JPH08305158A - Developer carrier and developing device - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a developer carrier in which the developer on the developer carrier has a stable and appropriate electric charge, and which is capable of obtaining a uniform and high-quality image without density unevenness. thing. In a developing sleeve used in a developing device for developing a latent image formed on a latent image holding member with a developer carried and carried by a developing sleeve, the developing sleeve has at least a metal on its substrate. Phosphorus chalcogenide 1
A developing sleeve having a coating layer made of a resin containing one kind or two or more kinds, and a developing device having the developing sleeve.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer for developing a latent image formed on an image bearing member such as an electrophotographic photosensitive member or an electrostatic recording dielectric in the electrophotographic method to visualize the latent image. The present invention relates to a carrier (hereinafter referred to as a developing sleeve) and a developing device using the developing sleeve.

[0002]

2. Description of the Related Art Conventionally, a number of electrophotographic methods are known, but generally, a photoconductive material is used to form an electric latent image on a photoconductor by various means, and then the electrophotographic image is formed. The latent image is developed with toner to form a visible image, and the toner image is transferred to a transfer material such as paper, if necessary, and then the toner image is fixed on the transfer material by heat and / or pressure to make a copy. Is what you get.

In recent years, in addition to conventional copying machines, there have been many printers, facsimile machines, and the like using electrophotographic methods. Particularly in printers and facsimiles, a developing device using one-component toner is often used because it is necessary to reduce the size of the copying device.

Unlike the two-component system, the one-component developing system does not require carrier particles such as glass beads or iron powder, and therefore the developing device itself can be made compact and lightweight. Further, in the two-component developing method, it is necessary to keep the toner concentration in the developer constant, so that a device for detecting the toner concentration and supplying a required amount of toner is required. Therefore, also in this case, the developing device becomes large and heavy. The one-component developing method does not require such an apparatus and is preferable because it can be made small and light.

In addition, LED and LBP printers have become the mainstream of the market in recent years as a printer device, and the direction of technology is higher resolution, that is, 400, 600, 800 dpi instead of 240, 300 dpi in the past. It is coming. Therefore, the developing system is also required to have higher definition.

[0006] Further, the copying machine is also highly functionalized, and for this reason, it is being advanced to the digitalization. In this direction, the method of forming an electrostatic charge image by a laser is mainly used, and therefore, it is also advancing toward high resolution, and here also, as with a printer, a high resolution and high definition developing method is required. JP-A-1-112253 and JP-A-2
A toner having a small particle size is proposed in Japanese Patent Publication No.-284158.

For example, in a developing device for developing an electrostatic latent image formed on the surface of a photosensitive drum as an image bearing member with a magnetic toner of a one-component type developer, friction between magnetic toner particles and magnetic force between the developing sleeve and the magnetic toner particles. By the friction of the toner particles,
An electrostatic latent image charge on the photosensitive drum and an electric charge having a polarity opposite to the developing reference potential are applied to the magnetic toner particles, and the magnetic toner is applied to the developing sleeve in an extremely thin manner so that the photosensitive drum and the developing sleeve face each other. It is known that an electrostatic latent image is visualized as a toner image by the action of a magnetic field of a magnet that is conveyed to an area and is fixedly installed in the developing sleeve in the developing area.

However, in the above conventional developing device, the developer particles (hereinafter referred to as toner) coated on the developing sleeve and the charge amount (while the developing sleeve is repeatedly rotated with the continuous development). Tribo) becomes too high, and toner is transferred from the developing sleeve to the image carrier (drum).
A so-called charge-up phenomenon, which makes it difficult to move to the upper latent image, is likely to occur particularly in low humidity. When such a charge-up occurs, the amount of toner developed decreases, so that the line image becomes thin in the line image and the solid image becomes an image in which the image density is low.

Further, a position where a solid image having a high image density is once developed on the developing sleeve comes to the same position at the next rotation of the developing sleeve, and when the halftone image is developed there, the solid image is formed on the halftone image. The phenomenon in which the mark of “I” appears, that is, a so-called sleeve ghost phenomenon is likely to occur.

As a method of solving such a phenomenon, instead of the conventional developing sleeve of a metal cylindrical tube, Japanese Unexamined Patent Publication (Kokai) No. Hei.
As described in Japanese Patent Application Laid-Open No. 105181 and Japanese Patent Application Laid-Open No. 3-36570, a method of forming a resin coating film made of a resin, conductive fine powder, a solid lubricant or the like on the surface of a metal cylindrical tube and using it in a developing device is known. Proposed. By using this method, the toner carried on the developing sleeve can be provided with sufficient tribo for development, the tribo distribution of the toner is stabilized, and it is possible to suppress charge-up and sleeve ghost.

As a developing roller (developing sleeve) which has been generally put into practical use, a cylindrical metal tube made of aluminum, stainless steel or the like and a magnet as a magnetic field generating means arranged inside the cylindrical tube are used. The magnet is often used in the form of a magnet roll. In many cases, the surface of the metal cylindrical tube is appropriately roughened by means such as sand blasting or sanding to improve the toner carrying force.

However, in such a developing sleeve, various problems such as toner coat unevenness, poor coating, ghost, and density decrease may occur depending on the environmental conditions, the physical properties of the toner, the condition of the surface of the developing sleeve, and the like.
For example, as the developing sleeve repeatedly rotates, the charge amount (tribo) of the toner coated on the developing sleeve becomes too high due to the contact with the developing sleeve, and the toner has a mirror image with the surface of the developing sleeve. Due to this, a so-called charge-up phenomenon, in which the toner becomes immobile on the surface of the developing sleeve and does not move from the developing sleeve to the latent image on the latent image carrier (drum), is apt to occur particularly under low humidity. When such a charge-up occurs, the toner in the upper layer is less likely to have tribo, and the developing amount of the toner is reduced, so that an image in which the line image is thinned or the solid black image has a low image density is generated.

Further, since the toner layer forming states of the image portion (toner consuming portion) and the non-image portion are changed and the charging states are different, the position where the solid image having a high image density is once developed is the developing sleeve. When the halftone image is developed at the developing position at the next rotation and the halftone image is developed, a phenomenon that a trace of a solid image appears on the image, a so-called sleeve ghost phenomenon easily occurs.

Recently, in order to improve the image quality of electrophotography,
The toner has a small particle size and fine particles. In order to increase the resolution and sharpness and faithfully reproduce the latent image,
It is general to use a toner having a weight average particle diameter of about 6 to 7 μm. Furthermore, the fixing temperature of the toner tends to be lowered for the purpose of shortening the first copy time and saving power. In such a situation, the toner is more likely to be electrostatically attached to the developing sleeve, and the external physical force is applied to the developing sleeve, so that the developing sleeve surface is apt to be contaminated or the toner is fused.

As a method for solving such a phenomenon, instead of the conventional metal cylindrical tube developing sleeve, Japanese Unexamined Patent Publication (Kokai) No. 2-10 has been proposed.
As described in JP-A-5181 and JP-A-3-36570, there is proposed a method in which a resin coating film made of resin, conductive fine powder, solid lubricant, etc. is formed on the surface of a metal cylindrical tube and used in a developing device. ing.

However, in the above method, when the toner used is easily charged up, a resin coating containing a large amount of conductive fine powder, solid lubricant, etc. in the resin is formed on the surface of the metal cylindrical tube. As a result, the strength of the resin coating on the surface of the developing sleeve decreases, and when used for a long period of time, the resin coating layer on the surface of the developing sleeve is liable to be scraped or peeled off, which may cause a problem.
Also, when a resin coating film containing a large amount of conductive fine powder, solid lubricant, etc. in the resin is formed on the surface of the metal cylindrical tube, the charge imparting property to the toner becomes insufficient under high temperature and high humidity environment. In some cases, a decrease in image density may occur.

[0017]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a developing sleeve which improves lubricity on the surface of the developing sleeve and prevents toner from adhering to the developing sleeve. Another object of the present invention is to provide a developing sleeve with high durability and stable image quality, which does not cause deterioration of the coating on the surface of the developing sleeve or peeling due to repeated copying or durability.

A further object of the present invention is to provide a developing sleeve capable of obtaining a high-quality image in which density reduction and sleeve ghost do not occur for a long period of time even under different environmental conditions. Another object of the present invention is to provide a developing sleeve which reduces uneven charging of the toner layer on the surface of the developing sleeve, which appears when a toner having a small particle size is used, and gives a proper charge amount to the toner. .
Another object of the present invention is to provide a stable and high-quality image by a developing device and an electrophotographic apparatus which are constructed by using the developing sleeve of the present invention.

[0019]

The above object can be achieved by the present invention described below. That is, the present invention relates to a developing sleeve used in a developing device for developing a latent image formed on a latent image holding member with a developer carried and carried by the developing sleeve, the developing sleeve being on a substrate thereof. And a developing sleeve having a coating layer made of a resin containing at least one kind or two or more kinds of metal phosphorus chalcogenide, and a developing device having the developing sleeve.

[0020]

In order to solve the above-mentioned problems, the present inventors have conducted extensive studies and as a result, found that the conductive fine powder, the solid lubricant and other pigments contained in the resin coating on the surface of the developing sleeve were It has been found that it is one of the main causes of these problems, that it is easy to disperse evenly in the resin coating, the strength of the resin coating is not reduced, and even if it is used for a long time in different environments, the toner It was found that an excellent substance capable of properly adjusting the amount of charge of 1 is used. Specifically, it was found that at least one kind or two or more kinds of metal phosphorus chalcogenide should be contained in the resin.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The present invention relates to a developing sleeve having a surface coated with a resin coating containing at least one kind or two or more kinds of metal phosphorus chalcogenide, and using this developing sleeve, a one-component developer carried on the developing sleeve ( A major feature is that the latent image formed on the image carrier (photosensitive drum) is developed with toner. In the resin coating on the surface of the developing sleeve, a conductive agent is preferably added in addition to the above metal phosphorus chalcogenide.

In the present invention, the metal phosphorus chalcogenide has a chalcogen element such as sulfur (S), selenium (Se) and tellurium (Te) in its molecule, and also has phosphorus (P). It also contains metallic elements such as Zn, Mg and Pb.
It was also found that this substance becomes a crystal having a layered structure, and that this substance is a solid lubricant excellent in extreme pressure properties and seizure resistance. Further, in the metal phosphorus chalcogenide having this layered structure, various guests can be inserted (intercalated) between the layers to form an intercalation compound. When the experiment was repeated using various guests focusing on this, the intercalation compound obtained when an alkylamine, an aromatic amine, pyridine or a quaternary alkylammonium salt was used without any measure The most excellent extreme pressure property and seizure resistance were observed in the crystal powder itself.

Next, when further research was carried out, depending on the type of organic matter of the guest, excellent thickening was obtained.
It was also found to have an effect. Therefore, the layered crystal of metal phosphorus chalcogenide or its intercalation compound used in the present invention can be used as a powder as a solid lubricant having excellent extreme pressure properties.

That is, in another preferred embodiment of the present invention, one of the intercalation compounds in which the host layer is a metal phosphorus chalcogenide and the guest is an alkylamine, an aromatic amine, pyridine or a quaternary alkylammonium chloride.
There is provided a developing sleeve having a coating layer made of a resin layer containing 0.1% by weight or more of one kind or two kinds or more, and a developing device having the developing sleeve.

In the present invention, when the content of each of the metal phosphorus chalcogenide and / or the above-mentioned intercalation compound in the coating layer of the developing sleeve is less than 0.1% by weight, the effect of significantly improving lubricity does not appear. The metal phosphorus chalcogenide used in the present invention is a compound represented by the following molecular formula (1), and a metal and phosphorus and a chalcogen element or a metal sulfide, phosphorus and a chalcogen element are heated and reacted by a known method. Can be manufactured. MPX ₃ (1) (M in the molecular formula is a metal element (for example, Mg, Ca, V,
Mn, Fe, Co, Ni, Pb, Zn, Cd, Hg, S
n, Nb, etc., and X is a chalcogen element (S, S
e or Te))

Therefore, specific examples of the metal phosphorus chalcogenide include ZnPS ₃ , ZnPSe ₃ , ZnPTe ₃ and Ni.
PS ₃ , FePSe ₃ , MnPS ₃ , MgPS ₃ , MgPS
e ₃ etc. can be mentioned. Each of these has a layered crystal structure, and a guest can enter between the layers to form an intercalation compound.

In the present invention, examples of the alkylamine used as a guest of the above-mentioned intercalation compound include compounds represented by the following molecular formula (2). (R ₁ , R ₂ and R ₃ represent a hydrogen atom or a linear or branched alkyl group having 1 to 24 carbon atoms)

Specifically, n-butylamine, octylamine, 2-octylamine, dodecylamine, hexadecylamine, octadecylamine, oleylamine,
Examples thereof include N-methyloctadecylamine and N, N-dimethyldioctadecylamine. Examples of aromatic amines include aniline, p-dodecylaniline, N-ethylene-toluidine and the like. Further, pyridine, which is a nitrogen-containing heterocyclic compound, can be exemplified.

In the present invention, examples of the alkyl ammonium chloride used in the intercalation compound include compounds represented by the following molecular formula (3). (Two of _{R 4, R 5, R 6} , R 7 is a straight-chain or branched-chain alkyl group having a methyl group or a C 4-24, remaining two represents a methyl group)

Specifically, trimethylhexadecyl ammonium chloride, trimethyl octadecyl ammonium chloride, dimethyl dioctadecyl ammonium chloride and the like can be mentioned.

The above-mentioned intercalation compound which can be used in the present invention can be obtained by bringing the substance of formula (1) into contact with the substance of formula (2) or the substance of formula (3) to cause a reaction. It is not necessary to specify, but if one example is shown, the substance of the formula (2) or the substance of the formula (3) heated and vaporized under reduced pressure is used as the formula (1).
Gas phase reaction method of contacting and reacting with the substance of (3), mixing method of directly mixing and stirring both of them, heating of them as necessary, pressurizing method of pressurizing and heating if necessary, the substance of formula (2) or (3 ) And the solvent method of reacting with
An alkylamine having a small molecular weight, specifically, n-butylamine is inserted into the substance of the formula (1), and an alkylamine having a large molecular weight, an aromatic amine, pyridine, ammonium chloride is dissolved in a suitable solvent, By adding the previously prepared n-butylamine intercalation compound to the solution, an alkylamine having a large molecular weight,
Aromatic amines, pyridines, alkylammonium chlorides and the like can be intercalated into the substance of formula (1).

Although any of these methods can be used, an amine or ammonium compound, which is easily denatured by heating and hardly vaporized, is used as a guest to prevent the solvent from adsorbing and adversely affecting. If the mixed method,
It is desirable to use a pressure method without heating. Equation (1)
The reaction amount of the substance of the formula (2) or the substance of the formula (3) with respect to the substance is generally in the range of 0.1 to 5 mol.

Next, the binder resin used for forming the resin film is, for example, a styrene resin, a vinyl resin, a polyether sulfone resin, a polycarbonate resin, a polyphenylene oxide resin, a polyamide resin, a fluororesin, a fibrous resin, Thermoplastic resin such as acrylic resin;
A thermosetting resin such as an epoxy resin, a polyester resin, an alkyd resin, a phenol resin, a melamine resin, a polyurethane resin, a urea resin, a silicone resin or a polyimide resin; or a photocurable resin can be used. Among them, those with releasability such as silicone resin and fluororesin,
More preferred are those having excellent mechanical properties such as polyether sulfone, polycarbonate, polyphenylene oxide, polyamide, phenol resin, polyester, polyurethane and styrene resin.

The amount of the metal phosphorus chalcogenide added in the present invention is 1 to 100% by weight based on the weight of the binder resin.
Particularly preferable results are given in the range. If the addition amount is less than 1% by weight, the effect of adding the metal phosphorus chalcogenide is small, and the toner cannot be appropriately charged. If the amount added exceeds 200% by weight, the mechanical strength of the resin coating formed on the developing sleeve may deteriorate.

In the present invention, the resin coating layer is formed on the substrate of the developing sleeve by using the above materials. As a substrate to be used, a substrate used in a conventional developing sleeve, for example, a cylindrical shape made of aluminum stainless steel or nickel is preferably used. The above-mentioned resin coating layer is preferably formed by a coating method, and the coating liquid used for the coating is a suitable solvent for each of the above components, for example, methanol, isopropyl alcohol, toluene, N-methylpyrrolidone, normal hexane, It is prepared by dissolving and dispersing it in MEK, butyl acetate, or a mixed solvent thereof by an appropriate method such as a sand mill, a ball mill, a high speed dissolver or the like.

The composition of the coating liquid is the binder resin 10 described above.
About 1 to 200 parts by weight of metal phosphorus chalcogenide with respect to 0 part by weight.
The range of about 10 to 300 parts by weight of the conductive agent is preferable, the concentration of the solid content of the coating liquid is about 5 to 50% by weight, and the viscosity is about 10 to 1000 mPas.
The range of s is preferable. The method of applying the coating liquid to the substrate is not particularly limited, but, for example, a spray method, a dipping method, a roller coating method, a bar coating method, an electrostatic coating or the like is preferably used. After coating, if necessary, drying, crosslinking and curing treatments are performed.

The thickness of the resin coating formed as described above is
It is usually about 0.1 to 100 μm, preferably about 0.1.
It is in the range of 5 to 50 μm. The volume resistance of the resin coating is usually about 10 ⁻³ to 10 ² Ω · cm, preferably about 10 ⁻¹ to 10 ¹ Ω · cm.

Next, a developing device incorporating a roller having the developing sleeve of the present invention will be described and illustrated. FIG.
Is a diagram showing a conventional developing device, and reference numerals in the drawings have the same meanings as those in FIGS. 2 to 4 are views for explaining a developing device having the developing sleeve of the present invention. In FIG. 2, an image carrier that carries an electrostatic latent image formed by a known process,
For example, the electrophotographic photosensitive drum 1 is rotated in the arrow B direction. The developing sleeve 8 of the developing roller 11 is
By carrying the magnetic toner 4 as the one-component magnetic developer supplied by the hopper 3 and rotating in the direction of arrow A, the toner 4 is conveyed to the developing section D where the developing sleeve 8 and the photosensitive drum 1 face each other. To do.

Inside the developing sleeve 8, a magnet 5 is arranged for magnetically attracting and carrying the magnetic toner 4 on the developing sleeve 8. The developing sleeve 8 has a resin layer 7 coated on the metal cylinder 6. Reference numeral 9 is a gap indicating that the developing sleeve and the magnet are not in contact with each other. The toner 4 rubs against the resin layer 7 on the developing sleeve 8 to obtain a triboelectric charge capable of developing the electrostatic latent image on the photosensitive drum 1. In order to regulate the layer thickness of the magnetic toner 4 conveyed to the developing section D, the regulating blade 2 made of a ferromagnetic metal faces the developing sleeve 8 with a gap width of about 100 to 300 μm from the surface of the developing sleeve. In addition, it is suspended from the hopper 3.

The magnetic lines of force from the magnetic pole N1 of the magnet 5 are concentrated on the blade 2 to form a thin layer of the magnetic toner 4 on the developing sleeve 8. A non-magnetic blade may be used as the blade 2. The thin layer of the magnetic toner 4 formed on the developing sleeve 8 is preferably thinner than the minimum gap between the developing sleeve 8 and the photosensitive drum 1 in the developing section D. The developing sleeve of the present invention is particularly effective for a developing device of the type that develops an electrostatic latent image with such a thin toner layer, that is, a non-contact type developing device. However, the developing sleeve of the present invention is also applicable to a developing device in which the thickness of the toner layer in the developing portion is not less than the minimum gap between the developing sleeve 8 and the photosensitive drum 1, that is, a contact type developing device. Can be done.

The developing sleeve 8 has a bearing 1
In order to fly the magnetic toner 4 which is the component magnetic developer,
A developing bias voltage is applied by the power supply 10. When a direct current voltage is used as the developing bias voltage, the image portion of the electrostatic latent image (the area where the toner 4 is attached and visualized)
It is preferable that a voltage having a value between the potential of 1 and the potential of the background portion is applied to the developing sleeve 8. On the other hand, in order to increase the density of the developed image or improve the gradation, an alternating bias voltage is applied to the developing sleeve 8 to form an oscillating electric field in which the direction is alternately inverted in the developing portion D. Good.

In this case, it is preferable to apply to the developing sleeve 8 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.
Further, in so-called normal development in which toner is visualized by adhering toner to a high potential portion of an electrostatic latent image having a high potential portion and a low potential portion, 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 visualized by adhering toner to the low potential portion of the electrostatic latent image, the toner used is charged to the same polarity as the polarity of the electrostatic latent image. The high potential or the low potential is an absolute value. In any case, the toner 4 is charged by friction with the developing sleeve 8.

FIG. 3 is a block diagram showing another embodiment of the developing device of the present invention, and FIG. 4 is a schematic configuration diagram showing still another embodiment of the developing device of the present invention. In the developing device of FIGS. 3 and 4, as a member for controlling the layer thickness of the magnetic toner 4 on the developing sleeve 8, a material having rubber elasticity such as urethane rubber or silicon rubber, or metal elasticity such as phosphor bronze or stainless steel is used. The elastic plates 20 and 21 made of a material having the above are used. In FIG. 3, the elastic plate 20 is pressed in the direction of the rotation direction of the developing sleeve 8 and the forward direction. In FIG. The feature is that the sleeve 8 is pressed in the opposite direction to the rotating direction.

The other basic structure of the developing device shown in FIGS. 3 and 4 is the same as that of the developing device shown in FIG. 2, and the same symbols indicate basically the same members. 2-4
It is needless to say that there are various forms such as the shape of the container, the presence / absence of the stirring member, and the arrangement of the magnetic poles. Of course, it may be used as a two-component developing device using carrier particles.

Next, the developing sleeve of the present invention or the developer (toner) used to obtain a visible image by the developing device having the developing sleeve will be described. Toners are roughly classified into dry toners and wet toners. However, since wet toners have a large problem of solvent volatilization, currently dry toners are the mainstream. The toner is a fine powder in which a resin, a release agent, a charge control agent, a colorant and the like are melt-kneaded, solidified and then pulverized, and then classified and the like to make the particle size distribution uniform.

As the binder resin used in the toner, generally known resins can be used. For example, styrene,
A homopolymer of styrene such as α-methylstyrene and p-chlorostyrene and a substitution product thereof; a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-
Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer,
Styrene-dimethylaminoethyl copolymer, styrene-
Methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone Styrene-based copolymers such as copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethylmethacrylate, polybutylmethacrylate, Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, tempel resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, paraffin wax, carnauba wax, etc. Alone It can be used in mixing.

Further, the toner may contain a pigment and / or a dye. For example, carbon black, nigrosine dye, lamp black, Sudan black SM, first yellow G, benzidine yellow, pigment
Yellow, India First Orange, Irgadine
Red, paranitroaniline red, toluidine red, carmine FB, permanent Bordeaux FRR,
Pigment Orange R, Resor Red 2G, Rake Red C, Rhodamine FB, Rhodamine B Rake,
Methyl violet red B lake, phthalocyanine blue, pigment blue, brilliant green B,
Phthalocyanine Green, Oil Yellow GG, Pomelo First Yellow CGG, Kayaset Y963, Kayaset YG, Pomelo Fast Orange RR, Oil Scarlet, Orazol Brown B, Pomelo
First scarlet CG, oil pink OP, etc. can be used.

In order to use the toner as a magnetic toner, magnetic powder may be contained in the toner. As such magnetic powder, a substance that is magnetized by being placed in a magnetic field is used, and examples thereof include powders of ferromagnetic metals such as iron, cobalt and nickel, or alloys and compounds such as magnetite, hematite and ferrite. is there. The content of the magnetic powder is preferably 15 to 70% by weight based on the weight of the toner. Further, various releasing agents may be used in the toner, and as such releasing agents, polyfluorinated ethylene, fluororesin, fluorocarbon oil,
Silicon oil, low molecular weight polyethylene, low molecular weight polypropylene, various waxes and the like can be mentioned. Furthermore,
If necessary, a charge control agent for facilitating positive or negative charging may be added.

[0049]

EXAMPLES Next, the present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples. A specific example of a method for synthesizing a metal phosphorus chalcogenide will be described. (Synthesis Example 1) Commercially available zinc sulfide, red phosphorus and powdered sulfur were mixed in a prescribed molar ratio, and heat-synthesized in a sealed tube. That is, zinc sulfide (reagent) 5.06 parts by weight ... 1 (molar ratio), red phosphorus 1.61 parts by weight ... 1 (molar ratio), powdered sulfur 3.33 parts by weight ... 2 ( (Mole ratio) was weighed and rubbed well in a mortar. After the mixture was put into a glass tube having one end sealed, the open portion of the glass tube was connected to a suction tube of a vacuum pump to evacuate the inside of the glass tube. Then, the open part of the glass tube was melted with a gas burner and sealed. The sealed glass tube was placed in a horizontal tubular furnace and gradually heated at 450 ° C. ± 5 ° C. for 1 week,
A pale tan product was obtained. When this product was ground in a mortar and the crystal structure was examined by X-ray diffraction, the interlayer distance was 6.
ZnP having a layered crystal structure with a unique diffraction peak of 46Å
S ₃ was gotten.

(Synthesis Example 2) Magnesium powder (reagent),
Red phosphorus and powdered sulfur were mixed in the following ratio, and heat-synthesized in a sealed tube in the same manner as in Synthesis Example 1. However, the glass tube of Synthesis Example 1 was a quartz tube, and the heating temperature was 800 ± 5 ° C.・ Magnesium powder (reagent) 1.61 parts by weight ・ ・ ・ 1 (molar ratio) ・ Red phosphorus 2.04 parts by weight ・ ・ ・ 1 (molar ratio) ・ Sulfur powder 6.35 parts by weight ・ ・ ・ 3 (molar ratio) ) From the X-ray diffraction pattern of the obtained product, the interlayer distance is 6.75.
MgPS ₃ having a unique diffraction peak of Å was obtained.

(Synthesis Example 3) Calcium sulfide (reagent), red phosphorus and powdered sulfur were mixed in the following ratio, and heat synthesis was carried out in a sealed tube in the same manner as in Synthesis Example 1. However, the glass tube of Synthesis Example 1 was a quartz tube, and the heating temperature was 750 ± 5 ° C.・ Calcium sulfide (reagent) 4.31 parts by weight ・ ・ ・ 1 (molar ratio) ・ Red phosphorus 1.85 parts by weight ・ ・ ・ 1 (molar ratio) ・ Sulfur powder 3.83 parts by weight ・ ・ ・ 2 (molar ratio) ) From the X-ray diffraction diagram of the obtained product, the interlayer distance is 6.00Å
CaPS ₃ having a unique diffraction peak of was obtained.

(Synthesis Example 4) Zinc sulfide, calcium sulfide,
Red phosphorus and powdered sulfur were mixed in the following ratio, and heat-synthesized in a sealed tube in the same manner as in Synthesis Example 1. However, the glass tube of Synthesis Example 1 was a quartz tube, and the heating temperature was 750 ± 5 ° C. Commercially available zinc sulfide 3.68 parts by weight 0.7 (molar ratio) Calcium sulfide (reagent) 1.17 parts by weight 0.3 (molar ratio) Red phosphorus 1.61 parts by weight · 1 (molar ratio) · 3.48 parts by weight of powdered sulfur ··· 2 (molar ratio) The X-ray diffraction pattern of the obtained product shows a diffraction peak similar to ZnPS ₃ with an interlayer distance of 6.46Å. _0.7 Ca _0.3 P
S ₃ was obtained.

Example 1 Phenolic resin 100 parts by weight Carbon black 30 parts by weight Methanol 100 parts by weight Isopropyl alcohol 300 parts by weight Resin coating material of the above composition and Mg prepared in Synthesis Example 1
PS ₃ (70 parts by weight) is mixed, zirconia beads having a diameter of 1 mm are added as media particles (beads used in a sand mill), dispersed for 2 hours in a sand mill, the beads are separated using a sieve, and a stock solution for forming a film is formed. Got

Further, this stock solution was diluted with isopropyl alcohol to a solid content of 25% by weight to obtain a coating solution, and a coating film having a thickness of 10 μm was formed on a stainless developing sleeve substrate having a diameter of 20 mm by a spray method, followed by hot air drying. The developing sleeve of the present invention was produced by drying and curing in an oven at 150 ° C. for 30 minutes.

(Evaluation 1) Next, the developing sleeve obtained in Example 1 was incorporated into GP55 (Canon copying machine), and an image forming test was conducted. The following toner was used. -Styrene-acrylic resin 100 parts by weight-Magnetite 80 parts by weight-Negative charge control agent 2 parts by weight (3,5-ditertiary butylsalicylic acid chromium complex) -Low molecular weight polypropylene 3 parts by weight

The above materials are kneaded, pulverized and classified by a general dry toner manufacturing method, and those having an average particle diameter of 7.5 μm and a particle diameter of 4 μm or less are 16% in number% and 12.7 μm.
The toner containing the above is 0.7% by weight. The particle size distribution is measured with a 100 μm aperture of Multisizer II. The result of the image output test,
The image density under a normal temperature and normal humidity environment of 23.5 ° C./60% RH was as high as 1.43, and a good image without ghost and density unevenness was obtained. Furthermore, 15 ℃ / 10% RH
Even in a low temperature and low humidity environment, the image density was as high as 1.45, the ghost level was good, and 32.5 ° C /
The image density is 1.3 even in a high temperature and high humidity environment of 85% RH.
It was as high as 7, and neither uneven density nor ghost was generated.
As described above, variations in image density and image quality were small even under different environmental conditions. Furthermore, under different environmental conditions, the image density was stable even after repeated copying of 100,000 sheets, and uneven density and ghost did not pose a problem.

Example 2 Among the materials in Example 1, metal phosphorus chalcogenide 7
A developing sleeve of the present invention was prepared in the same manner as in Example 1 except that 0 part by weight was 70 parts by weight prepared in Synthesis Example 2, and an image forming experiment was conducted to evaluate the same. The results are also shown in Table 1.

Example 3 Among the materials in Example 1, metal phosphorus chalcogenide 7
A developing sleeve of the present invention was prepared in the same manner as in Example 1 except that 0 part by weight was 80 parts by weight prepared in Synthesis Example 3, and an image forming experiment was conducted to evaluate the same. The results are also shown in Table 1.

Example 4 Of the materials in Example 1, metal phosphorus chalcogenide 7
A developing sleeve of the present invention was prepared in the same manner as in Example 1 except that 0 part by weight was 80 parts by weight prepared in Synthesis Example 4, and an image forming experiment was conducted to evaluate. The results are also shown in Table 1.

Comparative Example 1 A developing sleeve of Comparative Example 1 was prepared in the same manner as in Example 1 except that the metal phosphorus chalcogenide was not used among the materials in Example 1, and an image forming experiment was conducted for evaluation. The results are also shown in Table 1. Also, when 100,000 sheets are repeatedly copied, the resin coating on the surface of the developing sleeve is peeled off and scraped off, the density unevenness and ghost are deteriorated, and the image density is remarkably lowered particularly in a low temperature and low humidity environment. The density of 1.42 dropped to 1.20 after 100,000 sheets.

Comparative Example 2 Among the materials in Example 1, metal phosphorus chalcogenide 7
A developing sleeve of Comparative Example 1 was prepared in the same manner as in Example 1 except that 0 part by weight was replaced with 70 parts by weight of graphite, which is widely used as a solid lubricant having a normal layered crystal structure, and an image forming experiment was conducted. I went and evaluated it. The results are also shown in Table 1. Similar to Comparative Example 1, good results were not obtained.

Comparative Example 3 Among the materials in Example 1, metal phosphorus chalcogenide 7
A developing sleeve of Comparative Example 1 was prepared in the same manner as in Example 1 except that 0 part by weight was replaced by 70 parts by weight of molybdenum disulfide, which is widely used as a solid lubricant having a normal layered crystal structure. An experiment was conducted and evaluated. The results are also shown in Table 1.

Table 1-1: Examples 1-4 and Comparative Examples 1-3
Evaluation result (image density)

Table 1-2: Examples 1-4 and Comparative Examples 1-3
Evaluation results (density unevenness) Note) ○: Very good, ○ △: Good, △: Slightly bad, △
×: Quite bad, ×: Very bad

Table 1-3: Examples 1-4 and Comparative Examples 1-3
Evaluation result (ghost) Note) ○: Very good, ○ △: Good, △: Slightly bad, △
×: Quite bad, ×: Very bad

[0066]

As described above, according to the present invention, deterioration of the coating layer or peeling due to repeated copying or durability does not occur, the image density is high for a long time, and high quality without density unevenness and ghost. Image is obtained. In addition, the change in image density is small even under different environmental conditions, and the proper toner charge is maintained even under low temperature and low humidity environmental conditions, so that density reduction due to charge-up, density unevenness, ghost, etc. do not occur. , Can maintain high quality images.

[Brief description of drawings]

FIG. 1 is a sectional view showing an example of a conventional developing device.

FIG. 2 is a sectional view showing an example of a developing device of the present invention.

FIG. 3 is a cross-sectional view showing another example of the developing device of the present invention.

FIG. 4 is a cross-sectional view showing another example of the developing device of the present invention.

[Explanation of symbols]

 1: Photosensitive drum 2: Magnetic regulation blade 3: Container 4: Developer (toner) 5: Magnet roll 6: Metal cylinder 7: Resin coating layer 8: Development sleeve 9: Gap 10: Development bias power supply 11: Development roller 12 : Developing roller 13: Developing sleeve 20: Elasticity regulating blade 21: Elasticity regulating blade N1, S1, N2, S2: Magnetic pole

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenji Fujishima 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (4)

[Claims] 1. A developer carrying member used in a developing device for developing a latent image formed on a latent image carrying member with a developer carried and conveyed by a developer carrying member. Which has a coat layer made of a resin containing at least one kind or two or more kinds of metal phosphorus chalcogenide on the substrate. 2. A metal phosphorus chalcogenide which is a metal phosphorus chalcogenide as a host layer and an alkylamine, an aromatic amine, pyridine or a quaternary alkylammonium chloride as a guest. The developer carrying member according to 1. 3. The one-component developer housed in a developing container is carried on a developer carrier, and a thin layer of the developer is formed on the developer carrier by a developer layer regulating member, while the developing is carried out. In a developing device that conveys the developer to a developing unit facing the latent image carrier by the agent carrier, and develops the latent image formed on the latent image carrier, the developer carrier of the developing device is , At least one of the metal phosphorus chalcogenides on its substrate
A developing device having a coat layer made of a resin containing one kind or two or more kinds. 4. A metal phosphorus chalcogenide which is a metal phosphorus chalcogenide as a host layer and an alkylamine, an aromatic amine, pyridine or a quaternary alkylammonium chloride as a guest. The developing device according to 1.