JP2000338688A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stable image forming method over a long term even when environment fluctuates in the image forming method provided with toner whose particle diameter is made small, an organic photoreceptor and a mechanism removing the toner from the photoreceptor. SOLUTION: This image forming method is provided with the mechanism removing the toner remaining on the organic photoreceptor after transferring a toner image formed by developing an electrostatic latent image formed on the organic photoreceptor with the toner to an image forming supporting body. In the method, the amount of organic solvent remaining on the organic photoreceptor is 0.1 to 2.0 wt.%, the volume average particle diameter of the toner is 3 to 9 μm and the amount of a polymerizable monomer remaining in the toner is 0.05 to 2.5 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method used for a copying machine, a printer, and the like.

[0002]

2. Description of the Related Art In recent years, the electrophotographic development system has been used in various fields. For example, it is used not only in monochrome copying machines but also in fields such as printers that are output terminals of computers, color copying machines, color printers, and the like. As these applications have advanced, demands on image quality have increased.

There are various proposals for improving the image quality by reducing the particle size of the toner in order to improve the image quality, and there are no shortfalls in the list. A so-called polymerization toner is known as a technique for coping with the reduction in particle diameter. Japanese Patent Application Laid-Open No.
A method of preparing by a suspension polymerization method as shown in JP-A-130762, a method of producing a polymerization toner in which resin particles and colorant particles are bonded as shown in JP-A-63-186253, and the like. Are known.

An organic photoreceptor is used as a photoreceptor from the viewpoint of suppressing waste. Examples of the organic photoconductor include a stacked organic photoconductor in which a so-called charge transport layer and the like are formed on a charge generation layer formed on a conductive support.
Unlike the inorganic photoreceptor, the organic photoreceptor is made of a so-called low-risk material, and is therefore variously used because it is easy to dispose and easy to manufacture. In order to manufacture this organic photoreceptor, a solution in which a charge transporting substance is added and dissolved in an organic solvent in which a binder is dissolved is applied to a conductive support (so-called aluminum or the like) coated with a charge generating layer, A method of manufacturing by drying is common. At this time, a method of drying the organic solvent used for coating through various drying steps is generally used. This organic photoreceptor is composed of a composite resin in which a charge transporting substance is dissolved in a polymer resin. In an image forming method using electrophotography, a method of transferring toner developed on the surface of the organic photoreceptor to paper or the like as an image forming support, cleaning the toner remaining on the surface of the organic photoreceptor, and repeatedly forming an image is known. General. For this reason, depending on the cleaning method for removing the toner remaining on the photoconductor surface,
If the photoreceptor is polished and the abrasion of the photoreceptor proceeds easily, there is a problem that the life of the photoreceptor is shortened due to a decrease in charge retention ability. Further, there is also a problem that the resin is brittle, so-called cracks are generated, and there is also a problem that an image defect is easily generated. In particular, in an image forming method using a toner having a small particle diameter, it is necessary to clean the toner having a small particle diameter and high adhesiveness, so that a particularly large cleaning force is required, so that the photoreceptor is worn out or cracked. The problem of occurrence is becoming a bigger issue.

As described above, in the image forming method using an organic photoreceptor and a toner having a small particle diameter, it is difficult at present to form a stable image over a long period of time. .

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an image forming method having a toner having a reduced particle size, an organic photosensitive member, and a mechanism for cleaning the toner from the photosensitive member. Even in such a case, an object of the present invention is to provide an image forming method that is stable over a long period of time.

[0007]

The object of the present invention can be achieved by adopting one of the following constitutions.

[1] A mechanism for developing an electrostatic latent image formed on an organic photoreceptor with toner, transferring the formed toner image onto an image forming support, and cleaning the toner remaining on the organic photoreceptor. The amount of the organic solvent remaining in the organic photoreceptor is 0.1 to 2.0% by weight, the toner has a volume average particle diameter of 3 to 9 μm, and 0.05 to 2.
An image forming method, wherein the amount is 5% by weight.

[2] In the image forming method described in [1], the amount of the organic solvent remaining on the organic photoreceptor is 0.3 to 1.8.
Wherein the amount of the polymerizable monomer remaining in the toner is 0.1 to 2.0% by weight.

[3] The image forming method according to [1], wherein the cleaning mechanism is a blade cleaning system.

[4] In the image forming method described in [1], the toner has an arithmetic mean value of the shape factor represented by the following formula in the range of 1.3 to 2.2 and the shape factor is 1 .5
An image forming method, wherein the number of toner particles in the range of from 2.0 to 2.0 is at least 80% by number.

Shape factor = ((maximum diameter / 2) ² × π) / projected area As a result of intensive studies, the present inventors have found that the solvent and the polymerizable monomer remaining in the organic photoreceptor and the toner are not enough to form an image. They have found that they have a significant effect on stability, and have completed the present invention.

That is, it is presumed that the cleaning mechanism for the photoreceptor and the adhesion of the toner to the photoreceptor greatly affect the depletion of the photoreceptor, and the object of the present invention has been solved. 2. Description of the Related Art A photoreceptor manufactured using an organic solvent is subjected to a drying process to reduce the amount of the organic solvent as much as possible. In a photoreceptor with an organic solvent remaining, especially when used in a high-temperature environment such as a high-temperature and high-humidity environment, the so-called filming phenomenon occurs due to the shear stress applied to the toner when cleaning the toner remaining untransferred on the photoreceptor. Is easy to occur. Therefore, the cleaning force applied by the cleaning mechanism is increased, and as a result, the wear of the photoconductor is promoted.

However, it has been found that when the amount of the organic solvent is extremely small, cracks tend to be easily generated. This is because, for example, volatile components present in gears used in copiers and printers and silicone oil used in fixing devices tend to be easily adsorbed to the photoconductor, and as a result, cracks tend to occur. It is presumed that it has become.

As a result of studying various methods for suppressing the adsorption of the volatile components, it has been found that the occurrence of cracks due to the adsorption can be suppressed by the presence of an organic solvent to some extent. Although the reason for this is not clear, it is presumed that by leaving a certain amount of organic solvent in the photoreceptor, the adsorption site of the volatile matter was previously closed, and the occurrence of cracks could be suppressed.

Further, regarding the filming of the toner on the photoreceptor, it is considered that the problem can be solved by reducing the adhesion of the small particle size toner itself, and the present invention has been completed. . That is, the toner is mainly composed of resin. The resin is composed of a polymer material.
The function of retaining charges has been strengthened. When the charge holding ability is increased, the overcharged toner is likely to be present due to the accumulation of the charged charge, and the electrostatic adhesion to the photoconductor is likely to be increased. From this viewpoint, as a result of intensive studies, the presence of a certain amount of a polymerizable monomer or an organic solvent in the toner can increase the mobility of molecules and suppress excessive accumulation of charges. It was presumed that, as a result, the adhesion to the photoreceptor could be reduced.

As a result of examination from the above viewpoints, the amount of the organic solvent remaining in the organic photoreceptor is controlled in the range of 0.1 to 2.0% by weight, and the toner has a volume average particle diameter of 3 to 9 μm. And the amount of polymerizable monomer remaining in the toner is reduced to 0.1.
It has been found that by controlling the amount in the range of from 0.5 to 2.5% by weight, it is possible to form a stable image for a long period of time without impairing the cleaning property, and the present invention has been completed.

As the organic photoreceptor, for example, JP-A-9-43
No. 887 can be cited.

That is, an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the binder resin used as the electrophotographic photosensitive member contains a polycarbonate resin represented by the following general formula.

The polycarbonate resin used in the present invention preferably has the following general formula (I), (II) or (III)
And a resin having a viscosity average molecular weight of 40,000 or more. In particular, the viscosity average molecular weight is greater than 100,000,
000 or less resins are preferred.

[0021]

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In the formula, R _{1 to} R ₈ and R _{21 to} R ₂₈ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group. , Z represents an atom group forming a 4 to 11 saturated or unsaturated carbocyclic ring, and R ₉ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms or an aryl group.

[0023]

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In the formula, R _{31 to} R ₃₈ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group.

R _{1 to} R ₈ and R _{21 of the} polycarbonate resin having the structural unit of the general formula (I), (II) or (III)
To R ₂₈ and R ₃₁ to R ₃₈ is a hydrogen atom or 1 to 3 carbon atoms
Is preferred, and Z is an unsubstituted cyclopentyl ring or cyclohexyl ring. These polycarbonate resins may be homopolymers having the structural unit of the general formula (I), (II) or (III) of the present invention, or copolymers or block polymers containing other copolymerization components. In the case of a copolymer or a block polymer, a combination of structural units of the general formula (I), (II) or (III) of the present invention is preferred.

Specific examples of the polycarbonate resin include BPZ: poly (4,4'-cyclohexylidenediphenyl) carbonate and polycarbonate resin having the structural unit of the general formula (I), As a polycarbonate resin having a structural unit, BP
A: There is poly (4,4'-isopropylidenediphenyl) carbonate. Examples of the polycarbonate resin having a structural unit represented by the general formula (III) include BPPC: poly (4,4'-diphenyl) carbonate. it can. These materials can also be obtained as commercial products. For example, polycarbonate resins having a structural unit of the general formula (I) include TS-2050 (Teijin Co., Ltd.)
Z-800 (Mitsubishi Gas Chemical Co., Ltd.), a polycarbonate resin having a structural unit of the general formula (II) is ML-523
7 (GE Plastics).

In order to form a photoreceptor using these polycarbonate resins, there is a method in which the resin, a solvent and a charge transport material are dissolved and applied. Examples of the solvent used include n-butylamine, Diethylamine,
Ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, benzene,
Toluene, xylene, chloroform, dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1, -trichloroethane, trichloroethylene, tetrachloroethane, tetrahydrofuran, dioxane, dioxolan, methanol , Ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve and the like. The preferred solvent is not particularly limited, but examples thereof include dichloromethane, 1,2-dichloroethane, dioxolan, and methyl ethyl ketone.

Preferred configurations of the organic photoreceptor of the present invention include the configurations shown in FIGS. That is, FIG. 1A shows a charge generation material (CGM) and a charge transport material (CTM) on a conductive support 1 via an intermediate layer 2.
1 (b) is a photoconductor having a single-layered photosensitive layer 6 which contains both a charge transport material and a charge transport material containing a charge transport material as a main component via an intermediate layer 2 on a conductive support 1. CT
L) 3 and a photosensitive layer 6 having a charge generating layer (CGL) 4 containing a charge generating substance (CGM) as a main component laminated in this order, and FIG. A charge generation layer (CGL) 4 containing a charge generation material (CGM) as a main component and a charge transport layer (CTL) 3 containing a charge transport material as a main component on a body 1 via an intermediate layer 2 in that order. This is a photoconductor having a photoconductive layer 6 formed by lamination. FIGS. 1 (d), (e), and (f) are (a),
(B) and (c) show a configuration in which a protective layer 5 is laminated on the photosensitive layer. The configuration diagrams shown in FIGS. 1A to 1F show typical configurations, and the present invention is not limited to this configuration. Further, the intermediate layer 2 shown in these configurations is provided as needed, and may not be provided unless particularly necessary.

Further, silica or organic fine particles can be added to the protective layer 5. Further, CTM may be added to the protective layer.

The charge generating material (CGM) used in the photoreceptor shown in FIG. 1 is as follows. For example, phthalocyanine pigments, polycyclic quinone pigments, azo pigments, perylene pigments, indigo pigments, quinacridone pigments, azurenium pigments, squarylium dyes, cyanine dyes, pyrylium dyes, thiopyrylium dyes, xanthene dyes, triphenylmethane dyes, styryl dyes, etc. These may be used alone or as a mixture to form a layer with an appropriate binder resin.

A particularly preferred CGM is a phthalocyanine pigment, and a titanyl phthalocyanine type pigment is particularly preferably used.

The charge transport material (CTM) contained in the photosensitive layer 6 includes, for example, an oxazole derivative,
Oxadiazole derivatives, thiazole derivatives, triazole derivatives, imidazole derivatives, imidazoline derivatives, imidazolone derivatives, bisimidazolidine derivatives,
Styryl derivatives, hydrazone derivatives, benzidine derivatives, pyrazoline derivatives, stilbene derivatives, amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly- N-carbazole, poly-1-vinylpyrene, poly-9-vinylanthracene and the like can be mentioned. These CTMs can usually form a layer together with a binder.

Particularly preferred CTMs are shown below.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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As the binder contained in the photosensitive layer 6 having a single-layer structure and the CGL and CTL having a laminated structure, in addition to the polycarbonate resin of the present invention, polyester, styrene resin, acrylic resin, vinyl chloride resin, polyvinyl butyral, Examples include polyvinyl acetal, styrene-butadiene resin, urethane resin, silicone resin, and phenol resin.

The ratio of CGM to binder resin in CGL is preferably from 1: 5 to 5: 1 by weight. Further, the thickness of the CGL is preferably 5 μm or less, particularly 0.05 to 2.0 μm.
m is preferred.

The CTL is formed by dissolving the above-mentioned CTM and a binder resin in the above-mentioned organic solvent, coating and drying. The ratio between CTM and binder resin in CTL is preferably 3: 1 to 1: 3 by weight.

When a plurality of CTLs are formed,
It is preferable that the binder resin contained in the CTL formed on the uppermost layer has a high molecular weight. With this configuration, the mechanical strength can be improved.

Particularly, the molecular weight of the polycarbonate resin as the binder resin used for the CTL of the uppermost layer is preferably 50,000 or more in terms of viscosity average molecular weight, and particularly preferably 100,000 to 500,000. Further, the viscosity average molecular weight of the polycarbonate resin contained in the CTL formed in the lower layer is preferably smaller than that of the uppermost layer. The preferred molecular weight range in this case is less than 50,000, preferably 20,000.
0 to 40,000. With this configuration, the amount of the remaining organic solvent can be controlled. Although the reason is not clear, by increasing the molecular weight of the uppermost layer, the rate of volatilization of the organic solvent from the uppermost layer can be reduced, and as a result, a specific range of the organic solvent can be left. It is estimated to be.

The thickness of the CTL is 5 to 50 μm, preferably 10 to 40 μm, particularly preferably 15 to 35 μm.

In the present invention, the amount of the organic solvent remaining on the organic photoreceptor is 0.1 to 2.0% by weight, preferably 0.1 to 2.0% by weight.
3 to 1.8% by weight. If the organic solvent remains beyond this range, the surface of the photoreceptor is likely to be softened, causing a problem of toner filming and image defects. On the other hand, if the amount of the residual solvent is small, as described above, cracks are likely to occur, and there is a problem that an image defect occurs due to this phenomenon.

The residual solvent can be measured by using a head space gas chromatograph, using a flame ionization detector (FID), and performing quantification using an internal standard. . This method is not limited to the method of measuring the residual solvent of the photoreceptor, and is also used when measuring the amount of residual polymerizable monomer in the toner.

In order to adjust the residual solvent amount in the present invention, the drying temperature condition and time may be controlled. The drying temperature is from 90 to 120 ° C, and preferably the glass transition temperature of the photosensitive layer ± 20 ° C. Further, the drying time is not particularly limited, but after the reduced-rate drying state, the residual solvent during the drying is monitored, and the drying may be stopped when the solvent falls within the range of the present invention. When the temperature of the photoreceptor becomes lower than the glass transition temperature of the photosensitive layer in the reduced-rate drying state, the drying is stopped and the state in which the residual organic solvent is retained can be maintained.

Examples of the conductive support for constituting the photoreceptor of the present invention include: 1) a conductive metal such as aluminum and stainless steel; and 2) aluminum, palladium and gold on the surface of an insulating substrate such as paper or plastic film. 3) A layer of a conductive compound such as a conductive polymer, indium oxide, or tin oxide was formed on the surface of an insulating substrate such as paper or a plastic film by coating or vapor deposition. Things and the like.

Coating methods for producing the photoreceptor of the present invention include dip coating, spray coating described in JP-A-3-90250 and JP-A-3-269238, and JP-A-58-189061. There is an application method such as the circular amount control type application described above. Among them, the circular amount control type coating method is preferably used as a method for producing a laminated structure because it is a method capable of coating the upper layer without dissolving the lower layer.

The toner of the present invention is obtained by emulsion polymerization of a monomer in a suspension polymerization method or a liquid to which an emulsion of necessary additives is added.
It can be produced by a method of producing fine polymer particles, and then adding an organic solvent, a coagulant and the like to associate.
A method of preparing by mixing and associating with a dispersion liquid such as a release agent or a colorant necessary for the composition of the toner at the time of association, or dispersing a toner component such as a release agent or a colorant in a monomer. And then emulsion polymerization. Here, the association means that a plurality of resin particles and colorant particles are fused.

The production method of the suspension polymerization method is not particularly limited, but the following production methods can be used.

That is, a coloring agent and, if necessary, various constituent materials such as a release agent, a charge control agent, and a polymerization initiator are added to the polymerizable monomer, and a homogenizer, a sand mill, a sand grinder, and an ultrasonic disperser are added. Various constituent materials are dissolved or dispersed in the polymerizable monomer by a machine or the like. The polymerizable monomer in which these various constituent materials are dissolved or dispersed is dispersed in an aqueous medium containing a dispersion stabilizer into oil droplets of a desired size as a toner using a homomixer, a homogenizer, or the like. Thereafter, the stirring mechanism is moved to the above-described reaction device, which is the stirring blade, and heated to cause the polymerization reaction to proceed. After completion of the reaction, the toner of the present invention is prepared by removing the dispersion stabilizer, filtering, washing and drying.

Further, as a method for producing the toner of the present invention, there is a method in which resin particles are prepared by fusing them in an aqueous medium. Although this method is not particularly limited, for example, JP-A-5-265252, JP-A-6-329947, and JP-A-9-159.
The method disclosed in Japanese Patent Publication No. 04-2004 can be cited. That is, a method of associating a plurality of resin particles and dispersed particles of a constituent material such as a colorant, or fine particles composed of a resin and a colorant, particularly, after dispersing these in water using an emulsifier, the critical aggregation concentration At the same time as adding the above coagulant and salting out, the formed polymer itself is heated and fused at a temperature equal to or higher than the glass transition temperature, and the particles are heated and dried in a fluid state while keeping a water-containing state. Can be formed. Here, an organic solvent infinitely soluble in water may be added together with the coagulant.

The shape of the toner obtained by fusing has an arithmetic mean value of the shape coefficient represented by the following equation of 1.3 to 1.3.
2.2 and the shape factor is 1.5 to 2.0
Is preferably 80% or more by number.

Shape factor = ((maximum diameter / 2) ² × π) / projected area This shape factor is obtained by taking a photograph in which toner particles are magnified 500 times with a scanning electron microscope, and SCANNING IMAGE ANALYS
Analyze the photographic image using "ER" (manufactured by JEOL Ltd.). At this time, the shape factor of the present invention is measured by using the above formula using 500 toner particles, and the arithmetic average value is obtained.

If the arithmetic mean value of the shape factor is less than 1.3, the shape becomes rounded and the adhesion to the photoreceptor increases. When the average value exceeds 2.2, the irregularity increases, so that the adhesion to the photoreceptor is small and the cleaning property is improved, but the toner is deformed when subjected to stress inside the developing device. This is because they are likely to occur, generate fine powder and the like, adhere to the photoreceptor, easily cause image defects, and it becomes difficult to maintain an image without image defects for a long period of time.

Further, when the number of toner particles having a shape coefficient in the range of 1.5 to 2.0 is at least 80% by number, the shape distribution can be made uniform, and the effect of the present invention can be more remarkably exhibited. can do.

The particle size of the resin particles for producing the developing toner particles of the present invention is measured using an electrophoretic light scattering photometer ELS-800 manufactured by Otsuka Electronics Co., Ltd., using a dispersion of the resin particles. It is the value indicated by the weight average particle size. In the present invention, it is 50 to 2000 nm, preferably 80 to 500 nm.

As the polymerizable monomer constituting the resin, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4- Dichlorostyrene,
p-phenylstyrene, p-ethylstyrene, 2,4-
Dimethylstyrene, pt-butylstyrene, pn-
Hexylstyrene, pn-octylstyrene, pn
-Nonylstyrene, pn-decylstyrene, pn-
Styrene or a styrene derivative such as dodecylstyrene, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate,
Stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, methacrylate derivatives such as dimethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate,
T-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, acrylate derivatives such as phenyl acrylate, olefins such as ethylene, propylene and isobutylene; Halogen vinyls such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, and vinylidene fluoride; vinyl esters such as vinyl propionate, vinyl acetate and vinyl benzoate; and vinyl ethers such as vinyl methyl ether and vinyl ethyl ether , Vinyl methyl ketone, vinyl ethyl ketone, vinyl ketones such as vinyl hexyl ketone,
N-vinyl carbazole, N-vinyl indole, N-
There are N-vinyl compounds such as vinylpyrrolidone, vinyl compounds such as vinylnaphthalene and vinylpyridine, and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide. These vinyl monomers can be used alone or in combination.

Further, it is more preferable to use a polymerizable monomer constituting the resin in combination with one having an ionic dissociation group. For example, those having a substituent such as a carboxyl group, a sulfonic acid group, and a phosphate group as a constituent group of the monomer, specifically, acrylic acid, methacrylic acid,
Maleic acid, itaconic acid, cinnamic acid, fumaric acid, monoalkyl maleate, monoalkyl itaconate, styrenesulfonic acid, allylsulfosuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxyethyl Methacrylate,
3-chloro-2-acid phosphooxypropyl methacrylate and the like.

Further, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate,
Polyfunctional vinyls such as neopentyl glycol diacrylate can be used to form a crosslinked resin.

These polymerizable monomers can be polymerized using a radical polymerization initiator. In this case, an oil-soluble polymerization initiator can be used in the suspension polymerization method. As the oil-soluble polymerization initiator, 2,2'-azobis- (2,4
-Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvalero Nitroles, azo or diazo polymerization initiators such as azobisisobutyronitrile,
Benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis (4,4
Examples thereof include peroxide-based polymerization initiators such as -t-butylperoxycyclohexyl) propane and tris- (t-butylperoxy) triazine, and polymer initiators having a peroxide in a side chain.

When the emulsion polymerization method is used, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, and hydrogen peroxide.

Examples of the dispersion stabilizer include tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, and calcium sulfate. , Barium sulfate,
Bentonite, silica, alumina and the like can be mentioned. Further, a surfactant generally used as a surfactant such as polyvinyl alcohol, gelatin, methyl cellulose, sodium dodecylbenzenesulfonate, ethylene oxide adduct, and higher alcohol sodium sulfate can be used as a dispersion stabilizer.

The resin excellent in the present invention preferably has a glass transition point of 20 to 90 ° C. and a softening point of 8 ° C.
The thing of 0-220 ° C is preferred. The glass transition point is measured by a differential calorimetric analysis method, and the softening point can be measured by a Koka flow tester. Furthermore, these resins have a number average molecular weight (Mn) of 10 as measured by gel permeation chromatography.
00 to 100000, weight average molecular weight (Mw) 200
Those having 0 to 1,000,000 are preferred. Further, as a molecular weight distribution, Mw / Mn is 1.5 to 100, particularly 1.8.
-70 are preferred.

The flocculant to be used is not particularly limited, but those selected from metal salts are preferably used. Specifically, as a monovalent metal, for example, a salt of an alkali metal such as sodium, potassium, and lithium, and as a divalent metal, for example, a salt of an alkaline earth metal such as calcium and magnesium, or a divalent metal such as manganese or copper Salt,
Examples include salts of trivalent metals such as iron and aluminum, and specific salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Can be.
These may be used in combination.

It is preferable to add these coagulants at a concentration higher than the critical coagulation concentration. The critical aggregation concentration is an index relating to the stability of the aqueous dispersion, and indicates the concentration at which aggregation occurs when a coagulant is added. This critical aggregation concentration is
It varies greatly depending on the emulsified component and the dispersant itself. For example, Seizo Okamura et al., “Polymer Chemistry 1
7, 601 (1960), edited by The Society of Polymer Science, Japan, and the like, and a detailed critical aggregation concentration can be determined.
As another method, a desired salt is added to a target particle dispersion at a different concentration, the 添加 (zeta) potential of the dispersion is measured, and the salt concentration at which this value changes is determined as a critical aggregation concentration. You can also.

The addition amount of the coagulant of the present invention may be not less than the critical coagulation concentration, but is preferably 1.2 to the critical coagulation concentration.
It is better to add it at least twice, more preferably at least 1.5 times.

The solvent which is infinitely soluble means a solvent which is infinitely soluble in water, and a solvent which does not dissolve the formed resin in the present invention is selected.
Specifically, methanol, ethanol, propanol,
Examples thereof include alcohols such as isopropanol, t-butanol, methoxyethanol and butoxyethanol, nitriles such as acetonitrile, and ethers such as dioxane. Particularly, ethanol, propanol and isopropanol are preferred.

The amount of the solvent to be dissolved infinitely is 1 to 100% by volume based on the polymer-containing dispersion to which the flocculant has been added.
Is preferred.

In order to make the shape uniform, it is preferable to prepare a colored particle, and after the filtration, a slurry in which 10% by weight or more of water is present in the particle is fluidized and dried. Those having a polar group in the polymer are preferred. It is considered that the reason for this is that the water existing in the polymer having the polar group has an effect of swelling to some extent, so that the shape is particularly easily uniformized.

As the colorant used in the toner of the present invention, carbon black, magnetic substance, dye, pigment and the like can be arbitrarily used. As the carbon black, channel black, furnace black, acetylene black, thermal black lamp and the like can be used. Black or the like is used. As the magnetic material, ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys which do not contain ferromagnetic metals but show ferromagnetism by heat treatment, For example, an alloy of a type called a Heusler alloy such as manganese-copper-aluminum, manganese-copper-tin, chromium dioxide, or the like can be used.

As the dye, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 1
22, C.I. I. Solvent Yellow 19, 44, 7
7, 79, 81, 82, 93, 98, 10
3, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 9
5 and the like, and mixtures thereof can also be used. Examples of the pigment include C.I. I. Pigment Red 5,
48: 1, 53: 1, 57: 1, 122, 1
39, 144, 149, 166, 177, 1
78, 222, C.I. I. Pigment Orange 31, 43 and C.I. I. Pigment Yellow 14, 17, and 9
3, 94, 138, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 3, 60 and the like, and mixtures thereof can also be used. The number average primary particle size varies depending on the type, but
About 200 nm is preferable.

As a method of adding a colorant, a method of adding polymer particles prepared by an emulsion polymerization method at the stage of coagulation by adding a coagulant to color the polymer, or a process of polymerizing monomers. And a method of adding a colorant, polymerizing, and forming colored particles can be used. When the colorant is added at the stage of preparing the polymer, it is preferable to use the colorant after treating the surface with a coupling agent or the like so as not to inhibit the radical polymerizability.

Further, low molecular weight polypropylene (number average molecular weight = 1500 to 9000), low molecular weight polyethylene, or the like as a fixing property improving agent may be added.

Also, an azo metal complex as a charge control agent,
A quaternary ammonium salt or the like may be used.

The polymerizable monomer described above is contained in the toner in an amount of 0.05 to 2.5% by weight, preferably 0.1 to 2.
It must be contained at 0% by weight. A method for controlling the amount of the remaining polymerizable monomer can be controlled by the amount of the polymerization initiator, the reaction temperature, and the chain transfer agent. Further, there is a method in which the polymerization reaction is suppressed by adding a polymerization inhibitor to the polymerizable monomer, and the residual amount of the polymerizable monomer is adjusted.

Specifically, by reducing the amount of the polymerization initiator added, the amount of radicals generated can be suppressed, and the amount of residual polymerizable monomer can be increased. Also, the reaction temperature depends on the amount of the polymerization initiator added, but when a small amount of the polymerization initiator is used, the reaction can be performed on the high temperature side to increase the residual amount. If you use
By allowing the reaction to proceed for a long time on the low temperature side, the residual amount can be increased.

In addition to the residual control of the polymerizable monomer by the above reaction control, the residual amount of the polymerizable monomer is simultaneously controlled in a drying step for removing water after the production of a so-called polymerized toner. The method is also suitable. in this case,
When a method of drying at a temperature equal to or lower than the glass transition temperature of the resin is used, the molecular motion of the resin itself is small, so that drying of the polymerizable monomer remaining in the resin is reduced, and the residual amount increases. When drying is performed at a temperature equal to or higher than the glass transition temperature of the resin, it is preferable to dry the resin in as short a time as possible.

As a device used for drying, various drying devices such as a flash drying device and a reduced-pressure drying device can be used. Preferable examples of the drying apparatus include a flash jet dryer as a flash dryer, a fluidized bed dryer, and a vibrating fluidized dryer.

The drying conditions are not particularly limited, but when a flash jet drier is used, the inlet temperature in the drying is 100-1.
Preferably, the outlet temperature is 50 ° C. and the glass transition temperature of the resin is ± 5 ° C. The temperature data is fed back to the particle supply amount while monitoring the temperature so that drying is performed under the condition that the outlet temperature can be controlled within this range. It is particularly preferable to perform such control.

The structure of the flash dryer is not particularly limited. For example, the inlet temperature of the flash dryer is 100 to 150 ° C., and the outlet temperature is the glass transition temperature of the resin constituting the colored particles ± 5. It is preferable to carry out under the condition of ° C.

FIG. 2 is a sectional view showing the structure of an example of a flash dryer that can be used in the present invention. In the figure, 11 is the dryer body, 12 is the inlet for the wet cake, 13 is the nozzle,
14 is a collection nozzle, 15 is an outlet for dry powder (colored particles), 16A is a drying area, 16B is an up-stack area, 16C is a classification area, 17 is a hot air supply unit, and 18 is a hot air inlet.

In this flash dryer, when heated compressed air is supplied from the hot air inlet 18 into the hot air supply unit 17, the compressed air (hot air) passes through the nozzle 13 opened in the hot air supply unit 17 and is supplied to the dryer body. 11 is discharged at a supersonic speed, and the flow path (drying area 16A → upstack area 16B and classification area 16C → drying area 1)
Circulate inside the dryer body along 6A). At this time, the inside of the dryer has a slight negative pressure near the inlet 12.

When the wet cake is supplied from the charging port 12 in such a hot air circulating state, the wet cake becomes
The powder is dispersed and crushed (pulverized) by the hot air circulating inside the dryer main body 11, and the formed powder moisture is quickly removed. This powder (colored particles) is conveyed by hot air to the classification area 16C, and passes through the collection nozzle 14 and exits from the discharge port 15 in a state where the water content of the powder and the amount of the residual polymerizable monomer have reached a predetermined value or less. When the powder is discharged and is larger than the value of the moisture or residual polymerizable monomer in the powder, the powder is conveyed to the drying area 16A and dried again.

Further, a vibration fluidized drying method is also preferable. This method is a method in which toner particles are suspended and suspended by mechanical vibration and gas blowing, and dried while forming a fluidized bed. As this device, the container used for suspending and suspending by mechanical vibration and gas blowing and drying while forming a fluidized bed is one in which the lower part is narrowed down from the upper part, and the lower part is It is preferable that the linear velocity of the gas in the gas blowing section is twice or more the linear velocity of the upper gas. Further, it is preferable that the container has a jacket for heating at an outer peripheral portion.

Hereinafter, a detailed description will be given with reference to the drawings as necessary. This method can be used without particular limitation as long as a mechanical vibration is applied to the colored particles, the particles are suspended and suspended by blowing gas, and can be dried while forming a fluidized bed while drying. . For example, FIG.
And 4 are cross-sectional views of the vibration fluidized-bed drying apparatus. A vibration fluidized-bed drying device having such a configuration is preferably used. The drying device as shown in the figure has a cylindrical shape as a whole, and a gas inlet 22, a perforated plate 23 for rectifying gas, and a fluidized bed of particles and gas are formed along the gas flow path. Drying room 2
4. It comprises a filter 25 for capturing particles and an exhaust port 26. The exhaust port 26 is connected to an exhaust blower to perform exhaust. Further, two vibration motors (vibrators) 20 are attached to the opposing wall surfaces of the gantry at the bottom 21 of the drying chamber, so that vibration can be applied to the entire drying chamber. The amplitude of the vibration can be adjusted by the mounting angle between the unbalanced weights mounted on both ends of the shaft of the vibration motor, and the frequency can be arbitrarily set by the inverter. The dried raw material is supplied from an inlet 28 at the upper part of the drying chamber, and the dried product is discharged from an outlet 29 at the lower part of the drying chamber as shown in FIG.
As shown in FIG.

The drying operation using this drying device is performed, for example, as follows. That is, the water-containing toner particles introduced into the drying chamber are blown up by the mechanical vibration given by the vibration motor and the hot air introduced from the gas inlet and introduced through the perforated plate, and flow together with the gas. Become The toner particles floating in the drying chamber to form a fluidized bed are uniformly mixed with the gas inside the fluidized bed and dried. The toner particles blown up to the upper part of the drying chamber 24 (exhaust port 26 side) are captured by the filter 25,
For example, by applying a backwash pulse to the filter, the toner particles are washed off the filter and returned downward. In the case of toner particles having a small particle size and strong adhesion and containing a low softening point substance, toner aggregation is likely to occur near the perforated plate 23. Therefore, it is effective to increase the linear velocity of the gas. If the linear velocity is high, particles rising to the upper part of the drying chamber will increase, causing adverse effects such as easy clogging of the filter. Therefore, the drying chamber 24 has a sectional area perpendicular to the gas flow path as shown in FIG. It is preferable to have a shape in which the lower part is narrower than the upper part, and it is preferable that the linear velocity of the gas near the perforated plate 23 at the lower part of the drying chamber is at least twice the linear velocity of the gas at the upper part of the drying chamber. Further, it is more preferable that the outer periphery of the drying chamber has a jacket structure, and the drying efficiency is increased by circulating warm water and heating. The type of gas introduced into the drying chamber is not particularly limited, and an inert gas such as nitrogen or air is used.
Preferably, heated inert gas or dehumidified and heated dry air is used. The temperature of the gas is preferably 30 to 80C. The temperature of this gas is preferably a high temperature from the viewpoint of efficient drying, but is a temperature not higher than the glass transition point of the raw toner particles from the viewpoint of suppressing deformation and fusion of the raw toner particles. Is desirable. The gas is preferably dehumidified and used at a relative humidity of 50% or less (more preferably, 30% or less).

Similarly, it is desirable that the outer periphery of the drying chamber has a jacket structure, and the temperature in the case of heating by circulating warm water is not higher than the glass transition point of the raw material toner particles.

As the vibration fluidized bed drying apparatus preferably used in the present invention, a vibration fluidized bed drying apparatus VUA type manufactured by Chuo Kakoki Co., Ltd. is specifically mentioned.

Further, in the toner of the present invention, more effects can be exhibited by adding and using fine particles such as inorganic fine particles and organic fine particles as an external additive. The reason for this is presumed to be that, as described above, the burying and detachment of the external additive can be effectively suppressed, and the effect is remarkable.

As the inorganic fine particles, it is preferable to use inorganic oxide particles such as silica, titania, and alumina. Further, it is preferable that these inorganic fine particles have been subjected to a hydrophobic treatment with a silane coupling agent or a titanium coupling agent. preferable. The degree of the hydrophobization treatment is not particularly limited.
Those having 0 to 95 are preferred. Methanol wettability is to evaluate the wettability to methanol. In this method, 0.2 g of inorganic fine particles to be measured is placed in 50 ml of distilled water placed in a beaker having a content of 250 ml.
Weigh and add. Methanol is slowly dropped from a burette whose tip is immersed in the liquid until the whole of the inorganic fine particles is wet with slow stirring. The amount of methanol required to completely wet the inorganic fine particles is a
(Ml), the degree of hydrophobicity is calculated by the following equation.

Degree of hydrophobicity = {a / (a + 50)} × 100 The amount of the external additive to be added is 0.1 to 5.
0% by weight, preferably 0.5 to 4.0% by weight. Various external additives may be used in combination.

The toner of the present invention has a volume average particle diameter of 3 to 9 μm. This particle size can be controlled by the concentration of the flocculant, the amount of the organic solvent added, and the composition of the polymer itself. Also, toner particles (colored particles)
Is a volume average particle size measured with a Coulter Counter TA-II or a Coulter Multisizer.

The toner of the present invention can be used as a one-component magnetic toner containing a magnetic material, for example, when used as a two-component developer by mixing with a so-called carrier, or when a non-magnetic toner is used alone. Any of them can be suitably used, but in the present invention, it is more preferable to use as a two-component developer to be used by mixing with a carrier.

As the carrier constituting the two-component developer, either an uncoated carrier composed of only magnetic material particles such as iron or ferrite, or a resin-coated carrier having the magnetic material particle surfaces coated with a resin or the like can be used. Is also good. The average particle size of this carrier is 30 to 1 in terms of volume average particle size.
50 μm is preferred. The resin for coating is not particularly limited, and examples thereof include a styrene-acrylic resin and a silicone resin.

The developing system in which the toner of the present invention can be used is not particularly limited. It can be suitably used for a contact developing method or a non-contact developing method. Further, the toner of the present invention has a high charge rising property, and is useful for a non-contact developing method. That is, in the non-contact development method, since the change in the development electric field is large, a minute change in the charge is large and acts on the development itself. However, since the toner of the present invention has a high charge rising property, the change in charge is small, and a stable charge amount can be secured. Therefore, a stable image can be formed for a long time even by the non-contact developing method. it can.

Hereinafter, an example of the non-contact developing system will be described with reference to FIGS.

The developer carrier is constituted by a sleeve in which a magnet fixed inside is arranged, and the developer (toner) is transported to the developing area by rotating the sleeve. The material is preferably stainless steel or aluminum. A particularly preferred example is one in which a phenol resin in which conductive carbon is dispersed is coated on the surface of an aluminum sleeve. The sleeve preferably has a diameter of 10 to 50 mm.

The developer layer regulating member is used to uniformly regulate the toner layer on the developer carrier, and may be made of a magnetic plate or a non-magnetic plate. A method to regulate the toner layer by forming a certain gap between
Alternatively, a method in which a member having rubber elasticity such as urethane is brought into contact with the developer carrying member, and a method in which an elastic metal plate such as a phosphor bronze plate is brought into contact with the developer carrying member can be given.

The developer layer is conveyed to the developer carrier in a layer thinner than the gap (a) between the developer carrier and the electrostatic latent image carrier. The preferred range of the gap (a) is 100 to 500 μm, and the developer layer is conveyed to be thinner than this gap.
It is preferable to be transported in a layer of 0 to 300 μm.

Further, it is preferable to apply an alternating electric field between the developer carrier and the electrostatic latent image carrier. By applying this alternating electric field, the toner can fly effectively. As the condition of the alternating electric field, it is preferable that the AC frequency f is 200 to 4,000 Hz and the AC voltage Vpp is 500 to 3,000 V. When this alternating electric field is used, it is necessary that the toner has uniform chargeability and magnetism. That is, when the toner has a distribution of magnetism and chargeability among toners, the effect of pulling back weakly chargeable toner and the like due to the alternating electric field is offset, and as a result, the effect of improving image quality is reduced. The image quality can be further improved by the shape uniformity and magnetic uniformity of the toner formed by fusing in an aqueous medium as in the present invention.

Hereinafter, the developing device of the image forming method of the present invention will be specifically described.

FIG. 5 is a sectional view showing the structure of the developing device according to the present invention.

In FIG. 5, an image carrier for carrying an electrostatic latent image formed by a known process, for example, an electrophotographic photosensitive drum 31, is rotated in the direction of arrow B. The developing sleeve 38 as a developer carrying member carries the magnetic toner 34 as a magnetic one-component developer supplied by the hopper 33, and rotates in the direction of arrow A so that the developing sleeve 38 and the photosensitive drum 31 are separated. The toner 34 is transported to the developing area D facing the toner. In the developing sleeve 38, a magnet 35 is disposed for magnetically attracting and holding the magnetic toner 34 on the developing sleeve 38. Magnetic toner 34
Obtains a triboelectric charge that can develop the electrostatic latent image on the photosensitive drum 31 by friction with the developing sleeve 38.

In order to regulate the layer thickness of the magnetic toner 34 conveyed to the developing area D, a regulating blade 32 made of a ferromagnetic metal is moved from the surface of the developing sleeve 38 by 100 to 500
It is hung from the hopper 33 so as to face the developing sleeve 38 with a gap width of μm. By the magnetic field lines from the magnetic pole N of the magnet 35 being concentrated on the blade 32,
A thin layer of the magnetic toner 34 is formed on the developing sleeve 38. As the blade 32, a non-magnetic blade can be used.

The thickness of the thin layer of the magnetic toner 34 formed on the developing sleeve 38 is smaller than the minimum gap between the developing sleeve 38 and the photosensitive drum 31 in the developing area D. The present invention is particularly effective for a developing device of a type that develops an electrostatic latent image with such a thin toner layer, that is, a non-contact developing type developing device. However, in the developing area, the thickness of the toner layer is
The present invention can also be applied to a developing device having a thickness not less than the minimum gap between them, that is, a contact developing type developing device.

In order to avoid the complexity of the description, the following description will be made by taking a non-contact developing type developing device as an example.

The developing sleeve 38 is supplied with a developing bias voltage by a power source 39 in order to cause the magnetic toner 34 to fly from the toner layer of the magnetic toner 34, which is a magnetic one-component developer, carried on the developing sleeve 38 toward the photosensitive drum 31. Is applied. When a DC voltage is used as the developing bias voltage, a voltage having a value between the potential of the electrostatic latent image portion (the region where the magnetic toner 34 is adhered and visualized) and the potential of the background portion is used. 38 is preferably applied. On the other hand, an alternating bias voltage is applied to the developing sleeve 38 to increase the density of the developed image or improve the gradation.
An oscillating electric field whose direction is alternately reversed may be formed in the developing region D. In this case, it is preferable to apply to the developing sleeve 38 an alternating bias voltage on which a DC voltage component having a value between the potential of the image portion and the potential of the background portion is superimposed.

In so-called regular development in which toner is adhered to a high potential portion of an electrostatic latent image having a high potential portion and a low potential portion to visualize the toner, a toner charged to a polarity opposite to the polarity of the electrostatic latent image is used. On the other hand, in so-called reversal development in which toner is adhered to a low-potential portion of an electrostatic latent image to visualize the toner, a toner charged to the same polarity as the polarity of the electrostatic latent image is used. Note that the high potential and the low potential are expressed by absolute values. In any case, the magnetic toner 34 is charged to a polarity for developing the electrostatic latent image by friction with the developing sleeve 38.

FIG. 6 is a structural sectional view showing another embodiment of the developing device according to the present invention, and FIG. 7 is a structural sectional view showing still another embodiment of the developing device according to the present invention.

In the developing device shown in FIGS. 6 and 7, as a member for regulating the layer thickness of the magnetic toner 34 on the developing sleeve 38, a material having rubber elasticity such as urethane rubber or silicone rubber, phosphor bronze, stainless steel or the like is used. An elastic plate 30 made of a material having metal elasticity is used.
6 is characterized in that it is pressed against the developing sleeve 38 in a posture opposite to the rotation direction in the developing device of FIG. 6, and the developing device in FIG. 7 is pressed against the developing sleeve 38 in the same direction as the rotation direction. In such a developing device, a thinner toner layer can be formed on the developing sleeve. Other configurations of the developing device of FIGS. 6 and 7 are basically the same as those of the developing device shown in FIG. 5. In FIGS. 6 and 7, the same reference numerals as those shown in FIG. 5 denote the same members.

The developing device for forming a toner layer on the developing sleeve 38 as described above, as shown in FIGS.
It is suitable for those using a magnetic one-component developer containing a magnetic toner as a main component. In any case, since the toner is rubbed onto the developing sleeve 38 by the elastic plate 30, the amount of triboelectric charge of the toner increases, and the image density is improved.
Therefore, it is suitable for coping with a shortage of toner charge in a high quality environment.

The developing sleeve 38 is formed on the surface of the sleeve base 36 on which fine irregularities are provided, that is, on the rough surface.
A resin coating layer 37 containing and dispersing at least conductive fine particles such as graphite is formed. The magnetic toner 34 is frictionally charged by the resin coating layer 37 to have a polarity for developing a latent image. Fine particles such as graphite contained therein are exposed on the surface of the resin coating layer 37. Since the conductive fine particles such as graphite leak excessively charged toner 34 and have excellent solid lubricating properties,
This is useful for reducing the adhesion of the fine powder toner to the developing sleeve 38.

In the present invention, a blade cleaning system is preferred as a cleaning mechanism. The configuration of the cleaning mechanism in the present invention is as shown in FIG. Reference numeral 41 denotes an elastic blade which is in contact with the photosensitive drum 31 while being held by the holder 43 while a certain amount of contact pressure is applied. FIG.
Reference numeral 44 denotes a member for applying the contact pressure.

In FIG. 8, the arrow indicates the traveling direction of the photosensitive drum 31. Reference numeral 45 denotes a guide plate 46 for guiding the toner on the photosensitive drum 31 scraped off by the elastic blade to the waste toner transporting unit 45. Since the guide plate 46 is thin and soft, the toner adhering to the latent image forming member once passes under the guide plate 46 and is scraped off by the elastic blade. Reference numeral 47 denotes an outer wall of the cleaning mechanism.

FIG. 9 shows a situation in which the toner on the photosensitive drum 31 is scraped off by the elastic blade 41. As described above, the toner tends to accumulate and be crushed at the tip of the elastic blade 41.

FIG. 10 shows a holder 43 of the elastic blade 41.
FIG. 4 is a diagram illustrating an intersection angle φ between the photoconductor drum 31 and the photoconductor drum 31. That is, when the intersection angle φ is less than 90 °, the extension line is extended in the direction (Y-Y) in which the elastic blade of the holder is supported, and the portion P on the surface of the latent image forming body reaches the latent image forming surface. When a tangent line (XX) is drawn, the angle between the tangent line and the extension line is less than 90 °.

If this angle is 90 ° or more and sufficient cleaning properties are to be ensured, the toner will adhere to the latent image forming member during long-term use due to the force acting to crush the toner. Is difficult to secure.
Although there is no particular lower limit angle,
It is preferable that the angle is 15 ° or more in terms of cleaning power. In addition, a preferable range of the angle is 20 to
90 °, more preferably 25 to 80 °.

Further, as the material of the elastic blade used in the present invention, urethane rubber, silicone rubber, fluorine rubber, chloroprene rubber, butadiene rubber and the like can be used. Among them, urethane rubber-based materials are preferable. Particularly, as described in JP-A-59-30574, a polycaprolactone ester containing a caprolactone ester component of 30% by weight or more and having an average molecular weight of 1,000 to 4,000 is mixed with a polyisocyanate. Urethane rubber obtained by reaction curing is preferred.

The average molecular weight is defined as the amount of potassium hydroxide that neutralizes acetic acid produced when acetylation reaction is carried out with polycaprolactone ester using an acetylation reagent consisting of acetic anhydride and pyridine, to determine the amount of terminal OH. The group was quantified and the number average molecular weight was calculated.

The general formula of the polycaprolactone ester preferably used in the present invention can be shown below.

HO-[-X _1- ] _m -R-[-X _2- ] _n -OH Here, X ₁ and X ₂ are cleavage residues of a caprolactone ring and may be the same or different from each other. Well, the sum of m and n is 2
-35, m: n = 3: 1 to 1: 3. R is a linking group of X ₁ and X ₂ and is a divalent organic group having 300 or less carbon atoms. The compound represented by the above general formula has an average molecular weight of 1,000 to 4,000, and the content of the caprolactone ester component is 30% by weight or more.

The average molecular weight is determined by adding the esterification reagent consisting of acetic anhydride and pyridine to the polycaprolactone ester, acetylating it at a specified reaction temperature and for a certain time, and neutralizing the amount of potassium hydroxide required to neutralize the acetic acid produced. Shows the value when the terminal OH group is quantified and the number average molecular weight is measured.

In order to produce this polycaprolactone ester, the same or different caprolactone compounds 2
One mole of the polymerization initiator is added to 35 moles,
The polycaprolactone ester having an average molecular weight of 1,000 to 4,000 is obtained by ring-opening addition polymerization at 0 to 300 ° C. Examples of the polymerization initiator include -OH group, -N
Examples of the organic compound include two or more active hydrogens such as an H ₂ group or a —SH group.

The caprolactone compound for forming the caprolactone ring-cleaving residue of the above general formula is a compound having a 3- to 7-membered ring and having 6 carbon atoms. Those to which a lower alkyl group such as a methyl group or an ethyl group is bonded are also included.

Specific examples are shown below.

[0129]

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[0130]

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Examples of the polymerization initiator for forming the linking group R in the above general formula include the following compound examples.

[0132]

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[0133]

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[0134]

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[0135] Commercially available polycaprolactone esters advantageously used in the cleaning blade according to the present invention include, for example, those having the following trade names.

"NIAXPCP 0240" (manufactured by Union Carbide) "CATA 220" (manufactured by Rapolde) "ODX 640" (manufactured by Dainippon Ink and Chemicals) It reacts to form urethane rubber, which is the material of the cleaning blade according to the present invention. Here, as the polyisocyanate, for example, the following can be mentioned as preferable ones.

[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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The following are specific examples of the curing agent.

[0143]

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[0144]

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The method for producing the cleaning blade composed of the above polycaprolactone ester or the like is not particularly limited, but for example, the following method can be mentioned.

That is, the dehydrated polycaprolactone ester and polyisocyanate are mixed and reacted at a temperature of 70 to 150 ° C. for 10 to 120 minutes to prepare a urethane prepolymer. And a liquid rubber composition by adding a curing agent in such a ratio that the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups and / or amino groups by the polyester and the curing agent becomes 1.00 to 1.30. Making,
This rubber composition is poured into a centrifugal casting machine kept at a temperature of 140 ° C., for example. Then, the film is stretched to a uniform thickness on the inner surface of the rotor by the centrifugal force rotated at a high speed to form a cylindrical film. Thereafter, a cross-linking reaction by the curing agent proceeds and is solidified to form a urethane rubber.

In the present invention, the elastic blade preferably has a pressing force of 15 to 25 g / cm when used, and has a physical property of a hardness of 60 to 9 measured according to JIS K 6301.
It is preferable that the material has 0 °, a tensile strength of 250 kg / cm ² or more, and a rebound resilience of 20 kg / cm ² or more. Preferably, it has a tensile strength of 250 to 800 kg / cm ² , more preferably 300 to 600 kg / cm ² , and a rebound resilience of 20 to 800 kg / cm ² .
-100 kg / cm ² , more preferably 30-90 kg
/ Cm ² .

A preferable fixing method used in the present invention is a hot roll fixing method.

In this fixing method, in many cases, a heat source is provided inside a metal cylinder made of iron, aluminum, or the like whose surface is coated with tetrafluoroethylene or polytetrafluoroethylene-perfluoroalkoxyvinyl ether copolymer. It is formed of a roller and a lower roller formed of silicone rubber or the like. As a heat source, a linear heater was used, and the surface temperature of the upper roller was set to 1
Heating to about 20 to 200 ° C. is a typical example. In the fixing section, pressure is applied between the upper roller and the lower roller to deform the lower roller and form a so-called nip. The nip width is 1 to 10 mm, preferably 1.5
７7 mm. The fixing linear velocity is 40 mm / sec to 400
mm / sec is preferred. When the nip is narrow, heat cannot be uniformly applied to the toner, causing uneven fixing. On the other hand, if the nip width is wide, the melting of the resin is promoted, and a problem occurs in that the fixing offset becomes excessive.

A fixing cleaning mechanism may be provided for use. As this method, a method in which a silicone oil is supplied to a roller or a film after fixing, or a method in which a silicone oil-impregnated pad, roller, web or the like is used for cleaning can be used.

[0151]

Next, the embodiments of the present invention and the effects thereof will be described specifically, but the present invention is not limited to these embodiments.

(Production Example of Colored Particle 1: Example of Emulsion Polymerization Method) n
-0.90 kg of sodium dodecyl sulfate and 10.0 of pure water
and dissolve with stirring. To this solution, add Regal 330R
(Cabot Co., Ltd. carbon black) 1.20 kg was gradually added, and the mixture was stirred well for 1 hour, and then continuously dispersed for 20 hours using a sand grinder (medium type disperser).
This is referred to as “colorant dispersion liquid 1”. A solution composed of 0.055 kg of sodium dodecylbenzenesulfonate and 4.0 l of ion-exchanged water is referred to as “anionic surfactant solution A”.

0.014 kg of a 10 mol adduct of nonylphenol polyethylene oxide and 4.0 l of ion-exchanged water
Is referred to as “nonionic surfactant solution B”.
223.8 g of potassium persulfate was added to 12.0 l of deionized water.
Is referred to as "initiator solution C".

A 100-liter GL (glass-lined) reactor equipped with a temperature sensor, a cooling pipe,
3.41 kg of AX emulsion (polypropylene emulsion having a number average molecular weight of 3000: number average primary particle diameter = 120 nm / solid concentration = 29.9%), the entire amount of “anionic surfactant solution A” and “nonionic surfactant solution B” Add the whole amount and start stirring. Next, ion-exchanged water 4
Add 4.0 l.

Heating was started, and when the liquid temperature reached 75 ° C., the entire amount of “initiator solution C” was added dropwise. Then, while controlling the liquid temperature to 75 ° C. ± 1 ° C., the styrene 1
2.1 kg, n-butyl acrylate 2.88 kg, methacrylic acid 1.04 kg and t-dodecyl mercaptan 54
8 g are added dropwise. After the completion of the dropwise addition, the temperature of the solution was raised to 80 ° C. ± 1 ° C., and the mixture was heated and stirred for 6 hours. Next, the liquid temperature was cooled to 40 ° C. or less, stirring was stopped, and the mixture was filtered with a pole filter to obtain “latex-A”.

The glass transition temperature of the resin particles in latex-A is 57 ° C., the softening point is 121 ° C., and the molecular weight distribution is as follows: weight average molecular weight = 12.7 million, weight average particle diameter is 12
It was 0 nm.

A solution obtained by dissolving 0.055 kg of sodium dodecylbenzenesulfonate in 4.0 l of ion-exchanged pure water is referred to as “anionic surfactant solution D”. Also,
A solution obtained by dissolving 0.014 kg of nonylphenol polyethylene oxide 10 mol adduct in 4.0 l of ion-exchanged water is referred to as “nonionic surfactant solution E”.

Potassium persulfate (manufactured by Kanto Chemical Co.) 200.
A solution obtained by dissolving 7 g in 12.0 l of ion-exchanged water is referred to as "initiator solution F".

WAX emulsion (polypropylene emulsion having a number average molecular weight of 3000: number average primary particle diameter: 120 nm / solid content: 29.9) was placed in a 100-liter GL reactor equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a comb baffle. %), 3.41 kg, the whole amount of “anionic surfactant solution D” and the whole amount of “nonionic surfactant solution E” are added, and stirring is started. Then, ion-exchanged water 44.0
1 is input. Heating is started, and when the liquid temperature reaches 70 ° C., “Initiator solution F” is added. Then, 11.0 kg of styrene and 4.00 kg of n-butyl acrylate
And 1.04 kg of methacrylic acid and 9.02 g of t-dodecylmercaptan are added dropwise.
After completion of the dropwise addition, the mixture was heated and stirred for 6 hours while controlling the liquid temperature at 72 ° C. ± 2 ° C. Further, the liquid temperature was raised to 80 ° C. ± 2 ° C., and the mixture was heated and stirred for 12 hours. The liquid temperature is cooled to 40 ° C. or less, and the stirring is stopped. Filter with a pole filter,
This filtrate was designated as "latex-B".

The glass transition temperature of the resin particles in Latex-B was 58 ° C., the softening point was 132 ° C., and the molecular weight distribution was weight average molecular weight = 245,000 and weight average particle size was 11
It was 0 nm.

Sodium chloride 5.36k as salting-out agent
g in 20.0 l of ion-exchanged water is referred to as "sodium chloride solution G".

A solution obtained by dissolving 1.00 g of a fluorine-based nonionic surfactant in 1.00 l of ion-exchanged water is referred to as "nonionic surfactant solution H".

Temperature sensor, cooling pipe, nitrogen introduction device, 1
In a 00 l SUS reaction vessel, 20.0 kg of the latex-A prepared above, 5.2 kg of latex-B, 0.4 kg of colorant dispersion 1 and 20.0 k of ion-exchanged water were prepared.
g and stirred. Then, the mixture was heated to 40 ° C., and sodium chloride solution G and isopropanol (manufactured by Kanto Chemical Co., Ltd.)
6.00 kg of nonionic surfactant solution H are added in this order. Then, after leaving it to stand for 10 minutes, the temperature is started to rise to a liquid temperature of 85 ° C. in 60 minutes. Liquid temperature 85 ° C
Heat and stir at ± 2 ° C. for 6 hours for salting out / fusion. Thereafter, the mixture is cooled to 40 ° C. or lower and the stirring is stopped. Aperture 45
The solution is filtered through a sieve of μm, and this filtrate is used as an association liquid. Next, non-spherical particles in the form of a wet cake were collected by filtration from the associated liquid using a Nutsche. Thereafter, the substrate was washed with ion-exchanged water.

The non-spherical particles were dried using a flash jet drier and a fluidized bed drier to adjust the amount of various residual solvents. The volume average particle size of the obtained colored particles was 6.5 μm.

(Production Example 2 of Colored Particles: Example of Emulsion Polymerization Method) In Production Example 1 of colored particles, the reaction temperature for producing latex-A was 80 ° C., and dodecylmercaptan was used for producing latex-B. Colored particles were produced in the same manner except that they were not used. The volume average particle size of the obtained colored particles was 6.6 μm.

(Colored Particle Production Example 3: Example of Emulsion Polymerization Method) Colored particles were produced in the same manner as in Colored Particle Production Example 1, except that the amount of dodecyl mercaptan used in producing Latex-A was 274 g. did. The volume average particle size of the obtained colored particles was 6.4 μm.

(Colored Particle Production Example 4: Example of Emulsion Polymerization Method) In the colored particle production example 1, magnetic powder (spherical magnetite: number average primary particle diameter = 210 nm) was used instead of carbon black as the coloring agent. Colored particles were obtained in the same manner except that 0 kg was used. Its volume average particle size is 6.3 μm
Met.

(Coloring Particle Production Example 5: Example of Emulsion Polymerization Method) In Coloring Particle Production Example 2, magnetic powder (spherical magnetite: number average primary particle size = 210 nm) was used instead of carbon black as the coloring agent. Colored particles were obtained in the same manner except that 0 kg was used. Its volume average particle size is 6.3 μm
Met.

(Coloring Particle Production Example 6: Example of Emulsion Polymerization Method) In Coloring Particle Production Example 3, a magnetic powder (spherical magnetite: number average primary particle diameter = 210 nm) was used instead of carbon black as the coloring agent. Colored particles were obtained in the same manner except that 0 kg was used. Its volume average particle size is 6.3 μm
Met.

(Production Example 7 of Colored Particles: Example of Suspension Polymerization Method) Styrene = 165 g, n-butyl acrylate = 35 g,
Carbon black = 10 g, metal di-t-butylsalicylate = 2 g, styrene-methacrylic acid copolymer =
8 g and paraffin wax (mp = 70 ° C.) = 20 g were heated to 60 ° C. and uniformly dissolved and dispersed at 12,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 10 g of 2'-azobis (2,4-valeronitrile) was added and dissolved to prepare a polymerizable monomer composition. Then, 450 g of a 0.1 M sodium phosphate aqueous solution was added to 710 g of ion-exchanged water, and the mixture was stirred at 13000 rpm with a TK homomixer for 1.0 g.
68 g of M calcium chloride was gradually added to prepare a suspension in which tricalcium phosphate was dispersed. The polymerizable monomer composition was added to the suspension, and the suspension was added to a TK homomixer.
The mixture was stirred at 000 rpm for 20 minutes to granulate the polymerizable monomer composition. After reacting at 80 ° C. for 10 hours, tricalcium phosphate was dissolved and removed with hydrochloric acid, and then filtered and washed, and dried under various drying conditions in the same manner as in Production Example 1 to reduce the amount of residual solvent. Controlled. This had a volume average particle size of 6.9 μm.

(Production Example 8 of Colored Particles: Example of Suspension Polymerization Method) In Production Example 7 of colored particles, 5 g of dodecyl mercaptan was used.
Colored particles were obtained in the same manner except that 2 g of ethylene glycol dimethacrylate was added. The volume average particle size of the obtained colored particles was 6.8 μm.

(Colored Particle Production Example 9: Example of Suspension Polymerization Method) Colored particles were obtained in the same manner as in Colored Particle Production Example 7, except that the polymerization reaction temperature was 70 ° C. In addition, the volume average particle diameter of the obtained colored particles was 6.7 μm.

(Production Example 10 of Colored Particles: Example of Suspension Polymerization Method)
Colored particles were obtained in the same manner as in Colored Particle Production Example 7, except that 120 g of magnetic powder (spherical magnetite: number average primary particle size = 210 nm) was used instead of carbon black as a coloring agent. This had a volume average particle size of 6.7 μm.

(Coloring Particle Production Example 11: Example of Suspension Polymerization Method)
Colored particles were obtained in the same manner as in Colored Particle Production Example 8, except that 120 g of magnetic powder (spherical magnetite: number average primary particle size = 210 nm) was used instead of carbon black as a coloring agent. This had a volume average particle size of 6.7 μm.

(Coloring Particle Production Example 12: Example of Suspension Polymerization Method)
Colored particles were obtained in the same manner as in Colored Particle Production Example 9 except that 120 g of magnetic powder (spherical magnetite: number average primary particle size = 210 nm) was used instead of carbon black as the colorant. This had a volume average particle size of 6.7 μm.

The following table shows the molecular weight and glass transition temperature of the resin corresponding to the production examples obtained above.

[0177]

[Table 1]

Even when the following drying conditions and the like are changed, the above physical properties do not greatly change.

[0179]

[Table 2]

[0180]

[Table 3]

Production Example of Photoconductor A 1.5 parts by weight of a polyamide resin (Amilan CM-8000: manufactured by Toray Industries, Ltd.) was dissolved in a mixed solvent of 90 parts by volume of methanol and 10 parts by volume of butanol on an aluminum drum having a diameter of 60 mm. The coating solution was dip coated to a film thickness of 0.23.
A μm intermediate layer was formed. Then, 0.8 parts by weight of polyvinyl butyral (S-LEC BL-S: manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 100 parts by weight of methyl isopropyl ketone,
A coating solution obtained by mixing and dispersing 2 parts by weight of titanyl phthalocyanine in the obtained solution was applied onto the intermediate layer by dip coating to form a charge generating layer having a thickness of 0.2 μm after drying. Then, as a polycarbonate, 20 parts by weight of BPZ (viscosity average molecular weight = 30,000) and a charge transport material (T-9)
A coating solution obtained by dissolving 15 parts by weight and 100 parts by volume of 1,2-dichloroethane was applied onto the charge generation layer by dip coating to form a first charge transport layer (CTL) having a thickness of 25 μm after drying. . Then, a coating solution prepared by dissolving 6 parts by weight of BPZ (viscosity average molecular weight = 80,000) in 100 parts by volume of 1,2-dichloroethane was used as a polycarbonate on the first charge transport layer by using a circular amount control coating machine. And a second charge transport layer (CT) having a thickness of 1 μm after drying.
L) was formed.

Production Example of Photoreceptor B In the production example of Photoreceptor A, polycarbonate was used for the second charge transport layer, and the viscosity average molecular weight of BPZ was 180,
A photoreceptor was manufactured in the same manner except that the number was changed to 000.

Production Example of Photoreceptor C In the production example of Photoreceptor A, polycarbonate was used for the first charge transport layer from BPZ to BPPC (viscosity average molecular weight = 32,000), and for the second charge transport layer. BPZ
Was changed to BPPC (viscosity average molecular weight = 120,000) to produce a photoreceptor in the same manner.

Production Example of Photoreceptor D A photoreceptor was produced in the same manner as in Production Example of Photoreceptor A, except that the second charge transport layer was not applied.

Using the photoreceptors A to D described above, various drying conditions were changed to prepare photoreceptors having different residual solvents.

[0186]

[Table 4]

The glass transition temperature of the CTL is the value measured by DSC, and the intersection of the baseline and the slope of the endothermic peak is defined as the glass transition point. Specifically, using a differential scanning calorimeter, the temperature was raised to 200 ° C., left at that temperature for 3 minutes, and then dropped to 10 ° C./mi.
Cool to room temperature with n. Next, when this sample was measured at a heating rate of 10 ° C./min, an extension of the baseline below the glass transition point and a tangent showing the maximum slope from the rising portion of the peak to the peak of the peak. The intersection is indicated as the glass transition point. Specifically, it was measured using DSC-7 manufactured by PerkinElmer.

External additives shown separately were added to the colored particles 1 to 40, and mixed with a Henschel mixer to prepare a toner.

[0189]

[Table 5]

[0190]

[Table 6]

* Silica A: number average primary particle diameter = 12 nm
/ Hexamethyldisilazane treatment / hydrophobicity = 69 * Silica B: number average primary particle size = 12 nm / dimethyl silicone oil treatment / hydrophobicity = 68 * Silica C: number average primary particle size = 10 nm / dichlorodimethylsilane treatment / Titania A: number-average primary particle size = 25 nm / octyltrimethoxysilane treatment / hydrophobicity = 64 * Titania B: number-average primary particle size = 35 nm / hexyltrimethoxysilane treatment / hydrophobicity = 68 * titania C: number average primary particle size = 20 nm / zinc stearate treatment / hydrophobization degree = 58 evaluation (contact development method: two-component development) A silicone resin was used for these toners 1 to 10 and 21 to 30. A two-component developer having a toner concentration of 7% by weight was prepared by mixing with a coated ferrite carrier having a volume average particle diameter of 60 μm. . Using the developer prepared here,
The actual photographing evaluation was performed using a digital copying machine Konica 7060 manufactured by Konica Corporation. The conditions are as shown below. As the photoreceptor, a laminated organic photoreceptor having the above configuration was used.

Developing conditions DC bias; -500 V Dsd (distance between photosensitive member and developing sleeve); 600 μm Developer layer regulation: Magnetic H-Cut system Developer layer thickness: 700 μm Developing sleeve diameter: 40 mm Also remaining on the photosensitive member The untransferred toner has a thickness of 3.0 mm
A cleaning method using a urethane rubber blade was adopted. The angle formed between the blade and the photoconductor was 45 °.

The urethane rubber blade is A-5.
Ε-caprolactone obtained by polymerizing ethylene glycol with ethylene glycol having a caprolactone content of 98% by weight and an average molecular weight of 2,500.
After reacting for 0 minutes, 1,4 butanediol as a cross-linking agent was further added and reacted at 120 ° C., and further charged into a centrifugal casting machine, and reacted at 140 ° C. for 80 minutes while rotating at 1000 rpm. used. JIS
K6301 is the hardness 70 ° measured with a tensile strength of 393kg / cm ^2, the rebound resilience is 52kg / cm ^2. Further, the pressing force was 18 g / cm. When the toners 19 to 27 are used, cleaning may not be completely performed by blade cleaning.
Before the blade cleaning, a fur brush was installed to improve the cleaning property before use.

The image support to be used has a continuous weight of 55 k
g of plain paper was used to form an image in the horizontal direction. Also,
Image forming conditions include a low temperature and low humidity environment (10 ° C., 15% R
H) and a high-temperature and high-humidity environment (30 ° C., 80% RH) were used to evaluate printing using the above developer.
Printing was performed continuously using a halftone image in which a one-dot image was formed at two-dot intervals, and a total of 50,000 sheets were printed.

The image after 50,000 sheets (50 kc) was visually checked for image defects. The criteria are as follows.

A: No image defect B: Less than 5 black spots having a diameter of 0.5 mm or less exist in the solid white image C: 5 or more black spots having a diameter of 0.5 mm or less exist in the solid white image D: Five or more black spots with a diameter of 0.5 mm or less are present in the solid white image, and black spots with a diameter of 0.5 mm or more are also present. The surface of the photoreceptor was observed, and the surface condition and the image were evaluated.

A defect: A thin filmed material which does not become an image defect is formed on the surface of the organic photoreceptor. B defect: A filmed material is formed on the surface of the organic photoreceptor.
Streak-like defects are thinly formed on the image. C defect: Image defects on the streaks are formed on the image. The image quality was evaluated by comparing the image density and the fog density. The image density was compared with the absolute reflection density using RD-918 manufactured by Macbeth. Fog was compared by relative reflection density where the density of paper was "0".

(Evaluation of high temperature and high humidity environment)

[0199]

[Table 7]

[0200]

[Table 8]

(Evaluation of low temperature and low humidity environment)

[0202]

[Table 9]

[0203]

[Table 10]

Evaluation (Non-Contact Developing Method: Magnetic One-Component Development) Using toners 11 to 20 and toners 31 to 40, evaluation was performed in magnetic one-component development.

Using the developer prepared as described above, a digital copying machine Konica 7050 manufactured by Konica Corporation was remodeled and changed to magnetic one-component development to evaluate a real image. The conditions are as shown below. A laminated organic photoreceptor was used as the photoreceptor.

Charger: Scorotron Charged voltage: photosensitive member charging potential (initial charging potential) 720 V Development condition DC bias: -500 V AC bias: Vpp = 1800 V, frequency = 20 k
Hz Dsd (distance between photoreceptor and developing sleeve); 600 μm Developer layer regulation; magnetic H-Cut method Developer layer thickness: 300 μm Developing sleeve diameter: 40 mm (with phenol resin coating with conductive carbon black dispersed on the surface) The untransferred toner remaining on the photoconductor has a thickness of 3.0 mm.
A cleaning method using a urethane rubber blade was adopted. The angle formed between the blade and the photoconductor was 45 °.

The urethane rubber blade is A-5.
Ε-caprolactone polymerized with ethylene glycol and having a caprolactone content of 99% by weight and an average molecular weight of 3900, ginphenylmethane diisocyanate as an isocyanate,
After reacting for 0 minutes, 1,4 butanediol as a cross-linking agent was further added and reacted at 120 ° C., and further charged into a centrifugal casting machine, and reacted at 140 ° C. for 80 minutes while rotating at 1000 rpm. used. JIS
The hardness measured by K6301 is 65 °, the tensile strength is 374 kg / cm ² , and the rebound resilience is 55 kg / cm ² . Further, the pressing force was 18 g / cm. When the toners 28 to 36 are used, cleaning may not be completely performed by blade cleaning.
Before the blade cleaning, a fur brush was installed to improve the cleaning property before use.

The image support to be used has a continuous weight of 55 k
g of plain paper was used to form an image in the horizontal direction. Also,
Image forming conditions include a low temperature and low humidity environment (10 ° C., 15% R
H) and a high-temperature and high-humidity environment (30 ° C., 80% RH) were used to evaluate printing using the above developer.
Printing is performed continuously using a halftone image in which a one-dot image is formed at two-dot intervals.
Zero printing was performed.

The image after 50,000 sheets (50 kc) was visually inspected for image defects. The criteria are as follows.

A: No image defect B: Less than 5 black spots having a diameter of 0.5 mm or less exist in a solid white image C: Five or more black spots having a diameter of 0.5 mm or less exist in a solid white image D: Five or more black spots with a diameter of 0.5 mm or less are present in the solid white image, and black spots with a diameter of 0.5 mm or more are also present. The surface of the photoreceptor was observed, and the surface condition and the image were evaluated.

A: No image defect.

B: Less than 5 black spots having a diameter of 0.5 mm or less are present in a solid white image. C: 5 or more black spots having a diameter of 0.5 mm or less are present in a solid white image. D: 0.5 mm diameter or less. There are 5 or more black spots in the solid white image, and there are also black spots with a diameter of 0.5 mm or more (high temperature and high humidity environment evaluation)

[0213]

[Table 11]

[0214]

[Table 12]

(Evaluation of low temperature and low humidity environment)

[0216]

[Table 13]

[0219]

[Table 14]

As is clear from the characteristics shown in Tables 7 to 14, only those within the scope of the present invention have good characteristics.

[0219]

As shown in the above embodiments, according to the present invention, in an image forming method having a toner having a reduced particle size, an organic photoreceptor, and a mechanism for cleaning the toner from the photoreceptor, the environment is improved. Can be provided even over a long period of time.

[Brief description of the drawings]

FIG. 1 is a diagram showing a preferred configuration of an organic photoconductor of the present invention.

FIG. 2 is a structural sectional view of an example of a flash dryer that can be used in the present invention.

FIG. 3 is a cross-sectional view of a vibrating fluidized drying apparatus that can be used in the present invention.

FIG. 4 is a cross-sectional view of a vibrating fluidized drying apparatus that can be used in the present invention.

FIG. 5 is a sectional view of the configuration of a developing device according to the present invention.

FIG. 6 is a sectional view of another configuration of the developing device according to the present invention.

FIG. 7 is a sectional view of still another configuration of the developing device according to the present invention.

FIG. 8 is a sectional view of the configuration of a cleaning mechanism according to the present invention.

FIG. 9 is a sectional view of an elastic blade of the cleaning mechanism according to the present invention.

FIG. 10 is a diagram illustrating an intersection angle α in cleaning according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Conductive support 2 Intermediate layer 3 Charge transport layer (CTL) 4 Charge generation layer (CGL) 5 Protective layer 6 Photosensitive layer 11 Dryer main body 12 Water-containing cake input port 13 Nozzle 14 Recovery nozzle 15 Dry powder (colored particles) 16A Drying area 16B Up-stack area 16C Classification area 17 Hot air supply unit 18 Hot air inlet 20 Vibration motor (vibrator) 21 Drying chamber bottom 22 Gas inlet 23 Gas plate 23 for rectifying gas 24 Drying chamber 26 Exhaust port 28 Input Port 29 discharge port 31 photosensitive drum 38 developing sleeve 41 elastic blade 43 holder

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Makoto Kono 2970 Ishikawacho, Hachioji-shi, Tokyo Konica Corporation F-term (reference) 2H005 AA15 AB06 DA07 EA05 EA07 2H034 BF00 2H068 EA16 FC08 FC15

Claims (4)

[Claims] 1. A mechanism for developing an electrostatic latent image formed on an organic photoreceptor with toner, transferring the formed toner image onto an image forming support, and cleaning the toner remaining on the organic photoreceptor. In the image forming method, the amount of the organic solvent remaining in the organic photoreceptor is 0.1 to 2.0% by weight,
An image forming method, wherein the toner has a volume average particle size of 3 to 9 μm, and the amount of the polymerizable monomer remaining in the toner is 0.05 to 2.5% by weight. 2. The image forming method according to claim 1, wherein
The amount of the organic solvent remaining in the organic photoreceptor is 0.3 to 1.8% by weight, and the amount of the polymerizable monomer remaining in the toner is 0.1 to 2.0% by weight. Image forming method. 3. The image forming method according to claim 1, wherein
An image forming method, wherein the cleaning mechanism is a blade cleaning method. 4. The image forming method according to claim 1, wherein
The arithmetic mean value of the shape factor of the toner represented by the following formula is 1.
Within a range of 3 to 2.2 and a shape factor of 1.5 to
An image forming method, wherein the number of toner particles in the range of 2.0 is at least 80% by number. Shape factor = ((maximum diameter / 2) ² × π) / projected area