JP2006079022A - Color carrier and developer for electrostatic latent image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a good electrophotographic carrier and developer capable of forming a fine image having excellent durability and no edge effect over a long period of time and free from color stains, and the developer To provide a process cartridge using
A carrier having a resin coating layer on the surface of a core material, the coating layer comprising an indium oxide layer containing tin dioxide on a tin oxide layer, the surface of which is treated with a silane coupling agent. An electrophotographic carrier comprising conductive particles having a conductive coating layer, wherein the carbon content of the conductive particles is 0.1 wt% or more and 0.5 wt% or less.
[Selection] Figure 1

Description

  The present invention relates to a color carrier and a developer used for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like.

  In electrophotographic image formation, a latent image is formed by an electrostatic charge on an image carrier such as a photoconductive substance, and a charged toner particle is attached to the electrostatic latent image to form a visible image. After that, the toner image is transferred to a recording medium such as paper and fixed to form an output image. In recent years, the technology of copiers and printers using an electrophotographic system has been rapidly expanding from monochrome to full color, and the full color market tends to expand. Color image formation by full-color electrophotography generally reproduces all colors by laminating three color toners of three primary colors, yellow, magenta, and cyan, or four color toners with black added thereto. . Therefore, in order to obtain a clear full color image with excellent color reproducibility, it is necessary to smooth the fixed toner image surface to some extent to reduce light scattering. For these reasons, the image gloss of conventional full-color copying machines or the like is often 10 to 50% of medium to high gloss.

  In general, as a method for fixing a dry toner image on a recording medium, a contact heating fixing method in which a roller or belt having a smooth surface is heated and pressed against the toner is frequently used. This method has high thermal efficiency and high-speed fixing, and is advantageous in that it can give gloss and transparency to the color toner. However, the surface of the heat-fixing member is brought into contact with the molten toner under pressure. The post-peeling causes a so-called offset phenomenon in which a part of the toner image adheres to the surface of the fixing roller and re-transfers to another image. In order to prevent this offset phenomenon, a method is generally adopted in which the fixing roller surface is formed of silicone rubber or fluororesin with excellent releasability, and then a release oil such as silicone oil is applied to the fixing roller surface. It had been. However, this method is extremely effective in preventing toner offset, but a device for supplying release oil is necessary, and the fixing device becomes large and unsuitable for downsizing the machine. For this reason, in a monochrome toner, by adjusting the molecular weight distribution of the binder resin so that the melted toner does not break internally, the viscoelasticity at the time of melting of the toner is increased, and a release agent such as wax is further included in the toner. There is a tendency to employ a method in which the release oil is not applied to the fixing roller (oilless) or the amount of oil applied is very small.

  On the other hand, in the case of color toners as well as monochrome toners, there is a tendency toward oil-less for the purpose of downsizing machines and simplifying the configuration. However, as described above, in order to improve the color reproducibility of the color toner, it is necessary to smooth the surface of the fixed image, so the viscoelasticity at the time of melting must be lowered, and it is easier to offset than the glossy monochrome toner. Therefore, it is more difficult to make the fixing device oil-free and to apply a small amount. In addition, when a release agent is contained in the toner, the adhesion of the toner is increased and the transfer property to the transfer paper is lowered. Further, the release agent in the toner contaminates the frictional charging member such as a carrier to reduce the charging property. This causes a problem that the durability is lowered.

  On the other hand, regarding the carrier, prevention of filming of toner components on the carrier surface, formation of a uniform carrier surface, prevention of surface oxidation, prevention of moisture sensitivity deterioration, extension of developer life, prevention of carrier adhesion to the surface of the photoreceptor, photoreceptor For the purpose of protection from scratches or abrasion by the carrier, control of the charge polarity or adjustment of the charge amount, a hard and high-strength coating layer is usually provided by coating with an appropriate resin material. For example, those coated with a specific resin material [Japanese Patent Laid-Open No. 58-108548 (Patent Document 1)], and various additives added to the coating layer [Japanese Patent Laid-Open No. 54-1555048 ( Patent Document 2), Japanese Patent Application Laid-Open No. 57-40267 (Patent Document 3), Japanese Patent Application Laid-Open No. 58-108549 (Patent Document 4), Japanese Patent Application Laid-Open No. 59-166968 (Patent Document) 5), Japanese Patent Publication No. 1-19584 (Patent Document 6), Japanese Patent Publication No. 3-628 (Patent Document 7), Japanese Patent Application Laid-Open No. 6-202381 (Patent Document 8)], and an additive on the carrier surface. Those using an attached material [Japanese Patent Laid-Open No. 5-273789 (Patent Document 9)], and those using a coating film containing conductive particles larger than the coating thickness [Japanese Patent Laid-Open No. 9-160304] Gazette (patent document 10)] etc. are disclosed. Japanese Patent Laid-Open No. 8-6307 (Patent Document 11) describes that a benzoguanamine-n-butyl alcohol-formaldehyde copolymer is used as a main component for a carrier coating material, and Japanese Patent No. 2683624 (Patent Document 12). ) Describes that a cross-linked product of a melamine resin and an acrylic resin is used as a carrier coating material.

  However, durability and carrier adhesion suppression are still insufficient. Concerning durability, there are problems such as spent toner on the carrier surface, destabilization of the charge amount, and reduction of the coating layer due to film removal of the coating resin and accompanying resistance reduction. However, as the number of copies increases, the quality of the copied image deteriorates, which is a problem. Therefore, improvement is necessary.

  Furthermore, while the demand for faster and more beautiful is increasing, the speed of machines in recent years is remarkable. Along with this, the stress received by the developer has also increased dramatically, and it has become impossible to obtain a sufficient life even with a carrier that has been long-lived in the past. In addition, carbon black has been used as a carrier resistance adjusting agent in the past, but there is a concern about color stains caused by film removal or / and migration of carbon black into a color image due to carbon black detachment. As a countermeasure, various methods have been proposed and demonstrated their effects. For example, Japanese Patent Laid-Open No. 7-140723 (Patent Document 13) proposes a carrier in which a conductive agent (carbon black) is present on the surface of the core material and no conductive material is present in the resin coating layer. In addition, the coating resin layer has a carbon black concentration gradient in the thickness direction, and the coating resin layer has a lower carbon black concentration toward the surface, and a carrier in which no carbon black exists on the surface of the coating layer. This is proposed in Japanese Laid-Open Patent Application No. 8-179570 (Patent Document 14). Further, a two-layer coated carrier in which an inner coating resin layer containing conductive carbon is provided on the surface of core material particles and a surface coating resin layer containing a white conductive material is further provided thereon is disclosed in JP-A-8 -286429 (Patent Document 15). However, it cannot cope with the recent increase in stress, and color stains have become a problem and need to be improved.

  As a drastic measure against color stains, it is clear that eliminating carbon black that causes color stains is most effective. However, when carbon black is simply pulled out, the resistance of the carrier increases because carbon black has the property of low electrical resistance as described above. In general, when a carrier having a high resistance is used as a developer, on the image surface of a large area of a copy image, the image density at the center is very thin and only the edges are expressed deeply, so-called edge effect is sharply used. It becomes the image that was. In addition, when the image is a character or a thin line, the image is clear due to the edge effect. However, when the image is halftone, there is a defect that the image is very reproducible.

  Generally, as a resistance adjuster other than carbon black, for example, titanium oxide, zinc oxide, etc. are known, but as an effect of lowering resistance, an effect sufficient to replace carbon black cannot be obtained, and there is a problem It has not yet been resolved and needs to be improved.

JP 58-108548 A JP 54-1555048 A JP 57-40267 A JP 58-108549 A JP 59-166968 A Japanese Patent Publication No. 1-19584 Japanese Examined Patent Publication No. 3-628 JP-A-6-202381 JP-A-5-273789 JP-A-9-160304 JP-A-8-6307 Japanese Patent No. 2683624 Japanese Unexamined Patent Publication No. 7-140723 JP-A-8-179570 JP-A-8-286429

  The present invention has been made in view of the above problems, and is capable of forming a fine image with excellent durability and no edge effect over a long period of time. It is to provide a developer and to provide a process cartridge using the developer.

That is, the said subject is solved by (1)-(16) of this invention.
(1) “A carrier having a resin coating layer on the surface of a core material, the coating layer comprising an indium oxide layer containing tin dioxide on a tin oxide layer, the surface of which is treated with a silane coupling agent. Electrophotographic carrier comprising conductive particles having a conductive coating layer, wherein the amount of carbon in the conductive particles is 0.1 wt% or more and 0.5 wt% or less ”;
(2) The above-mentioned (1), wherein the conductive particle substrate is made of one or more of aluminum oxide, titanium dioxide, zinc oxide, silicon dioxide, barium sulfate, and zirconium oxide. The electrophotographic carrier according to the item);
(3) “The electrophotographic carrier according to (1) or (2) above, wherein the conductive particles have a powder specific resistance of 200 (Ω · cm) or less”;
(4) "The electrophotographic carrier according to any one of (1) to (3) above, wherein the resin coating layer contains particles other than conductive particles";
(5) “Volume resistivity is 10 [Log (Ω · cm)] or more and 16 [Log (Ω · cm)] or less, wherein any one of (1) to (4) above The electrophotographic carrier according to Crab ";
(6) “The carrier for electrophotography according to any one of (1) to (5) above, wherein the weight average particle diameter is 20 μm or more and 65 μm or less”;
(7) "The electrophotographic carrier according to any one of (1) to (6) above, wherein the binder resin of the resin coating layer is at least a silicon resin";
(8) "The electrophotographic carrier according to any one of (1) to (6) above, wherein the binder resin of the resin coating layer is at least an acrylic resin";
(9) "The electrophotographic carrier according to any one of (1) to (6) above, wherein the binder resin of the resin coating layer is at least an acrylic resin and a silicon resin";
(10) The first aspect is characterized in that the particle diameter (D) of the conductive particles contained in the coating layer and the film thickness (h) of the coating layer are 1 <[D / h] <10. The electrophotographic carrier according to any one of (1) to (9);
(11) The content ratio of the conductive particles in the coating layer is 10% by weight or more and 70% by weight or less, according to any one of (1) to (10), Electrophotographic carrier ";
(12) The magnetic moment at 1000 (10 ^ 3 / 4π · A / m) is 40 (Am ^ 2 / kg) or more and 90 (Am ^ 2 / kg) or less. ) To the electrophotographic carrier according to any one of items (11)];
(13) "Electrophotographic developer comprising at least a toner composed of a binder resin and a colorant and the carrier according to any one of Items (1) to (12)";
(14) "Electrophotographic color developer according to item (13) above, wherein the toner is a color toner";
(15) “Forming an electrostatic latent image on an image carrier, developing the electrostatic latent image with a developer composed of at least a carrier and a toner, and forming a visible image; An image forming method comprising a step of transferring and fixing to a recording member, wherein the developer uses the electrophotographic developer according to item (13) or (14). Forming method ";
(16) In a process cartridge that integrally supports a developing unit and at least one developing unit selected from a photosensitive member, a charging unit, and a cleaning unit and is detachable from the main body of the image forming apparatus, the developing unit A process cartridge, wherein the developer is held, and the developer is the developer according to item (13) or (14).

  With the carrier of the present invention, there is no occurrence of carrier adhesion, and a high-definition image with good reproducibility of fine lines such as character portions and the edge effect suppressed can be obtained. Furthermore, since there is little change in the charge amount and resistance, the image quality deterioration of the copy image that occurs as the number of copies increases is greatly improved, and an excellent effect that a good image can be maintained over a long period of time is achieved. is there.

Hereinafter, the present invention will be described in more detail.
As a result of continuous studies to solve the above-described problems of the prior art, the present inventors have found that in a carrier having a coating layer on the core surface, the lower layer is a tin dioxide layer, and the upper layer is an indium oxide layer containing tin dioxide. And having a conductive coating layer whose surface is treated with a silane coupling agent and having a carbon content of 0.1 wt% or more and 0.5 wt% or less, more preferably 0.1 wt% or more and 0.4 wt% or less. Thus, it has been found that the improvement effect is particularly remarkable when the carrier coating layer contains conductive particles of 0.2 wt% or more and 0.4 wt% or less. This is because the conductive particles have a structure in which a tin dioxide layer is provided on the lower layer of the surface of the base particles, and an indium oxide layer containing tin dioxide as a conductive layer is provided thereon and subjected to appropriate treatment. Since the upper conductive layer can be fixed uniformly and firmly on the particle surface, the resistance adjustment effect can be sufficiently exerted, and it is important that the carbon content is in the above range.
When the amount of carbon is less than 0.1% by weight, the surface treatment of the conductive fine particles with the silane coupling agent is not completely covered, and the resistance changes with time due to the ingress of oxygen and moisture. The carrier resistance value will change. On the other hand, if it exceeds 0.5% by weight, the surface of the conductive particles is completely covered, and the coupling agent-treated layer becomes an insulator of the conductive film, resulting in loss of conductivity. The adjustment effect cannot be demonstrated. In addition, the brightness decreases and the whiteness is lost. Here, the appropriate treatment of the layer on the surface of the conductive particles refers to 0.2 to 0.6% by weight / m ² / g, but is not necessarily limited thereto.

The carbon amount measurement method in the present invention was measured using IR-212 manufactured by LECO. Weigh 0.5 g of the sample in a ceramic crucible, add auxiliary combustors (LECOCEL II and IRON CHIP ACCELERATOR), set in a device and measure.
The data after the measurement is taken as the carbon content.

  Furthermore, the improvement effect is remarkable when the base of the conductive particles is any one of aluminum oxide, titanium dioxide, zinc oxide, silicon dioxide, barium sulfate, and zirconium oxide. This is compatible with the particle surface and the conductive layer treatment material, but the compatibility with the particles is very good, and the conductive treatment effect is exhibited well. Moreover, in this invention, it is not limited to the said particle | grain, In addition to these, what exhibits a favorable effect can be used.

Furthermore, the improvement effect is remarkable when the powder specific resistance of the conductive particles is 200 (Ω · cm) or less. This is because the purpose of containing the conductive particles is to adjust the resistance, and therefore it is necessary to obtain an effect of efficiently reducing the resistance. However, when the specific resistance exceeds 200 (Ω · cm), the effect is insufficient. The conductive particles in the present invention preferably have a particle size (number average particle size) of 0.2 to 0.6 μm.
The following aspects are mentioned as a more detailed manufacturing method of the electroconductive particle suitable for this invention.

There are various methods for forming a lower layer of tin dioxide hydrate film. For example, a method of adding an alkali or acid after adding a tin salt or stannate solution to an aqueous suspension of a white inorganic pigment, adding a tin salt or tin hydrochloric acid and an alkali or acid separately in parallel There is a method of covering and processing. In order to uniformly coat the surface of the white inorganic pigment particles with the hydrated tin oxide, the latter parallel addition method is more suitable. At this time, the water suspension should be kept warm at 50 to 100 ° C. Is more preferable. Moreover, pH at the time of adding a tin salt or a stannate and an alkali or an acid in parallel is set to 2 to 9. Since the isoelectric point of tin dioxide hydrate is pH = 5.5, it is important to maintain pH = 2-5 or pH 6-9, whereby the hydrolysis product of tin is converted into a white inorganic pigment. It can be uniformly deposited on the particle surface.
As the tin salt, for example, tin chloride, tin sulfate, tin nitrate or the like can be used. Moreover, as a stannate, sodium stannate, potassium stannate, etc. can be used, for example.

Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, ammonia water, and ammonia gas. Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and the like. .
The coating amount of the hydrate of tin dioxide is 0.5 to 50% by weight, preferably 1.5 to 40% by weight as SnO _{2 with} respect to the white inorganic pigment of the substrate. If the amount is too small, the coating state of the hydrate of indium oxide containing tin oxide coated thereon becomes non-uniform, and the volume resistivity of the powder increases due to the influence of the inorganic pigment of the substrate. When the amount is too large, the amount of tin oxide hydrate not adhered to the surface of the inorganic pigment particles of the substrate increases, and the coating tends to be uneven.

  Next, there are various methods for forming a coating of indium oxide hydrate containing tin dioxide as an upper layer. However, in order not to dissolve the coating of hydrated tin dioxide, the tin salt and indium salt are not dissolved. A method in which a mixed solution and an alkali are separately added in parallel to form a film is more preferable. At this time, it is more preferable to heat the aqueous suspension to 50 to 100 ° C. In addition, it is important that the pH when the mixed solution and the alkali are added in parallel is 2 to 9, and preferably maintained at pH 2 to 5 or pH 6 to 9, so that the hydrolysis reaction product of tin and indium is uniform. Can be deposited.

As a raw material of tin, for example, tin chloride, tin sulfate, tin nitrate or the like can be used. As the indium raw material, for example, indium chloride, indium sulfate, or the like can be used.
The amount of tin dioxide added is 0.1 to 20% by weight, preferably 2.5 to 15% by weight as SnO _{2 with} respect to In ₂ O ₃ , and the desired conductivity is too small or too large. Cannot be obtained.

The treatment amount of indium oxide is 5 to 200% by weight, preferably 8 to 150% by weight, as In ₂ O _{3 with} respect to the inorganic pigment of the substrate. If the amount is too small, the desired conductivity cannot be obtained and too much. However, the conductivity is hardly improved, and it is expensive and not preferable from the viewpoint of cost.

In the present specification, the “conductive” powder means a powder having a volume resistivity value of 1 to 500 Ω · cm. As will be shown in the examples described later, according to the present invention, a white conductive powder having excellent electrical conductivity of 100 Ω · cm or less, and in some cases 10 Ω · cm or less, comparable to that of an antimony-containing product can be obtained. .
When the heat treatment is performed, it is preferably performed in a non-oxidizing atmosphere at 350 to 750 ° C., and the volume resistivity of the powder can be lowered by 2 to 3 orders of magnitude as compared with the heat treatment in air. .

  An inert gas can be used to create a non-oxidizing atmosphere. As the inert gas, for example, nitrogen, helium, argon, carbon dioxide gas or the like can be used. Industrially, it is advantageous in terms of cost to perform the heat treatment while blowing nitrogen gas, and a product with stable characteristics can be obtained.

The temperature at the time of heating is 350 to 750 ° C., preferably 400 to 700 ° C., and it is difficult to obtain desired conductivity even when the temperature is lower or higher than this range. In addition, the heating time is not effective when the heating time is too short, and if the heating time is too long, no further effect can be expected, so about 15 minutes to 4 hours is appropriate, preferably about 1 to 2 hours. It is.
The fired product obtained is pulverized, and a predetermined amount of a silane coupling agent is added to the pulverized product while stirring. Further, the treated product is heat-treated at 90 to 120 ° C. for 1 hour. As the silane coupling agent, an amino silane coupling agent, a methacryloxy silane coupling agent, a vinyl silane coupling agent, or a mercapto silane coupling agent can be used.

  Furthermore, the improvement effect is remarkable by containing particles other than electroconductive particle in a carrier coating layer. This is because when the resistance is adjusted only by the conductive particles, the amount of filler in the coating layer changes, which may be undesirable because the coating layer configuration changes. By using the particles other than the conductive particles and the conductive particles in a well-balanced manner, the resistance can be adjusted while maintaining the configuration of the coating layer. The particles other than the conductive particles mentioned here include, for example, inorganic oxide particles, resin fine particles and the like, and include those used for the base of the conductive particles, but are not limited thereto. Further, from the viewpoint of making the configuration of the coating resin more uniform, it can be said that it is preferable to use the same particles as the particles used for the base of the conductive particles.

  Furthermore, the improvement effect is remarkable when the volume specific resistance of the carrier is 10 [Log (Ω · cm)] or more and 16 [Log (Ω · cm)] or less. This is not preferable because, when the volume resistivity is less than 10 [Log (Ω · cm)], carrier adhesion occurs in the non-image area. On the other hand, if the volume resistivity exceeds 16 [Log (Ω · cm)], the edge effect is deteriorated to an unacceptable level. In addition, when it falls below the measurable lower limit of the high resist meter, the volume specific resistance value is not substantially obtained, and it will be treated as a breakdown. The volume resistivity referred to in this specification is a value obtained by measuring a resistance value measured with a high resist meter 30 seconds after DC1000V is applied between both electrodes after a carrier is injected between parallel electrodes separated by a gap of 2 mm. The value converted into volume resistivity.

  Furthermore, when the weight average particle diameter is 20 μm or more and 65 μm or less, the improvement effect is remarkable. This is not preferable when the weight average particle diameter is less than 20 μm, because problems such as carrier adhesion occur due to a decrease in the uniformity of the particles and a failure to establish a technique that can be fully used on the machine side. On the other hand, if it exceeds 65 μm, the reproducibility of image details is poor and a fine image cannot be obtained, which is not preferable.

  Furthermore, at least the binder resin is a silicon resin, so that the improvement effect is remarkable. This is because the silicone resin has a low surface energy, so that it is difficult for the toner component to be spent and the accumulation of the spent component due to film scraping is difficult to obtain.

  As used herein, the term “silicon resin” refers to all commonly known silicon resins, such as straight silicon consisting only of organosilosan bonds, and silicon resins modified with alkyd, polyester, epoxy, acrylic, urethane, etc. However, it is not limited to this. Examples of commercially available straight silicon resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical, SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicon. In this case, it is possible to use the silicon resin alone, but it is also possible to simultaneously use other components that undergo a crosslinking reaction, charge amount adjusting components, and the like. Further, as modified silicone resin, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical, SR2115 (epoxy modified) manufactured by Toray Dow Corning Silicon Co., Ltd. , SR2110 (alkyd modified) and the like.

  Moreover, the improvement effect is remarkable because at least the binder resin is an acrylic resin. This is because acrylic resin has strong adhesion and low brittleness, so it has very excellent properties in abrasion resistance, and it is difficult for deterioration such as coating film scraping and film peeling, so the coating layer can be maintained stably. In addition, the particles contained in the coating layer such as conductive particles can be firmly held due to the strong adhesiveness. In particular, a powerful effect can be exhibited in holding particles having a particle size larger than the coating layer thickness.

  The acrylic resin referred to in this specification refers to all resins having an acrylic component, and is not particularly limited. In addition, it is possible to use the acrylic resin alone, but it is also possible to use at least one other component that undergoes a crosslinking reaction at the same time. Examples of other components that undergo a crosslinking reaction include amino resins and acidic catalysts, but are not limited thereto. The amino resin here refers to guanamine, melamine resin and the like, but is not limited thereto. Moreover, what has a catalytic action can be used with an acidic catalyst here. For example, it has a reactive group such as a fully alkylated type, a methylol group type, an imino group type, and a methylol / imino group type, but is not limited thereto.

  Furthermore, at least the binder resin is an acrylic resin and a silicon resin, so that the improvement effect is remarkable. As mentioned above, acrylic resin has a very excellent property of abrasion resistance due to its strong adhesiveness and low brittleness, but on the other hand, it is a combination with a toner that is easy to spend because of its high surface energy. In such a case, problems such as a decrease in charge amount due to accumulation of toner component spent may occur. In this case, this problem can be solved by using together a silicon resin that has an effect that it is difficult to spend the toner component due to the low surface energy and the accumulation of the spent component is difficult to progress due to film scraping. However, since silicon resin has weak adhesiveness and high brittleness, it also has a weak point that it has poor wear resistance. Therefore, it is important to obtain a good balance between the properties of these two types of resins, which makes it difficult to spend. It is possible to obtain a coating film having wear characteristics.

  The amount of the binder resin in the carrier coating layer in the present invention is preferably in the range of 0.1% by weight to 1.5% by weight. When the content is less than 0.1% by weight, there is almost no coating film, so that the effect of the coating film cannot be sufficiently exhibited, which is not preferable. On the other hand, when it exceeds 1.5% by weight, it is not preferable because the amount of chipping of the film tends to increase as the film thickness increases, but it is not limited thereto. The content rate of a binder resin here is shown with the following formula | equation.

  Furthermore, the improvement effect is remarkable when the particle diameter (D) of the conductive particles contained in the carrier coating layer and the coating layer thickness (h) are 1 <[D / h] <10. This is because when the conductive particle diameter (D) and the coating resin film thickness (h) are 1 <[D / h] <10, the particles are more convex than the coating film. By agitation for frictionally charging the agent, contact with a strong impact on the binder resin due to friction with toner or friction between carriers can be reduced. As a result, it is possible to suppress film scraping of the binder resin, which is a place where charging occurs. In addition, since there are many particles on the carrier surface that are more convex than the coating film, it also exhibits a cleaning effect that efficiently scrapes off the spent component of the toner adhering to the carrier surface due to frictional contact between the carriers. Can be prevented. When [D / h] is 1 or less, the conductive particles are buried in the binder resin, which is not preferable because the effect is remarkably lowered. When [D / h] is 10 or more, the contact area between the particles and the binder resin is small, so that a sufficient restraining force cannot be obtained, and the particles are easily detached.

  Furthermore, when the content of the particles is 10 (wt%) or more and 70 (wt%) or less, the improvement effect is remarkable. This is because when the amount is less than 10% by weight, the proportion of the particles occupies less than the proportion of the binder resin on the surface of the carrier particles, and therefore, the effect of alleviating contact with a strong impact on the binder resin. Is not preferable because sufficient durability cannot be obtained. On the other hand, when the amount is more than 70% by weight, the proportion of the particles is excessive as compared with the proportion of the binder resin on the surface of the carrier. Thus, sufficient charging ability cannot be exhibited. In addition, since the amount of particles is too large compared to the amount of binder resin, the ability to hold particles by the binder resin becomes insufficient, and the particles are likely to be detached. Durability cannot be obtained, which is not preferable. The content rate of a particle | grain here is shown with the following formula | equation.

Further, the magnetic moment at 1000 (10 ^ 3 / 4π · A / m) is 40 (Am ^
2 / kg) or more and 90 (Am ^ 2 / kg) or less, the improvement effect is remarkable. This is because, within this range, the retention force between the carrier particles is appropriately maintained, so that the dispersion (mixing) of the toner into the carrier or developer is quickly and favorably improved. However, the magnetic moment at 1 KOe is 40 Am ^2. If it is less than / kg, carrier adhesion occurs due to insufficient magnetic moment, which is not preferable. On the other hand, when the magnetic moment at 1 KOe exceeds 90 Am ² / kg, the ears of the developer formed at the time of development become too hard, so that the reproducibility of image details is poor and a fine image cannot be obtained, which is not preferable.

  Furthermore, the improvement effect is remarkable by using an electrophotographic developer combining at least a toner composed of a binder resin and a colorant and the carrier of the present invention. This is because the carrier of the present invention can provide a high-definition image and has a longer life, and therefore, the developer using the carrier of this patent can obtain excellent quality.

  Further, since the toner is a color toner, the improvement effect is remarkable. This is because the carrier of the present invention does not contain carbon black in the coating layer, and therefore does not cause image color staining due to carbon black due to film scraping or the like. Therefore, it is very suitable for a color developer in which color reproducibility is regarded as important. The color toner referred to here includes not only a color toner generally used for a single color but also a black toner in addition to yellow, magenta, cyan, red, green, blue and the like used for full color.

[toner]
Here, the toner in the present invention will be described in detail. The toner in the present invention includes all the general toners regardless of whether they are monochrome toner, color toner or full color toner. For example, conventionally kneaded and pulverized toners and various polymerized toners that have been used in recent years can be used. Further, so-called oilless toner having a releasing agent can also be used. In general, oilless toner contains a release agent, so that the release agent is likely to be transferred to the carrier surface, and so-called spent is likely to occur. Quality can be maintained. In particular, oilless full color toners are generally said to be spent easily because the binder resin is soft, but it can be said that the carrier of the present invention is very suitable.

  As the binder resin used in the toner of the present invention, known resins can be used. For example, styrene such as polystyrene, poly-p-styrene and polyvinyltoluene, and homopolymers thereof, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene- Methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, Styrene-methacrylic acid copolymer Corp., Styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, Styrene-methacrylic acid Butyl copolymer, styrene-α-chloromethacrylic acid methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, Styrene-isopropyl copolymer, styrene-male Styrene copolymer such as acid ester copolymer, polythyme methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polyester, polyurethane, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified Rosin, terpene resin, phenol resin, aliphatic or aromatic hydrocarbon resin, aromatic petroleum resin, or the like can be used alone or in combination.

  And as a binder resin for pressure fixing, a well-known thing can be mixed and used. For example, polyolefin such as low molecular weight polyethylene and low molecular weight polypropylene, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, styrene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-chlorinated Vinyl copolymers, ethylene-vinyl acetate copolymers, olefin copolymers such as ionomer resins, epoxy resins, polyester resins, styrene-butadiene copolymers, polyvinyl pyrrolidone, methyl vinyl ether-maleic anhydride, maleic acid-modified phenol resins Phenol-modified terpene resins and the like can be used alone or in combination, but are not limited thereto.

  Further, the toner used in the present invention may contain a fixing aid in addition to the binder resin, the colorant, and the charge control agent. Accordingly, it can be used in a fixing system in which toner fixing prevention oil is not applied to the fixing roll, so-called oilless system. Known fixing aids can be used. For example, polyolefins such as polyethylene and polypropylene, fatty acid metal salts, fatty acid esters, paraffin waxes, amide waxes, polyhydric alcohol waxes, silicone varnishes, carnauba waxes and ester waxes can be used, but are not limited thereto.

  As the colorant used in the toner such as the color toner of the present invention, known pigments and dyes capable of obtaining yellow, magenta, cyan, and black toners can be used, and are not limited to those listed here. Examples of yellow pigments include cadmium yellow, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, and Tartrazine Lake. Can be mentioned.

  Examples of the orange pigment include molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK.

  Examples of red pigments include Bengala, Cadmium Red, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B.

  Examples of purple pigments include fast violet B and methyl violet lake.

  Examples of blue pigments include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, fast sky blue, and indanthrene blue BC.

  Examples of the green pigment include chrome green, chromium oxide, pigment green B, and malachite green lake.

Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.
Moreover, these colorants can use 1 type (s) or 2 or more types.

  The toner such as the color toner of the present invention may contain a charge control agent in the toner as necessary. For example, the color toner of the present invention can contain a charge control agent in the toner as needed. For example, nigrosine, an azine dye containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), a basic dye (for example, CI Basic Yellow 2 (CI 41000), CI Basic Yellow 3, C.I.Basic Red 1 (C.I. 45160), C.I.Basic Red 9 (C.I. 42500), C.I.Basic Violet 1 (C.I. 42535), C I. Basic Violet 3 (C.I. 42555), C. I. Basic Violet 10 (C.I. 45170), C.I.Basic Violet 14 (C.I. 42510), C.I.Basic Blueet 1 (C.I. 42025), C.I.Basic Blue 3 (C.I.51005), C.I. ascii blue 5 (C.I. 42140), C.I.Basic Blue 7 (C.I.42595), C.I.Basic Blue 9 (C.I.522015), C.I.Basic Blue 24 (C. CI Basic Blue 25 (C.I.52025), C.I.Basic Blue 26 (C.I.44045), C.I.Basic Green 1 (C.I.42040), Lake pigments of these basic dyes, such as CI Basic Green 4 (CI 42000), CI Solvent Black 8 (CI 26150), benzoylmethylhexadecyl ammonium chloride, decyltrimethyl chloride Quaternary ammonium salts such as dibutyl or dioctyl Dialkyl tin compounds, dialkyl tin borate compounds, guanidine derivatives, vinyl polymers containing amino groups, polyamine resins such as condensation polymers containing amino groups, Japanese Patent Publication No. 41-20153, Japanese Patent Publication No. 43-27596 A metal complex salt of a monoazo dye described in JP-B-44-6397 and JP-B-45-26478, salicylic acid described in JP-B-55-42752, JP-B-59-7385, Examples include dialkyl salicylic acid, naphthoic acid, dicarboxylic acid metal complexes such as Zn, Al, Co, Cr, and Fe, sulfonated copper phthalocyanine pigments, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds, and the like. . Naturally, color toners other than black should avoid the use of charge control agents that impair the target color, and white metal salts of salicylic acid derivatives are preferably used.

  As for the external additive, transferability and durability are further improved by externally adding inorganic fine particles such as silica, titanium oxide, alumina, silicon carbide, silicon nitride, boron nitride and resin fine particles to the base toner particles. This effect can be obtained by covering the wax that lowers transferability and durability with these external additives and reducing the contact area due to the toner surface being covered with fine particles. The surface of these inorganic fine particles is preferably subjected to a hydrophobic treatment, and metal oxide fine particles such as silica and titanium oxide subjected to the hydrophobic treatment are preferably used. As the resin fine particles, polymethyl methacrylate or polystyrene fine particles having an average particle size of about 0.05 to 1 μm obtained by a soap-free emulsion polymerization method are suitably used. In addition, the combination of hydrophobized silica and hydrophobized titanium oxide increases the amount of hydrophobized titanium oxide externally added compared to the amount of hydrophobized silica externally charged. The toner can also be excellent in stability. In combination with the above inorganic fine particles, external additives conventionally used such as silica having a specific surface area of 20 to 50 m / g and resin fine particles having an average particle diameter of 1/100 to 1/8 of the average particle diameter of the toner. The durability can be improved by externally adding an external additive having a particle size larger than that of the agent to the toner. This is because the metal oxide particles externally added to the toner tend to be embedded in the base toner particles in the process where the toner is mixed and stirred with the carrier in the developing device, charged, and used for development. This is because it is possible to prevent the metal oxide fine particles from being embedded by externally adding an external additive having a particle size larger than that of the oxide fine particles to the toner. The above-mentioned inorganic fine particles and resin fine particles are contained (internally added) in the toner, but the effect is reduced as compared with the case of external addition, but the effect of improving transferability and durability can be obtained and the pulverization property of the toner can be improved. Can do. In addition, since external addition and internal addition can be used together to suppress embedding of externally added fine particles, excellent transferability can be stably obtained and durability can be improved.

  In addition, the following are mentioned as a typical example of the hydrophobization processing agent used here. Dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, Chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, p-chlorophenyltrichlorosilane, 3-chloropropyltrichlorosilane, 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinylmethoxysilane, vinyl-tris (β-methoxyethoxy) ) Silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinyldichlorosilane, dimethylvinylchlorosilane, octyl Trichlorosilane, decyl-trichlorosilane, nonyl-trichlorosilane, (4-t-propylphenyl) -trichlorosilane, (4-t-butylphenyl) -trichlorosilane, diventyl-dichlorosilane, dihexyl-dichlorosilane, dioctyl-dichlorosilane, dinonyl -Dichlorosilane, didecyl-dichlorosilane, didodecyl-dichlorosilane, dihexadecyl-dichlorosilane, (4-t-butylphenyl) -octyl-dichlorosilane, dioctyl-dichlorosilane, didecenyl-dichlorosilane, dinonenyl-dichlorosilane, di-2-ethylhexyl-dichlorosilane, di- 3,3-dimethylbenthyl-dichlorosilane, trihexyl-chlorosilane, trioctyl-chlorosilane, tridecyl-chlorosilane Dioctyl-methyl-chlorosilane, octyl-dimethyl-chlorosilane, (4-t-propylphenyl) -diethyl-chlorosilane, octyltrimethoxysilane, hexamethyldisilazane, hexaethyldisilazane, diethyltetramethyldisilazane, hexaphenyldisilazane , Hexatolyl disilazane and the like. In addition, titanate coupling agents and aluminum coupling agents can also be used. In addition, as an external additive for the purpose of improving cleaning properties, a lubricant such as a fatty acid metal salt or a fine particle of polyvinylidene fluoride can be used in combination.

  As the carrier core material in the present invention, those known as two-component carriers for electrophotography, such as ferrite, Cu-Zn ferrite, Mn ferrite, Mn-Mg ferrite, Mn-Mg-Sr ferrite, magnetite, iron, What is necessary is just to select suitably according to the use of a carrier, such as nickel, and a use purpose, and it is not restricted to an example.

  Conventionally known methods such as a pulverization method and a polymerization method can be applied to the toner production method of the present invention. For example, in the case of the pulverization method, as a device for kneading the toner, a batch type two roll, a Banbury mixer or a continuous twin screw extruder, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM manufactured by Toshiba Machine Co., Ltd. Type twin screw extruder, KCK twin screw extruder, Ikegai Iron Works PCM type twin screw extruder, Kurimoto Iron Works KEX type twin screw extruder, continuous single screw kneader, for example Buss Co-kneader is preferably used. The melt-kneaded product obtained as described above is cooled and then pulverized. For pulverization, for example, coarsely pulverized using a hammer mill, a funnel plex or the like, and further, a fine pulverizer using a jet stream or mechanical pulverization A machine can be used. The pulverization is desirably performed so that the average particle diameter is 3 to 15 μm. Furthermore, it is preferable that the particle size of the pulverized product is adjusted to 5 to 20 μm by a wind classifier or the like. Subsequently, the external additive is externally added to the base toner. The base toner and the external additive are mixed and stirred using a mixer, and the external additive is crushed and coated on the toner surface. At this time, it is important in terms of durability that external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the base toner. The above is only an example, and the present invention is not limited to this.

[Image forming apparatus, process cartridge]
FIG. 1 shows a schematic configuration of an image forming apparatus having a process cartridge having a developer of the present invention. In FIG. 1, the figure shows the entire process cartridge, which includes a photoconductor, a charging unit, a developing unit, and a cleaning unit.

  In the present invention, among the constituent elements such as the above-described photoreceptor, charging means, developing means, and cleaning means, the developing means using the developer of the present invention and one or more other means are used as a process cartridge. The process cartridge is configured so as to be integrally connected, and is configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

  In an image forming apparatus equipped with a process cartridge having developing means using the developer of the present invention, the photosensitive member is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member receives a uniform positive or negative electric potential on its peripheral surface by the charging means, and then receives image exposure light from an image exposure means such as slit exposure or laser beam scanning exposure. An electrostatic latent image is sequentially formed on the peripheral surface of the body, and the formed electrostatic latent image is then developed with toner by a developing unit, and the developed toner image is transferred between the photosensitive member and the transfer unit from the paper feeding unit. Then, the image is sequentially transferred to the transfer material fed in synchronization with the rotation of the photosensitive member by the transfer means. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed on the image, and printed out as a copy (copy). The surface of the photoreceptor after the image transfer is cleaned by removing the transfer residual toner by the cleaning means, and after being further neutralized, it is repeatedly used for image formation.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these. Parts are based on weight.

Example 1
[Conductive fine particles]
200 g of aluminum oxide (average primary particle size 0.40 μm) was dispersed in 2.5 liters of water to obtain a water suspension. This suspension was kept warm at 80 ° C. A separately prepared solution of 25 g of stannic chloride (SnCl ₄ .5H ₂ O) in 200 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia were added so as to maintain the pH of the suspension at 7-8. . Subsequently, a solution prepared by dissolving 75 g of indium chloride (InCl ₃ ) and 10 g of stannic chloride (SnCl ₄ .5H ₂ O) separately prepared in 800 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia was adjusted to a pH of 7 to It was dripped so that it might hold at 8. After completion of the dropwise addition, the treated suspension was filtered and washed, and the resulting treated pigment cake was dried at 120 ° C.
Next, the obtained dry powder was heat-treated at 500 ° C. for 1.5 hours in a nitrogen gas stream (1 liter / min). The obtained fired product is pulverized, and 4% by weight of γ-mercaptopropyltrimethoxysilane is added to the pulverized product with stirring in a Henschel mixer heated to 70 ° C. Furthermore, the processed product was heat-treated at 100 ° C. for 1 hour to obtain the target white conductive powder A.

[Carrier coating layer]
・ Silicon resin solution [solid content: 23% by weight
(SR2410: manufactured by Toray Dow Corning Silicone Co.)] 132.2 parts by weight Aminosilane [solid content: 100% by weight
(SH6020: manufactured by Toray Dow Corning Silicone)] 0.66 parts by weight Conductive particle A [Substrate: Alumina,
Surface treatment; lower layer = tin dioxide / upper layer = indium oxide containing tin dioxide,
Particle size: 0.40 μm, carbon content: 0.33% by weight,
Particle powder specific resistance: 3.7 Ω · cm] 31 parts by weight Toluene 300 parts by weight was dispersed with a homomixer for 10 minutes to obtain a silicon resin coating film forming solution. Average particle size: 35 μm calcined ferrite powder is used as the core material, and the coating film forming solution is coated on the surface of the core material at a coater temperature of 40 ° C. by a Spira coater (Okada Seiko Co., Ltd.) so that the film thickness is 0.15 μm. It was applied and dried. The obtained carrier was baked by standing in an electric furnace at 240 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 63 μm, and the particle content: 50% by weight, D / h: 2.3, volume resistivity: 12.9 [Log (Ω · cm)], Magnetization: [Carrier 1] of 68 Am ² / kg was obtained.

[Career]
For the measurement of the average particle diameter of the core material, an SRA type of Microtrac particle size analyzer (Nikkiso Co., Ltd.) was used, and the measurement was performed with a range setting of 0.7 μm or more and 125 μm or less.
The measurement of the binder resin film thickness was performed by observing the cross section of the carrier with a transmission electron microscope so that the coating film covering the carrier surface could be observed.
Magnetization measurement was performed by the following method using VSM-P7-15 manufactured by Toei Industry Co., Ltd. A value obtained by weighing about 0.15 g of a sample, filling the sample in a cell having an inner diameter of 2.4 mmφ and a height of 8.5 mm, and under a magnetic field of 1000 oerste (Oe).

[toner]
On the other hand, toner
-Binder resin: 100 parts of polyester resin-Release agent: Carnauba wax 6 parts-Charge control agent: E-84 [manufactured by Orient Chemical Co., Ltd.] 1.5 parts-Colorant: Carbon black 5 parts Mixing with a mixer, melt-kneading at 120 ° C. for 40 minutes with two rolls, cooling, coarsely pulverizing with a hammer mill, and finely pulverizing with an air jet pulverizer, classifying the powder, weight average particle size 5 μm Toner base particles were made. Further, to 100 parts of the toner base material, 1 part of silica whose surface was hydrophobized and 1 part of titanium oxide whose surface was hydrophobized were added and mixed with a Henschel mixer to obtain yellow toner [Toner 1 ] Was obtained.
7 parts of [Toner 1] and 93 parts of [Carrier 1] thus obtained were mixed and stirred to obtain a developer having a toner concentration of 7% by weight, color stains, carrier adhesion, edge effect, image definition, durability (charging) The amount of decrease and the amount of change in resistance were evaluated. The results are shown in Table 1.

The evaluation methods and conditions in the examples are shown below.
[Carrier adhesion]
Set developer on a commercially available digital full color printer (IPSiO CX8200 manufactured by Ricoh), fix the ground potential at 150V, and measure the number of carriers attached to the surface of the photoconductor on which the imageless chart is developed by loupe observation. The field of view was counted, and the average number of adhered carriers per 100 cm ² was defined as the amount of adhered carriers. The evaluation was as follows: ◎: 20 or less, ○: 21 or more and 60 or less, Δ: 61 or more and 80 or less, ×: 81 or more, ◎ ○ △ was passed and × was rejected.

[Edge effect]
A developer is set on a commercially available digital full color printer (IPSiO CX8200 manufactured by Ricoh), and a test pattern having a large area image is output. The difference between the thinness of the image density at the central portion of the image pattern thus obtained and the darkness of the edge portion was ranked as follows. ◎ if there is no difference, ◯ if there is a slight difference, △ if there is a difference but acceptable, × if there is a difference to an unacceptable level, ◎ ○ △ is accepted and x is rejected did.

[Image definition]
The image definition was evaluated by the reproducibility of the character image portion. The evaluation method is that a developer is set on a commercially available digital full-color printer (IPSiO CX 8200 manufactured by Ricoh), and a character chart (size of one character; about 2 mm × 2 mm) with an image area of 5% is output. Character reproducibility was evaluated by images and ranked as follows. ◎: Very good, ○: Good, △: Acceptable, ×: Unusable for practical use, ◎ ○ △ was accepted and x was rejected.

[durability]
The developer was set on a commercially available digital full color printer (IPSiO CX 8200 manufactured by Ricoh Co., Ltd.), and a running evaluation of 100,000 sheets in a single color was performed. The determination was made based on the charge reduction amount and resistance reduction amount of the carrier after the running.

  The amount of charge reduction referred to here is a general blow-off method [TB-200 manufactured by Toshiba Chemical Co., Ltd.] prepared by friction charging with a mixture of 5% by weight of toner with respect to 95% by weight of the initial carrier. ], The amount of charge (Q2) measured by the same method as that described above was subtracted from the amount of charge (Q1) measured in the above method, from the carrier from which the toner in the developer after running was removed by the blow-off device. It refers to the quantity, and the target value is within 10.0 (μc / g). Further, since the cause of the decrease in the charge amount is the toner spent on the carrier surface, the decrease in the charge amount can be suppressed by reducing the toner spent.

  The amount of change in resistance here means that the initial carrier is put between resistance measurement parallel electrodes: electrodes with a gap of 2 mm, the resistance value after 30 sec is applied by DC250V, and the value measured with a high resist meter is converted into volume resistivity. The amount obtained by subtracting the value (R2) measured by the same method as the resistance measuring method from the value (R1) obtained by removing the toner in the developer after running by the blow-off device. In other words, the target value is an absolute value within 3.0 [Log (Ω · cm)]. Also, the cause of the resistance change is scraping of the binder resin film of the carrier, spent toner components, large particle detachment in the carrier coating film, etc., and reducing these can suppress the resistance change amount. it can.

(Example 2)
[Conductive fine particles]
200 g of aluminum oxide (average primary particle size 0.40 μm) was dispersed in 2.5 liters of water to obtain a water suspension. This suspension was kept warm at 80 ° C. A separately prepared solution of 25 g of stannic chloride (SnCl ₄ .5H ₂ O) in 200 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia were added so as to maintain the pH of the suspension at 7-8. . Subsequently, a solution prepared by dissolving 75 g of indium chloride (InCl ₃ ) and 10 g of stannic chloride (SnCl ₄ .5H ₂ O) separately prepared in 800 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia was adjusted to a pH of 7 to It was dripped so that it might hold at 8. After completion of the dropwise addition, the treated suspension was filtered and washed, and the resulting treated pigment cake was dried at 120 ° C.
Next, the obtained dry powder was heat-treated at 500 ° C. for 1.5 hours in a nitrogen gas stream (1 liter / min). The obtained fired product is pulverized, and this pulverized product is added and treated with 3.5% by weight of γ-aminopropyltriethoxysilane while stirring with a Henschel mixer heated to 70 ° C. Furthermore, the processed product was heat-treated at 100 ° C. for 1 hour to obtain the desired white conductive powder B.
-Silicone resin solution [solid content 23 wt% (SR2410:
Toray Dow Corning Silicone Co., Ltd.] 132.2 parts by weight Aminosilane [solid content 100% by weight (SH6020:
Toray Dow Corning Silicone Co.)] 0.66 parts by weight Conductive particles B [particle size: 0.40 μm, carbon content: 0.27% by weight,
Particle powder specific resistance: 4.7 Ω · cm] 5.7 parts by weight • 300 parts by weight of toluene was dispersed with a homomixer for 10 minutes to obtain a silicon resin coating film forming solution. Average particle size: 35 μm calcined ferrite powder is used as the core material, and the coating film forming solution is coated on the surface of the core material at a coater temperature of 40 ° C. by a Spira coater (Okada Seiko Co., Ltd.) so that the film thickness is 0.15 μm. It was applied and dried. The obtained carrier was baked in an electric furnace at 240 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 63 μm, and the particle content: 50% by weight, D / h: 2.3, volume resistivity: 12.1 [Log (Ω · cm)], Magnetization: [Carrier 2] of 68 Am ² / kg was obtained.
[Carrier 2] and [Toner 1] thus obtained were developed into a developer by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 3)
The particle content: 50% by weight, D / h: 2.3, volume resistivity, except that the coating layer formulation is changed to a mixed system of acrylic resin and silicon resin as described below. : [Carrier 3] of 12.9 [Log (Ω · cm)] and magnetization: 68 Am ² / kg.
・ Acrylic resin solution (solid content 50% by weight) 39.7 parts by weight ・ Guanamine solution (solid content 70% by weight) 12.4 parts by weight ・ Acid catalyst (solid content 40% by weight) 0.22 parts by weight ・ Silicone resin solution [Solid content 20% by weight
(SR2410: manufactured by Toray Dow Corning Silicone Co., Ltd.)] 185.8 parts by weight • Aminosilane [solid content: 100% by weight
(SH6020: manufactured by Toray Dow Corning Silicone Co., Ltd.)] 0.42 parts by weight / conductive particles B [the same particle size as in Example 2: 0.40 μm, carbon content:
0.27 wt%, particle powder specific resistance: 3.7 Ω · cm] 66.2 parts by weight Toluene 800 parts by weight The thus obtained [Carrier 3] and [Toner 1] were obtained in the same manner as in Example 1. The developer was evaluated. The results are shown in Table 1.

Example 4
In Example 3, except that the base of the conductive particles was changed to titanium oxide, the same as in Example 3, particle content: 50% by weight, D / h: 2.3, volume resistivity: 11.9 [Carrier 4] having [Log (Ω · cm)] and magnetization of 68 Am ² / kg was obtained.
Physical property of conductive particles [Substrate of Example 1 was changed to titanium oxide having an average primary particle size of 0.39 μm Carbon amount: 0.29 wt%, particle powder specific resistance: 4.0 Ω · cm]
[Carrier 4] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 5)
In Example 3, except that the base of the conductive particles was changed to zinc oxide, the same as in Example 3, particle content: 50% by weight, D / h: 2.1, volume resistivity: 13.7 [Carrier 5] with [Log (Ω · cm)] and magnetization: 68 Am ² / kg was obtained.
Physical properties of conductive particles [Substrate of Example 1 was changed to zinc oxide having an average primary particle size of 0.44 μm Carbon amount: 0.32 wt%, particle powder specific resistance: 3.3 Ω · cm]
[Carrier 5] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 6)
In Example 3, except that the conductive particle substrate was changed to silicon dioxide, the same as in Example 3, particle content: 50% by weight, D / h: 2.1, volume resistivity: 13.1 [Carrier 6] having [Log (Ω · cm)] and magnetization of 68 Am ² / kg was obtained.
Physical property of conductive particles [Substrate of Example 1 having an average primary particle size of 0.42 μm
The amount of carbon: 0.32% by weight, particle powder specific resistance: 3.5 Ω · cm]
[Carrier 6] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 7)
In Example 3, except that the base of the conductive particles was changed to barium sulfate, the same as in Example 3, the particle content: 50% by weight, D / h: 2.1, volume resistivity: 12.7 [Carrier 7] having [Log (Ω · cm)] and magnetization: 68 Am ² / kg was obtained.
Physical property of conductive particles [Substrate of Example 1 having an average primary particle size of 0.40 μm
The amount of carbon: 0.32% by weight, particle powder specific resistance: 5.4 Ω · cm]
[Carrier 7] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 8)
In Example 3, except that the base of the conductive particles was changed to zirconium oxide, the particle content: 50% by weight, D / h: 2.4, volume resistivity: 12.1 [Carrier 8] with [Log (Ω · cm)] and magnetization: 68 Am ² / kg was obtained.
Physical properties of conductive particles [Substrate of Example 1 having an average primary particle size of 0.39 μm
The amount of carbon: 0.30% by weight, the specific resistance of the particle powder: 6.2 Ω · cm]
[Carrier 8] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

Example 9
In Example 1, particle content: 65% by weight, D / h: 2.3, in the same manner as in Example 1 except that the volume resistivity of the carrier was changed to 10.9 (Ω · cm). [Carrier 10] having a magnetization of 68 Am ² / kg was obtained. In order to reduce the volume resistivity, the conductive particles were changed to the following.
Physical properties of conductive particles [Substrate: Alumina,
Surface treatment; lower layer = tin dioxide / upper layer = indium oxide containing tin dioxide,
Particle size: 0.39 μm, carbon content: 0.33% by weight,
Powder specific resistance: 1.6 Ω · cm]
[Carrier 10] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 10)
In Example 3, except that the weight average particle diameter of the carrier was changed to 18 μm, the particle content: 50% by weight, D / h: 2.3, volume resistivity: 12.7 [Log ( Ω · cm)] and magnetization: 66 Am ² / kg [Carrier 11]. [Carrier 11] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 11)
In Example 3, except that the weight average particle diameter of the carrier was changed to 71 μm, the particle content: 50% by weight, D / h: 2.3, volume resistivity: 12.5 [Log ( Ω · cm)], magnetization: 69 Am ² / kg [Carrier 12]. [Carrier 12] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 12)
In Example 3, particle content: 50% by weight, D / h: 0.8, volume specific, except that the average primary particle size of aluminum oxide, which is the base of conductive particles, was changed to 0.15 μm. [Carrier 13] having a resistance of 12.0 [Log (Ω · cm)] and a magnetization of 68 Am ² / kg was obtained. The physical properties of the conductive particles are as follows.
[Substrate: alumina, surface treatment; lower layer = tin dioxide / upper layer = tin dioxide
Indium oxide containing, particle size: 0.15 μm,
Carbon amount: 0.15 wt%, powder specific resistance: 2.4 Ω · cm]
The thus obtained [Carrier 13] and [Toner 1] were converted into a developer by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 13)
In Example 3, D / h: 2.3, volume resistivity: 15.1 [Log (Ω · cm)], magnetization: 68 Am, except that the particle content was changed to 5.1 wt%. ² / kg of [Carrier 14] was obtained. [Carrier 14] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 14)
In Example 3, except that the particle content was changed to 75% by weight, D / h: 2.3, volume resistivity: 10.3 [Log (Ω · cm)], magnetization: 68 Am ² / kg of [Carrier 15] was obtained. [Carrier 15] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 15)
In Example 3, the particle content: 50% by weight, D / h: 2.3, volume resistivity, except that 35 μm sintered ferrite having a low magnetization was used and the magnetization was changed to 35 Am ² / kg. : [Carrier 16] of 13.9 [Log (Ω · cm)] was obtained. [Carrier 16] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 16)
In Example 3, a 35 μm sintered ferrite having a high magnetization was used and the magnetization was changed to 93 Am ² / kg. Similarly, the particle content: 50% by weight, D / h: 2.3, volume resistivity [Carrier 17] of 10.9 [Log (Ω · cm)] was obtained. [Carrier 17] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Example 17)
In Example 3, except that the conductive particles and the non-conductive particles were used as follows, the particle content: 50% by weight, D / h: 2.3, volume resistivity: 13.2 [Carrier 18] of [Log (Ω · cm)] was obtained.
Conductive particles B [the same particle size as in Example 2: 0.40 μm,
Carbon amount: 0.27 wt%, particle powder specific resistance: 3.7 Ω · cm] 3.1 parts by weight • Non-conductive particles [substrate: alumina,
[Surface Treatment: None, Particle Size: 0.34 μm] 33.1 parts by weight [Carrier 18] and [Toner 1] thus obtained were developed into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Comparative Example 1)
200 g of aluminum oxide (average primary particle size 0.40 μm) was dispersed in 2.5 liters of water to obtain a water suspension. This suspension was kept warm at 80 ° C. A separately prepared solution of 25 g of stannic chloride (SnCl ₄ .5H ₂ O) in 200 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia were added so as to maintain the pH of the suspension at 7-8. . Subsequently, a solution prepared by dissolving 75 g of indium chloride (InCl ₃ ) and 10 g of stannic chloride (SnCl ₄ .5H ₂ O) separately prepared in 800 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia was adjusted to a pH of 7 to It was dripped so that it might hold at 8. After completion of the dropwise addition, the treated suspension was filtered and washed, and the resulting treated pigment cake was dried at 120 ° C.
Next, the obtained dry powder was heat-treated at 500 ° C. for 1.5 hours in a nitrogen gas stream (1 liter / min). The obtained fired product is pulverized, and 1% by weight of γ-mercaptopropyltrimethoxysilane is added to the pulverized product with stirring in a Henschel mixer heated to 70 ° C. Furthermore, the processed product was heat-treated at 100 ° C. for 1 hour to obtain the desired white conductive powder C.
In Example 1, except that the carbon amount of the conductive particles C was changed to 0.05% by weight, the particle content: 50% by weight, D / h: 5.0, volume resistivity: [Carrier 19] of 10.9 [Log (Ω · cm)] and magnetization: 68 Am ² / kg was obtained. The physical properties of the conductive particles are as follows.
[Substrate: alumina, surface treatment; lower layer = tin dioxide / upper layer = tin dioxide
Indium oxide containing, powder specific resistance: 2.7 Ω · cm]
[Carrier 19] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

(Comparative Example 2)
[Conductive fine particles]
200 g of aluminum oxide (average primary particle size 0.40 μm) was dispersed in 2.5 liters of water to obtain a water suspension. This suspension was kept warm at 80 ° C. A separately prepared solution of 25 g of stannic chloride (SnCl ₄ .5H ₂ O) in 200 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia were added so as to maintain the pH of the suspension at 7-8. . Subsequently, a solution prepared by dissolving 75 g of indium chloride (InCl ₃ ) and 10 g of stannic chloride (SnCl ₄ .5H ₂ O) separately prepared in 800 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia was adjusted to a pH of 7 to It was dripped so that it might hold at 8. After completion of the dropwise addition, the treated suspension was filtered and washed, and the resulting treated pigment cake was dried at 120 ° C.
Next, the obtained dry powder was heat-treated at 500 ° C. for 1.5 hours in a nitrogen gas stream (1 liter / min). The obtained fired product is pulverized, and 6.5% by weight of γ-mercaptopropyltrimethoxysilane is added to the pulverized product with stirring in a Henschel mixer heated to 70 ° C. Furthermore, the processed product was heat-treated at 100 ° C. for 1 hour to obtain the target white conductive powder D.

[Career]
In Example 4, except that the conductive particles are changed to the conductive particles D, the particle content: 50% by weight, D / h: 2.1, volume resistivity: 16.2 [ Log (Ω · cm)] and magnetization: 68 Am ² / kg [Carrier 20]. The physical properties of the conductive particles are as follows.
Conductive particles [base: alumina,
Surface treatment; lower layer = tin dioxide / upper layer = indium oxide containing tin dioxide,
Particle size: 0.40 μm, carbon content: 0.60% by weight,
Particle specific resistance: 15 Ω · cm]

  [Carrier 20] and [Toner 1] thus obtained were converted into developers by the same method as in Example 1 and evaluated. The results are shown in Table 1.

From Table 1, Examples 1 to 17 which are within the scope of the present invention are good within the target value range in all evaluation items of the edge effect, carrier adhesion, fine image, charge reduction amount, and resistance reduction amount. Results were obtained.
On the other hand, in Comparative Example 1 in which the carbon amount of the conductive particles was 0.05% by weight, the solid part carrier adhesion occurred in a high-temperature and high-humidity environment.
Furthermore, in Comparative Example 2 in which the carbon content of the conductive particles was 0.60% by weight, the resistance adjustment effect was not obtained, and the edge effect deviated from the target value. Further, since the carrier adhered to the non-image area due to the increase in charge, image evaluation was not performed.

FIG. 3 is a diagram illustrating an example of an image forming apparatus having a process cartridge using the developer of the present invention. It is a figure which shows another example of the image forming apparatus which has a process cartridge using the developing agent of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photosensitive drum 2 Developing device 3-3 Staying developer 3a Toner 3b Magnetic carrier 4 Developing sleeve 5 Magnet roller 6 Doctor blade 7 Developer accommodating case 7a Predoctor 8 Toner hopper 8a Toner replenishing port 9 Agitator 50 Charging roller 58 Cleaning device 80 Magnetic field forming means D Development area S Developer container

Claims (16)

  A carrier having a resin coating layer on the surface of a core material, wherein the coating layer comprises an indium oxide layer containing tin dioxide on a tin oxide layer, and a conductive coating layer whose surface is treated with a silane coupling agent. An electrophotographic carrier comprising conductive particles having a carbon content of 0.1 wt% or more and 0.5 wt% or less.   2. The electrophotographic carrier according to claim 1, wherein the conductive particle base is any one of aluminum oxide, titanium dioxide, zinc oxide, silicon dioxide, barium sulfate and zirconium oxide, and is used alone or in plural.   3. The electrophotographic carrier according to claim 1, wherein the conductive particles have a powder specific resistance of 200 (Ω · cm) or less.   The electrophotographic carrier according to claim 1, further comprising particles other than the conductive particles.   5. The electrophotographic carrier according to claim 1, wherein the volume resistivity of the carrier is 10 [Log (Ω · cm)] or more and 16 [Log (Ω · cm)] or less.   6. The electrophotographic carrier according to claim 1, wherein the weight average particle diameter is 20 μm or more and 65 μm or less.   The electrophotographic carrier according to claim 1, wherein at least the binder resin is a silicon resin.   7. The electrophotographic carrier according to claim 1, wherein at least the binder resin is an acrylic resin.   The electrophotographic carrier according to claim 1, wherein at least the binder resin is an acrylic resin and a silicon resin.   The particle diameter (D) of the particles contained in the coating layer and the coating layer film thickness (h) satisfy 1 <[D / h] <10. Carrier for electrophotography.   The carrier for electrophotography according to any one of claims 1 to 10, wherein the content of the particles is 10 wt% or more and 70 wt% or less.   The magnetic moment at 1000 (10 ^ 3 / 4π · A / m) is 40 (Am ^ 2 / kg) or more and 90 (Am ^ 2 / kg) or less. An electrophotographic carrier as described in 1.   An electrophotographic developer comprising at least a toner composed of a binder resin and a colorant, and the carrier according to claim 1.   The electrophotographic color developer according to claim 13, wherein the toner is a color toner.   Forming an electrostatic latent image on the image bearing member; developing the electrostatic latent image with a developer comprising at least a carrier and a toner to form a visible image; and transferring the obtained visible image to a recording member An image forming method comprising a fixing step, wherein the developer uses the developer for developing an electrostatic latent image according to claim 1. In a process cartridge that integrally supports at least one developing unit selected from a photosensitive member, a charging unit, a developing unit, and a cleaning unit, and is detachable from the image forming apparatus main body, the developing unit holds a developer, The process cartridge according to claim 1, wherein the developer is the developer according to claim 1.

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