JPH05307277A - Electrophotographic development method - Google Patents

Abstract

PURPOSE:To provide the electrophotographic development method which decreases the surface friction resistance of an org. photosensitive body and improves the sliding characteristic thereof and improves the running characteristic thereof without cleaning defects and the inversion of a cleaning blade by incorporating a fluorine compd. and/or fluorine-contained resin into the surface of the org. photosensitive body, unlike the development method using the conventional org. photosensitive body, as the electrophotographic development method using a synthetic toner. CONSTITUTION:This electrophotographic development method consists in visualizing the electrostatic latent image formed on the surface of the photosensitive body by the static electric force of the synthetic toner electrostatically charged within the electric field between the photosensitive body and the developing electrode disposed to face this photosensitive body. The org. photosensitive body contg. the fluorine compd. and/or fluorine-contained resin in the surface layer is used in the above-mentioned electrophotographic development method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic developing method used in plain paper copying machines, laser printers, plain paper facsimiles and the like.

[0002]

2. Description of the Related Art In recent years, with the rapid development of the information industry, high-quality image recording has been desired for industrial or office use. In response to these requests, electrophotography,
Various methods such as thermal transfer method and ink jet method have been proposed,
It has been put to practical use. Among them, the electrophotographic method is widely used in offices because of its high-speed printability and high image quality, but recently, the number of cases of recording graphic images has increased, and even higher image quality is required. There is. Further, as copying machines and printers using the electrophotographic method are personalized, demands for lower prices are also increasing.

In response to these requirements, the development of precision equipment, the development and use of inexpensive parts, and the like have been proposed and studied from the device development side. On the other hand, from the side of toner development, low-temperature fixing type toner is being actively developed by reducing the toner size to improve the image quality and reducing the energy cost. In the development of these toners, the conventional pulverization method in which a colorant and a binder resin are kneaded, pulverized, and classified to obtain a toner has a limitation in particle size reduction and low-temperature fixing. Therefore, a new toner production method is proposed. Have been actively studied. Among them, an ethylenically unsaturated monomer containing a colorant is dispersed in water in the presence of a dispersant, and then a polymerized toner obtained by polymerization or a thermoplastic resin as a core material is prepared by various encapsulation methods. Capsule toners (these toners are referred to as synthetic toners) having a shell material adhered to the surface thereof have attracted attention and are being actively researched and developed.

However, although these synthetic toners have various merits, since they are chemically synthesized, their shapes are almost spherical or nearly spherical, unlike the pulverized toner. For this reason, when a printing test is actually performed with a copying machine or a printer, there is a drawback that troubles related to cleaning such as defective cleaning and reversing of a cleaning blade frequently occur. Against these drawbacks,
From the side of toner development, an attempt has been proposed to solve this problem by changing the shape of the toner from spherical to potato-like or worm-like, but it is not enough. On the other hand, in reality, no attempt has been made to improve these drawbacks from the photoconductor side.

[0005]

As described above, the electrophotographic developing method using the synthetic toner has a problem in the cleaning property of the photoconductor, particularly the organic photoconductor, and its improvement has been demanded. The present invention provides an electrophotographic developing method which solves the above problems and which is free from cleaning failure and cleaning blade inversion even in an electrophotographic developing method using a synthetic toner as a toner and which is excellent in running characteristics. With the goal.

[0006]

That is, the gist of the present invention is as follows.
Electrophotographic development in which an electrostatic latent image formed on the surface of a photoconductor is visualized by an electrostatic force of a charged synthetic toner in an electric field between the photoconductor and a developing electrode arranged to face the photoconductor. In the method, an organic photoconductor containing a fluorine compound and / or a fluorine-containing resin in the surface layer is used, which relates to an electrophotographic developing method.

The organic photoconductor used in the electrophotographic development method of the present invention is one in which a photosensitive layer is provided on a conductive substrate, and the conductive substrate is, for example, a metal such as aluminum, nickel or stainless steel, or A film obtained by coating a metal on a film such as polyethylene terephthalate or polybutylene terephthalate is used. The photosensitive layer is generally composed of a charge-generating substance, a charge-transporting substance (charge-transporting material), and a binder, and in the present invention, a single layer type in which they form the same layer, or a charge-generating layer containing the charge-generating substance. And a charge-transporting layer containing a charge-transporting substance. In the case of a laminated type photoreceptor, a photoreceptor in which a charge generation layer and a charge transport layer are laminated in this order on a conductive substrate, or a charge transport layer and a charge generation layer are laminated in this order on a conductive substrate Any of the above described photoconductors may be used.

In the present invention, the surface layer means a layer containing a fluorine compound and / or a fluorine-containing resin, which layer is provided on the surface of the photoreceptor. Therefore, in the case of a single-layer type photoreceptor, the photosensitive layer is the surface layer, and in the case of the laminated type photoreceptor, the layer provided on either surface of the charge generation layer or the charge transport layer is the surface layer. Yes, it contains a fluorine compound and / or a fluorine-containing resin.

Examples of the fluorine compound used include 2,2,3,3,3-pentafluoropropanol, 1
H, 1H, 7H-dodecafluoroheptanol, 2-
Fluoroalkyl alcohols such as (perfluorooctyl) ethanol, 6- (perfluoroethyl) hexanol, 6- (perfluorooctyl) hexanol (manufactured by Daikin Industries, Ltd., trade name A series); 3-
Perfluorooctyl-1,2-epoxypropane, 3
-Perfluorodecyl-1,2-epoxypropane, 3
-(Perfluoro-7-methylhexyl) -1,2-epoxypropane, 3- (1H, 1H, 9H-hexadecafluorononyloxy) -1,2-epoxypropane (manufactured by Daikin Industries, Ltd., trade name) O-series) and other epoxy-modified fluoroalkyl compounds; 2, 2, 3, 3,
3-pentafluoropropyl methyl ether, 1,1,
Fluoroalkyl ethers such as 3,3,3-pentafluoro-2-trifluoromethylpropyl methyl ether (manufactured by Daikin Industries, Ltd., trade name E series);
Fluorinated carboxylic acids such as methyl perfluorooctanoate, ethyl perfluorooctanoate, ethyl 5H-octafluoropentanate, ethyl 11H-icosafluoroundecanoate (manufactured by Daikin Industries, Ltd., trade name E series) Esters and the like can be mentioned. Of these, the epoxy-modified fluoroalkyl compound is preferably selected from the compatibility with the binder. These fluorine compounds may be used alone or in combination of two or more.

Examples of the fluorine-containing resin include fluorinated polycarbonate, fluorinated epoxy resin, fluorinated alkyl (meth) acrylate polymer, fluorinated vinyl polymer, fluorinated polyester, fluorinated alkyd resin, and fluorinated melamine resin, In addition, a copolymer having these as a copolymer composition is included. Fluorinated vinyl (co) polymers include fluorinated ethylene polymers, fluoroalkyl styrene polymers and fluorinated ethylene / alkyl acrylate copolymers, fluorinated ethylene / alkyl methacrylate copolymers, fluorinated ethylene / styrene copolymers. , Fluorinated ethylene / acrylonitrile copolymer, fluoroalkyl styrene / alkyl acrylate copolymer, fluoroalkyl styrene / alkyl methacrylate copolymer, fluoroalkyl styrene / styrene copolymer and the like. Examples of fluorinated alkyl (meth) acrylate copolymers include fluoroalkyl (meth) acrylate / alkyl (meth) acrylate copolymers and fluoroalkyl (meth) acrylate / styrene copolymers. Of these, fluorinated polycarbonate, fluorinated epoxy resin, fluorinated alkyl acrylate copolymer, and fluorinated vinyl copolymer are preferably selected from the viewpoint of compatibility with the binder. These fluorine-containing resins can be used alone or in combination of two or more. Here, as the molecular weight of the resin, a resin having a number average molecular weight of several thousand to several hundred thousand is used.

The above-mentioned fluorine compound and fluorine-containing resin may be used in combination, and the addition amount of these fluorine compound and / or fluorine-containing resin is 0.05 to the surface layer to be prepared.
It is 10% by weight, preferably 0.1 to 8% by weight. If the amount added is less than 0.05% by weight, cleaning failure will occur. On the contrary, if the amount added is more than 10% by weight, the sensitivity of the photoreceptor will be deteriorated, which is not preferable.

The charge generating substance used in the present invention is not particularly limited, and examples thereof include inorganic materials such as selenium, amorphous silicon, and amorphous silicon carbide, and azo pigments, perylene pigments, quinone pigments, and metal-free phthalocyanines. Organic materials such as pigments, metal phthalocyanine pigments, squarylium pigments, and pyrrole-pyrrole pigments are used. Of these, organic materials are preferably used because of their low toxicity and ease of device design.

In the case of the laminated type, the charge generation layer is vapor-deposited, CV
It is desirable that the charge generation layer is formed by coating when the charge generation material is an organic material. Specifically, a charge generating substance and a binder are mainly dispersed and dissolved in a solvent, which is applied and dried. When using a coating method, the means is not particularly limited,
For example, a dip coater, a bar coater, a calendar coater, a gravure coater, a spin coater, or the like can be used as appropriate, and electrodeposition coating, spray coating, or the like can also be used. As the binder, for example, polyester, polystyrene, polyacrylate, polyvinyl butyral, polyvinyl chloride-vinyl acetate, polycarbonate, polysulfone, polyarylate, epoxy resin, phenol resin or the like is used. Examples of the solvent include aromatic solvents such as benzene, toluene and xylene; halogen solvents such as dichloroethane, chloroform and chlorobenzene; ester solvents such as ethyl acetate and propyl acetate; ketone solvents such as methyl ethyl ketone and cyclohexanone; dioxane; Examples thereof include ether solvents such as tetrahydrofuran; alcohol solvents such as ethanol and butanol; dimethylformamide and dimethyl sulfoxide.

When the charge-generating layer is the surface layer, a coating method is used, and a fluorine compound and / or a fluorine-containing resin is added to the coating liquid containing the above-mentioned charge-generating substance to prepare a coating liquid for the surface layer. It At this time, as the solvent, one of the above-mentioned solvents which does not dissolve the charge transport layer is used. Whether the charge generation layer is a surface layer or not, the weight ratio of the charge generation substance to the binder is 30:70 to 80:20,
The thickness of the charge generation layer produced is about 0.05 to 2 μm.

The charge transport material used in the present invention is not particularly limited, and examples thereof include a hydrazone derivative, a butadiene derivative, a triphenylamine derivative, a stilbene derivative, a pyrazoline derivative, and an oxadiazole derivative. In the case of the laminated type, the charge transport layer is prepared mainly using a charge transport substance, a binder and a solvent in the same manner as the charge generation layer, and the binder is polycarbonate, polyarylate, polystyrene, polyacrylate, polystyrene. -Acrylate, polyester, polysulfone, polyamideimide, epoxy resin,
Phenol resin, urethane resin, diallyl phthalate resin and the like are used.

When the charge transport layer serves as a surface layer, a coating method is used, and a fluorine compound and / or a fluorine-containing resin is added to the coating liquid containing the above charge transporting substance to prepare a coating liquid for the surface layer. It The solvent used at this time is not particularly limited as long as it does not dissolve the charge generation layer. The weight ratio of the charge transport material to the binder is 30:70 to 7 regardless of whether the charge transport layer is a surface layer.
It is 0:30, and the thickness of the charge transport layer produced is 10 to 10.
It is about 30 μm.

In the case of a single-layer type photoreceptor, it is prepared by a coating method or the like using the above charge generating substance, charge transporting substance, binder, fluorine compound and / or fluorine containing resin, and solvent. The type of each component, the weight ratio of the charge generating substance and the binder, the weight ratio of the charge transporting substance and the binder, etc. are the same as those of the laminated type. The film thickness of the obtained photosensitive layer is 10 to 30 μm.
It is about m. The organic photoreceptor of the present invention may have an intermediate layer and an adhesive layer between the conductive substrate and the photosensitive layer, if necessary.

The organic photoreceptor used in the present invention is prepared as described above. However, since the organic photoreceptor contains a fluorine compound and / or a fluorine-containing resin in the surface layer, mechanical abrasion of the photoreceptor is caused. Property is improved and slidability is improved. Therefore, as described above, even when the synthetic toner having a problem in cleaning property is used, the cleaning property and the cleaning blade are not reversed and the running property is excellent.

That is, the electrophotographic developing method of the present invention is characterized in that it can be used not only for pulverized toner but also for synthetic toner. In the present specification, the synthetic toner is a toner obtained by synthesizing, and as the representative one as described above, the following polymerized toner or capsule toner can be mentioned. As the polymerized toner, for example, JP-A-56-130 is used.
761, JP-A-56-130762, JP-A-57-114149, and JP-A-57-11415.
As described in JP-A-0, etc., in a presence of a dispersant, a polymerizable composition containing a monomer, a colorant and optionally a wax is heated in a state of being suspended in an aqueous dispersion medium. A polymerized toner obtained by polymerizing is described.

Examples of the dispersant to be used include polymer dispersants such as polyvinyl alcohol, methyl cellulose and polyacrylic acid, and poorly water-soluble or insoluble inorganic dispersants such as phosphates, polyphosphates and silica. The monomer is not particularly limited as long as it is hydrophobic, and for example, a hydrophobic ethylenic unsaturated monomer is used, and specifically, styrene, o-methylstyrene, p-methylstyrene, α-methyl. Styrene, styrene derivatives such as vinylnaphthalene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Examples thereof include alkyl (meth) acrylate derivatives such as octyl acid, butadiene derivatives and the like.

As the colorant, various kinds of carbon black produced by thermal black method, acetylene black method, channel black method, lamp black method, etc., grafted carbon black in which the surface of carbon black is coated with resin, and nigrosine dye , Phthalocyanine Blue, Permanent Brown FG, Brilliant Fast Scarlet, Pigment Green B, Rhodamine-B Base, Solvent Red 49, and the like, and the addition amount is preferably 1 to 15% by weight with respect to the monomer. To obtain a magnetic toner, magnetic powder treated with a titanium coupling agent, a silane coupling agent, or the like may be added. As the wax used as necessary,
Examples thereof include polyolefin, fatty acid metal salt, higher fatty acid, higher alcohol, paraffin wax, amide wax, and aliphatic fluorocarbon. The addition amount is preferably 1 to 20% by weight with respect to the monomer. Examples of the aqueous dispersion medium include water and a water-alcohol mixed solution.

The capsule toner used in the present invention is, for example, JP-A-61-56352 and JP-A-4-56352.
Those described in Japanese Patent Application No. 212169, Japanese Patent Application No. 4-259088 and the like are mentioned. These are produced by an interfacial polymerization method, an in situ polymerization method, a spray drying method, or the like. The interfacial polymerization method is to disperse a core substance solution or dispersion in a W / O or O / W type emulsification system, and at the same time collect a monomer (A) at the interface, and at the next step, the monomer at the interface is
This is a method of reacting (B) with the monomer (A). in
The in situ polymerization method is a method in which a core substance is dispersed in a dispersion medium and a regent that is present inside or outside the core substance is reacted to form a shell. What is the spray dry method?
In this method, the core substance is dispersed in a polymer non-aqueous solution or a polymer emulsion, and then this dispersion is spray-dried. In the present invention, the capsule toner produced by any method may be used. In the interfacial polymerization method, not only the functional separation of the core material and the shell material is easy, but also a uniform toner can be produced in an aqueous system, and a substance having a low softening point can be used for the core material. A toner having desirable properties can be obtained.

Generally, in capsule toners, many shell materials such as styrene resin, polyamide resin, epoxy resin, polyurethane resin, polyurea resin are used. The heat-meltable resin contained in the core material has a glass transition point (Tg) of 10 ° C. or higher and 80 or higher.
Thermoplastic resins such as polyester resins, polyamide resins, polyester polyamide resins and vinyl resins having a temperature of not higher than 0 ° C. are used. The capsule toner obtained by the interfacial polymerization method will be specifically described. The capsule toner is a polymerizable composition containing, for example, a monomer, a colorant, a wax used as necessary, and a divalent or higher valent epoxy compound. Is polymerized in a state of being suspended in an aqueous dispersion medium in the presence of a divalent or higher alcohol compound, an amine compound or the like and a dispersant, or similarly, a monomer, a colorant, and a wax optionally used, And a polymerizable composition containing a divalent or higher valent isocyanate compound, an isothiocyanate compound, etc., is polymerized in a state of being suspended in an aqueous dispersion medium in the presence of a divalent or higher valent phenol compound, etc. and a dispersant. It

At this time, as the monomer, the colorant, the dispersant and, if necessary, the wax used are the same as those used in the production of the above-mentioned polymerized toner, and the addition amount is also the same. Further, when obtaining a magnetic toner, similar magnetic powder may be added.

One of the materials used for forming the shell material of the capsule toner will be described. Examples of the epoxy compound include bisphenol A type epoxy resin, resorcin type epoxy resin, bisphenol F type epoxy resin, and cyclic aliphatic epoxy resin. it can. Further, as the isocyanate compound, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate,
Aromatic isocyanate compounds such as triphenylmethane-triisocyanate; aliphatic isocyanate compounds such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic isocyanate compounds such as isophorone diisocyanate and 4,4′-methylenebis (cyclohexyl isocyanate) Can be mentioned. Further, examples of the isothiocyanate compound include xylylene-1,4-diisothiocyanate and ethylidyne diisothiocyanate.

The alcohol compound which is the other material for forming the shell material is a diol such as ethylene glycol, propylene glycol, butylene glycol or hexamethylene glycol; glycerin, trimethylolpropane, trimethylolethane, 1,2,6. Examples thereof include polyols such as hexanetriol and pentaerythritol. As the amine compound, ethylenediamine, hexamethylenediamine, diethylenetriamine,
Examples thereof include iminobispropylamine, phenylenediamine, xylylenediamine and the like. As phenol compounds, catechol, 4-methylcatechol, 4-
Catechol derivatives such as acetylcatechol, 4-methoxycatechol, 4-phenylcatechol; resorcin,
Examples thereof include resorcin derivatives such as 4-methylresorcin, 4-ethylresorcin, 4-hexylresorcin, 4-chlororesorcin, and 4-benzylresorcin, and thiophenol derivatives thereof.

Further, in the present invention, the capsule toner obtained by the in situ polymerization method in which the outer grain is made of amorphous polyester can also be preferably used. As will be specifically described below, the amorphous polyester forming the outer grain is usually one or more alcohol monomers (2
Valency, trivalence or more) and one or more carboxylic acid monomers (2
A polyhydric alcohol monomer and / or a monomer containing at least a trivalent or more polyvalent carboxylic acid monomer. It is obtained by polycondensation (Japanese Patent Application No. 4-259088).

Examples of the dihydric alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,
2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-Hydroxyphenyl) propane, polyoxypropylene (6) -2,2-
Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl Glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, bisphenol A
Propylene adduct, bisphenol A ethylene adduct, hydrogenated bisphenol A, and the like.

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol and 1,4
-Sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,
4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like can be mentioned. Preferably, trihydric alcohol is used. In the present invention, these dihydric alcohol monomers and polyhydric alcohol monomers having a valence of 3 or more may be used alone or in combination.

The acid component is a carboxylic acid component and is a divalent monomer such as maleic acid, fumaric acid,
Citraconic acid, itaconic acid, glutaconic acid, phthalic acid,
Isophthalic acid, terephthalic acid, succinic acid, adipic acid,
Sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, n-dodecylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid,
And anhydrides of these acids, or lower alkyl esters.

Examples of the trivalent or higher carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid and 1,2,4- Butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-
2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl)
Methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimer acid and their acid anhydrides,
Lower alkyl ester and the like can be mentioned. Preferably 3
A valent carboxylic acid or its derivative is used. In the present invention, these divalent carboxylic acid monomers and 3
A carboxylic acid monomer having a valence of 3 or more may be used alone or in combination.

The method for producing the amorphous polyester in the present invention is not particularly limited, and it can be produced by esterification or transesterification reaction using the above monomer. Here, amorphous is one that does not have a definite melting point, and when crystalline polyester is used in the present invention, the amount of energy required for melting is large and the toner fixability cannot be improved, which is not preferable.

The amorphous polyester thus obtained preferably has a glass transition point of 50 to 80 ° C. If it is less than 50 ° C, the storage stability of the toner will be poor, and if it exceeds 80 ° C, the fixing property of the toner will be poor.
In the present invention, the glass transition point is a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd.) and the temperature rising rate is 10 ° C./min.
The temperature at the intersection of the extension line of the base line below the glass transition point and the tangent line showing the maximum slope from the rising portion of the peak to the apex of the peak when measured in.

The acid value of the amorphous polyester is 3
It is preferably -50 (KOHmg / g), more preferably 10-30 (KOHmg / g). Three
If it is less than (KOHmg / g), the amorphous polyester as the shell material is hard to come out at the interface, and the storage stability is poor,
When it exceeds 50 (KOHmg / g), the polyester tends to migrate to the aqueous phase, resulting in poor production stability. Here, the method of measuring the acid value is according to JIS K0070.

A capsule toner whose outer grain is preferably made of amorphous polyester is preferably used in the present invention.
It is produced by a known method such as a polymerization method. This capsule toner is composed of a thermoplastic core material containing at least a thermoplastic resin and a colorant, and an outer grain provided so as to cover the surface of the core material.

The resin used as the main component of the heat-melting core material of the capsule toner whose outer shell is made of amorphous polyester in the present invention is thermoplastic resin such as polyester resin, polyester-polyamide resin, polyamide resin, vinyl resin and the like. Examples of the resin include a vinyl-based resin. The glass transition point derived from the thermoplastic resin which is the main component of such a heat-meltable core material is 10 to 50 ° C.
However, if the glass transition point is less than 10 ° C., the storage stability of the capsule toner deteriorates, and if it exceeds 50 ° C., the fixing strength of the capsule toner deteriorates, which is not preferable.

Among the above-mentioned thermoplastic resins, examples of the monomer constituting the vinyl resin include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene and p-ethylstyrene. , 2,4-
Styrene or styrene derivatives such as dimethylstyrene, p-chlorostyrene, vinylnaphthalene, etc., ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene, etc., such as vinyl chloride,
Vinyl esters such as vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl formate, vinyl caproate, etc., such as acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, N-Butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, acrylic acid Stearyl, methoxyethyl acrylate, acrylic acid 2-
Hydroxyethyl, glycidyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-chloromethyl acrylate, methacrylic acid, methyl methacrylate,
Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, methacrylic acid. Decyl, lauryl methacrylate, methacrylic acid 2
-Ethylhexyl, stearyl methacrylate, methoxyethyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, phenyl methacrylate,
Ethylenic monocarboxylic acids such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like, and esters thereof such as ethylenic monocarboxylic acid substitution products such as acrylonitrile, methacrylonitrile, acrylamide, etc., such as ethylenic acid such as dimethyl maleate. Dicarboxylic acids and substituted compounds thereof, vinyl ketones such as vinyl methyl ketone, vinyl ethers such as vinyl methyl ether, vinylidene halides such as vinylidene chloride, such as N-
Examples thereof include N-vinyl compounds such as vinylpyrrole and N-vinylpyrrolidone.

When a crosslinking agent is added to the monomer composition constituting the resin for the core material according to the present invention, for example, divinylbenzene, divinylnaphthalene, polyethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diethylene Acrylate, 1,3-
Butylene glycol dimethacrylate, 1,6-hexylene glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4-methacryloxydiethoxyphenyl) propane, 2 General crosslinking such as 2,2'-bis (4-acryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, dibromoneopentyl glycol dimethacrylate, diallyl phthalate Appropriate agent (2 if necessary
A combination of two or more species can be used.

The amount of these crosslinking agents used is 0.001 to 15% by weight, preferably 0.1 to 10% by weight, based on the polymerizable monomer. The amount of these crosslinkers used is 15
If it is more than 5% by weight, the toner is less likely to be melted by heat, resulting in poor heat fixing property or heat pressure fixing property. Also the amount used
If it is less than 0.001% by weight, it is difficult to prevent the offset phenomenon in which a part of the toner adheres to the roller surface without being completely fixed to the paper and is transferred to the next paper in the heat and pressure fixing. Further, the above monomer may be polymerized in the presence of unsaturated polyester to give a graft or crosslinked polymer, which may be used as a resin for the core material.

Further, as the polymerization initiator used in producing the thermoplastic resin for the core material, 2,2'-azobis (2,4
-Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4
-Dimethylvaleronitrile, other azo or diazo polymerization initiators: benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, dicumyl peroxide Examples thereof include peroxide type polymerization initiators such as oxides.

Two or more kinds of polymerization initiators may be mixed and used for the purpose of controlling the molecular weight and the molecular weight distribution of the polymer or the reaction time. The amount of the polymerization initiator used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymerized monomer.

The method for producing a capsule toner having an outer shell of amorphous polyester in the present invention by the in situ polymerization method will be described below. In this manufacturing method, the outer shell is formed by dispersing a mixed liquid of a core constituent material and an outer shell constituent material composed of amorphous polyester in a dispersion medium so that the outer shell constituent material is unevenly distributed on the surface of the droplet. Can be done using. That is, the core material-constituting material and the outer shell-constituting material are separated from each other in the droplets of the mixed liquid due to the difference in the solubility index, and in this state, the polymerization proceeds to form a capsule structure. According to this method, since the outer shell is formed as a layer made of amorphous polyester having a substantially uniform thickness, the charging characteristics of the toner are uniform.

In the case of this method, it is necessary to contain a dispersion stabilizer in the dispersion medium in order to prevent aggregation and coalescence of dispersoids. Examples of the dispersion stabilizer include gelatin, gelatin derivatives, polyvinyl alcohol, polystyrene sulfonic acid, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, sodium polyacrylate, sodium dodecylbenzene sulfonate, sodium tetradecyl sulfate, and pentadecyl sulfate. Sodium, sodium octyl sulfate, sodium allyl-alkyl-polyethersulfonate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, 3,3-disulfonediphenyl Urea-4,4-diazo-bis-amino-β-
Naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-
Tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-sodium disulfonate, colloidal silica, alumina, tricalcium phosphate, ferric hydroxide, titanium hydroxide, aluminum hydroxide and others are used. can do. Two or more kinds of these dispersion stabilizers may be used in combination.

Examples of the dispersion medium of the dispersion stabilizer include water, methanol, ethanol, propanol, butanol, ethylene glycol, glycerin, acetonitrile, acetone, isopropyl ether, tetrahydrofuran and dioxane. It is also possible to use these individually or in mixture.

The amount of the amorphous polyester added is usually 3 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the core material. If it is less than 3 parts by weight, the film thickness of the outer shell becomes too thin and the storage stability deteriorates. If it exceeds 50 parts by weight, the viscosity becomes high and atomization becomes difficult and the production stability deteriorates.

The polymerized toner and the capsule toner used in the present invention may contain a fluidity improver, a cleaning improver and the like, if necessary. Examples of the fluidity improver include silica, alumina, titanium oxide, barium titanate, magnesium titanate, zinc oxide, clay, mica, zirconium oxide, silicon carbide, silicon nitride and the like, preferably silica fine powder. is there. Further, as the silica, those whose surface is treated with a silane coupling agent, a titanium coupling agent, a fluororesin or the like are also preferably used. Examples of the cleaning property improver include metal salts of higher fatty acids typified by zinc stearate, and fine powders of fluororesins. The electrophotographic development method of the present invention may be either a regular development method typified by a copying machine or a reversal development method typified by a laser printer, and the development method is a two-component magnetic brush development method or a magnetic one-component development method. Alternatively, either a non-magnetic one-component developing method may be used.

[0047]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Synthesis of polymerized toner 80 parts by weight of styrene, 2-ethylhexyl acrylate 2
0 parts by weight, divinylbenzene 0.3 parts by weight, "Mitsubishi Carbon Black # 44" (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 7 parts by weight, "Spiron Black TRH" (manufactured by Hodogaya Chemical Co., Ltd.) 1 part by weight Part, polypropylene "Viscor 55
10 parts by weight of 0P "(manufactured by Sanyo Kasei Co., Ltd.) and 3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) were well mixed in a sand mill to obtain a polymerizable composition. In water containing 3% by weight tricalcium phosphate and 0.01% by weight sodium dodecylbenzene sulfonate.
A suspension was obtained by adding 0% by weight and dispersing with a homogenizer so that the average particle size was 10 μm. Then, this suspension was placed in a three-necked flask equipped with a stirrer, and heated at 70 ° C. for 10 hours with stirring to polymerize the suspension.
Tricalcium phosphate was removed with an aqueous hydrochloric acid solution, washed with water, and then dried to obtain a polymerized toner. This polymerized toner 10
Hydrophobic silica fine powder "Aerosil R-97" in 0 part by weight
0.3 part by weight of 2 "(manufactured by Aerosil Co., Ltd.) was added and mixed to obtain the polymerized toner of the present invention.

Synthesis of Capsule Toner 130 parts by weight of styrene, 60 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of carbon black "Monarch880" (manufactured by Cabot Corporation), "Spiron Black TR"
H ”(Hodogaya Chemical Co., Ltd.) 1.5 parts by weight, 2,
2'-azobis (2,4-dimethylvaleronitrile) 5
Parts by weight, diphenomethane-4,4-diisocyanate "Millionate MT" (manufactured by Nippon Urethane Industry Co., Ltd.) 1
0 part by weight and 5 parts by weight of an epoxy compound "Epicoat 819" (produced by Yuka Shell Epoxy Co., Ltd.) were added and well mixed and dispersed in a sand mill to obtain a polymerizable composition. This was added to an aqueous colloidal solution containing 2% by weight of tricalcium phosphate and 0.02% by weight of sodium dodecylbenzenesulfonate so as to be 15% by weight, and the average particle size was 10 with a homogenizer.
A suspension was obtained by dispersing so as to have a thickness of μm. Then, this suspension was placed in a four-necked flask equipped with a stirrer and a dropping funnel, 8 parts by weight of 1,6-hexamethylenediamine was added with stirring, and the mixture was heated at 60 ° C. for 20 hours to react. .. After cooling, tricalcium phosphate was removed with an aqueous hydrochloric acid solution, washed with water, and then dried to obtain a capsule toner. Hydrophobic silica fine powder "Aerosil R-972" (manufactured by Aerosil Co., Ltd.) was added to 100 parts by weight of this capsule toner.
3 parts by weight were added and mixed to obtain a capsule toner according to the present invention.

Synthesis of Capsule Toner 70 parts by weight of styrene, 2-ethylhexyl acrylate 3
0 parts by weight, 1 part by weight of divinylbenzene, magnetic powder "BL-
120 "(manufactured by Titanium Industry Co., Ltd.), 10 parts by weight of carbon black" Monarch 880 "(manufactured by Cabot Corp.), 4 parts by weight of 2,2'-azobisisobutyronitrile, 4,4'- Diphenylmethane diisocyanate "Millionate MT" (manufactured by Nippon Polyurethane Industry Co., Ltd.)
9.5 parts by weight were thoroughly mixed with a sand mill to obtain a polymerizable composition. This polymerizable composition was mixed with tricalcium phosphate at 4% by weight.
Was added to 30% by weight of water containing and was dispersed by a homogenizer so that the average particle size was 9 μm to obtain a suspension. Then, this suspension was placed in a 4-necked flask equipped with a stirrer and a dropping funnel, and 22 parts by weight of resorcinol, 3.6 parts by weight of diethyl malonate, 1,4-
0.5 part by weight of diazabicyclo [2.2.2] octane,
After adding a mixed solution of 40 parts by weight of ion-exchanged water dropwise, the mixture was heated at 80 ° C. for 10 hours for reaction. After cooling
Tricalcium phosphate was removed with an aqueous hydrochloric acid solution, washed with water, and then dried to obtain a capsule toner. Hydrophobic silica fine powder "Aerosil R" is added to 100 parts by weight of this capsule toner.
-972 "(manufactured by Aerosil Co., Ltd.) 0.3 part by weight was added and mixed to obtain a capsule toner of the present invention.

Synthesis of Capsule Toner Propylene oxide adduct of bisphenol A 36
7.5 g, bisphenol A ethylene oxide adduct 146.4 g, terephthalic acid 126.0 g, dodecenyl succinic anhydride 40.2 g, trimellitic anhydride 77.
7 g was placed in a glass 2-liter four-necked flask, equipped with a thermometer, a stainless stir bar, a downflow condenser, and a nitrogen introduction tube, and allowed to react at 220 ° C. in a mantle heater under a nitrogen stream. ..

The degree of polymerization was traced from the softening point according to ATSM E28-67, and the reaction was terminated when the softening point reached 110 ° C. The glass transition point of the obtained resin was measured by a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd.) and found to be 65 ° C. In addition, the softening point and the acid value were measured and 110 ° C and 18 KOHmg /
It was g. The acid value was measured by a method according to JIS K0070.

69.0 parts by weight of styrene, 31.0 parts by weight of 2-ethylhexyl acrylate, 0.9 parts by weight of divinylbenzene, and 7.0 parts by weight of carbon black "# 44" (manufactured by Mitsubishi Kasei Co., Ltd.), 20 parts by weight of the resin obtained as described above and 3.5 parts by weight of 2,2′-azobisisobutyronitrile were added, and the mixture was put into an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.) and heated to 10 ° C. And dispersed for 5 hours to obtain a polymerizable composition. 4% by weight of tricalcium phosphate prepared in advance in a 2 liter glass separable flask.
The amount of 30% by weight was added to 800 g of the aqueous colloidal solution of, and TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used to emulsify and disperse for 5 minutes at 5 ° C. and 12000 rpm.

Next, a 4-port glass lid was attached, a reflux cooling tube, a thermometer, a nitrogen introduction tube, and a stainless steel stirring rod were attached, and the glass was placed in an electric heating mantle heater. While continuing stirring under nitrogen, the temperature was raised to 85 ° C. and the reaction was performed for 10 hours. After cooling, the dispersion medium is dissolved with a 10% hydrochloric acid aqueous solution, filtered, washed with water, and then at 45 ° C. for 12 hours for 20 hours.
Dry under reduced pressure at mmHg, classify with a wind classifier, average particle size 8
An encapsulated toner having an outer shell of μm of amorphous polyester was obtained.

To 100 parts by weight of this capsule toner, 0.4 parts by weight of hydrophobic silica fine powder "Aerosil R-972" (manufactured by Aerosil Co., Ltd.) was added and mixed to obtain a capsule toner of the present invention. The glass transition point derived from the resin in the core material was 30.6 ° C, and the softening point was 125.5 ° C.

Example 1 A solution consisting of 10 parts by weight of an alcohol-soluble polyamide "Amilan CM8000" (manufactured by Toray Industries, Inc.) and 190 parts by weight of methanol / butanol (7/3) was dip-coated on an aluminum drum, and the solution was coated at 100 ° C. Let it dry for 30 minutes,
An undercoat layer having a film thickness of 0.6 μm was formed. Next, 7 parts by weight of X-type metal-free phthalocyanine "8120B" (manufactured by Dainippon Ink and Chemicals, Inc.), 7 parts by weight of polyvinyl butyral "S-REC BM-1" (manufactured by Sekisui Chemical Co., Ltd.), and 336 parts by weight of cyclohexanone. The mixture consisting of was mixed with a ball mill to obtain a dispersion. This dispersion is dip-coated on the undercoat layer and dried at 100 ° C. for 30 minutes to give a film thickness of 0.5 μm.
m charge generating layer was formed. Next, polycarbonate "Upilon E-2000" (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.)
20 parts by weight, butadiene-based charge transport material "T-405"
(Anan Co., Ltd.) 20 parts by weight, epoxy-modified fluoroalkyl compound “O-110” (Daikin Industries, Ltd.)
0.4 parts by weight and 1,2-dichloroethane 168
Dip coating a solution consisting of parts by weight on the charge generation layer,
By drying at 100 ° C. for 30 minutes, a charge transport layer having a film thickness of 20 μm was formed to obtain a laminated photoreceptor.

An organic photoconductor (genuine organic photoconductor) equipped with this photoconductor on a commercially available laser printer (12 sheets / minute machine, two-component developing system, blade cleaning system)
Replace the developer with the new one, and use the polymerized toner synthesized as described above and a pure carrier prepared to a toner concentration of 4% by weight to perform a printing test on 5,000 sheets and clean the photoreceptor. The image characteristics that markedly reflect the characteristics are evaluated. Here, the evaluation of the cleaning property is determined by the presence or absence of fog on the photoconductor and the presence or absence of the reversal of the blade, and the evaluation of the image characteristics is performed by the image density of the printing portion and the background portion using the Macbeth densitometer and the color difference meter. Was measured.

Example 2 A solution consisting of 10 parts by weight of alcohol-soluble polyamide "Amilan CM8000" (manufactured by Toray Industries, Inc.) and 190 parts by weight of methanol / butanol (7/3) was dip-coated on an aluminum drum, and the solution was applied at 100 ° C. Let it dry for 30 minutes,
An undercoat layer having a film thickness of 0.6 μm was formed. Next, 7 parts by weight of X-type metal-free phthalocyanine "8120B" (manufactured by Dainippon Ink and Chemicals, Inc.), 7 parts by weight of polyvinyl butyral "S-REC BM-1" (manufactured by Sekisui Chemical Co., Ltd.), and 336 parts by weight of cyclohexanone. The mixture consisting of was mixed with a ball mill to obtain a dispersion. This dispersion is dip-coated on the undercoat layer and dried at 100 ° C. for 30 minutes to give a film thickness of 0.5 μm.
m charge generating layer was formed. Next, polycarbonate "Upilon E-2000" (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.)
19 parts by weight, fluorinated polycarbonate "PC-AF"
A solution comprising 1 part by weight (manufactured by Teijin Chemicals Ltd.), 20 parts by weight of butadiene-based charge transport material "T-405" (manufactured by Anan Co., Ltd.), and 168 parts by weight of 1,2-dichloroethane is used as the charge generation layer. It was applied by dip coating on the surface and dried at 100 ° C. for 30 minutes to form a charge transport layer having a film thickness of 20 μm to obtain a laminated type photoreceptor. This photoreceptor was mounted on the same commercially available laser printer as in Example 1 in the same manner, and the developer was prepared from the above-mentioned encapsulated toner and a genuine carrier to a toner concentration of 4% by weight, and a printing test was performed on 5,000 sheets. Then, the image characteristics and the cleaning property of the photoconductor were evaluated in the same manner as in Example 1.

Example 3 A solution consisting of 10 parts by weight of an alcohol-soluble polyamide "Amilan CM8000" (manufactured by Toray Industries, Inc.) and 190 parts by weight of methanol / butanol (7/3) was applied onto an aluminum drum by dip coating, and at 100 ° C. Let it dry for 30 minutes,
An undercoat layer having a film thickness of 0.6 μm was formed. Next, 7 parts by weight of X-type metal-free phthalocyanine "8120B" (manufactured by Dainippon Ink and Chemicals, Inc.), 7 parts by weight of polyvinyl butyral "S-REC BM-1" (manufactured by Sekisui Chemical Co., Ltd.), and 336 parts by weight of cyclohexanone. The mixture consisting of was mixed with a ball mill to obtain a dispersion. This dispersion is dip-coated on the undercoat layer and dried at 100 ° C. for 30 minutes to give a film thickness of 0.5 μm.
m charge generating layer was formed. Next, polycarbonate "Upilon E-2000" (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.)
20 parts by weight, hydrazone charge transport material "CTC-19"
A solution consisting of 20 parts by weight of 1 "(manufactured by Anan Co.), 0.5 parts by weight of fluorinated alkyl acrylate copolymer" Modiper F100 "(manufactured by NOF Corporation), and 168 parts by weight of 1,2-dichloroethane. Was applied onto the above charge generation layer by dip coating and dried at 100 ° C. for 30 minutes to form a charge transport layer having a film thickness of 20 μm to obtain a laminated type photoreceptor. A printer was mounted in the same manner as described above, and a developer prepared from the above-mentioned capsule toner and a genuine carrier to a toner concentration of 4% by weight was used to perform a printing test on 5000 sheets. , And the cleaning properties of the photoconductor were evaluated.

Example 4 A solution consisting of 10 parts by weight of an alcohol-soluble polyamide "Amilan CM8000" (manufactured by Toray Industries, Inc.) and 190 parts by weight of methanol / butanol (7/3) was applied onto an aluminum drum by dip coating, and at 100 ° C. Let it dry for 30 minutes,
An undercoat layer having a film thickness of 0.6 μm was formed. Next, 7 parts by weight of oxytitanyl phthalocyanine, polyvinyl butyral "ESREC BM-1" (manufactured by Sekisui Chemical Co., Ltd.) 7
A mixture of 1 part by weight and 336 parts by weight of cyclohexanone was obtained by a ball mill to obtain a dispersion liquid. This dispersion is applied onto the undercoat layer by dip coating and dried at 100 ° C. for 30 minutes,
A charge generation layer having a thickness of 0.3 μm was formed. Next, 20 parts by weight of polycarbonate "Iupilon E-2000" (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.) and hydrazone charge transport material "C"
TC-191 "(Anan Co., Ltd.) 20 parts by weight, fluorinated vinyl copolymer" GF-150 "(Toa Gosei Chemical Co., Ltd.) 0.5 parts by weight, and 1,2-dichloroethane 168 parts by weight. Part of the solution was applied onto the charge generation layer by dip coating and dried at 100 ° C. for 30 minutes to form a charge transport layer having a film thickness of 25 μm to obtain a laminated type photoreceptor. The same commercially available laser printer was mounted in the same manner, and the developer was prepared from the above-mentioned capsule toner and genuine carrier to a toner concentration of 4% by weight.
A printing test was performed on 5,000 sheets, and the image characteristics and the cleaning property of the photoconductor were evaluated in the same manner as in Example 1.

Example 5 As a charge transport material in Example 3, a hydrazone compound was changed to a tristyryl compound (synthesized according to the synthesis example of JP-A-2-279767) to prepare a laminated type photoreceptor. This photoconductor is mounted on a commercially available copying machine (20-sheet / min machine, two-component developing system, blade cleaning system) in exchange for a genuine organic photoconductor, and the developer is a capsule toner synthesized as described above. Using a toner prepared from a genuine carrier with a toner concentration of 4% by weight, a printing test was performed on 5,000 sheets, and the image characteristics and the cleaning property of the photoconductor were evaluated in the same manner as in Example 1.

Examples 6 to 8 A printing test of 5,000 sheets was carried out in the same manner as in Examples 2 to 4 except that the above-mentioned capsule toner was used instead of the capsule toner in Examples 2 to 4, and the image characteristics and photosensitivity were measured. The body cleaning properties were evaluated.

Comparative Example 1 A laminated type photoreceptor was prepared in the same manner as in Example 3 except that the fluorinated alkyl acrylate copolymer was not added during the charge transport. This photoreceptor was mounted on the same commercially available laser printer as in Example 1 in the same manner, and the developer was prepared from the above-mentioned capsule toner and a genuine carrier to a toner concentration of 4% by weight, and a printing test of 5000 sheets was performed. Then, the image characteristics and the cleaning property of the photoconductor were evaluated in the same manner as in Example 1.

Comparative Example 2 In Example 1, the pure organic photoreceptor (laminated organic photoreceptor, hydrazone charge transport material, polycarbonate binder) mounted on the laser printer was used as it was,
A printing test was conducted using a developer containing the same polymerized toner as the developer, and the image characteristics and the cleaning property of the photoconductor were evaluated in the same manner as in Example 1.
This genuine organic photoreceptor does not contain a cleaning property improver such as a fluorine compound or a fluorine-containing resin in the surface layer.

Comparative Example 3 A printing test was conducted in the same manner as in Example 1 except that the developer containing the encapsulated toner obtained as described above was used instead of the developer containing the polymerized toner. The image characteristics and the cleaning property of the photoconductor were evaluated. The results of the above Examples and Comparative Examples are shown in Table 1.

[0066]

[Table 1]

As shown in the results of Table 1, in the electrophotographic development methods of Examples 1 to 8 using the organic photoreceptor of the present invention containing a fluorine compound and / or a fluorine-containing resin in the surface layer, the photoreceptor was No reversal of the blade, decrease in image density, and increase in background were observed without causing the above fog. On the other hand, as in Comparative Example 1, when a photoconductor prepared so as not to contain a fluorine compound or the like is used, or as in Comparative Examples 2 and 3, a fluorine compound or the like provided in a commercially available laser printer is used. When a genuine photoconductor which does not contain the photoconductor was used, fog on the photoconductor was generated, which caused an increase in the background, and when it was severe, the blade was inverted.

[0068]

INDUSTRIAL APPLICABILITY In the present invention, in the electrophotographic developing method using a synthetic toner, unlike the conventional developing method using an organic photoreceptor, a fluorine compound and / or a fluorine-containing resin is provided on the surface layer of the organic photoreceptor. By including it, the surface frictional resistance of the organic photoreceptor can be reduced and the slidability can be improved. As a result, it is possible to provide an electrophotographic developing method which is excellent in running characteristics without causing cleaning failure or inversion of the cleaning blade.

Claims (3)

[Claims] 1. A visible image of an electrostatic latent image formed on the surface of a photoconductor by an electrostatic force of a charged synthetic toner in an electric field between the photoconductor and a developing electrode arranged to face the photoconductor. In the electrophotographic developing method for converting into a compound, an organic photoconductor containing a fluorine compound and / or a fluorine-containing resin in a surface layer is used. 2. The fluorine compound is an epoxy-modified fluoroalkyl compound, and the fluorine-containing resin is selected from the group consisting of a fluorinated polycarbonate, a fluorinated epoxy resin, a fluorinated alkyl acrylate copolymer, and a fluorinated vinyl copolymer. The electrophotographic developing method according to claim 1, which is at least one kind. 3. The electrophotographic developing method according to claim 1, wherein the synthetic toner is a polymerized toner or a capsule toner.