant causes the resistance value of the toner to vary, making it difficult to maintain a stable charge. It is.
If the specific surface area is less than 25 m ² / g, it may be difficult for the colorant to sufficiently color the toner base particles, and the colorant is not suitable as a colorant for toner.

The charge control agents used in the present invention include:
It is preferable to use a quaternary ammonium salt compound and a triphenylmethane dye in combination. As the quaternary ammonium salt-based compound, for example, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate,
Tetrabutylbenzylammonium tetrafluoroborate and the like can be used. For triphenylmethane dyes, dyes of triphenylmethane derivatives,
For example, diaminotriphenylmethane dye, triaminotriphenylmethane dye, oxyfuchsone dye and the like can be used. Among them, it is particularly preferable to use a triaminotriphenylmethane dye.

When the quaternary ammonium salt compound is used alone, the toner is provided with environmental stability and stability over time upon charging, but has a low charge-giving ability, so that sufficient charge is imparted to the toner. Is difficult to perform, and problems such as a decrease in image density, fogging, and scattering in the machine occur. Also, when a triphenylmethane dye alone is used, an appropriate amount of charge can be imparted to the toner, but the stability of the initial image is low due to instability due to lack of stability or immediately after switching on the developer. There is a point. By using a quaternary ammonium salt compound and a triphenylmethane dye in combination, the disadvantages of both can be overcome, and a stable and good charge can be imparted to the toner, and a good image can be obtained. These charge control agents, when used in combination, are usually 0.1 to 1 part by weight based on 100 parts by weight of the binder resin.
0 parts by weight, preferably 0.5 to 8 parts by weight. The mixing ratio of the quaternary ammonium salt compound and the triphenylmethane dye in combination is 10:90 to 90:10 when the total of the charge control agents is 100. If the ratio deviates from this ratio, the effect of using two kinds of charge control agents in combination cannot be found.

Specific examples of the binder resin used in the toner base particles of the present invention include styrene-based polymers such as styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and single-substituted polymers thereof. Coalesce, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer,
Styrene-vinyl naphthalene copolymer, styrene-acrylic copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl Ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene diethylaminoethyl acrylate copolymer, styrene-
Styrene-based copolymers such as butyl acrylate-diethylaminoethyl methacrylate copolymer, cross-linked styrene-based copolymers and the like; polyester resins, for example, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, aromatic dialcohols, diphenols Polyester resin having a monomer selected from structural units as a structural unit, cross-linked polyester resin, etc .; other polyvinyl chloride, phenolic resin, modified phenolic resin, maleic resin, rosin-modified maleic resin, polyvinyl acetate, silicone resin, polyurethane resin , Polyamide resin, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, xylene resin, aliphatic or aliphatic hydrocarbon resin, petroleum resin and the like.

The acrylic monomers used in the styrene acrylic copolymer include, for example, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, and the like.
(Meth) such as butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate
Acrylic esters are mentioned, and further, as monomers that can be used together therewith, acrylonitrile, methacrylonitrile, acrylamide, maleic acid, maleic acid half ester such as butyl maleate, or diesters, vinyl acetate, chloride Examples thereof include vinyl ethers such as vinyl, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and vinyl butyl ether, and vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl hexyl ketone.

Examples of the crosslinking agent used for producing the above-mentioned crosslinked styrenic polymer include compounds mainly having two or more unsaturated bonds. Specifically, for example, divinylbenzene, divinyl Aromatic divinyl compounds such as naphthalene; carboxylic esters having two or more unsaturated bonds such as ethylene glycol diacrylate and ethylene glycol dimethacrylate; divinyl compounds such as divinyl aniline, divinyl ether, divinyl sulfide and divinyl sulfone; and unsaturated Compounds having three or more bonds can be used alone or as a mixture. The crosslinking agent is used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on 100 parts by weight of the binder resin.

These resins can be used alone or in combination of two or more. Of these resins, styrene-based polymers and polyester resins are preferred because they exhibit particularly excellent charging characteristics. Further, the molecular weight distribution measured by GPC (gel permeation chromatography) has at least one peak in a region of ³ × 10 ³ to 5 × 10 ⁴ and at least one peak or shoulder in a region of 10 ⁵ or more. Styrene-based copolymers, and furthermore, two or more kinds of resins, such as a combination of the styrene resin and a styrene-acrylic copolymer or a combination of two or more styrene-acrylic copolymers. The resin composition having a distribution is preferable in terms of the pulverizability and fixing property of the toner base particles.

Further, when a pressure fixing system is used, a binder resin for a pressure toner can be used. Such resins include, for example, polyethylene, polypropylene, polymethylene, polyurethane elastomers, ethylene-ethyl acrylate copolymer, styrene-isoprene copolymer, linear saturated polyester, paraffin, and other waxes.

The toner base particles of the present invention may contain additives, such as a release agent, which have been conventionally used in producing toner particles, as long as they do not have a substantial adverse effect. Examples of the release agent include, for example, aliphatic hydrocarbons, fatty acid metal salts, higher fatty acids, fatty acid esters or partially saponified products thereof, silicone oil, various kinds of oils, which improve the releasability (offset prevention property) at the time of hot roll fixing. Wax. Among these, waxes such as low molecular weight polyethylene or low molecular weight polypropylene having a weight average molecular weight of about 1,000 to 10,000, microcrystalline wax, carnauba wax, sasol wax, paraffin wax and the like are preferable. Other additives include a fluidizing agent, a lubricant, a conductivity-imparting agent, and the like.

The toner base particles used in the present invention are preliminarily mixed with the above-mentioned components of the toner base particles by a dry blender, a Henschel mixer, a ball mill, or the like. Melt kneading with a heat kneader such as extruder,
It is preferable that the obtained kneaded material is cooled and then pulverized, and if necessary, classified to a desired particle size. But,
The method for producing the toner base particles used in the present invention,
The method is not limited to the kneading and pulverizing method.For example, a method of dispersing a toner base particle constituent material in a binder resin solution and then spray drying, or a method in which a predetermined material is added to a monomer to form the binder resin. It is needless to say that any known method such as a method of obtaining toner base particles by mixing to form an emulsion suspension and then polymerizing may be used. The toner base particles used in the present invention have a volume average particle diameter of 3 to 35 μm.
m, more preferably 5 to 25 μm. In the case of a small particle size toner, the toner is used with a particle size of about 4 to 15 μm.

As the external additive used in the toner of the present invention, a fluidizing agent, an abrasive, a conductivity-imparting agent, a lubricant and the like can be used. As the base material of the fluidizing agent used in the present invention, for example, using fine powder such as silica, alumina, titania, magnesia, amorphous silicon-aluminum co-oxide, amorphous silicon-titanium co-oxide Can be. The fluidizing agent as an external additive not only has the purpose of imparting fluidity to the toner particles, but also has the role of imparting and controlling the chargeability of the toner. That is, the external additive has a great effect on the chargeability of the toner by adhering to the outermost part of the toner particles.

If particles used as a fluidizing agent are used without surface treatment, environmental stability is impaired due to hygroscopicity, and the fluidizing agent adheres to the surface of the photosensitive drum. However, there is a problem that filming is caused and an image defect is caused. If environmental stability is impaired due to moisture absorption, the fluidizing agent is affected by moisture in a high-humidity environment, and the charge of the toner is attenuated. I will. Therefore, it is preferable to perform a surface treatment on the particles used for the fluidizing agent to impart hydrophobicity. The fluidizing agent used in the present invention is preferably used in combination with inorganic fine particles surface-treated with a silane coupling agent and inorganic fine particles surface-treated with silicone oil.

Examples of silane coupling agents that can be used as a surface treatment agent for inorganic fine particles include organoalkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, dimethyldichlorosilane, trimethylchlorosilane, octadecyltrichlorosilane, t
Organochlorosilanes such as -butyldimethylchlorosilane; silazanes such as hexamethyldisilazane; and organoaminosilanes such as bis (dimethylamino) dimethylsilane. On the other hand, as the surface treatment agent for silicone oil, straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil and the like, and further modified silicone oil can be used. As the modifying group used in the modified silicone oil, a methylstyrene group, a long-chain alkyl group, a polyether group, a carbinol group, an amino group, an epoxy group, a carboxyl group, a higher fatty acid group, a mercapto group, a methacryl group, or the like is used. Can be.

When the fluidizing agent treated with the silane coupling agent is used alone, there is a problem that the fluidizing agent component acts as a nucleus, causing the toner component to adhere to the photoreceptor and cause filming. When the fluidizer treated with silicone oil is used alone, the silicone oil is linear and has excellent slipperiness, and is less likely to adhere to the photosensitive drum and filming. It is difficult to impart good fluidity to the toner. For example, the toner is clogged at the outlet portion of the toner container and the supply is stagnated. Further, the toner is aggregated in the stagnant portion to generate coarse particles, leading to a problem such as image omission. In addition, the aggregated inorganic fine particles cause transfer defects such as white spots on the image. By using the inorganic fine particles treated with the silane coupling agent and the inorganic fine particles treated with the silicone oil together as a fluidizing agent, the disadvantages of both are eliminated, no aggregation occurs, and the fluidity is excellent. In addition, it is possible to obtain good characteristics without causing adhesion to the photosensitive drum and filming.

When these fluidizing agents are used in combination, they are usually used in an amount of 0.1 to 1.0 part by weight based on 100 parts by weight of the toner base particles. The mixing ratio of the inorganic fine particles treated with the silane coupling agent and the inorganic fine particles treated with the silicone oil in combination is 10
When it is set to 0, it is necessary to use at a ratio of 10:90 to 90:10. If the ratio is out of this range, the effect of using two types of fluidizing agents cannot be found.

As the external additives other than the fluidizing agent used in the present invention, the following known additives can be used for a lubricant, an abrasive, a conductivity imparting agent and the like. Examples of the lubricant include polytetrafluoroethylene and aene stearate, and examples of the abrasive include fine powder such as strontium titanate, calcium titanate, barium titanate, calcium carbonate, chromium oxide, silicon carbide, and tungsten carbide. Can be These abrasives have the effect of removing the toner component deposits on the surface of the photoreceptor drum by polishing and filming the filming material, and are used in combination with the fluidizing agent that has been surface-treated with the silicone oil. Thus, a great effect can be found. A metal oxide such as tin oxide may be added as the conductivity-imparting agent. However, these examples are merely exemplifications, and what is added to and mixed with the electrophotographic developer of the present invention is not limited to those specifically exemplified above.

In order to finally produce the toner, it is necessary to add and mix an external additive to the toner base particles obtained above. Generally, an external additive is added to and mixed with the toner base particles using a Henschel mixer, a super mixer, or the like. Also in this mixing step, the quality and characteristics of the developer vary depending on the process conditions. Factors that can be controlled in this mixing step include the filling amount in the mixer, the number of rotations, the mixing time, and the like. In the present invention, it is important to control the number of revolutions of the mixer. Preferably, the developer is mixed at a low speed condition of 10 to 30 m / sec. It is possible to do. By producing under these mixing conditions, an external additive can be dispersed on the toner base particles to maintain appropriate fluidity. If the mixing is performed at a peripheral speed that can exceed 30 m / sec., The fluidizing agent may be physically strongly adhered to the toner base particles and the fluidity may be reduced. In addition, 10 m / sec. If the peripheral speed is lower than the above, it is difficult to sufficiently mix and disperse the toner base particles and the external additive depending on the material. As a final step after the addition and mixing of the external additive, the toner is manufactured through a sieving step for the purpose of removing foreign substances in the toner particles.

When the electrostatic image developer of the present invention is a two-component dry developer, the developer of the present invention contains a carrier. The carrier particles used in the two-component developer of the present invention may be any of carriers conventionally used in a two-component dry developer, for example, a ferromagnetic metal such as iron powder or an alloy powder of a ferromagnetic metal, nickel,
Ferrite powders and magnetite powders composed of elements such as copper, zinc, magnesium and barium are preferred. These carriers may be coated with a resin such as a styrene-methacrylate copolymer, a styrene polymer, or a silicone resin. As a method of coating the carrier with a resin, a coating resin is dissolved in a solvent, and this is coated on the core particles by a dipping method, a spray method, a fluidized bed method, etc., dried, and then heated and coated as necessary. Any known method such as a method of curing a film can be used. The average particle size of the carrier is usually 15 to 500 μm, preferably 20 to 300 μm.

[0026]

EXAMPLES The present invention will be described more specifically with reference to Production Examples, Examples and Comparative Examples, but the embodiments of the present invention are not limited to these Examples. In the following, all parts are parts by weight.

[Example 1] Binder resin Styrene acrylic copolymer resin 86 parts Colorant carbon black (specific surface area 65 m ² / g) 8 parts Charge control agent tributylbenzylammonium-1-hydroxy-4-naphthosulfonate Compound 1.5 parts Charge control agent Triaminotriphenylmethane dye 1.5 parts Wax Polyolefin wax 3 parts was blended, kneaded, pulverized and classified to obtain toner mother particles having an average particle diameter of 12 μm. 0.15 parts of hydrophobic silica surface-treated with dichlorodimethylsilane and 0.15 parts of hydrophobic silica surface-treated with silicone oil were added to 100 parts of the toner base particles and 100 parts of the toner base particles. A peripheral speed of 20 m / sec. After removing foreign matter using a mesh sieve having an opening of 100 μm, a toner was obtained. 4 parts of the obtained toner and an average particle diameter of 10
100 parts of a 0 μm silicone resin-coated carrier were mixed using a ball mill to prepare a developer. Next, using this developer and the toner, a real copying test was performed using a commercially available copying machine FP-3280 manufactured by Matsushita Electric Industrial Co., Ltd., and even after 100,000 copies of actual copying, fog was small and image density was stable. As a result, no image defect was observed due to the toner component adhering to the photosensitive drum. Also, no scattering of toner in the machine was observed.

[Example 2] Binder resin Styrene acrylic copolymer resin 86 parts Colorant carbon black (specific surface area 125 m ² / g) 8 parts Charge control agent tributylbenzylammonium-1-hydroxy-4-naphthosulfonate Compound 1.5 parts Charge control agent Triaminotriphenylmethane dye 1.5 parts Wax Polyolefin wax 3 parts Compounded, kneaded, pulverized and classified to obtain toner mother particles having an average particle diameter of 12 μm. 0.15 parts of hydrophobic silica surface-treated with dichlorodimethylsilane and 0.15 parts of hydrophobic silica surface-treated with silicone oil were added to 100 parts of the toner base particles and 100 parts of the toner base particles. A peripheral speed of 20 m / sec. After removing foreign matter using a mesh sieve having an opening of 100 μm, a toner was obtained. 4 parts of the obtained toner and an average particle size of 1
A 100 μm silicone resin-coated carrier was mixed with 100 parts of a carrier using a ball mill to prepare a developer. Next, using this developer and the toner, a real copying test was performed using a commercially available copying machine FP-3280 manufactured by Matsushita Electric Industrial Co., Ltd., and even after 100,000 copies of actual copying, fog was small and image density was stable. As a result, no image defect was observed due to the toner component adhering to the photosensitive drum. Also, no scattering of toner in the machine was observed.

Example 3 Binder resin Styrene acrylic copolymer resin 86 parts Colorant carbon black (specific surface area 65 m ² / g) 8 parts Charge control agent tributylbenzylammonium-1-hydroxy-4-naphthosulfonate Compound 1.5 parts Charge control agent Triaminotriphenylmethane dye 1.5 parts Wax Polyolefin wax 3 parts Compounded, kneaded, pulverized and classified to obtain toner mother particles having an average particle diameter of 12 μm. 0.15 parts of hydrophobic silica surface-treated with dichlorodimethylsilane and 0.15 parts of hydrophobic silica surface-treated with silicone oil were added to 100 parts of the toner base particles and 100 parts of the toner base particles. Using a Henschel mixer, the peripheral speed is 40 m / sec. After removing foreign matter using a mesh sieve having an opening of 100 μm, a toner was obtained. 4 parts of the obtained toner and an average particle size of 1
A 100 μm silicone resin-coated carrier was mixed with 100 parts of a carrier using a ball mill to prepare a developer. Next, using this developer and the toner, a real copying test was performed using a commercially available copying machine FP-3280 manufactured by Matsushita Electric Industrial Co., Ltd., and even after 100,000 copies of actual copying, fog was small and image density was stable. As a result, no image defects due to the components of the toner particles adhering to the photosensitive drum were observed. Also, no scattering of toner in the machine was observed.

Example 4 Binder resin Styrene acrylic copolymer resin 86 parts Colorant carbon black (specific surface area 65 m ² / g) 8 parts Charge control agent tributylbenzylammonium-1-hydroxy-4-naphthosulfonate Compound 0.5 part Charge control agent Triaminotriphenylmethane dye 2.5 parts Wax Polyolefin-based wax 3 parts were blended, kneaded, pulverized and classified to obtain toner mother particles having an average particle diameter of 12 μm. To 100 parts of the toner base particles and 0.05 part of hydrophobic silica surface-treated with dichlorodimethylsilane and 0.25 part of hydrophobic silica surface-treated with silicone oil were added to 100 parts of the toner base particles. A peripheral speed of 20 m / sec. After removing foreign matter using a mesh sieve having an opening of 100 μm, a toner was obtained. 4 parts of the obtained toner and an average particle size of 1
A 100 μm silicone resin-coated carrier was mixed with 100 parts of a carrier using a ball mill to prepare a developer. Next, using this developer and the toner, a real copying test was performed using a commercially available copying machine FP-3280 manufactured by Matsushita Electric Industrial Co., Ltd., and even after 100,000 copies of actual copying, fog was small and image density was stable. As a result, no image defects due to the components of the toner particles adhering to the photosensitive drum were observed. Also, no scattering of toner in the machine was observed.

Comparative Example 1 Binder resin Styrene acrylic copolymer resin 86 parts Colorant carbon black (specific surface area 65 m ² / g) 8 parts Charge control agent triaminotriphenylmethane dye 3 parts Wax Polyolefin-based wax 3 parts Was blended, kneaded, pulverized, and classified to obtain toner base particles having an average particle size of 12 μm. 0.15 parts of hydrophobic silica surface-treated with dichlorodimethylsilane and 0.15 parts of hydrophobic silica surface-treated with silicone oil were added to 100 parts of the toner base particles and 100 parts of the toner base particles. A peripheral speed of 20 m / sec. After removing foreign matter using a mesh sieve having an opening of 100 μm, a toner was obtained. 4 parts of the obtained toner particles and a silicone resin-coated carrier 100 having an average particle diameter of 100 μm.
Were mixed using a ball mill to prepare a developer. Next, using this developer and the toner particles, a commercial photographing test was performed using a commercially available copier FP-3280 manufactured by Matsushita Electric Industrial Co., Ltd., and the initial image density was low. , The variation was large. 50
The test was stopped because fog became noticeable at 00 sheets.

Comparative Example 2 Binder resin Styrene acrylic copolymer resin 86 parts Colorant carbon black (specific surface area 65 m ² / g) 8 parts Charge control agent tributylbenzylammonium-1-hydroxy-4-naphthosulfonate Compound 3 parts Wax Polyolefin-based wax 3 parts were blended, kneaded, pulverized and classified to obtain toner mother particles having an average particle diameter of 12 μm. 0.15 parts of hydrophobic silica surface-treated with dichlorodimethylsilane and 0.15 parts of hydrophobic silica surface-treated with silicone oil were added to 100 parts of the toner base particles and 100 parts of the toner base particles. A peripheral speed of 20 m / sec. After removing foreign matter using a mesh sieve having an opening of 100 μm, a toner was obtained. 4 parts of the obtained toner and an average particle size of 1
A 100 μm silicone resin-coated carrier was mixed with 100 parts of a carrier using a ball mill to prepare a developer. Next, using this developer and the toner, a commercial photographing test was performed using a commercially available copying machine FP-3280 manufactured by Matsushita Electric Industrial Co., Ltd. The test was discontinued.

Comparative Example 3 Binder resin Styrene acrylic copolymer resin 86 parts Colorant carbon black (specific surface area 65 m ² / g) 8 parts Charge control agent tributylbenzylammonium-1-hydroxy-4-naphthosulfonate Compound 1.5 parts Charge control agent Triaminotriphenylmethane dye 1.5 parts Wax Polyolefin wax 3 parts Compounded, kneaded, pulverized and classified to obtain toner mother particles having an average particle diameter of 12 μm. The toner base particles and 100 parts of the toner base particles were mixed with 0.3 part of hydrophobic silica surface-treated with silicone oil in a Henschel mixer at a peripheral speed of 20 m / sec. After removing foreign matter using a mesh sieve having an opening of 100 μm, a toner was obtained.
4 parts of the obtained toner and 100 parts of a silicone resin-coated carrier having an average particle diameter of 100 μm were mixed using a ball mill to prepare a developer. Next, a commercially available copying machine F manufactured by Matsushita Electric Industrial Co., Ltd.
When a real-photographing test was performed using P-3280, it was as good as in Example 1 up to 20,000 sheets after real-photographing,
Thereafter, a replenishment trouble occurred at the entrance of the developing device, and a trouble that toner was not supplied into the developing device occurred. Upon confirmation, the test was stopped because the toner was aggregated and solidified.

Comparative Example 4 Binder resin Styrene acrylic copolymer resin 86 parts Colorant carbon black (specific surface area 65 m ² / g) 8 parts Charge control agent tributylbenzylammonium-1-hydroxy-4-naphthosulfonate Compound 1.5 parts Charge control agent Triaminotriphenylmethane dye 1.5 parts Wax Polyolefin wax 3 parts Compounded, kneaded, pulverized and classified to obtain toner mother particles having an average particle diameter of 12 μm. The toner base particles and 0.3 part of hydrophobic silica surface-treated with dichlorodimethylsilane were added to 100 parts of the toner base particles by a Henschel mixer at a peripheral speed of 20 m / sec. And mix with 100μ
After removing foreign matter using a sieve having a mesh of m, a toner was obtained. 4 parts of the obtained toner and 100 parts of a silicone resin-coated carrier having an average particle diameter of 100 μm were mixed using a ball mill to prepare a developer. Next, using this developer and the toner particles, a commercial photographing test was performed using a commercially available copying machine FP-3280 manufactured by Matsushita Electric Industrial Co., Ltd. The test was halted because the film was adhered and filmed, and the portion filmed on the white background was developed to cause an image defect that turned black. The filmed material on the photoreceptor was sampled and subjected to compositional analysis. As a result, the element of Si was confirmed, and it was confirmed that the silica was hydrophobic silica surface-treated with dichlorodimethylsilane.

Comparative Example 5 Binder resin Styrene acrylic copolymer resin 86 parts Colorant carbon black (specific surface area 20 m ² / g) 8 parts Charge control agent Nigrosine dye 3 parts Wax Polyolefin-based wax 3 parts Compounding and kneading The resulting mixture was pulverized and classified to obtain toner base particles having an average particle size of 12 μm. 0.15 parts of hydrophobic silica surface-treated with dichlorodimethylsilane and 0.15 parts of hydrophobic silica surface-treated with silicone oil were added to 100 parts of the toner base particles and 100 parts of the toner base particles. A peripheral speed of 20 m / sec. After removing foreign matter using a mesh sieve having an opening of 100 μm, a toner was obtained. 4 parts of the obtained toner and an average particle size of 1
A 100 μm silicone resin-coated carrier was mixed with 100 parts of a carrier using a ball mill to prepare a developer. Next, a real-photographing test was performed using a commercially available copying machine FP-3280 manufactured by Matsushita Electric Industrial Co., Ltd. using the developer and the toner.

[0036]

According to the present invention, by using two specific kinds of charge control agents and two specific kinds of inorganic fine particles to be treated as a fluidizing agent, the fogging caused by continuous copying using a copying machine or a printer is repeated. No increase in the image density, no decrease in the image density, and no adhesion of the toner particle component to the surface of the photoreceptor did not occur.

Claims (6)

[Claims] 1. A toner prepared by mixing toner base particles containing a binder resin, a colorant and a charge control agent with a fluidizing agent as an external additive, wherein the charge control agent is a triphenylmethane dye. And a quaternary ammonium salt compound, wherein the fluidizing agent is inorganic fine particles whose surface is treated with a silane coupling agent and inorganic fine particles whose surface is treated with silicone oil. 2. The toner according to claim 1, wherein both the inorganic fine particles are silica. 3. The specific surface area of the colorant according to the BET method is 25.
3. The toner according to claim 1, wherein the toner content is in the range of 100 to 100 m ² / g. 4. The toner according to claim 1, wherein the colorant is carbon black. 5. The method according to claim 1, wherein the toner base particles and the fluidizing agent are mixed at a peripheral speed of 10
30 m / sec. 5. The toner according to claim 1, wherein the toner is mixed. 6. A two-component developer for electrophotography, comprising the toner according to claim 1 and a carrier.