JP2001042631A - Triboelectric charge imparting member and developing device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a triboelectric charge imparting member capable of controlling quantity of electric charges on the toner to desirable level from the member side in matching with the electrostatic charge characteristics of the toner by disposing a resin coating layer formed with a specified resin composition which contains a bonding resin, a quaternary ammonium salt compound and a nitrogen-containing heterocyclic compound on the surface of a member brought into contact with the toner. SOLUTION: The surface of this triboelectric charge imparting member brought into contact with a toner has a resin coating layer formed with a resin composition containing a bonding resin, a quaternary ammonium salt compound having positive chargeability with respect to iron powder and a nitrogen-containing hetercyclic compound. A part or all of the bonding resin has at least one type selected from among -NH2 group, =NH group and -NH- bonding in its molecular structure and the nitrogen-containing heterocyclic compound is an imidazole compound. An electrically conductive fine powder may also be contained in the resin coating layer. The triboelectric charge imparting member is preferably a developing sleeve, a member for regulating the thickness of a developer layer or a carrier.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a frictional charging member for applying a triboelectric charge to a developer (toner) used in an electrophotographic apparatus, and a developing device using the same.

[0002]

2. Description of the Related Art Conventionally, many methods have been known as electrophotography. In general, a photoconductive substance is used, and an electric latent image bearing member (photoreceptor) is electrically charged by various means. A latent image is formed, and then the latent image is developed with a developer (toner) to visualize the toner image. If necessary, the toner image is transferred to a transfer material such as paper. A copy is obtained by fixing a toner image thereon.

[0003] The developing system in the electrophotographic method is mainly classified into a one-component developing system and a two-component developing system.

In the two-component developing method, each toner is frictionally charged by stirring the toner and the carrier, and an electrostatic latent image is visualized using the charged toner. The methods belonging to this method are called a magnetic brush method using a material having magnetism such as iron powder, a cascade method using a bead carrier, a fur brush method using fur, and the like, depending on the type of carrier that transports the toner. .

[0005] Further, those belonging to the one-component developing method include a powder cloud method in which toner particles are used in a spray state, a contact developing method in which toner particles are brought into direct contact with an electrostatic latent image surface and developed, and a toner. A jumping development method in which toner particles fly toward the latent image surface by the action of an electric field between the electrostatic latent image and the developer carrier without bringing the particles into direct contact with the electrostatic latent image surface. For example, there is a magnedry method in which development is performed by contacting the surface of the latent image.

As a toner applied to these developing methods, a fine powder in which a colorant is dispersed in a natural or synthetic resin has been conventionally used. For example, a dispersion of colored particles such as various pigments, dyes, carbon black, and iron oxide in a binder resin such as a styrene-acrylic resin or a polyester resin is made into fine particles having an average particle size of about 4 to 15 μm. Is used as a toner.

Any toner must have a positive or negative charge depending on the polarity of the electrostatic latent image to be developed.
As a method of retaining the electric charge in the toner, a method of utilizing the triboelectric property of the binder resin of the toner, a method of giving triboelectric properties to various particles added to the toner, and is generally used.
In particular, a specific substance called a charge control agent is generally added to the toner.

[0008] These toners usually generate triboelectric charge when they come into contact with various members used in a developing device. The main component is a carrier in a two-component developer, a developing sleeve or a developer layer thickness regulating blade in a one-component developer, and other components such as a developer supply member and a stirring member. Members, transport screws, etc. can also be involved in tribocharging.

[0009] In general, in the development process, when the toner is to be provided with an appropriate charge, first of all, the toner is composed of a material capable of triboelectric charging, that is, as described above. In addition, the material is selected from a binder resin, an additive, and a substance suitable as a charge control agent. However, for example, the binder resin, which accounts for the majority of the toner components, plays an important role not only in development but also in the fixing step, so that it is not possible to select a material that emphasizes only development (triboelectric charging). recent years,
From the viewpoint of energy saving and the like, a technique for fixing at a lower temperature or a lower wattage is required. However, in terms of toner, generally, a binder resin having a good fixing property is inferior in chargeability. As an example of a method for selecting a toner material for fixing a toner with low energy, Tg of a binder resin is used.
Although there is a method of increasing the low molecular weight component in the (glass transition point) and the molecular weight distribution of the resin, such a binder resin is often inferior in chargeability. In addition, so-called waxes are often added to the toner for the purpose of improving the anti-offset property in the fixing process or for enhancing the plasticizing effect of the resin to improve the fixing property. It is easy to give a property in a bad direction to the developing property.

[0010] On the other hand, a method of adding a charge control agent to the toner to improve the triboelectric charging property of the toner is used, but there are various problems here as well. For example, the charge control agent itself can easily exhibit its performance when present in the surface layer of the toner particles.In general, when the toner raw materials are dispersed and kneaded and then finely divided, the proportion of the surface to the amount added is present. Is naturally low, and a large amount of addition is required to hold a sufficient charge. However, if a large amount is added, there is a high possibility that other adverse effects are caused. For example, a charge control agent of a pigment / dye system is released when the toner is atomized, and the charge control agent contained in the toner but exposed on the toner surface easily contaminates a drum, a blade, a developing sleeve, and other members. Further, it is known that a resin-based charge control agent easily causes inhibition of fixing property and deterioration of offset resistance.

Further, in the case of a toner, a charge control agent is added, or the volume resistivity of the toner is too high.
It is also known that a so-called charge-up phenomenon occurs, which tends to cause a decrease in image density and image unevenness, and it is difficult to control charges.

As a second method for imparting an appropriate charge to the toner, there have been proposed a number of methods for balancing the charge of the toner by using an appropriate material for the frictional charging member.

In general, iron powder has been used for a carrier as a frictional charging member used in a two-component developer, but in recent years, in order to adjust the charge amount of a toner, a magnetic substance has been used. A carrier material using iron powder, ferrite, or the like as a material is often used by applying a coating material made of an acrylic resin, a fluorine resin, a silicone resin, a phenol resin, or the like to the surface.

Also, the developer layer thickness regulating member (regulating blade) is known to affect the triboelectric charging of the toner because the toner contacts the blade when the toner passes between the sleeve and the blade in the developing device. In the case of a one-component non-magnetic developer compared to a one-component magnetic developer,
High influence. As the blade, a material such as metal or rubber is used, but when elastically contacting the developer carrier, a rubber blade such as urethane rubber is often used. In this case, for example, when a negatively charged toner is used, a nylon-based elastomer is used for a surface layer that comes into contact with the toner, or when the toner is positively charged,
There is known a technique of making a toner easily have an electric charge by using a silicone-based elastomer, and a method of using the above triboelectric material by coating a resin on a metal or rubber is also known.

In addition, since the developing sleeve carries a developer on its surface and has many opportunities for contact with the toner, it has a strong influence on the charge of the toner in any case.

Conventionally, a developing sleeve used in a non-contact developing device has conventionally been formed by molding a metal, an alloy thereof, or a compound thereof into a cylindrical shape, and the surface thereof is formed to a predetermined surface roughness by electrolysis, blasting, sanding, or the like. What was processed so that it might become. However, in this case, the developer existing near the developer carrier surface in the developer layer formed on the developer carrier surface by the regulating member has an extremely high charge, and is strongly attracted to the carrier surface. As a result, there is no chance of friction between the uncharged toner and the carrier, so that a suitable charge is not given to the developer, which causes a so-called charge-up phenomenon. In such a situation, good development and transfer are not performed, resulting in an image having a low image density and having many image irregularities and scattered characters. In order to prevent the generation of a developer having such an excessive charge and the strong adhesion of the developer, a film in which a conductive substance such as carbon black and graphite or a solid lubricant is dispersed in a triboelectrically chargeable resin. Is formed on the above-described developer carrier base, as disclosed in JP-A-1-277265 and the like. However, in recent years, high definition electrophotographic images have been required, and the resolution of
The mainstream is 0, 800, and 1200 dpi, and accordingly, a technique for increasing and stabilizing the charge (tribo) of the toner is required. According to the method disclosed above, it is possible to prevent charge-up of the toner and stabilize the tribo, but it is difficult to stabilize the tribo higher.

In a so-called contact developing method in which a developer carrier is brought into direct contact with a latent image carrier to perform development,
Generally, an elastic body such as urethane rubber, EPDM rubber, or silicone rubber is molded on a cylinder on the main shaft of a metal such as stainless steel, or an elastomer layer is formed on the surface of a cylindrical member of aluminum or stainless steel. Used. In these cases, the so-called rubber contains impurities such as a plasticizer, a vulcanizing agent, a release agent, and a low molecular weight component.
When this comes into contact with the latent image carrier and the developer layer forming member,
Since these members and the image are adversely affected by bleeding, layers such as a barrier layer and a protective layer are provided on the surface of the rubber layer to prevent the above-mentioned adverse effects. Furthermore, on the outermost surface,
It is also known that the surface layer is formed of a material having good releasability or a resin which easily gives a triboelectric charge to the toner.

Further, in order to increase the charge applied to the toner by the surface layer of the frictional charge providing member, the binder resin has a strong frictional charge providing property, for example, a silicone resin,
Many techniques for using a fluorine resin, a nylon resin, a nitrogen-containing acrylic resin, and the like, and further including a charge control agent and chargeable particles in a binder resin have been disclosed. Further, Japanese Patent Application Laid-Open No. H02-108083 discloses a developing device having a layer thickness regulating member having a resin surface containing a positive charge control agent and a negative charge control agent, and a toner transport member.

[0019]

However, there are many difficult points in using such a triboelectric charging material. For example, the amount of triboelectric charge in the material used for the toner and the charging member is almost determined by what is used for the material, and it is difficult to control the charging level to a more preferable level, and the level is too high or too low. Is the most. Further, with respect to a system using a mixture of the two positive and negative control agents, for example, when forming a surface layer, one of the substances is more likely to come out to the surface due to the combination thereof, so that it is charged as expected. Is difficult to control. Also, even if both are exposed, either of the charge imparting properties will be superior, and the toner will be biased to the polarity of the one which has won, and it is difficult to stably charge to a medium level. I know that.

Therefore, there is a need for a technology that can be adjusted to an appropriate level in the development process using a frictional charging member in accordance with the charging performance of the toner. Further, there is a need for a triboelectric charging member which has little scraping and contamination, has good durability, has a stable charging level even in long-term image formation, and can stabilize image performance.

Accordingly, an object of the present invention is to provide a method and a frictional charging member capable of controlling the toner charge amount to a preferable level from the frictional charging member side in accordance with the charging characteristics of the toner.

It is a further object of the present invention to provide a triboelectric charging member which has little scraping and contamination, has good durability, has a stable charging level even in long-term image formation, and can stabilize image performance. It is.

A further object of the present invention is to provide a two-component developing apparatus using a carrier, which gives a stable and suitable triboelectric charge to a toner and reduces fog and image unevenness due to a decrease in image density due to charge-up of the toner and an insufficient amount of charge. An object of the present invention is to provide a carrier and a developing device that do not generate the carrier.

It is a further object of the present invention to provide a developer layer thickness regulating member capable of imparting an appropriate amount of triboelectric charge to toner with less scraping and contamination even during long-term durability.

It is a further object of the present invention to provide a developer carrier (sleeve) capable of imparting an appropriate amount of triboelectric charge to a toner with less scraping and contamination even during long-term durability.

It is a further object of the present invention to provide a developing device which has high definition and high density even in long-term durability and does not cause fogging, streaks, and unevenness.

[0027]

According to the present invention, there is provided a frictional charging member for use in an electrophotographic apparatus, wherein at least a surface of the frictional charging member which comes into contact with the toner is formed with a toner. Triboelectric charging characterized by having a resin coating layer formed of a resin composition having at least a quaternary ammonium salt compound which is positively chargeable with respect to an iron powder and an iron powder, and a nitrogen-containing heterocyclic compound. It is a member.

In the present invention, a part or all of the binder resin of the resin coating layer has at least -N in its molecular structure.
It preferably has one of an H ₂ group, ＮＨNH group, and —NH— bond, and the nitrogen-containing heterocyclic compound in the resin coating layer is preferably an imidazole compound.

The resin coating layer may further contain a conductive fine powder.

It is most preferable that the frictional charging member of the present invention is a developing sleeve, a developer layer thickness regulating member, or a carrier.

Further, the above object has a developing container and a developer carrying member for carrying the developer held in the developing container and transporting the developer to a developing area facing the latent image carrying member. ,
A developing device for developing a latent image on a latent image carrier with a developer carried and conveyed by the developer carrier and visualizing the latent image is achieved by a developing device having at least one of the above-described frictional charging members. Is done.

Prior to the present invention, the present inventors have found that a quaternary ammonium salt compound conventionally known as a positive charge control agent for toner, that is, a quaternary ammonium salt compound which itself is positively chargeable with respect to iron powder. using a quaternary ammonium salt compound, as a binder resin, in particular, some or all of the binder resin, in its molecular structure, at least -NH ₂ group, = NH group, -NH-
When the coating layer of the triboelectric charging member is formed using one having any of the bonds, the quaternary ammonium salt compound is incorporated into the binder resin, and the resin (resin layer) itself exhibits strong negative charging properties, It has been found that the toner exhibits good charge-imparting property with respect to the chargeable toner, and it has been proposed that a very good image can be obtained by using this as a frictional-charging member in a developing device. The advantage of this method, for example, in comparison with a system in which silica, a fluororesin powder, and a negative charge control agent are added to impart a positive charge to a toner, is that a quaternary ammonium Since the salt compound is dissolved and can be uniformly present in the resin, when the resin layer is formed, the entire resin layer becomes a uniform negatively chargeable material,
Compared to a silica-added system which is dispersed in a matrix, it exhibits good charge-providing properties, and since it is not a powder-added system, it has good mechanical strength, that is, durability.

Further, a nitrogen-containing heterocyclic compound is known as a positively chargeable charge control agent to be added to a triboelectric charging member for improving the triboelectric charge of a negatively chargeable toner, and an imidazole compound has been proposed. . It has been confirmed that when a nitrogen-containing heterocyclic compound, particularly an imidazole compound, is dispersed in a resin layer and used as a triboelectric charging member, the negative charge of the negatively chargeable toner is improved.

However, as a result of various studies by the present inventors, when these substances are added, as described above, as will be described later in Examples, the charge amount of the toner reaches a certain amount. However, there was a phenomenon that the effect was not obtained until a certain amount was added.

In view of these points, as a result of various studies, it was found that the quaternary ammonium salt compound, which has been known as a conventional positive charge control agent for toner, that is, itself has a positive charge property with respect to iron powder. When a certain quaternary ammonium salt compound is used, particularly as a binder resin, a part or all of the binder resin has at least a —NH ₂ group, ＮN
The triboelectric charge amount of the toner is adjusted to a suitable level by forming a coating layer of the triboelectric charging member using a nitrogen-containing heterocyclic compound as a base based on a compound having either an H group or an -NH- bond. Chargeable, that is, the fourth
By changing the addition amount and the amount ratio of the ammonium salt compound and the nitrogen-containing heterocyclic compound, it was found that the charge amount changed linearly and that a suitable triboelectric charge level for the toner could be set. Reached. Further, as a comparative sample, an attempt was made to form a resin coating layer in which the addition ratio of both the positively-charged nitrogen-containing heterocyclic compound and the negatively-chargeable di-tertiary-butylsalicylic acid Cr complex was changed while changing the addition ratio. As a result, it was found that the linearity as described above could not be obtained, and that the triboelectric charging property was inclined to one of the charging properties.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION The quaternary ammonium salt compounds having the above-mentioned functions, which are preferably used in the present invention, include:
What has a positive charge property with respect to iron powder is used. For example, a compound represented by the following general formula (I) can be mentioned.

[0037]

Embedded image (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group. or it may be different .X ^- represents an anion of acid).

On the other hand, fluorinated quaternary ammonium salt compounds which themselves have a negative charge on iron powder, such as those represented by the following formula (II), were examined. It was found that the desired object of the present invention was not achieved by the addition of. That is, since the compound represented by the following formula (II) has a fluorine resin atom having a strong electron-withdrawing property in the structure, the compound itself has a negative charge property with respect to iron powder. Even if a resin composition obtained by dispersing the compound in a resin is used as a coating resin, and this is heated and dried to form a coating layer on the carrier core material, itself is positively charged with respect to iron powder. As high as in the case of the present invention in which a resin containing a quaternary ammonium salt compound is used as the coating resin, a high triboelectric charging property to a positively chargeable developer could not be obtained.

[0039]

Embedded image

Specific examples of the quaternary ammonium salt compound suitably used in the present invention, which itself is positively charged with respect to iron powder, include the following compounds. The present invention is not limited to these.

[0041]

Embedded image

The fourth type used in the present invention as described above
The addition amount of the quaternary ammonium salt compound is preferably 1 to 100 parts by weight based on 100 parts by weight of the coating resin.
If the amount is less than 1 part by weight, no improvement in the charge imparting property by addition is observed, and if it exceeds 100 parts by weight, dispersion in the resin becomes poor, and the coating strength tends to decrease.

The resin used for the coating layer of the present invention is not particularly limited, but a part or all of the resin has at least a —NH ₂ group, ＝ NH group, or —N
It preferably has any structure of an H-bond. By forming a coating layer using such a resin,
The effect of the present invention can be easily exhibited. In the present invention, when a resin layer having the above structure is used as the resin layer of the triboelectric charging member, the clear reason for the change to the negative charging property is not clear, but is used in the present invention. A resin using a quaternary ammonium salt compound which itself is positively charged with respect to iron powder, and a resin having at least one structure of a -NH ₂ group, = NH group, or -NH-bond By forming the coating layer, a quaternary ammonium salt is incorporated into the structure of the resin. that time,
It is considered that the original structure of the quaternary alcohol salt having the positive polarity is lost, and the resin incorporating the quaternary alcohol salt has uniform and sufficient negative chargeability.

As the substance having a -NH ₂ group, R-
Primary amines or polyamines having them represented by NH _2, polyamide or the like having a first amide or they are represented by RCO-NH _2, as a substance having a = NH group, a is represented by R = NH Diamines or polyamines containing them, secondary amides represented by (RCO) ₂ ＮＨNH or polyamides containing them, etc.
Examples of the substance having an -NH- bond include, in addition to the above-described polyamines and polyamides, polyurethanes having an -NHCOO- bond, and the like, and one or more of the above substances, or a copolymer containing Industrially synthesized resins are preferably used. Among them, phenol resins, polyamide resins, urethane resins and the like using ammonia as a catalyst are preferred from the viewpoint of versatility and the like.

The nitrogen-containing heterocyclic compound used in the present invention includes imidazole, imidazoline, imidazolone,
Pyrazoline, pyrazole, pyrazolone, oxazoline,
Oxazole, oxazolone, thiazoline, thiazole, thiazolone, selenazoline, selenazole, selenazolone, oxadiazole, thiadiazole, tetrazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, benzoselenazole, pyrazine, pyrimidine, pyridazine, triazine,
Nitrogen-containing heterocycles such as oxazine, thiazine, tetrazine, polyazain, pyridazine, pyrimidine, pyrazine, indole, isoindole, indazole, carbazole, quinoline, pyridine, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, purine, pyrrole, triazole, phenazine and the like. And a compound having a group. In the present invention, an imidazole compound is particularly preferred because it promotes the effect of the interaction between the developer carrier and the toner used in the present invention.

In particular, among the imidazole compounds, the following general formula (1) or (2)

[0047]

Embedded image [Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ₁ and R ₂ may be the same or different. R ₃ and R _{4 each} have 3 to 3 carbon atoms.
Represents 30 linear alkyl groups, and R ₃ and R ₄ may be the same. ]

[0048]

Embedded image [Wherein, R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and R ₅ and R ₆ may be the same. R ₇ has a carbon number represents a linear alkyl group of 3 to 30. The imidazole compound represented by the formula (1) is more preferable from the viewpoints of quick and uniform chargeability of the toner and strength of the coating layer.

The reason is that the imidazole compound having the structure represented by the general formula (1) or (2) has a straight-chain alkyl group having 3 to 30 carbon atoms as a substituent.
This is presumably because the coating layer has good dispersibility in resin and has good triboelectric charging characteristics with the toner used in the present invention, which is in a dispersed state on the special surface.

The nitrogen-containing heterocyclic group constituting the nitrogen-containing heterocyclic compound may be monocyclic, may be condensed with another group, or may be substituted.

When the nitrogen-containing heterocyclic group is substituted, examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group and a urethane group. , Aryloxy, sulfamoyl, carbamoyl, alkyl or arylthio, alkyl or arylsulfonyl, alkyl or arylsulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl Group, acyloxy group, carbonamido group,
Sulfonamide group, carboxyl group, phosphoric acid amide group,
A diacylamino group, an imide group and the like can be used.
The above substituents may further have a substituent. As examples of the substituent, the substituents exemplified for the substituent of the nitrogen-containing heterocyclic ring can be used.

The above-mentioned nitrogen-containing heterocyclic compound has a number-average particle diameter of preferably 20 μm or less, more preferably 0.1 to 0.1 μm.
It is good to use a thing of 15 μm. When the number average particle diameter of the nitrogen-containing heterocyclic compound exceeds 20 μm, the effect of improving the charging performance is not sufficiently obtained due to poor dispersibility of the nitrogen-containing heterocyclic compound in the resin coating layer, which is not preferable.

As the binder resin material of the coating layer, generally known resins can be used. For example, styrene resin,
Vinyl resin, polyether sulfone resin, polycarbonate resin, polyphenylene oxide resin, polyamide resin, fluororesin, cellulose resin, acrylic resin,
A thermoplastic 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, and a polyimide resin, or a photocurable resin can be used.
Among them, those having releasability such as silicone resin and fluorine resin, or those having excellent mechanical properties such as polyether sulfone, polycarbonate, polyphenylene oxide, polyamide, phenol, polyester, polyurethane, styrene resin and acrylic resin are more preferable. preferable.

However, in order to easily achieve the object of the present invention, as described above, a binder resin having at least one structure of a —NH ₂ group, ＝ NH group, or —NH— bond is used. Preferably, it is used. It is also possible to use a mixture with the above general binder resin.

In the frictional charge imparting material of the present invention, other conductive fine particles may be dispersed and contained in the binder resin in order to adjust the volume resistance of the coating layer. Such conductive fine particles preferably have a number average particle size of 20 μm or less, and
The following is more preferred. In order to avoid irregularities formed on the resin surface, a resin having a thickness of 1 μm or less is used.

The conductive fine particles used in the present invention include carbon black such as furnace black, lamp black, thermal black, acetylene black, and channel black; titanium oxide, tin oxide, zinc oxide, molybdenum oxide, and titanic acid. Metal oxides such as potassium, antimony oxide and indium oxide; aluminum;
Metals such as copper, silver and nickel, graphite, metal fibers,
Examples include inorganic fillers such as carbon fibers.

The preferable amount of the conductive fine particles in the above-mentioned coating layer is in the range of 100 parts by weight or less based on 100 parts by weight of the binder resin. If the addition amount exceeds 100 parts by weight, the coating strength tends to decrease, and the addition of a large amount of non-chargeable particles may decrease the charge amount of the toner.

The constitution of the resin coating layer of the triboelectric charge imparting material of the present invention is preferably such that the effect of the present invention is further promoted by dispersing a lubricating substance in the coating resin layer. Examples of lubricating substances include graphite, molybdenum disulfide, boron nitride, mica, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, talc, fatty acid metal salts such as zinc stearate, and the like.
Particularly, graphite is preferably used because it does not impair the conductivity of the coating layer. These lubricating substances preferably have a number average particle size of about 0.2 to 20 μm, more preferably 0.3 to 15 μm.

Particularly preferable results are obtained when the amount of the lubricating substance is in the range of 10 to 120 parts by weight based on 100 parts by weight of the binder resin. If the amount exceeds 120 parts by weight, the film strength tends to decrease, and if a large amount of non-chargeable additive is added, the charge amount of the toner will decrease. Conversely, if the amount is less than 10 parts by weight, it is difficult to obtain the effect of preventing toner from adhering to the triboelectric charging member.

Next, the structure of the developer carrier used in the present invention will be described. The developer carrier comprises a base and a resin layer surrounding and covering the base. Examples of the substrate include a cylindrical member, a columnar member, a belt-like member, and the like. In a developing method without contacting the drum, a metal cylindrical tube is preferably used. As the metal cylindrical tube, a non-magnetic material such as stainless steel, aluminum, or an alloy thereof is preferably used. Further, in the case of the developing method of directly contacting the drum, urethane, EPD
A cylindrical member having a layer configuration containing a rubber or an elastomer such as M or silicone is preferably used.

The resin coating layer of the developer carrying member may have a particle size of 0.3 to 30 in addition to the additives described above.
By dispersing the spherical particles of μm in the coating resin layer, it is possible to stabilize the surface roughness and optimize the amount of toner coating on the developer carrier. The spherical particles maintain a uniform surface roughness on the surface of the coating layer of the developer carrying member, and at the same time, have a small change in the surface roughness of the coating layer even when the surface of the coating layer is worn out. This has the effect of making it less likely to wear.

The spherical particles used in the present invention have a number average particle size of preferably 0.3 to 30 μm, more preferably 2 to 20 μm. When the number average particle diameter of the spherical particles is less than 0.3 μm, the effect of imparting uniform roughness to the surface and the effect of enhancing the charging performance are small, and the rapid and uniform charging of the developer becomes insufficient and the coating layer becomes insufficient. Is not preferable because toner charge-up, toner contamination and toner fusion occur due to abrasion of the toner, and ghost suppression and image density decrease easily occur. When the number average particle diameter exceeds 30 μm, the surface roughness of the coating layer becomes too large, and it becomes difficult to sufficiently charge the toner.
It is not preferable because the mechanical strength of the coating layer is reduced.

More preferably, the true density of the spherical particles is:
3.0 g / cm ³ or less, preferably 2.7 g / cm ³ or less, it is better and more preferably from 0.9~2.3g / cm ^3. That is, the true density of the spherical particles is 3.0 g / cm ^3.
When the value exceeds, the dispersibility of the spherical particles in the coating layer becomes insufficient, so that it becomes difficult to impart uniform roughness to the surface of the coating layer. In addition, since the storage stability of the paint is not good, it is difficult to obtain a triboelectric charging member surface having uniform surface irregularities. Even when the true density of the spherical particles is less than 0.9 g / cm ³ , the dispersibility of the spherical particles in the coating layer becomes insufficient.

In the present invention, the term “spherical” in spherical particles means that the ratio of the major axis / minor axis of the particles is about 1.0 to 1.5. It is preferable to use particles having a ratio of 1.0 to 1.2.
When the ratio of the major axis / minor axis of the spherical particles exceeds 1.5,
The surface roughness of the coating layer becomes uneven, which is not preferable in terms of quick and uniform charging of the toner and strength of the conductive coating layer.

As the spherical particles used in the present invention, known spherical particles can be used. For example, there are spherical resin particles, spherical metal oxide particles, and spherical carbonized particles.

As the spherical resin particles, for example, spherical resin particles obtained by suspension polymerization, dispersion polymerization or the like are used. Spherical resin particles can obtain a suitable surface roughness with a smaller addition amount, and can easily obtain a more uniform surface shape. Examples of such spherical particles include acrylic resin particles such as polyacrylate and polymethacrylate, polyamide resin particles such as nylon, polyolefin resin particles such as polyethylene and polypropylene, silicone resin particles, phenol resin particles, and polyurethane resin particles. Resin particles, styrene resin particles, benzoguanamine particles, and the like. The resin particles obtained by the pulverization method may be used after subjecting them to thermal or physical sphering treatment.

Further, an inorganic substance may be attached to or fixed to the surface of the spherical particles. Such inorganic fine powders include SiO ₂ , SrTiO ₃ , CeO ₂ , CrO, A
oxides such as l ₂ O ₃ , ZnO, MgO, nitrides such as Si ₃ N ₄ , carbides such as SiC, CaSO ₄ , BaSO ₄ ,
Sulfates and carbonates such as CaCO _{3 and} the like.

Such an inorganic fine powder may be used after being treated with a coupling agent. In particular, it can be preferably used for the purpose of improving the adhesiveness to the binder resin or for imparting hydrophobicity to the particles. Examples of such a coupling agent include a silane coupling agent, a titanium coupling agent, a zircoaluminate coupling agent, and the like. More specifically, for example, as a silane coupling agent, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, Benzyldimethylchlorosilane,
Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan,
Triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 1 For example, dimethylpolysiloxane having 2 to 12 siloxane units per molecule and having a hydroxyl group bonded to one silicon atom at each terminal unit may be used. By treating the surface of the spherical resin particles with the inorganic fine powder in this manner, dispersibility in the coating layer, uniformity of the coating layer surface, stain resistance of the coating layer, charge imparting property to the toner, Abrasion resistance and the like can be improved.

The spherical particles used in the present invention are preferably conductive. That is, by giving conductivity to the spherical particles, charge is less likely to be accumulated on the surface of the particles due to the conductivity, and it is possible to reduce the adhesion of toner and improve the charge imparting property of the toner. In the present invention, the volume resistivity of the spherical particles is 1
0 ⁶ Ω · cm or less, more preferably 10 ^-3 ~10 ^{6 Ω} · c
m.

In the present invention, the spherical particles have a volume resistance of 1
0 exceeds ⁶ Omega · cm, spherical particles exposed on the coating layer surface by abrasion with easily occurs contamination and toner fusion as nuclei, it becomes difficult to rapid and uniform charging is performed, it is undesirable.

As a method for obtaining such conductive spherical particles, the following methods are preferable, but are not necessarily limited to these methods.

As a method of obtaining particularly preferred conductive spherical particles used in the present invention, for example, a resin-based spherical particle or mesocarbon microbeads may be calcined and carbonized and / or graphitized to obtain a low-density and good-sized conductive spherical particle. A method of obtaining conductive spherical carbon particles may be used. Examples of the resin used for the resin-based spherical particles include phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, and polyacrylonitrile.

The mesocarbon microbeads can be usually produced by washing the spherical crystals produced in the process of heating and firing the medium pitch with a large amount of a solvent such as tar, medium oil and quinoline.

A more preferable method for obtaining conductive spherical particles is to form a spherical resin particle surface such as a phenol resin, a naphthalene resin, a furan resin, a xylene resin, a divinylbenzene polymer, a styrene-divinylbenzene copolymer, and polyacrylonitrile on the surface. The bulk mesophase pitch is coated by a mechanochemical method, and the coated particles are heat-treated in an oxidizing atmosphere, and then calcined in an inert atmosphere or vacuum to be carbonized and / or graphitized to obtain conductive spherical carbon particles. Method. Spherical carbon particles obtained by this method are more preferable because, when they are graphitized, the coating of the obtained spherical carbon particles has advanced crystallization, so that the conductivity is improved.

The conductive spherical carbon particles obtained by the above-mentioned method can control the conductivity of the spherical carbon particles obtained by changing the firing conditions by any method, and are preferably used in the present invention. used. Further, in some cases, the spherical carbon particles obtained by the above method may be a conductive metal and / or metal within a range where the true density of the conductive spherical particles does not exceed ³ g / cm ³ in order to further increase the conductivity. Oxide plating may be applied.

As another method for obtaining the conductive spherical particles used in the present invention, the conductive fine particles having a smaller particle diameter than the core particles composed of spherical resin particles are mixed at an appropriate mixing ratio. After the conductive fine particles are uniformly attached around the core particles by the action of van der Waals force and electrostatic force by mechanical mixing, a local temperature rise caused by, for example, applying a mechanical impact force A method of softening the surface of the core particles, forming conductive fine particles on the surface of the core particles, and obtaining conductive resin-treated spherical resin particles.

Still another method for obtaining the conductive spherical particles used in the present invention is to uniformly disperse the conductive fine particles in the spherical resin particles, thereby obtaining the conductive spherical particles in which the conductive fine particles are dispersed. There is a method of obtaining. As a method of uniformly dispersing the conductive fine particles in the spherical resin particles, for example, after kneading the binder resin and the conductive fine particles to disperse the conductive fine particles, solidify by cooling, and pulverize to a predetermined particle size A method of obtaining conductive spherical particles by mechanical and thermal treatments to obtain conductive spherical particles; or adding a polymerization initiator, conductive fine particles and other additives to a polymerizable monomer, and uniformly dispersing with a dispersing machine. The dispersed monomer composition is suspended in an aqueous phase containing a dispersion stabilizer by a stirrer or the like so as to have a predetermined particle size, polymerization is performed, and spherical particles in which conductive fine particles are dispersed are obtained. A method of obtaining the same.

The carrier core material applicable to the present invention includes:
There is no particular limitation, and any conventionally known ones can be used. For example, iron, nickel, magnetic metals such as cobalt, and alloys thereof, or alloys containing rare earth, hematite, magnetite, manganese-zinc ferrite, nickel-zinc ferrite,
Examples include soft ferrites such as manganese-magnesium ferrite and lithium ferrite, iron-based oxides such as copper-zinc ferrite, and mixtures thereof. Further examples include ceramic particles such as glass and silicon carbide, resin powder, and resin powder containing a magnetic substance.

The substrate of the developer layer thickness regulating member applicable to the present invention is not particularly limited, and all conventionally known substrates can be used. For example, metals or alloys such as iron, stainless steel, nickel and aluminum,
In many cases, non-metallic materials such as ceramics, plastics, and rubber are used, and these materials are processed into a plate shape in many cases. However, a roll shape may be used. Further, a rubber plate may be attached to a metal base material, or an elastomer material may be attached to a portion of the metal elastic plate that comes into contact with the sleeve.

The method for forming the resin coating layer of the present invention is not particularly limited. For example, a coating solution containing the composition of the present invention is applied to a substrate of a triboelectric member by dipping, spraying, or brushing. The triboelectric charging member of the present invention can be obtained by applying and drying by a method such as a coating method. Further, it can also be produced by dispersing and containing the compound of the present invention in a moldable resin by a known method, and then molding it into a sleeve, a doctor blade or the like.

Next, the toner used in the developing device of the present invention will be described.

The toner is mainly a fine powder having a uniform particle size distribution by melting and kneading a resin, a releasing agent, a charge controlling agent, a colorant, etc., solidifying and pulverizing, and then classifying.

As the binder resin used for the toner, generally known resins can be used. For example, styrene,
Homopolymers of styrene such as α-methylstyrene, p-chlorostyrene and the substituted products; styrene-propylene copolymer, styrene-vinyltoluene copolymer, 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-based copolymers such as styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate , Polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyacrylic resin, rosin, modified rosin,
Tempel resins, phenolic resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, paraffin wax, carnauba wax and the like can be used alone or in combination.

The toner may contain a pigment. For example, carbon black, nigrosine dye,
Lamp Black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow,
India First Orange, Irgazine Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Permanent Bordeaux FRR, Pigment Orange R, Risor Red 2G, Lake Red C, Rhodamine FB, Rhodamine B Lake, Methyl・ Bio Red B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green B, Phthalocyanine Green, Oil Yellow CG, Pomelo First Yellow CGG, Kaya Set Y963, Kaya Set Y
G, Pomelo First Orange RR, Oil Scarlet, Orazol Brown B, Pomelo First Scarlet CG, Oil Pink OP, etc. can be applied.

In order to use the toner as a magnetic toner,
Magnetic powder may be contained in the toner. As such a magnetic powder, a substance which is magnetized in a magnetic field is used, and examples thereof include powder of a ferromagnetic metal such as iron, cobalt, and nickel, and alloys and compounds such as magnetite, hematite, and ferrite. The content of the magnetic powder is preferably 15 to 70% by weight based on the weight of the toner.

A wax can be contained in the toner for the purpose of improving the releasability at the time of fixing and improving the fixing property. Examples of such waxes include paraffin wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, and derivatives include oxides,
Includes block copolymers and graft-modified products with vinyl monomers. In addition, alcohols, fatty acids, acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, mineral waxes, petrolactam and the like can also be used.

If necessary, a charge control agent may be contained in the toner. The charge control agent includes a negative charge control agent and a positive charge control agent. For example, the following substances control the toner to be negatively charged. For example, an organic metal complex or a chelate compound is effective, and examples thereof include a monoazo metal complex, an acetylacetone metal complex, an aromatic hydroxycarboxylic acid, and an aromatic dicarboxylic acid-based metal complex. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. The following substances are used for positively charging the toner. Modified products such as nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and oniums such as phosphonium salts which are analogs thereof Salts and their lake pigments (as the lacking agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids ;
Dibutyltin oxide, dioctyltin oxide,
Diorganotin oxides such as dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate and dicyclohexyltin borate; guanidine compounds and imidazole compounds.

The toner is used, if necessary, by externally adding a powder such as an inorganic fine powder for the purpose of improving fluidity and the like. Examples of such fine powders include silica fine powder, metal oxides such as alumina, titania, germanium oxide, and zirconium oxide; carbides such as silicon carbide and titanium carbide; and inorganic fine powders such as nitrides such as silicon nitride and germanium nitride. The body is used. These fine powders can be used after being organically treated with an organosilicon compound, a titanium coupling agent or the like. For example, organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyl Dimethylchlorosilane,
α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule;
There is dimethylpolysiloxane containing a hydroxyl group bonded to individual Si. Further, an untreated fine powder treated with a nitrogen-containing silane coupling agent may be used.
Particularly, the case of a positively chargeable toner is preferable. Examples of such treating agents include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, Monobutylaminopropyltrimethoxysilane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltrimethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ -Propylbenzylamine, trimethoxysilyl-γ-propylpiperidine, trimethoxysilyl-γ-propylmorpholine,
And trimethoxysilyl-γ-propylimidazole.

The method of treating the inorganic fine powder with the silane coupling agent includes, for example, 1) a spray method,
There are 2) an organic solvent method and 3) an aqueous solution method. In general, the treatment by the spray method is a method in which a pigment is stirred, an aqueous solution or a solvent solution of a coupling agent is sprayed thereon, and then the water or the solvent is removed at about 120 to 130 ° C. and dried. The treatment by the organic solvent method means that a coupling agent is dissolved in an organic solvent (alcohol, benzene, halogenated hydrocarbon, etc.) containing a hydrolysis catalyst together with a small amount of water, and the pigment is immersed in the solution. The solid-liquid separation is carried out by filtration or pressing, followed by drying at about 120 to 130 ° C. The aqueous solution method is a method in which about 0.5% of a coupling agent is hydrolyzed in water or a water-solvent at a constant pH, and then the pigment is immersed therein, followed by solid-liquid separation and drying. is there.

As another organic treatment, fine powder treated with silicone oil can be used. Preferred silicone oils have a viscosity at 25 ° C. of about 0.5 to 10000 mm ² / s, preferably 1 to 100 mm ² / s.
0 mm ² / s, for example, methyl hydrogen silicone oil, dimethyl silicone oil,
Phenylmethyl silicone oil, chlorophenylmethyl silicone oil, alkyl-modified silicone oil,
Examples include fatty acid-modified silicone oil, polyoxyalkylene-modified silicone oil, and fluorine-modified silicone oil. Further, a silicone oil having a nitrogen atom in a side chain may be used. Particularly, the case of a positively chargeable toner is preferable. The treatment with the silicone oil can be performed, for example, as follows. The pigment is violently stirred while heating as necessary, and the silicone oil or a solution thereof is sprayed or vaporized and sprayed onto the pigment, or the pigment is slurried, and the silicone oil or the slurry is stirred while stirring. It can be easily treated by dropping the solution. These silicone oils are used singly or as a mixture of two or more, or used in combination or in multiple treatments. Moreover, you may use together with the process by a silane coupling agent.

It is preferable to use such a toner which has been subjected to a sphering treatment and a surface smoothing treatment by various methods, because the transferability is good. Such a method includes, for example, a device having a stirring blade or a blade, and a liner or a casing, for example, when the toner passes through a minute gap between the blade and the liner, the surface is smoothed by mechanical force. Or toner spheroids,
There are a method of suspending the toner in warm water to form a sphere, and a method of exposing the toner to a hot air flow to form a sphere. As a method for producing a spherical toner, there is a method in which a mixture containing a monomer as a main component as a toner binder resin is suspended in water and polymerized to form a toner. As a general method, a polymerizable monomer, a colorant, a polymerization initiator and, if necessary, a crosslinking agent, a charge control agent, a release agent, and other additives are uniformly dissolved or dispersed to form a single monomer. After the body composition, the monomer composition is dispersed in a continuous layer containing a dispersion stabilizer to an appropriate particle size using a suitable stirrer in, for example, an aqueous phase, and further subjected to a polymerization reaction. This is a method for obtaining a developer having a desired particle size.

Next, an example of a developing device in which the triboelectric charging member of the present invention is incorporated will be described.

FIG. 1 shows an example of a two-component developing apparatus using a carrier. A non-magnetic developing sleeve (developer carrier) 21 as a developer carrier opposing the electrostatic latent image holder 24 rotated in the direction of arrow B in a developing chamber 45 of the developing container 25.
A magnetic roller 22 as a magnetic field generating means is immovably installed in the developing sleeve 21.
1, N1, S2, N2, N3 are magnetized. In the developing chamber 45, a two-component developer 41 in which the toner 40 and the magnetic carrier 43 are mixed is accommodated. This developer 4
When the toner 1 is sent into the stirring chamber 42 of the developing container 25 through one opening (not shown) of the partition 48 which is open at the upper end at one end of the developing chamber 45, the toner 40 supplied from the toner chamber 47 into the stirring chamber 42 Is supplied to the other end of the stirring chamber 42 while being mixed by the first developer stirring and conveying means 50 in the stirring chamber 42. The developer 41 conveyed to the other end of the stirring chamber 42 is returned to the developing chamber 45 through the other opening (not shown) of the partition 48, where the second developer stirring and conveying means 51 in the developing chamber 45 , Transport means 5 in the upper part of the developing chamber 45
The developer is transported to the developing sleeve 21 while being agitated and transported by a third developer agitating / transporting unit 52 that transports the developer in a direction opposite to the transport direction of the developer 1.

The developer 41 supplied to the developing sleeve 21
The developer regulating member blade 2, which is magnetically constrained by the magnetic force of the magnet roller 22, is carried on the developing sleeve 21, and is provided substantially on the top of the developing sleeve 21.
While being formed as a thin layer of the developer 41 on the developing sleeve 21 by the regulation at 3, the developer is conveyed to the developing section C facing the latent image holding member 24 with the rotation of the developing sleeve 21 in the direction of the arrow A, where it is formed. The electrostatic latent image on the latent image holding member 24 is used for development. Residual developer 41 not consumed for development
Is collected in the developing container 25 by the rotation of the developing sleeve 21.

In the developing container 25, the remnant developer 41 remaining magnetically constrained on the developing sleeve 21 by the repulsive magnetic field between N2 and N3 of the same polarity is peeled off. In order to prevent the toner from scattering when the developer 41 rises along the line of magnetic force due to the magnetic pole N2, an elastic seal member 31 is provided at the lower part of the developing container 25 such that one end thereof contacts the developer 41. Fixed and installed.

FIG. 2 shows an example of a developing device which uses a one-component magnetic developer and is used in a non-contact developing method. 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 direction of arrow B. The sleeve 8 of the developing roller 12 carries the magnetic toner 4 as a one-component developer supplied by the hopper 3 and rotates in the direction of arrow A,
The toner 4 is transported to the developing section D where the developing sleeve 8 and the photosensitive drum 1 are opposed. A magnet 5 is disposed in the developing sleeve 8 to magnetically attract and hold the magnetic toner 4 on the developing sleeve 8. The developing sleeve 8 has a resin coating layer 7 coated on the metal cylindrical tube 6. A stirring blade 10 for stirring the magnetic toner 4 is provided in the hopper 3.

In the developing device shown in FIG. 2, a magnetic metal plate is attached so as to hang down from the developing container 3 toward the surface of the sleeve 8 as a member for regulating the layer thickness of the magnetic toner 4 on the developing sleeve 8. , With a certain gap from the sleeve surface. Sleeve 8 and blade 2
Is about 100 to 500 μm. The thickness of the thin layer of the magnetic toner 4 is preferably smaller than the minimum gap between the developing sleeve 8 and the photosensitive drum 1 in the developing section D. The magnetic toner 4 mainly obtains a triboelectric charge capable of developing the electrostatic latent image on the photosensitive drum 1 by friction with the resin coating layer 7 on the developing sleeve 8.

A power supply 9 applies a developing bias voltage to the developing sleeve 8 to fly the magnetic toner 4 as a one-component magnetic developer carried on the developing sleeve 8. When using a DC voltage as the developing bias voltage,
It is preferable that a voltage having a value between the potential of the image portion of the electrostatic latent image (the region where the magnetic toner 4 is adhered and visualized) 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 may be applied to the developing sleeve 8 to form an oscillating electric field in which the direction is alternately reversed in the developing section D. 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. In so-called regular development in which toner is attached 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. In so-called reversal development in which toner is attached to a low potential portion of an electrostatic latent image to visualize the toner, 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 4 is charged by friction with the developing sleeve 8.

In FIG. 3, a member having rubber elasticity is used as a member for regulating the layer thickness of the magnetic toner 4 on the developing sleeve 8. In the developing device shown in FIG. 3, the elastic plate 11 is pressed in the direction opposite to the rotation direction of the developing sleeve 8, but there is a method in which the elastic plate 11 is pressed in the forward direction. In such a developing device, a thinner toner layer can be formed on the developing sleeve 8 as compared with the developing device of FIG.

FIG. 4 schematically shows an example of the configuration of a developing device used when a non-magnetic one-component developer is used. In this example, since a non-magnetic toner is used, no magnet is provided inside the metal cylindrical tube 76. A cylindrical member may be used instead of the metal cylindrical tube.

In the apparatus shown in FIG. 4, a member 83 for removing the toner from the surface of the developing sleeve 78 is provided as shown in FIG. As the peeling member, a roller member such as resin, rubber, and sponge, and further, a belt member, a brush member, and the like are used. The roller-shaped member 83 shown in FIG. 4 is rotated in the direction opposite to the developing sleeve 78 at the contact surface. The developer that has not been transferred to the photoreceptor 71 is temporarily stripped from the sleeve surface by the stripping member 83, thereby preventing generation of immobile toner on the sleeve and uniformizing the charge of the developer. Have. In FIG. 4, the regulating blade 72,
Resin coating layers 74 and 77 are applied to each surface of the sleeve 76.
Is provided.

FIG. 5 is characterized in that the developing roll 95 is in contact with the photosensitive drum 91 at the portion E in FIG. The developing roll 95 includes a core bar 94, an elastic body 93, and a resin coating layer 92.
Consists of The toner supply member 98 includes a core bar 97 and a sponge-like member 96 or a brush member, and is arranged in contact with or close to the developing roll 95. The restricting member 101 includes an elastic plate 99 and an elastic layer 100. A resin coating layer may be provided on the surface of the elastic layer 100, or a resin coating layer may be provided directly on the elastic plate 99.
103 denotes an arbitrary stirring member.

FIGS. 1 to 5 are only schematic examples.
It goes without saying that there are various forms in the shape of the container, the presence or absence of the stirring member, the arrangement of the magnetic poles, and the like.

[0104]

The present invention will be described in more detail with reference to the following examples. Note that “%” and “part” in Examples and Comparative Examples
All parts are by weight unless otherwise specified.

First, the effect of the combined use of the quaternary ammonium salt compound and the nitrogen-containing heterocyclic compound in the present invention will be specifically described.

Phenol resin intermediate (phenol is converted to NH
Prepolymerized with formaldehyde using ₃ as a catalyst) 100 parts of a methanol solution was mixed with
After dissolving 30 parts of the quaternary ammonium salt compound (1) in methanol, they were mixed to obtain a paint (X-1).

Further, in a methanol solution of 100 parts of the above phenol resin intermediate, 28 parts of the above quaternary ammonium salt compound (1) was dissolved in methanol and mixed.
On the other hand, as a nitrogen-containing heterocyclic compound, imidazole compound particles (A
2) by weight of 1) was added and dispersed by a sand mill to prepare a paint (XY-2).

[0108]

Embedded image

Similarly, as shown in Table 1 below,
Paint (XY-3 to 6) in which the mixing ratio of quaternary ammonium salt compound (1) and imidazole compound particles (A1) is changed
Was prepared. Further, the phenol resin intermediate 10
In 0 parts of a methanol solution, imidazole compound particles (A
30 parts of -1) was added and dispersed by a sand mill to prepare a paint (Y-7).

When the amount of the imidazole compound particles added was 2
0, 15, 10, 5, 2 parts of paint (Y-8 ~
12) was produced.

These paints were applied to a stainless steel plate using a bar coater to have a uniform film thickness to obtain a sample for measuring the triboelectric charge.

[0112]

[Table 1]

100 parts of a polyester resin, 4 parts of a yellow pigment, and 4 parts of a negative charge controlling agent (Cr complex of 3,5-di-tert-butylsalicylic acid) were mixed in a Henschel mixer, and then sufficiently kneaded and dispersed with a three-roll mill. After cooling, 1
A coarsely pulverized toner product was obtained using a speed mill having a 5φ screen. The coarsely pulverized fine powder was repeatedly removed through a 60-mesh vibrating screen.

Using the sample plate and the coarsely pulverized toner,
The amount of triboelectric charge was measured using a surface charge amount measuring device (TS100AS manufactured by Toshiba Chemical Corporation) as shown in FIG. That is, the triboelectric charge when the coarsely pulverized product as a toner model and the sample plate having a surface coating layer as a triboelectric charging member model were in contact with each other was measured. In the apparatus shown in the figure, the amount of charge generated on the sample plate side is measured. It is considered that the same amount of charge having the opposite polarity as that of the triboelectric charge is generated on the toner side.

The results are shown in FIG. As can be seen from the graph, in the paint (Y-7 to 12) using only the imidazole compound particles (A1), the imidazole compound particles (A
In the case where the addition amount of 1) was 2 parts (Y-12), the charge amount was already in a saturated state, and even if the addition amount was increased, the change in the triboelectric charge amount was small. On the other hand, the quaternary ammonium salt compound (1) and the imidazole compound particles (A1)
It can be seen that when both were used and the addition amount was changed, the change in the triboelectric charge amount showed linearity.

That is, in the method of the present invention, it is possible to set an arbitrary triboelectric charging level by changing the mixing ratio of the quaternary ammonium salt compound and the nitrogen-containing heterocyclic compound. In addition, there is also a merit in production that the influence is hardly produced even when the amount of addition slightly fluctuates. As a comparative sample, a system in which an imidazole compound (positive charge control agent) and a Cr complex of 3,5-ditert-butylsalicylic acid (negative charge control agent) (Z) as shown in Table 2 were also examined.

[0117]

[Table 2]

As shown in FIG. 7, the charge amount was reduced only by adding a small amount of the Cr complex of 3,5-di-tert-butylsalicylic acid (negative charge control agent) (Z). It turned out that it did not show linearity.

Example 1 15 parts of the above quaternary ammonium salt compound (1) was added to 100 parts of a methanol solution of a phenol resin intermediate (phenol prepolymerized with formaldehyde using NH ₃ as a catalyst). After dissolving in methanol, they were mixed. On the other hand, 25 parts of conductive carbon black was added and dispersed by a sand mill. This is designated as Paint (M-19). Furthermore, M-
To 19, the imidazole compound (A1) was added and dispersion was continued. Thereafter, 20 parts of spherical carbon particles having a number average particle diameter of 5 μm were further added and dispersed to obtain a target paint (N-20).

Next, a resin coating layer was applied using this paint. As the substrate, a SUS cylindrical substrate having an outer diameter of 24.5 mmφ and having a magnet roller and a flange was used. The volume resistivity of the paint after curing was 25 Ω · cm. 35% of solid content of coating material (viscosity of coating liquid is 35mPa
・ After s), coating is performed by moving the spray gun up and down while rotating the work, and this is dried and cured at 150 ° C. for 60 minutes by a hot air drier, and a uniform conductive coating layer having a film thickness of 20 μm is formed. To form a developing sleeve. The surface roughness of this sleeve is, on average, Ra = 0.6 (μ
m). This developing sleeve is made of NP manufactured by Canon Inc.
-6750.

Next, a magnetic toner was prepared.

A polyester resin was used as the binder resin. Azo-based iron complex compound 2 was added to 100 parts of binder resin.
Parts, magnetic iron oxide (average particle size 0.2 μm, H _c = 120 Oe, σ _s = 75 emu / g, σ _r = 6 emu /
g) 95 parts and 5 parts of an alcohol wax are added,
After dispersing and mixing with a Henschel mixer, the mixture was melt-kneaded with a twin-screw extruder heated to 130 ° C., and the cooled mixture was roughly pulverized with a hammer mill. The coarsely pulverized material is finely pulverized by a jet mill, and the obtained finely pulverized material is classified by an air classifier,
The particle size distribution of the toner is 7.5 μm, 4 μm
A magnetic toner was obtained in which the number ratio of the following particles was 15.5% and the weight ratio of particles having a particle size of 12.7 μm or more was 1.0%. 0.8% of colloidal silica hydrophobized with a silane coupling agent was externally added to the toner.

Using this toner and the developing device, NP-67
Using 50, 23 ° C / 5% RH at room temperature and low temperature (N / L)
In an environment and a high-temperature and high-humidity (H / H) environment of 30 ° C./80% RH, image output was evaluated for up to 100,000 sheets.

[Evaluation Method] (1) Image Density The density of a 5 mmφ black circle on a test chart with an image ratio of 5.5% was measured with a reflection densitometer RD918 (manufactured by Macbeth) to measure the reflection density, and the average value of the five points was calculated. This was taken as the image density.

(2) Fog density The reflectance of a solid white image in an appropriate image was measured, and the reflectance of an unused transfer paper was further measured. (The worst value of the reflectance of a solid white image minus the reflectance of an unused transfer paper) The highest value of the reflectance) was defined as the fog density. The reflectance was measured with TC-6DS (manufactured by Tokyo Denshoku). However, when the measured value is visually judged, 1.5 or less is a level that can hardly be confirmed visually, and 2.0 to
A level of about 3.0 is a level that can be confirmed when viewed well, and a level that exceeds 4.0 is a level at which fog can be recognized at a glance.

(3) Toner charge amount (Q / M) and toner transport amount (M / S) The toner carried on the developing sleeve is collected by suction using a metal cylindrical tube and a cylindrical filter. From the charge amount Q stored in the condenser, the collected toner weight M, and the toner suction area S, the charge amount per unit weight Q / M (mC / kg) and the toner weight per unit area M / S (mg / cm ² ) was calculated, and the toner charge amount (Q / M) and the toner transport amount (M / S) were calculated.

(4) Blotch (defective image) Various images such as solid black, halftone and line images, and
At that time, the evaluation results were indicated by the following indices with reference to visual observation of toner coating defects on the sleeve, such as wavy unevenness and blotches (spotted unevenness) on the developing sleeve. A: Neither the image nor the sleeve can be confirmed at all. ：: Slightly confirmed on the sleeve, but hardly confirmed on the image. △: This can be confirmed by seeing through about one image out of several to several tens of images. Δ ○: The first halftone image or solid black image, which can be confirmed in the first cycle of the sleeve cycle. Δ: Confirmable with a halftone image or solid black image.
Practical level lower limit. Δ ×: Image defects can be confirmed on the entire solid black image. Impossible level. X: It can also be confirmed on a solid white image.

(5) Uniformity of Halftone (White Streaks, White Bands) In particular, linear and band-like streaks generated in halftone and running in the image traveling direction were evaluated by the following indexes. A: Neither the image nor the sleeve can be confirmed at all. : Slight confirmation is possible at a glance, but almost no confirmation at a glance. ○ △: Level slightly confirmed by halftone, but no problem with solid black. Δ ○: A level at which streaks can be confirmed in halftone, but can be slightly confirmed in solid black. Δ: Difference in shading can be confirmed even in a solid black image, but at the lower limit of a practical level. Δ ×: Difference in shading is conspicuous throughout the solid black image. Impossible level. ×: An image with low density and many streaks.

(6) Sleeve ghost After the solid white is washed out during image durability, a solid black bold character or a hieroglyphic image is placed on the white of one round of the sleeve of the image chart, and the image chart in which the remaining portion is halftone is displayed. It was used to evaluate how much ghosts of bold characters and hieroglyphic images occurred on halftone. ◎: No ghost. : Very slight difference in shading is observed but good. ○ △: A level at which slight differences in shading can be confirmed but do not pose a problem. ○: intermediate level between △ and △. Δ: The ghost is slightly conspicuous. Within practical level. N1: A negative ghost (thin ghost portion), which is a problem in practical use, appears for one round of the sleeve. P1: Positive ghost (dark ghost portion) which is a problem in practical use appears for one round of the sleeve. N2: Negative ghost, which is a problem in practical use, appears for two or more turns of the sleeve. P2: Positive ghost, which is a problem in practical use, appears for two or more turns of the sleeve.

The results are summarized in Tables 3 and 4.

<Example 2> A developing sleeve was prepared in the same manner as in Example 1 except that the imidazole compound was changed to the following (A2). The volume resistance of the paint after curing is 28Ω
Cm (paint N-21). The average surface roughness was also around Ra = 0.6 (μm) as in the developing sleeve of Example 1. The same evaluation as in Example 1 was performed using this sleeve. The results are summarized in Tables 3 and 4.

[0132]

Embedded image

Example 3 Imidazole compound (A1)
And the number average particle size of 5 for adjusting the surface roughness.
A developing sleeve was produced in the same manner as in Example 1, except that the spherical carbon particles of 20 μm were used. The volume resistance value of the paint after curing was 58 Ω · cm (Paint N-22).
The average surface roughness is also Ra as in the developing sleeve of Example 1.
= 0.6 (μm). The same evaluation as in Example 1 was performed using this sleeve. The results are summarized in Tables 3 and 4.

Example 4 A developing sleeve was produced in the same manner as in Example 1, except that the quaternary ammonium salt compound was changed to the above (3) and the addition amount of the imidazole compound (A1) was changed to 20 parts. The volume resistance of the paint after curing is 35
Ω · cm (Paint-23). The same evaluation as in Example 1 was performed using this sleeve. The results are shown in Tables 3 and 4.
Are shown together.

<Example 5> In Example 1, 40 parts of crystalline graphite having a volume average particle diameter of 4.5 μm and 20 parts of spherical carbon particles having a number average particle diameter of 5 μm were used in place of 25 parts of carbon black. A developing sleeve was produced in the same manner as in Example 1. The volume resistance of the paint after curing is
It was 15 Ω · cm (Paint N-24). The average surface roughness is Ra = 0.6 (μm) by reducing spherical carbon particles.
m). The same evaluation as in Example 1 was performed using this sleeve. The results are summarized in Tables 3 and 4.

Example 6 Using a nylon resin as a binder resin, the addition amount of the quaternary ammonium salt compound (1) was 10 parts and the addition amount of the imidazole compound (A1) was 30 parts based on 100 parts of the nylon resin. A developing sleeve was produced in the same manner as in Example 1 except that the amount of carbon black added was 30 parts. The volume resistance of the paint after curing is
It was 65 Ω · cm (Paint N-25). The same evaluation as in Example 1 was performed using this sleeve. Table 3 shows the results.
And 4 collectively.

Example 7 Using a polyurethane resin as a binder resin, the addition amount of the quaternary ammonium salt compound (1) was 20 parts and the addition amount of the imidazole compound (A1) was 20 parts based on 100 parts of the polyurethane resin. Other than that, a developing sleeve was manufactured in the same manner as in Example 1. The volume resistivity of the paint after curing was 35 Ω · cm (Paint N-26). The same evaluation as in Example 1 was performed using this sleeve. The results are summarized in Tables 3 and 4.

<Comparative Example 1> 25 parts of carbon black was added to 100 parts of the phenol resin intermediate of Example 1 and dispersed by a sand mill, and 25 parts of spherical carbon particles having a number average particle diameter of 5 μm were further added and dispersed. And paint (M-27)
And The volume resistance of the paint after curing was 10 Ω · cm. Using this coating material, a developing sleeve was produced in the same manner as in Example 1. The surface roughness is approximately Ra = 0.6
(Μm). The same evaluation as in Example 1 was performed using this sleeve.

<Comparative Example 2> 25 parts of carbon black was added to 100 parts of the phenolic resin intermediate of Example 1, dispersed by a sand mill, and the imidazole compound (A1) was further added.
15 and the dispersion was continued. Further, 25 parts of spherical carbon particles having a number average particle size of 5 μm were added and dispersed, and the paint (M-
28). The volume resistance of the paint after curing is 25Ω
cm. Using this coating material, a developing sleeve was produced in the same manner as in Example 1. The surface roughness is approximately Ra =
0.6 (μm). The same evaluation as in Example 1 was performed using this sleeve.

<Comparative Example 3> M-19 shown in Example 1 was used as a paint. The volume resistance of the paint after curing is 18
Ω · cm. Using this coating material, a developing sleeve was produced in the same manner as in Example 1. Surface roughness is approximately R
a = 0.6 (μm) The same evaluation as in Example 1 was performed using this sleeve.

<Comparative Example 4> 25 parts of carbon black was added to 100 parts of the phenol resin intermediate of Example 1 and dispersed by a sand mill, and the imidazole compound (A1) was added thereto.
And 15 parts of a chromium complex of 3,5-di-tert-butylsalicylic acid, which is a negative charge control agent, were added and dispersed. Further, 25 parts of spherical carbon particles having a number average particle size of 5 μm were added and dispersed, and the coating material (M- 28). The volume resistance of the paint after curing was 22 Ω · cm. Using this paint,
A developing sleeve was produced in the same manner as in Example 1. The surface roughness was approximately Ra = 0.6 (μm). The same evaluation as in Example 1 was performed using this sleeve.

Example 8 To a methanol solution of 100 parts of a phenol resin intermediate (phenol prepolymerized with formaldehyde using NH ₃ as a catalyst) was added 15 parts of the above quaternary ammonium salt compound (1). After dissolving in methanol, they were mixed. 20 parts of the powder of the imidazole compound (A2) was added thereto, and the mixture was dispersed using a sand mill to obtain a paint (N-30).

A carrier coating was performed using a ferrite carrier having an average particle size of 100 μm as a core material. N-
30 was diluted to a solids concentration of 10%. 5 kg of the ferrite core was put in a small Nauter mixer, the jacket was heated to 50 ° C., and the mixture was heated with stirring. Here, N
500 g of -30 was added dropwise while stirring was continued, and after completion of the addition, methanol was blown off while raising the temperature to 70 ° C. Thereafter, the mixture was discharged into an aluminum vat, the constant temperature dryer was set at 160 ° C., the resin was heated and cured, and the residual solvent was removed. After taking out from the dryer, the mixture was cooled with stirring and passed through a 60-mesh sieve to obtain a sample.

Next, a toner was prepared. To 100 parts of a styrene-butyl acrylate-maleic anhydride half ester copolymer, 4 parts of a phthalocyanine pigment, 2 parts of a low molecular weight polypropylene, and 3 parts of a 3,5-ditert-butylsalicylic acid Cr complex (negative charge control agent) were added. The mixture was dispersed and mixed with a Henschel mixer, melt-kneaded with a biaxial extruder heated to 130 ° C., and the cooled mixture was roughly pulverized with a hammer mill. The coarsely pulverized product is finely pulverized by a jet mill, and the obtained finely pulverized product is classified by an air classifier. The particle size distribution of the toner is such that the weight average particle size is 7.0 μm, and the number ratio of particles having a weight average particle size of 4 μm or less is 13.5. %, A weight percentage of particles having a particle size of 12.7 μm or more was 0.2%, thereby obtaining a cyan toner. 1.6% of colloidal silica hydrophobized with a silane coupling agent was externally added to this toner.

This toner and NP-5060 manufactured by Canon Inc. were used.
Was used to evaluate image output. The carrier and the toner were mixed at a toner concentration of 6% to prepare a start agent (D1). This starting agent is NP-5060
And the toner was replenished (toner concentration adjusted), and the durability up to 20,000 sheets was performed. 23 ° C / 5% RH
In a normal temperature and low temperature (N / L) environment and a high temperature and high humidity (H / H) environment of 30 ° C./80% RH, image output evaluation was performed for up to 20,000 sheets.

The results are summarized in Tables 5 and 6.

[Evaluation Method] (1) Image Density Image density was measured using a reflection densitometer RD918 (manufactured by Macbeth).
The density of the solid black (blue) part was measured.

(2) Tribo The amount of triboelectric charge between the toner and the carrier was measured using an apparatus as shown in FIG. A toner and a carrier are prepared so that the toner concentration becomes 6%, and the mixture is mixed with a turbulent mixer.
The measurement was performed after mixing for 2 seconds. The triboelectricity after the durability test was measured after removing the developer from the developing container and partially replenishing the toner or carrier so that the toner concentration became 6%. In the apparatus shown in FIG. 8, this developer is placed in a metal container 212 provided with a 500-mesh conductive screen 213 at a lower portion, and is suctioned by a suction device 211 through a suction port 217 to obtain a weight difference between before and after suction. Container 212
The amount of triboelectric charge is determined from the potential stored in the capacitor 218 connected to the. At this time, the suction pressure was set to 250 mmHg.
And With this method, the triboelectric charge of the toner or carrier is calculated using the following equation. Q (mC / kg) = (C × V) × (W1−W2) (where W1 is the weight before suction, W2 is the weight after suction, C is the capacity of the capacitor, and V is accumulated in the capacitor. Potential.)

(3) Fog density The reflectance of a solid white portion was measured, and the reflectance of unused paper was measured. The fog density was subtracted from the above value. value is,
It was shown by “average value−average value”. Reflectance is TC-6DS
(Manufactured by Tokyo Denshoku).

(4) Sleeve Ghost The difference in shading between the first round of the sleeve and the subsequent images, which occurs when a solid image is output, was evaluated according to the following criteria. ◎: There is no difference in shade. ：: It does not appear in the image density, but there is no problem as the difference in shading is slightly noticeable when seen through. △: Although hardly appearing in the image density, a difference in shading can be visually confirmed. Δ ○: The difference in shading is visually apparent, and there is a reflection density difference of about 0.01 measured by Macbeth. Δ: Difference in shading is somewhat noticeable. Practical lower limit level. Δ ×: Concentrated acid clearly appears in the image density difference. There is a problem in practical use. X: A level with a considerable density difference.

(5) Uniformity of Halftone The uniformity of halftone was evaluated according to the following criteria. A: Uniform image. ：: A level that is not bothersome, though there is a slight contrast when you look closely. ○ △: Although there is a slight difference in shading in the shape of stripes, a band-like shading difference is observed in the streak shape, but this is a level that does not cause any problem. Δ ○: intermediate between ○ △ and △. Δ: A haze-like shading difference or a streak or band-like shading difference can be confirmed even from a distance. Practical lower limit level. Δ ×: Shark-skinned moyamoya appears on the whole or streaks are confirmed quite clearly. ×: There is a portion where the density is not so high.

<Example 9> A carrier was prepared in the same manner as in Example 8, except that (5) was used as the quaternary ammonium salt compound.
The evaluation was performed in the same manner as described above. The results are summarized in Table 5 (Paint N-31).

<Comparative Example 5> A phenol resin intermediate used in Example 8 was used alone and carrier-coated. This was evaluated in the same manner as in Example 8. The results are summarized in Table 5 (Paint N-32).

<Comparative Example 6> A coated carrier was prepared and used in Example 8, except that the imidazole compound (A2) was not added (paint N-33). This was evaluated in the same manner as in Example 8. The results are summarized in Table 5.

<Comparative Example 7> In Example 8, the imidazole compound (A2) was dispersed by a sand mill without adding the quaternary ammonium salt compound (1) and used as a coating material (M-34). Produced. This was evaluated in the same manner as in Example 8. The results are summarized in Table 5.

Example 10 To a methanol solution of 100 parts of a nylon resin, 10 parts of a quaternary ammonium salt compound (3) was dissolved in methanol and mixed.
To this, 30 parts of the imidazole compound (A1) and 10 parts of crystalline graphite having a volume average particle size of 2.5 μm are added,
The mixture was sufficiently dispersed using a sand mill. Further, the solid content concentration was adjusted to 35% (Paint N-35). A urethane rubber (thickness 1 mm) is cut into a chip having a width of 5 mm, which is fixed to a pedestal, a spray device is moved at a constant speed in a fixed direction, spray-coated with N-35 paint, and the tip of the chip is elongated. A resin layer was formed on three surfaces in the directions. The chip was dried at 150 ° C. for 20 minutes using a thermostatic drier, and after cooling, both ends were cut into blade lengths. This was adhered to the end of the phosphor bronze (150 μm thick) plate on the surface where the resin layer was not formed to form a layer thickness regulating blade. This blade was attached to a Canon EP-H cartridge.
At this time, the following sleeve was used. In a methanol solution of 100 parts of a phenol resin, an average particle size of 4.
35 parts of 5 μm crystalline graphite and 4 parts of conductive carbon black were added, dispersed by sand mill, and applied to a metal cylinder (EP-H sleeve) using a spray gun to form a resin coating layer having a thickness of about 10 μm. Was formed.

Next, a toner was prepared. 100 parts of styrene-2 ethylhexyl acrylate-acrylic acid copolymer, 5 parts of carbon black, 6 parts of ester wax
Parts, 3 parts of an azo-based iron complex compound (negative charge control agent) were added, dispersed and mixed with a Henschel mixer, melt-kneaded with a twin-screw extruder heated to 130 ° C., and the cooled mixture was roughly pulverized with a hammer mill. did. The coarsely pulverized product is finely pulverized by a jet mill, and the obtained finely pulverized product is classified by an air classifier.
12.4%, 12.7 μm
A black nonmagnetic toner having a weight ratio of the above particles of 0.3% was obtained. 1.4% of colloidal silica hydrophobized with a silane coupling agent was externally added to this toner.

Image evaluation was performed using a Canon LBP-20.
30 modified machines were used. A normal temperature and low humidity (N / L) environment of 23 ° C./5% RH and a high temperature and high humidity (H / H) of 30 ° C./80% RH
/ H) In an environment, image output evaluation of up to 5,000 sheets was performed.
The results are summarized in Tables 7 and 8.

[Evaluation Method] (1) Image Density The density of a 5 mmφ black circle on a test chart with an image ratio of 5.5% was measured with a reflection densitometer RD918 (manufactured by Macbeth), and the average value of the five points was calculated. This was taken as the image density.

(2) Fog The reflectance of a solid white image in an image suitable for fogging was measured, and the reflectance of an unused transfer paper was further measured. (The worst value of the reflectance of a solid white image−the reflection of an unused transfer paper) The highest value of the rate was defined as the fog density. The reflectance was measured with TC-6DS (manufactured by Tokyo Denshoku). Here, when the measured value is visually judged, 1.5 or less is a level that can hardly be confirmed visually, and 2.0 to
A level of about 3.0 is a level that can be confirmed when viewed well, and a level that exceeds 4.0 is a level at which fog can be recognized at a glance.

(3) Toner Charge (Q / M) and Toner Conveyance (M / S) The toner carried on the developing sleeve is collected by suction using a metal cylindrical tube and a cylindrical filter. From the charge amount Q stored in the condenser, the collected toner weight M, and the toner suction area S, the charge amount per unit weight Q / M (mC / kg) and the toner weight per unit area M / S (g / m ² ) was calculated, and the respective toner charge amounts (Q / M) and toner transport amounts (M / S) were determined.

(4) Sleeve Ghost The difference in shading between the first round of the sleeve and the subsequent images, which occurs when a solid image is output, was evaluated according to the following criteria. ◎: There is no difference in shade. ：: It does not appear in the image density, but there is no problem as the difference in shading is slightly noticeable when seen through. △: Although hardly appearing in the image density, a difference in shading can be visually confirmed. Δ ○: The difference in shading is visually apparent, and there is a reflection density difference of about 0.01 measured by Macbeth. Δ: Difference in shading is somewhat noticeable. Practical lower limit level. Δ ×: The density difference clearly appears in the image density difference. There is a problem in practical use. X: A level with a considerable density difference.

(5) Uniformity of Halftone The uniformity of halftone was evaluated according to the following criteria. A: Uniform image. ：: A level that is not bothersome, though there is a slight contrast when you look closely. ○ △: A level that does not cause any problem although a slight difference in shading is observed, but a streak or band-like shading is confirmed. Δ ○: intermediate between ○ △ and △. Δ: A haze-like shading difference or a streak or band-like shading difference can be confirmed even from a distance. Practical lower limit level. Δ ×: Shark-skinned moyamoya appears on the whole or streaks are confirmed quite clearly. ×: There is a portion where the density is not so high.

<Example 11> A coating material was prepared in the same manner as in Example 10 except that the addition amount of the imidazole compound (A1) was changed to 20 parts (N-36).
Using this paint, a blade similar to that of Example 10 was manufactured, and the same evaluation as that of Example 10 was performed. The results are summarized in Tables 7 and 8.

Comparative Example 8 The nylon resin used in Example 10 was used alone and blade-coated.
This was evaluated in the same manner as in Example 10. The results are summarized in Tables 7 and 8 (Paint M-37).

<Comparative Example 9> [0166] A blade was prepared and coated in the same manner as in Example 10 except that the imidazole compound (A1) was not added (paint M-38). This was evaluated in the same manner as in Example 10. The results are summarized in Tables 7 and 8.

<Comparative Example 10> In Example 10, the imidazole compound (A1) was dispersed by a sand mill without adding the quaternary ammonium salt compound (3) and used as a paint (M-39). Produced. Example 1
Evaluation was performed in the same manner as in the case of 0. The results are shown in Tables 7 and 8.
Are shown together.

[0168]

[Table 3]

[0169]

[Table 4]

[0170]

[Table 5]

[0171]

[Table 6]

[0172]

[Table 7]

[0173]

[Table 8]

[0174]

As described above, according to the present invention,
By changing the formulation ratio of the quaternary ammonium salt compound and the nitrogen-containing heterocyclic compound in the resin layer, the charge amount can be changed linearly, so that it is possible to control the negatively chargeable toner to a suitable tribo. A triboelectric charging member can be provided. Further, since the change in the amount of charge with respect to the change in the prescription ratio is gentle, the deviation of the prescription of about the weighing error has a small effect on the toner tribo, and the latitude in production is wide.

Further, since the structure does not impair the strength of the resin coating layer, the surface property is stable, and a good image can be provided even in long-term image durability.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating a configuration example of a two-component developing device using a carrier.

FIG. 2 is a schematic diagram illustrating a configuration example of a developing device using a one-component magnetic toner.

FIG. 3 is a schematic diagram illustrating another configuration example of a developing device using a one-component magnetic toner.

FIG. 4 is a schematic diagram illustrating a configuration example of a developing device using one-component non-magnetic toner.

FIG. 5 is an example schematically showing a developing device for a developing method in which a sleeve contacts a drum.

FIG. 6 is a schematic diagram showing a measurement principle of a tilt type surface charge amount measuring device.

FIG. 7 is a graph showing the effect of the resin coating layer of the present invention on triboelectric charging characteristics and the triboelectric charging characteristics of a comparative example.

FIG. 8 is a schematic view of an apparatus for measuring a two-component tribo using a carrier.

[Explanation of symbols]

1, 24, 71, 91 electrostatic latent image carrier (photosensitive drum) 2, 11, 23, 72, 101 developer layer thickness regulating member (regulating blade) 3, 25, 73, 102 developing container (hopper) 4, 40, 41, 43, 87 Developer (toner, carrier) 5, 22 Magnet roller 6, 76, 94, 97, 99 Base 7, 74, 77, 92, 93, 96 Coating layer 8, 21, 78, 95 Development Agent carrier (developing sleeve) 9 Developing bias power supply 10, 80, 103 Stirring member 31 Sealing member 42, 45, 47 Stirring chamber 48 Partition wall 50, 51, 52, 98 Toner transport member A Developing sleeve rotation direction B Photoconductor rotation direction C, D, E development section

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kenji Fujishima 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Naoki Okamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Kazunori Saiki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Masayoshi Shimamura 3-30-2, Shimomaruko, Ota-ku, Tokyo Canon Inc. F Terms (reference) 2H005 BA02 BA06 BA07 CA28 CB18 DA01 DA09 2H077 AD06 AD13 AD17 AE03 AE04 AE05 AE06 EA01 EA11 FA13 FA25

Claims (16)

[Claims] 1. A frictional charging member used in an electrophotographic apparatus, wherein at least a surface of the frictional charging member in contact with toner has a quaternary ammonium salt which is positively chargeable with respect to a binder resin and iron powder. A triboelectric charging member, comprising a resin coating layer formed of a compound and a resin composition having at least a nitrogen-containing heterocyclic compound. 2. A method according to claim 1, wherein a part or all of the binder resin of the resin coating layer has at least a —NH ₂ group, ＮＨNH
The triboelectric charging member according to claim 1, wherein the triboelectric charging member has one of a group and a -NH- bond. 3. The method according to claim 1, wherein the nitrogen-containing heterocyclic compound in the resin coating layer is
The triboelectric charging member according to claim 1, wherein the triboelectric charging member is an imidazole compound. 4. The imidazole compound has the following formula (1)
Or (2) [Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ₁ and R ₂ may be the same or different. R ₃ and R _{4 each} have 3 to 3 carbon atoms.
Represents 30 linear alkyl groups, and R ₃ and R ₄ may be the same. [Chemical formula 2] [Wherein, R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and R ₅ and R ₆ may be the same. R ₇ has a carbon number represents a linear alkyl group of 3 to 30. The triboelectric charging member according to claim 3, wherein the compound is a compound represented by the following formula: 5. The triboelectric charging member according to claim 1, wherein the resin coating layer further contains a conductive fine powder. 6. The frictional charging member according to claim 1, wherein the frictional charging member is a developer carrier. 7. The friction charging member according to claim 1, wherein the friction charging member is a developer layer thickness regulating member. 8. The frictional charging member according to claim 1, wherein the frictional charging member is a carrier particle. 9. A developing container comprising: a developing container; and a developer carrying member which carries the developer having the toner held in the developing container and transports the developer to a developing region facing the latent image carrying member; A developing device that develops a latent image on the latent image carrier with toner charged by friction of the developer carried and conveyed by the developer carrier with the frictional charging member to visualize the latent image; At least the surface of the application member that comes into contact with the toner is a resin coating formed by a resin composition having at least a binder resin, a quaternary ammonium salt compound positively charged to iron powder, and a nitrogen-containing heterocyclic compound. A developing device comprising a layer. 10. A part or all of the binder resin of the resin coating layer has at least a —NH ₂ group and ＮＨNH in its molecular structure.
The developing device according to claim 9, having one of a group and a —NH— bond. 11. The developing device according to claim 9, wherein the nitrogen-containing heterocyclic compound in the resin coating layer is an imidazole compound. 12. The imidazole compound is represented by the following formula (1) or (2): [Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ₁ and R ₂ may be the same or different. R ₃ and R _{4 each} have 3 to 3 carbon atoms.
Represents 30 linear alkyl groups, and R ₃ and R ₄ may be the same. [Formula 4] [Wherein, R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and R ₅ and R ₆ may be the same. R ₇ has a carbon number represents a linear alkyl group of 3 to 30. The developing device according to claim 9, wherein the compound is a compound represented by the following formula: 13. The developing device according to claim 9, wherein the resin coating layer further contains a conductive fine powder. 14. The developing device according to claim 9, wherein the frictional charging member is a developer carrier. 15. The developing device according to claim 9, wherein the frictional charging member is a developer layer thickness regulating member. 16. The developing device according to claim 9, wherein the frictional charging member is a carrier particle.