JP4549275B2 - Electrophotographic carrier and developer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a good carrier for electrophotography excellent in durability, capable of forming fine images having no edge effect over a prolonged period of time, and causing no color stain. <P>SOLUTION: The carrier for electrophotography has a resin coating layer on a core material surface, wherein the carrier contains indium (In) in an amount of 0.0001-0.5 mass%. Conductive particles obtained by providing, on a base particle surface, a conductive coating layer consisting of a tin dioxide layer and a tin dioxide-containing indium oxide layer provided on the tin dioxide layer are preferably contained in the resin coating layer. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a 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 copying machines and printers using an electrophotographic system is 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 is transferred onto 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, as for color toners, there is a tendency toward oil-less for the purpose of downsizing machines and simplifying the configuration as in monochrome. 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, for 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 photoreceptor surface, photosensitivity For the purpose of protecting the body from scratches or abrasion by the carrier, controlling the polarity of the charge, or adjusting the amount of charge, 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 (see Patent Document 1), those in which various additives are added to the coating layer (see Patent Documents 2 to 8), and further additives are attached to the carrier surface. And the like (Patent Document 9), and those using a coating film containing conductive particles larger than the coat film thickness (see Patent Document 10) are disclosed. . Patent Document 11 describes the use of a benzoguanamine-n-butyl alcohol-formaldehyde copolymer as a main component for a carrier coating material, and Patent Document 12 describes a crosslinked product of a melamine resin and an acrylic resin as a carrier coating material. It is described to be used as.

  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 demands has increased, the speed of machines in recent years has increased significantly. 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, Patent Document 13 proposes a carrier in which a conductive material (carbon black) is present on the surface of the core material and no conductive material is present in the resin coating layer. Further, 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 there is a patent in which no carbon black exists on the surface of the coating layer. Proposed by reference 14. Moreover, Patent Document 15 discloses 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. Has been proposed. 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. An object is to provide a developer.

According to the present invention, the following electrophotographic carrier, developer, image forming method, and process cartridge are provided.
(1) A carrier having a resin coating layer on the surface of a core material, wherein the resin coating layer contains conductive particles, and the conductive particles are formed on the surface of the base particles, on the tin dioxide layer and the tin dioxide layer. Provided is a conductive coating layer comprising an indium oxide layer containing tin dioxide, and contains indium (In) atoms contained as indium oxide in a range of 0.0001 (mass%) to 0.5 (mass%). A carrier for electrophotography characterized by containing.
( 2 ) The above-mentioned ( 1 ), wherein one or two or more kinds selected from particles of aluminum oxide, titanium dioxide, zinc oxide, silicon dioxide, barium sulfate, and zirconium oxide are used as the base particles of the conductive particles. An electrophotographic carrier as described in 1.
( 3 ) The electrophotographic carrier according to any one of ( 1 ) to ( 2 ) above, wherein the conductive powder has a powder specific resistance of 200 (Ω · cm) or less.
( 4 ) The electrophotographic carrier according to any one of (1) to ( 3 ), wherein the resin coating layer contains non-conductive particles.

( 5 ) The volume specific resistance of the carrier is 10 [Log (Ω · cm)] or more and 16 [Log (Ω · cm)] or less, and any one of the above (1) to ( 4 ) An electrophotographic carrier as described in 1.
( 6 ) The electrophotographic carrier according to any one of (1) to ( 5 ) above, wherein the carrier has a volume average particle size of 20 (μm) to 65 (μm).
( 7 ) The electrophotographic carrier according to any one of (1) to ( 6 ) above, wherein the binder resin of the resin coating layer is a silicone resin.
( 8 ) The electrophotographic carrier according to any one of (1) to ( 6 ) above, wherein the binder resin of the resin coating layer is 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 an acrylic resin and a silicone resin.
( 10 ) The above ( 1 ) to ( 1 ), wherein the particle diameter (D) of the particles contained in the resin coating layer and the coating layer thickness (h) are 1 <[D / h] <10. The carrier for electrophotography according to any one of 9 ).
( 11 ) The content rate of the particles contained in the resin coating layer is 10 (wt%) or more and 70 (wt%) or less, wherein any of ( 1 ) to ( 10 ) above Electrophotographic carrier.
( 12 ) The magnetic moment at 1000 (10 ³ / 4π · A / m) of the carrier is 40 (Am ² / kg) or more and 90 (Am ² / kg) or less. 11 ) The electrophotographic carrier according to any one of 11 ).

( 13 ) An electrostatic latent image developing developer comprising at least a toner containing a binder resin and a colorant and the carrier according to any one of (1) to ( 12 ).
( 14 ) The developer for developing an electrostatic latent image according to the above ( 13 ), wherein the toner is a color toner.
( 15 ) A container containing the developer for developing an electrostatic latent image according to ( 13 ) or ( 14 ).
( 16 ) A step of forming an electrostatic latent image on the image carrier, a step of 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 including a step of transferring and fixing to a recording member, wherein the developer is the developer for developing an electrostatic latent image according to the above ( 13 ) or ( 14 ). .
( 17 ) In a process cartridge that is selected from a photosensitive member, a charging unit, a developing unit, and a cleaning unit and that supports at least the developing unit integrally and is detachable from the image forming apparatus main body, the developing unit holds a developer. And the developer is the developer for developing an electrostatic latent image according to the above ( 13 ) or ( 14 ).

  With the carrier of the present invention, there is no occurrence of carrier adhesion, and a high-definition image with excellent reproducibility of fine lines such as character portions can be obtained with suppressed edge effect. Further, since the change in the charge amount and resistance is small, the deterioration of the image quality of the copy image that occurs as the number of copies increases is greatly improved, and the 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 obtained a carrier having a resin coating layer on the surface of the core material, the carrier containing indium (In) of 0.0001 ( It has been found that the improvement effect is remarkable when the content is not less than mass% and not more than 0.5 (mass%). This is because In is present in the carrier as an oxide or other compound, and so on, to exert a resistance adjusting effect, and if contained in an amount in this range substantially in the carrier, the effect is good. Become. When the In content is less than 0.0001 (mass%), there is little formation of a conductive path that exhibits a resistance adjusting function, and a resistance adjusting effect cannot be obtained sufficiently, which is not preferable. On the other hand, if it exceeds 0.5 (mass%), the formation of the conductive path becomes excessive and the resistance becomes too low, so that carrier adhesion occurs and the quality deteriorates to a level where it cannot be practically used.

  Furthermore, the carrier has a resin coating layer on the surface of the core material, and the resin coating layer contains conductive particles, the conductive particles contain indium oxide, and the conductive particles further have a surface of the base particle. And a conductive coating layer comprising a tin dioxide layer and an indium oxide layer containing tin dioxide provided on the tin dioxide layer, wherein the carrier has an In content of 0.0001 (mass%). It has been found that the improvement effect is remarkable when the content is 0.5 (mass%) or less. This is because the conductive particles have a structure in which a tin dioxide layer is provided below the surface of the substrate particles by an appropriate method, and an indium oxide layer containing tin dioxide as a conductive layer is provided thereon. It is considered that the upper conductive layer can be uniformly and firmly fixed on the particle surface, so that the resistance adjusting effect can be sufficiently exhibited.

  Furthermore, it is important that the In content is in the above range. As described above, when the In content is less than 0.0001 (mass%), there is little formation of a conductive path that exhibits a resistance adjusting function, and a resistance adjusting effect cannot be obtained sufficiently, which is not preferable. On the other hand, if it exceeds 0.5 (mass%), the formation of the conductive path becomes excessive and the resistance becomes too low, so that carrier adhesion occurs and the quality deteriorates to a level where it cannot be practically used.

  Here, as a method for forming the conductive coating layer, for example, the surface of the substrate particles is coated with a hydrate of tin dioxide, and then an indium oxide hydrate containing a hydrate of tin dioxide is coated. A method of heat treatment at 350 to 750 ° C. in an inert gas atmosphere is preferable, but not necessarily limited thereto.

  The In content in the carrier referred to in the present invention can be measured using an EZ scan which is a contained element scanning function of ZSX100e type (manufactured by Rigaku Corporation) fluorescent X-ray. More specifically, the measurement sample is first treated by uniformly attaching the carrier to a seal obtained by applying an adhesive on a polyester film. This is set on a measurement sample stage, and the following conditions are selected [measurement range: BU, measurement diameter: 30 mm, sample form: metal, measurement time: long, atmosphere: vacuum], and obtained by measurement Can do.

  Furthermore, the improvement effect is remarkable when the base of the conductive particles uses any one of aluminum oxide, titanium dioxide, zinc oxide, silicon dioxide, barium sulfate, and zirconium oxide alone or in combination. This is considered to be because the compatibility with the conductive treatment of the particle surface is 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 because 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. The powder specific resistance of the conductive particles is preferably 0.1 (Ω · cm) or more, more preferably 0.1 (Ω · cm) to 100 (Ω · cm), and still more preferably 0.1 (Ω · cm). cm) to 15 (Ω · cm), particularly preferably 0.1 (Ω · cm) to 5.0 (Ω · cm).

The powder specific resistance of the conductive particles in the present invention can be measured as follows. For example, as shown in FIG. 2, 5 g of a sample is put in a cylindrical vinyl chloride tube having an inner diameter of 1 inch, and the upper and lower sides are sandwiched between electrodes. A pressure of 10 kg / cm ² is applied to these electrodes by a press. Subsequently, measurement with an LCR meter (Yokogawa-HEWLETT-PACKARD 4216A) is performed in this pressurized state to obtain resistance (r). The obtained specific resistance can be calculated by the following formula 1 to obtain the powder specific resistance.
<Formula 1>
Powder specific resistance (Ω · cm) = (2.54 / 2) ² × (π / H × r)
However, in Formula 1, H represents the thickness of the sample. r represents a resistance value.

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 in which a tin salt or stannate solution is added to an aqueous suspension of a white inorganic pigment on a substrate and then an alkali or acid is added, and a tin salt or stannate and an alkali or acid are separately provided in parallel Then, there is a method of adding and coating. 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 aqueous suspension should be kept warm at 50 to 100 ° C. Is more preferable. Moreover, pH at the time of adding tin salt or a stannate, an alkali, or an acid in parallel is set to 2-9. Since the isoelectric point of tin dioxide hydrate is pH 5.5, it is important to preferably maintain pH 2 to 5 or pH 6 to 9, so that the hydrolysis product of tin is uniformly distributed on the surface of white inorganic pigment particles. Can be deposited.

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 tin dioxide hydrate 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 of forming a coating of indium oxide hydrate containing tin dioxide as an upper layer. However, since the coating of the previously coated tin dioxide hydrate is not dissolved, a tin salt and an indium salt are used. 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 . 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 it is too small, the desired conductivity cannot be obtained, and it is too much. However, the conductivity is hardly improved, and it is expensive and not preferable from the viewpoint of cost.

  In this specification, “conductive” powder (particles) means a powder having a specific resistance value of 1 to 500 Ω · cm. As shown also in the examples described later, according to the present invention, a white conductive powder (conductive particles) having an excellent conductivity of 100 Ω · cm or less, 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 at 350 to 750 ° C. in a non-oxidizing atmosphere, and the non-resistance 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 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.

Furthermore, the improvement effect is remarkable by containing a nonelectroconductive particle. Thereby, the freedom degree of a coating layer structure can be ensured and it becomes easy to control arbitrarily the surface shape of a carrier and the physical property of a coating film. That is, by using conductive particles and non-conductive particles in a well-balanced manner, it is possible to adjust the resistance while maintaining the film strength of the coating layer, the surface shape of the carrier, and the like. Non-conductive particles herein include, for example, inorganic oxide particles, resin fine particles, and the like, and include those used for the base of conductive particles, but are not limited thereto. Further, from the viewpoint of making the configuration of the coating resin more uniform, it is preferable to use the same particles as the particles used for the base of the conductive particles.
The non-conductive particles in the present invention refer to those exceeding the resistance value range of the conductive particles described above. That is, it exceeds 500 Ω · cm, which is different from the general definition of non-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.

As shown in FIG. 3, the volume resistivity of the carrier in the present invention refers to a cell 31 made of a fluororesin container containing electrodes 32a and 32b having a distance between electrodes of 0.2 cm and a surface area of 2.5 cm × 4 cm. The carrier 33 is filled, and the tapping is performed at a drop height of 1 cm, a tapping speed of 30 times / min, and a tapping frequency of 10 times. Next, a DC voltage of 1000 V was applied between both electrodes, and the resistance value after 30 seconds was measured with a high resistance meter 4329A (manufactured by Yokogawa Hewlett-Packard Co., Ltd .: High Resistance Meter). The volume resistivity R is calculated by the following formula.
R = Log [r × (2.5 cm × 4 cm) ÷ 0.2 cm] [Log (Ω · cm)]

  Furthermore, the improvement effect is remarkable because the volume average particle diameter of the carrier is 20 (μm) or more and 65 (μm) or less. This is not preferable when the volume average particle size is less than 20 (μm), because the uniformity of the particles is deteriorated and a technique for sufficiently using the machine side has not been established, causing problems such as carrier adhesion. . 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, the improvement effect is remarkable because the binder resin contained in the resin coating layer is a silicone resin. This is because the silicone resin has a low surface energy, and thus it is difficult to spend the toner component, and it is difficult to accumulate the spent component due to film scraping.
The silicone resin referred to in the present invention refers to all generally known silicone resins, including straight silicones composed only of organosiloxane bonds, and silicone resins modified with alkyd, polyester, epoxy, acrylic, urethane, etc. However, it is not limited to this. For example, examples of commercially available straight silicone 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 silicone 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 resins, KR206 (alkyd modified), KR5208 (acrylic 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.

  Furthermore, the improvement effect is remarkable because the binder resin contained in the resin coating layer 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 the present invention 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 the other component that undergoes a crosslinking reaction include an amino resin and an acidic catalyst, 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 the acidic catalyst said 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, the improvement effect is remarkable because the binder resin contained in the resin coating layer is an acrylic resin and a silicone resin. As described 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 has a high surface energy, so it can be easily spent with toner. In the combination, 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 silicone 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 the silicone 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 resins. It is possible to obtain a coating film having wear characteristics.

About the amount of binder resin contained in the resin coating layer in this invention, the content rate has the preferable range of 0.1 to 1.5 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 said here is shown with the following formula | equation.
Binder resin content (wt%)
= [Coating resin solid content total amount / (Coating resin solid content total amount + core material amount)] × 100
Here, the total amount of the coating resin solid content means the total amount of only the resin (binder resin) in the resin coating layer.

Furthermore, when the particle diameter (average primary particle diameter) (D) of the particles contained in the coating layer and the coating layer thickness (h) are 1 <[D / h] <10, the improvement effect is remarkable. It is. This is because when the 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 frictional charging, 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 that are more convex than the coating film on the carrier surface, 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 carriers, preventing toner spent can do. When [D / h] is 1 or less, the 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.

In the present invention, the film thickness (h) of the resin coating layer and the particle diameter (average primary particle diameter) (D) of the particles contained in the coating layer are values measured as follows.
[Coating layer thickness h]
The measuring method of the coating layer thickness h is calculated based on the following definition by observing the carrier cross section using a transmission electron microscope (TEM). (See Figure 4)
(1) Thickness of the resin part existing between the surface of the core material and the particles: ha
(Ha is a value obtained by measuring a total of 50 points, one point per particle along the carrier surface along the carrier surface, and averaging the obtained measurement values. (The shortest distance on the core surface)
(2) Thickness of resin part existing between particles: hb
(Hb is a value obtained by measuring a total of 50 points at one point per particle gap between particles along the carrier surface and averaging the obtained measurement values. The measurement point is the gap between particles. The shortest part of
(3) Thickness of resin part on core material and particles: hc
(Hc is a value obtained by measuring 50 cross sections of the carrier along the carrier surface at intervals of 0.2 μm and averaging the obtained measurement values.)
h = (ha + hb + hc) / 3

[Average primary particle size D]
The average primary particle diameter D is measured by observing a carrier cross section using a transmission electron microscope (TEM) and calculating based on the following definition (see FIG. 4). That is, the average primary particle size is defined as the average particle size of 50 particles (including but not limited to either conductive particles or non-conductive particles) observed in the cross section in the coat layer.

Furthermore, the improvement effect is remarkable when the content rate of the particle | grains contained in a resin coating layer is 10 (weight%) or more and 70 (weight%) or less. 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, since the proportion of the particles is excessive as compared with the proportion of the binder resin on the carrier surface, the proportion of the binder resin that is a charging generation point is insufficient. Thus, sufficient charging ability cannot be exhibited. In addition, since the amount of particles is too much 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. It is not preferable because the properties cannot be obtained. The particle content referred to here is the content of the total of conductive particles and non-conductive particles, and is expressed by the following equation.
Particle content (% by weight) = [particles / (particles + total amount of coating resin solids)] × 100

Furthermore, when the magnetic moment of the carrier at 1000 (10 ³ / 4π · A / m) (1 KOe) 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 the developer becomes quick and good, but 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.

  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.

  Furthermore, the improvement effect is remarkable by using a developer for developing an electrostatic latent image in which at least a toner containing a binder resin and a colorant and the carrier of the present invention are combined. This is because the carrier of the present invention can provide a high-definition image and has a longer life, so that the developer using the carrier of the present invention can obtain excellent quality. Particularly when combined with a toner containing a release agent, the carrier of the present invention is preferable because of its long life.

  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 in a single color but also yellow, magenta, cyan, red, green, blue and the like used for full color.

  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 for the toner in 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, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate 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 copolymers 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 copolymer, ethylene-vinyl acetate copolymer, olefin copolymer such as ionomer resin, epoxy resin, polyester resin, styrene-butadiene copolymer, polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride, maleic acid modified phenol resin Phenol-modified terpene resins and the like can be used alone or in combination, but are not limited thereto.

  As the colorant used in the toner such as the color toner of the present invention, all known pigments and dyes capable of obtaining toners of yellow, magenta, cyan, and black 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, first sky blue, and indanthrene blue BC.

Examples of green pigments 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.

  Further, the toner used in the present invention may contain a fixing aid in addition to the binder resin and the colorant. 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. .

  The toner such as the color toner of the present invention may contain a charge control agent in the toner as necessary. 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, CI Basic Red 1 (CI 45160), CI Basic Red 9 (CI 42500), CI Basic Violet 1 (CI 42535), CI 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 Violet Blue 1 (C.I. 42025), C.I.Basic Blue 3 (C.I.51005), C.I. Basic Blue 5 (C.I. 42140), CI 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), benzoylmethyl hexadecyl ammonium chloride, decyltrimethyl chloride Quaternary ammonium salts, or dibutyl or dioctyl Polyamine resins such as dialkyl tin compounds, dialkyl tin borate compounds, guanidine derivatives, vinyl polymers containing amino groups, condensation polymers containing amino groups, Japanese Patent Publication No. 41-20153, Japanese Patent Publication No. 43-27596 Metal complex salts of monoazo dyes described in Japanese Patent Publication No. 44-6397 and Japanese Patent Publication No. 45-26478, and salicylic acid described in Japanese Patent Publication No. 55-42752 and Japanese Patent Publication No. 59-7385 , Metal complexes of dialkyl salicylic acid, naphthoic acid, dicarboxylic acid such as Zn, Al, Co, Cr, Fe, sulfonated copper phthalocyanine pigments, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds, etc. It is done. 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-mentioned inorganic fine particles, silica having a specific surface area of 20 to 50 m ² / g or resin fine particles having an average particle diameter of 1/100 to 1/8 of the average particle diameter of the toner can be used. The durability can be improved by externally adding an external additive having a particle size larger than that of the additive to the toner. This is because the external additive such as metal oxide fine particles added externally to the toner tends 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 and charged and used for development. However, 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 those of the metal 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.

  For the toner production method of the present invention, all conventionally known methods such as a pulverization method and a polymerization method can be applied. 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.

The developer of the present invention can be used in, for example, an image forming apparatus provided with a process cartridge as shown in FIG.
In the present invention, a plurality of components such as a photoconductor, a charging unit, a developing unit, and a cleaning unit are integrally combined as a process cartridge, and the process cartridge is formed in an image forming apparatus such as a copying machine or a printer. It is configured to be detachable from the apparatus main body.

  The process cartridge shown in FIG. 1 includes a photoreceptor, a charging unit, a developing unit, and a cleaning unit. Explaining the operation, the photosensitive member is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the charging unit, and then receives image exposure light from an image exposing unit 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 from the sheet feeding unit between the photosensitive member and the transfer 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 photoconductor after the image transfer is cleaned by removing the transfer residual toner by a 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.

(Production of conductive particles 1)
200 g of aluminum oxide (average primary particle size 0.35 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 separately prepared solution of 75 g of indium chloride (InCl ₃ ) and 10 g of stannic chloride (SnCl ₄ .5H ₂ O) dissolved in 800 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia was adjusted to a pH of 7 to 7%. 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.
Subsequently, the obtained dry powder was heat-treated at 500 ° C. for 1.5 hours in a nitrogen gas stream (1 liter / min) to obtain a desired white conductive powder (conductive particles 1).

(Production of conductive particles 2)
200 g of aluminum oxide (average primary particle size 0.12 μm) was dispersed in 7.3 liters of water to obtain a water suspension. This suspension was kept warm at 80 ° C. A solution prepared by dissolving 73 g of separately prepared stannic chloride (SnCl ₄ .5H ₂ O) in 587 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 220 g of indium chloride (InCl ₃ ) and 29 g of stannic chloride (SnCl ₄ .5H ₂ O) separately prepared in 2347 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia was adjusted to a pH of 7-7. 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) to obtain a desired white conductive powder (conductive particles 2).

(Production of conductive particles 3)
200 g of aluminum oxide (average primary particle size 0.35 μm) was dispersed in 0.18 liter of water to obtain a water suspension. This suspension was kept warm at 80 ° C. A solution prepared by dissolving 1.8 g of separately prepared stannic chloride (SnCl ₄ .5H ₂ O) in 15 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia so that the pH of the suspension is maintained at 7-8. Added. Subsequently, a separately prepared solution of 5.5 g of indium chloride (InCl ₃ ) and 0.73 g of stannic chloride (SnCl ₄ .5H ₂ O) dissolved in 59 ml of 2N hydrochloric acid and 12% by weight aqueous ammonia was added to the suspension. It was dripped so that pH might be kept at 7-8. 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) to obtain a desired white conductive powder (conductive particles 3).

(Production of conductive particles 4)
200 g of aluminum oxide (average primary particle size 0.35 μm) was dispersed in 14 liters of water to obtain a water suspension. This suspension was kept warm at 80 ° C. A separately prepared solution of 140 g of stannic chloride (SnCl ₄ .5H ₂ O) in 1120 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 separately prepared solution of 420 g of indium chloride (InCl ₃ ) and 56 g of stannic chloride (SnCl ₄ .5H ₂ O) dissolved in 4480 ml of 2N hydrochloric acid and 12 wt% aqueous ammonia was adjusted to a pH of 7 to 7%. 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) to obtain a desired white conductive powder (conductive particles 4).

[Example 1]
(Carrier production)
・ Silicone resin solution 132.2 parts [Solid content 23% by weight (SR2410: manufactured by Toray Dow Corning Silicone)]
Aminosilane 0.66 part [solid content 100% by weight (SH6020: manufactured by Toray Dow Corning Silicone)]
Conductive particle 1 31 parts [Substrate: alumina, surface treatment; lower layer = tin dioxide / upper layer = tin oxide containing tin oxide, particle size: 0.35 μm, particle powder specific resistance: 3.5 Ω · cm]
-300 parts of toluene was dispersed with a homomixer for 10 minutes to obtain a silicone resin coating film forming solution. Volume average particle size: 35 μm calcined ferrite powder is used as the core material, and the temperature inside the coater is 40 ° C. by a Spira coater (Okada Seiko Co., Ltd.) so that the coating film forming solution has a film thickness of 0.15 μm on the core material surface. And dried. The obtained carrier was fired in an electric furnace at 300 ° 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: 12.8 Log (Ω · cm), magnetization: 68 Am ² / kg, In content: 0.0073 (mass%), and [Carrier 1] having a volume average particle size of 35.3 μm were obtained.

The volume average particle size measurement of the core material and the carrier was performed using the SRA type of Microtrac particle size analyzer (Nikkiso Co., Ltd.) and setting the range from 0.7 [μm] to 125 [μm]. Was used.
The binder resin film thickness was measured based on the above definition by observing the carrier cross section with a transmission electron microscope.
Magnetization (magnetic moment) measurement is performed by the following method using VSM-P7-15 manufactured by Toei Industry Co., Ltd.
About 0.15 g of the sample was weighed, filled in a cell having an inner diameter of 2.4 mmφ and a height of 8.5 mm, and measured under a magnetic field of 1000 oerste (Oe).

(Manufacture of toner)
・ Binder resin: 100 parts of polyester resin
Number average molecular weight (Mn); 3800
Weight average molecular weight (Mw); 20000
Glass transition point (Tg); 60 ° C
Softening point: 122 ° C
・ Coloring agent: 5 parts of azo yellow pigment
C. I. P. Y. 180
・ Charge control agent: 2 parts of zinc salicylate ・ Release agent: 3 parts of carnauba wax
Melting point: 82 ° C
Is mixed with a Henschel mixer, melted and kneaded at 120 ° C. for 40 minutes with a two roll, cooled, coarsely pulverized with a hammer mill, finely pulverized with an air jet pulverizer, and the resulting fine powder was classified and weight averaged Toner base particles having a particle diameter of 5 μm were prepared. 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, ◎, ○, Δ were passed, and x 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, ◎, ○, Passed.

<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, Δ: Acceptable, ×: Unusable level for practical use ◎, ○, △ were 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 by mixing 7% by weight of toner with respect to 93% 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.

  Here, the amount of change in resistance means that an initial carrier is put between resistance measurement parallel electrodes: electrodes having a gap of 2 mm, DC 1000 V is applied, and a resistance value after 30 seconds is measured by a high resist meter and 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 within an absolute value of 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]
-Acrylic resin solution (solid content 50 wt%) 91.3 parts-Guanamin solution (solid content 70 wt%) 28.3 parts-Acidic catalyst (solid content 40 wt%) 0.52 parts-Conductive particles 1 65. 7 parts-800 parts of toluene was dispersed with a homomixer for 10 minutes to obtain an acrylic resin coating film forming solution. Volume average particle size: 35 μm calcined ferrite powder is used as the core material, and the temperature inside the coater is 40 ° C. by a Spira coater (Okada Seiko Co., Ltd.) so that the coating film forming solution has a film thickness of 0.15 μm on the core material surface. And dried. The obtained carrier was baked by standing in an electric furnace at 150 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 63 μm, the particle content: 50% by weight, D / h: 2.3, volume resistivity: 12.6 Log (Ω · cm), magnetization: 68 Am ² / kg, In content: 0.0070 (mass%), and [Carrier 2] having a volume average particle size of 35.5 μm were 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 coating layer formulation is described below, except that the mixture was changed to a mixed system of acrylic resin and silicone resin, in the same manner as in Example 2, particle content: 50% by weight, D / h: 2.3, volume resistivity : [Carrier 3] having 12.7 Log (Ω · cm), magnetization: 68 Am ² / kg, In content: 0.0071 (mass%), and a volume average particle diameter of 35.1 μm was obtained.
・ Acrylic resin solution (solid content 50 wt%) 39.7 parts ・ Guanamine solution (solid content 70 wt%) 12.4 parts ・ Acid catalyst (solid content 40 wt%) 0.22 parts ・ Silicone resin solution 185.8 Part [solid content 20% by weight (SR2410: manufactured by Toray Dow Corning Silicone)]
・ Aminosilane 0.42 part [solid content 100% by weight (SH6020: manufactured by Toray Dow Corning Silicone)]
Conductive particle 1 66.2 parts Toluene 800 parts [Carrier 3] and [Toner 1] thus obtained were developed into a developer in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

[Example 4]
In Example 3, except that the base of conductive particles was changed to titanium oxide, the same as in Example 3, particle content: 50% by weight, D / h: 2.3, volume resistivity: 11.4 Log [Carrier 4] having (Ω · cm), magnetization: 68 Am ² / kg, In content: 0.0071 (mass%), and a volume average particle diameter of 35.2 μm was obtained.
Physical properties of conductive particles [The substrate of Example 1 was changed to titanium oxide having an average primary particle size of 0.34 μm. Particle specific resistance: 2.2 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: 11.8 Log [Carrier 5] having (Ω · cm), magnetization: 68 Am ² / kg, In content: 0.0069 (mass%), and volume average particle diameter of 35.6 μm was obtained.
Physical property of conductive particles [Substrate of Example 1 was changed to zinc oxide with an average primary particle size of 0.32 μm, particle powder specific resistance: 2.3 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 base of the conductive particles was changed to silicon dioxide, the same as in Example 3, particle content: 50% by weight, D / h: 2.1, volume resistivity: 12.6 Log [Carrier 6] having (Ω · cm), magnetization: 68 Am ² / kg, In content: 0.0072 (mass%), and a volume average particle size of 35.8 μm was obtained.
Physical property of conductive particles [Substrate of Example 1 was changed to silicon dioxide having an average primary particle size of 0.32 μm, particle powder specific resistance: 4.1 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, particle content: 50% by weight, D / h: 2.1, volume resistivity: 12.5 Log [Carrier 7] having (Ω · cm), magnetization: 68 Am ² / kg, In content: 0.0070 (mass%), and a volume average particle diameter of 35.2 μm was obtained.
Physical properties of conductive particles [Substrate of Example 1 was changed to barium sulfate with an average primary particle size of 0.31 μm, particle powder specific resistance: 3.6 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 same as in Example 3, particle content: 50% by weight, D / h: 2.4, volume resistivity: 12.3 Log [Carrier 8] having (Ω · cm), magnetization: 68 Am ² / kg, In content: 0.0072 (mass%), and a volume average particle diameter of 35.1 μm was obtained.
Physical property of conductive particles [Substrate of Example 1 was changed to zirconium oxide having an average primary particle size of 0.36 μm, particle powder specific resistance: 3.2 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, D / h: 2.3, volume resistivity: 9.8 Log (Ω · cm), magnetization: 68 Am in the same manner except that the content of the conductive particles 1 became 65% by weight. ² / kg, In content: 0.0092 (mass%), and [Carrier 9] having a volume average particle size of 35.5 μm were obtained.
[Carrier 9] 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, the volume average particle size was 17.4 μm, the particle content was 50% by weight, D / h was 2.3, except that the volume average particle size of the core material was changed to 17 μm. [Carrier 10] having a volume resistivity: 12.9 Log (Ω · cm), magnetization: 66 Am ² / kg, and In content: 0.0073 (mass%) was obtained.
[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 11]
In Example 3, the volume average particle size was 70.2 μm, the particle content was 50% by weight, D / h was 2.3, except that the volume average particle size of the core material was changed to 70 μm. [Carrier 11] having a volume resistivity: 11.9 Log (Ω · cm), magnetization: 69 Am ² / kg, and In content: 0.0065 (mass%) was obtained.
[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 12]
In the same manner as in Example 3, except that the conductive particles were changed to the conductive particles 2 in which the aluminum oxide particle diameter of the substrate was changed to 0.12 μm, the particle content: 50% by weight, D / h: 0. 8. [Carrier 12] having a volume resistivity: 9.1 Log (Ω · cm), magnetization: 68 Am ² / kg, In content: 0.0215 (mass%), and a volume average particle diameter of 35.2 μm was obtained. The physical properties of the conductive particles are as follows.
[Substrate: alumina, surface treatment; lower layer = tin dioxide / upper layer = indium oxide containing tin dioxide, particle size: 0.12 μm, powder specific resistance: 1.9 Ω · cm]
[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 13]
In Example 3, except that the particle content was changed to 5% by weight, D / h: 2.3, volume resistivity: 15.4 Log (Ω · cm), magnetization: 68 Am ² / kg, In [Carrier 13] having a content rate of 0.0007 (mass%) and a volume average particle size of 35.6 μm was obtained.
[Carrier 13] 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, D / h: 2.3, volume resistivity: 10.5 Log (Ω · cm), magnetization: 68 Am ² / kg, In, except that the particle content was changed to 75% by weight. [Carrier 14] having a content ratio of 0.0113 (mass%) and a volume average particle size of 35.3 μm 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 15]
In Example 3, a 35 μm sintered ferrite having a low magnetization was used and the magnetization was changed to 35 Am ² / kg. Similarly, the particle content: 50% by weight, D / h: 2.3, volume resistivity : 14.2 Log (Ω · cm), In content: 0.0070 (mass%), and [Carrier 15] having a volume average particle size of 35.7 μm 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 16]
In Example 3, 35 μm sintered ferrite having high magnetization was used, and the particle content was 50 wt%, D / h was 2.3, and the volume resistivity was the same except that the magnetization was changed to 93 Am ² / kg. [Carrier 16] having 11.2 Log (Ω · cm), In content: 0.0071 (mass%), and a volume average particle size of 35.1 μm 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 17]
In Example 3, except that the conductive particles and the nonconductive particles were used as follows, the particle content: 50% by weight, D / h: 2.3, volume resistivity: 13.5 Log ( [Carrier 17] having an In content of 0.0072 (mass%) and a volume average particle diameter of 35.6 μm was obtained.
-Conductive particles 1 33.1 parts-Non-conductive particles 33.1 parts [Substrate: alumina, surface treatment: none, particle size: 0.34 μm,
Powder resistivity: 10 ¹⁴ Ω · cm]
[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.

[Comparative Example 1]
In Example 1, D / h: 2.3, volume resistivity: 16.3 Log (except that the conductive particles were changed to the conductive particles 3 and the particle content was changed to 5% by weight) [Carrier 18] having a magnetization of 68 Am ² / kg, an In content of 0.00005 (mass%), and a volume average particle size of 35.6 μm was obtained.
[Carrier 18] 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]
In Example 1, D / h: 0.8, volume resistivity: measurable range lower limit, except that the conductive particles were changed to the conductive particles 4 and the particle content was changed to 84% by weight. Hereinafter, [Carrier 19] having magnetization: 68 Am ² / kg, In content: 0.6 (mass%), and a volume average particle size of 35.3 μm was obtained.
[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 3]
In the same manner as in Example 4, except that the conductive particles were changed to titanium dioxide having no surface treatment, the particle content: 50% by weight, D / h: 2.1, volume resistivity: 16.2 Log [Carrier 20] having (Ω · cm), magnetization: 68 Am ² / kg, In content: 0 (mass%), and a volume average particle diameter of 35.2 μm was obtained. The physical properties of titanium dioxide are as follows.
[Substrate: titanium dioxide, surface treatment; no, particle size: 0.31 μm, powder specific resistance: 2.1 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 with an In content of 0.00005 (mass%), the carrier adhesion / definition image was within the target range and good results were obtained, but the resistance adjustment effect was not sufficiently obtained. As a result, the edge effect deviated from the target value, and the durability decreased in terms of charge and resistance significantly deviated from the target value.
Furthermore, in Comparative Example 2 with an In content of 0.6 (mass%), the edge effect was within the target range and good results were obtained, but the resistance was too low, and the carrier adhesion deviated from the target value. Regarding the durability, the decrease in charge was significantly out of the target value, and the result was not usable practically.
Furthermore, in Comparative Example 3 in which the conductive particles used titanium dioxide without surface treatment, the carrier adhesion / definition image was within the target range and good results were obtained, but the resistance adjustment effect was sufficiently obtained. As a result, the edge effect deviated from the target value, and the durability decreased in terms of charge and resistance significantly deviated from the target value.

  Since the developer using the electrophotographic carrier of the present invention is excellent in durability and can form fine images with no edge effect over a long period of time, it can be used for copying machines and printers using electrophotography. It can be used as a developer.

It is the schematic which shows the structure of the process cartridge of this invention. It is the schematic which shows the structure of the apparatus used for the measurement of the powder specific resistance of electroconductive particle. It is the schematic which shows the structure of the apparatus used for the measurement of the volume solid resistance of a carrier. It is the schematic for demonstrating the measurement of the film thickness of a resin coating layer.

Claims (17)

A carrier having a resin coating layer on the surface of a core material, the conductive coating particles being contained in the resin coating layer, and the conductive particles provided on the surface of the base particle on the tin dioxide layer and the tin dioxide layer. It is provided with a conductive coating layer composed of an indium oxide layer containing tin, and contains 0.0001 (mass%) to 0.5 (mass%) of indium (In) atoms contained as indium oxide. An electrophotographic carrier characterized by the above. 2. The electron according to claim 1, wherein one or two or more kinds selected from aluminum oxide, titanium dioxide, zinc oxide, silicon dioxide, barium sulfate, and zirconium oxide particles are used as the base particles of the conductive particles. Photo carrier. Powder specific conductive particles resistance, 200 (Ω · cm) electrophotographic carrier according to any one of claims 1 to 2, characterized in that less. The electrophotographic carrier according to any one of claims 1 to 3, characterized in that it contains non-conductive particles in the resin coating layer. The volume resistivity of the carrier is, 10 [Log (Ω · cm )] or 16 [Log (Ω · cm) ] for electrophotography according to any one of claims 1 to 4, wherein the less is Career. The electrophotographic carrier according to any one of claims 1 to 5, the volume average particle diameter of the carrier is characterized in that it is 20 ([mu] m) or 65 ([mu] m) or less. The electrophotographic carrier according to any one of claims 1 to 6 , wherein the binder resin of the resin coating layer is a silicone resin. The electrophotographic carrier according to any one of claims 1 to 6 , wherein the binder resin of the resin coating layer is an acrylic resin. The electrophotographic carrier according to any one of claims 1 to 6 , wherein the binder resin of the resin coating layer is an acrylic resin and a silicone resin. And the particle diameter of particles contained in the resin coating layer (D), the coating layer thickness (h) is 1 <either [D / h] of claim 1 to 9, wherein the <10 1 The electrophotographic carrier according to Item. The electrophotographic carrier according to any one of claims 1 to 10 , wherein the content of the particles contained in the resin coating layer is 10 (wt%) or more and 70 (wt%) or less. Magnetic moment in ^{1000 (10 3 / 4π · A} / m) of the carrier, 40 claim 1-11, characterized in that it is (Am ² / kg) or 90 (Am ² / kg) or less 1 The electrophotographic carrier according to Item. At least a toner containing a binder resin and a colorant, an electrostatic latent image developer comprising a carrier according to any one of claims 1 to 12. 14. The developer for developing an electrostatic latent image according to claim 13 , wherein the toner is a color toner. Container, characterized in that accommodating the electrostatic latent image developer according to claim 13 or 14. Forming an electrostatic latent image on the image carrier, developing the electrostatic latent image with a developer comprising at least a carrier and a toner to form a visible image, and using the obtained visible image as a recording member 15. An image forming method comprising a step of transferring and fixing, wherein the developer is the electrostatic latent image developing developer according to claim 13 or 14 . In a process cartridge that is selected from a photoconductor, a charging unit, a developing unit, and a cleaning unit, and that supports at least the developing unit and is detachable from the image forming apparatus main body, the developing unit holds a developer, and The process cartridge according to claim 13 or 14 , wherein the developer is a developer for developing an electrostatic latent image.

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