Development process for formation of high-quality image

Abstract: An optimum image can be obtained by carrying out the development while using a two-component type developer comprising an electroscopic toner and a magnetic carrier and having a specific toner concentration and maintaining the peripheral speed ratio of the magnet sleeve to the photosensitive material drum within a certain range according to the average particle size, saturation magnetization and electric resistance value of the magnetic carrier.

Description: Background of the Invention (1) Field of the Invention The present invention relates to a magnetic brush development process for forming a high-quality image by using a so-called two-component type developer in the electrophotography. (2) Description of the Prior Art In the electrostatic photography, there has been widely adopted a magnetic brush development process comprising supplying a two-component type developer comprising an electroscopic toner and a magnetic carrier onto a magnet sleeve to form a magnetic brush, and bringing the magnetic brush into sliding contact with the surface of a photosensitive material drum on which an electrostatic latent image is formed, to visualize the latent image and form a toner image. In this magnetic brush development process, however, not only characteristics of the developer and photosensitive material but also various mechanical conditions such as the peripheral speed of the photosensitive drum, the peripheral speed of the magnet sleeve, the drum-sleeve distance, the magnetic intensity of the magnet sleeve and the cutting length of the magnetic brush are important as factors for obtaining a good image, and setting of conditions for obtaining an optimum image is very difficult and complicated, see e.g. EP-A-183 509 and DE-A-3 590 683. By the optimum image is meant an image having a good image density and a good resolution. However, in general, the conditions for obtaining an image having a high image density are not in agreement with the conditions for obtaining an image having a high resolution, and it is very difficult to set the development conditions. Recently, high-speed reproduction is eagerly desired, and if the rotation speed of the photosensitive material drum is much increased over the speed adopted in the conventional electrostatic photographic apparatus, other development conditions should be drastically changed and the above-mentioned disadvantage becomes more serious. Furthermore, even if development conditions capable of providing a good image are set at the initial stage, when the developer or sleeve is deteriorated by the continuous reproduction for obtaining many prints, the agitating property and flowability of the developer, especially the brush-forming property, are changed and it becomes difficult to form an optimum magnetic brush, with the result that reduction of the image quality often takes place. This is especially conspicuous under high-temperature high-humidity undesirable conditions. Summary of the Invention The present invention is to obtain an image having a high quality by setting the ratio of the peripheral speed of the magnetic sleeve to the peripheral speed of the photosensitive material drum within a certain range in the magnetic brush development using a two-component type developer having a certain specific toner concentration according to the average particle size (µm), the saturation magnetization (emu/g) as measured at 50 KOe) and the electric resistance value (Ω-cm) of the magnetic carrier. More specifically, in accordance with the present invention, there is provided a magnetic brush development process for obtaining a high-quality image in the electrophotography, which comprises supplying a two-component type developer comprising an electroscopic toner and a magnetic carrier onto a magnet sleeve to form a magnetic brush and bringing the magnetic brush into sliding contact with the surface of a photosensitive material drum on which an electrostatic latent image is formed, to effect development, wherein a developer formed by mixing the toner and the magnetic carrier at a specific surface area ratio of from 0.7/1 to 1.3/1 is used, and the development is carried out under such conditions that the peripheral speed ratio K of the magnet sleeve to the photosensitive material drum satisfies the following requirement: wherein d represents the average particle size (µm) of the magnetic carrier, x represents the saturation magnetization (emu/g) of the magnetic carrier as measured at 50KOe, and R represents the electric resistance value (Ω-cm) of the magnetic carrier. In the present invention, it is preferred that a toner composition formed by adding a fine powder of an acrylic polymer and a fine powder of silica to an electroscopic toner be used as the electroscopic toner. It also is preferred that a magnetic carrier having an apparent density of 2.4 to 3.0 g/cm³ be used. Furthermore, it is preferred that the magnetic carrier used should have such a particle size distribution that the amount of particles having a particle size up to 0.5 times as large as the average particle size is smaller than 0.1% by weight and the amount of particles having a particle size 0.7 to 1.4 times as large as the average particle size is at least 90% by weight. A magnetic carrier covered with a resin is preferably used as the magnetic carrier. Brief Description of the Drawings Fig. 1 is a diagram illustrating an electrostatic photographic apparatus suitable for use in carrying out the development process of the present invention. Fig. 2 is an enlarged diagram illustrating a main part of a development apparatus. Detailed Description of the Preferred Embodiments The present invention is based on the novel finding that in the magnetic brush development process using a two-component type developer, the mechanical development conditions for obtaining an optimum image depend greatly on the peripheral speed ratio between a magnetic brush-delivering magnet sleeve and a photosensitive material drum and this peripheral speed ratio is appropriately set according to the particle size (µm), saturation magnetization (emu/g) as measured at 50 KOe and electric resistance value (Ω-cm) of the magnetic carrier used. In order to satisfy the requirement of formula (1) in the present invention, it is necessary that the toner concentration in the two-component type developer used should be such that the specific surface area ratio between the toner and carrier is in the range of from 0.7/1 to 1.3/1, especially from 0.9/1 to 1.1/1. More specifically, if the toner concentration is outside the above range, the requirement of formula (1) is not satisfied, and in this case, all of various mechanical conditions should be taken into consideration for setting optimum image-forming conditions, and the advantages of the present invention cannot be attained. If the development is carried out under such conditions that the peripheral speed ratio K fails to satisfy the requirement of formula (1), the following disadvantages are brought about. More specifically, if the peripheral speed ratio K is higher than (2d/x)(logR)/9, the resolution of the obtained copy is poor though the image density is sufficient, and if the peripheral speed ratio K is lower than (1.25d/x)(logR)/9, the density of the obtained image is low though the resolution is satisfactory. The above-mentioned formula (1) defining the development conditions is one empirically obtained, and the reason why an optimum image is obtained by carrying out the development under conditions satisfying the requirement of this formula (1) has not been elucidated, but it is presumed that this effect will probably be attained for the following reason. In order to obtain an optimum image, it is considered necessary that the electric resistance value of the magnetic brush in the development zone should be within a certain range, and it is considered that since the electric resistance value of the magnetic brush is set within a certain range according to the electric resistance value of the magnetic carrier if the requirement of formula (1) is satisfied, an optimum image can be obtained. This presumption is supported by the fact that in order to satisfy the requirement of formula (1), it is necessary that the toner concentration in the developer, that is, the toner/carrier ratio, should be set within a certain range. More specifically, if the toner/carrier ratio is outside a certain range, the mutual resistance between the electric resistance value of the carrier and the electric resistance value of the magnetic brush (the entire developer) is disturbed, and therefore, it is considered that the requirement of formula (1) is not satisfied. Accordingly, if the peripheral speed ratio K is higher than (2d/x)(logR)/9, the electric resistance value of the magnetic brush is reduced, and the resolution is reduced though the image density increases. If the peripheral speed ratio K is lower than (1.25d/x)(logR)/9, the image density is reduced even though the electric resistance of the magnetic brush increases and the resolution is sufficient. In accordance with one preferred embodiment of the present invention, a specific toner composition formed by externally adding a fine powder of an acrylic polymer and a fine powder of silica to a toner is used. In order to obtain images having a high quality stably for a long time, it is important that the state of formation of a magnetic brush which passes through a set developing zone should not be changed. If this specific toner composition is used, the dispersibility and transportability of the developer on the sleeve are improved and a uniform magnetic brush can be formed repeatedly, and furthermore, the dispersibility of the toner in the magnetic brush is uniformalized. Accordingly, the electric resistance is always kept stable in the magnetic brush and the toner moves evenly to the latent image, with the result that images having a high quality can be formed repeatedly over a long period. In another embodiment of the present invention, in order to satisfy the requirement of formula (1) for a long time, it is important that the apparent density of the magnetic carrier used should be 2.4 to 3.0 g/cm³. In order to satisfy the requirement of formula (1) over a long period, it is necessary that the electric resistance value of the magnetic brush should always be stably maintained within a certain range, and if the apparent density of the magnetic carrier is set within the above-mentioned range, it becomes possible to set the electric resistance value of the magnetic brush within a certain range for a long time, and good images can be stably obtained for a long time. Accordingly, in the case where the apparent density of the magnetic carrier is outside the above-mentioned range, if formation of images is repeated for a long time, it becomes difficult to maintain the electric resistance value of the magnetic brush within the certain range, and it often happens that the requirement of formula (1) is not satisfied. Furthermore, if the apparent density of the magnetic carrier is outside the above-mentioned range, when the developer is deteriorated by repeating formation of images for a long time, the image density becomes unstable and fogging is readily caused, and it often happens that a good image cannot be obtained. In still another embodiment of the present invention, in order to satisfy the requirement of formula (1), it is important that the magnetic carrier used should have such a particle size distribution that the amount of particles having a particle size up to 0.5 time as large as the average particle size is smaller than 0.1% by weight and the amount of particles having a particle size 0.7 to 1.4 times as large as the average particle size is at least 90% by weight. Namely, in order to satisfy the requirement of formula (1) for a long time, it is necessary that the electric resistance value of the magnetic brush should always be stable within a certain range, and by imparting the above-mentioned particle size distribution to the magnetic carrier, it becomes possible to maintain the electric resistance value of the magnetic brush within the certain range for a long period, and therefore, good images can be stably obtained for a long time. Accordngly, in the case where the particle size distribution of the magnetic carrier fails to satisfy the above-mentioned condition, while formation of images is repeated for a long time, it becomes impossible to maintain the electric resistance value of the magnetic brush within the certain range, and it often happens that the requirement of formula (1) is not satisfied. Furthermore, in the case where the particle size distribution of the magnetic carrier fails to satisfy the above condition, if formation of images is repeated for a long time, with deterioration of the developer, the scattering of the carrier is caused and it often becomes impossible to obtain a good image. In the development process of the present invention, a magnetic carrier having the surface covered with a resin is preferably used. In the magnetic brush development process using a two-component type developer, in general, a magnetic brush is formed by stirring and mixing a mixture of a toner and a carrier in the development apparatus. Accordingly, if formation of images is repeated for a long time, fusion bonding of the toner to the surface of the carrier is caused by collision between the toner and carrier in the development apparatus or collision between the development apparatus and the carrier. If the toner is fusion-bonded to the surface of the carrier, the electric resistance value of the magnetic brush is changed and the mutual relation between the electric resistance value of the carrier and the electric resistance value of the magnetic brush is disturbed, with the result that it often happens that the requirement of formula (1) is not satisfied. Accordingly, in order to satisfy the requirement of formula (1) over a long period, it is necessary to prevent fusion bonding of the toner to the carrier, and this prevention of fusion bonding of the toner to the carrier can be easily accomplished by coating the surface of the carrier with a resin. Namely, if the surface of the carrier is coated with a resin, the requirement of formula (1) can be satisfied even if formation of images is repeated for a long time. Developer Any of known two-component type developers comprising an electroscopic toner and a magnetic carrier can be used in the development process of the present invention. For example, a colored toner having an electroscopic property and a fixing property can be used as the toner. In general, this toner is composed of a granular composition having a particle size of 5 to 30 microns, which comprises a binder resin and, dispersed therein, a coloring pigment and a charge controlling agent. As the binder resin of the toner, there can be used a thermoplastic resin, an uncured thermosetting resin and a precondensate of a thermosetting resin. As preferable examples, there can be mentioned, in order of the importance, a vinyl aromatic resin such as polystyrene, an acrylic resin, a polyvinyl acetal resin, a polyester resin, an epoxy resin, a phenolic resin, a petroleum resin and an olefin resin. As the coloring pigment, there can be mentioned, for example, carbon black, cadmium yellow, molybdenum orange, Pyrazolone Red, Fast Violet B and Phthalocyanine Blue. These pigments can be used singly or in the form of a mixture of two or more of them. As the charge controlling agent, for example, oil-soluble dyes such as Nigrosine Base (CI 50415), Oil Black (CI 26150) and Spiron Black, metal salts of naphthenic acid, metal soaps of fatty acids and soaps of resin acids can be used according to need. As the fine powder of the acrylic polymer to be added to the above-mentioned toner, there can be mentioned spherical resin particle powders formed by emulsion polymerization, soap-free polymerization, dispersion polymerization and suspension polymerization, and powders obtained by pulverizing polymerization masses. It is generally preferred that the particle size of the fine powder of the acrylic polymer be 0.1 to 1 µm, especially 0.3 to 0.6 µm. As the monomer constituting the acrylic polymer, there can be mentioned acrylic monomers represented by the following formula: wherein R₃ represents a hydrogen atom or a lower alkyl group, and R₄ represents a hydrogen atom, a hydrocarbon group having up to 12 carbon atoms, a hydroxyalkyl group or a vinyl ester group, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-hydroxyacrylate, butyl δ-hydroxyacrylate, ethyl β-hydroxymethacrylate, ethylene glycol methacrylate and tetramethylene dimethacrylate. These acrylic monomers can be used singly or in the form of a mixture of two or more of them. Other radical-polymerizable monomer can be used together with the acrylic monomer. For example, there can be mentioned styrene type monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-methoxystyrene and p-chlorostyrene, carboxylic acids having an unsaturated double bond and alkyl esters thereof such as maleic acid, crotonic acid, itaconic acid and alkyl esters thereof, olefin monomers such as ethylene, propylene and butadiene, and vinyl acetate, vinyl chloride, vinylidene chloride, vinyl pyrrolidone and vinyl naphthalene. The fine powder of silica to be used in combination with the fine powder of the acrylic polymer is preferably a hydrophobic fine powder of silica having a primary particle size of 0.01 to 1 µm, especially 0.02 to 0.5 µm. As specific examples, there can be mentioned Aerosil R-927, Aerosil R-812 and Aerosil R-805 (supplied by Nippon Aerosil). The fine powder of the acrylic polymer is used in an amount of 0.01 to 0.2 part by weight, preferably 0.03 to 0.1 part by weight, per 100 parts by weight of the toner, and the fine powder of silica is used in such an amount that the silica fine powder/acrylic polymer fine powder weight ratio is from 1/1 to 1/5, preferably from 1/2.5 to 1/3.5. If the amount used of the fine powder of the acrylic polymer is outside the above-mentioned range, a magnetic brush is not stably formed on the development sleeve, resulting in reduction of the image quality. It is important that a specific amount of the fine powder of silica should be added to the fine powder of the acrylic polymer. By addition of the fine powder of silica, the transportability and dispersibility of the developer during the delivery from the agitating zone of the developing device to the sleeve and on the sleeve are improved, and an optimum state of the magnetic brush can be formed repeatedly over a long period without any influence by the change of the environment, and the number of obtainable copies can be drastically increased. If the amount added of the fine powder of silica is too small and below the above-mentioned range, the dispersion state (present amount) of the developer on the sleeve is often uneven, and if the amount of the fine powder of silica is too large and exceeds the above-mentioned range, migration of the toner in the magnetic brush to the photosensitive material becomes difficult. Known magnetic carriers such as triiron tetroxide, ferrite and iron powder can be used as the magnetic carrier in combination with the above-mentioned toner in the present invention. It is preferred that the average particle size of the magnetic carrier be 20 to 200 µm, especially 40 to 130 µm, and it also is preferred that the saturation magnetization, as measured at 50 KOe, of the magnetic carrier be 30 to 70 emu/g, especially 40 to 50 emu/g. According to one preferred embodiment of the present invention, a magnetic carrier having an apparent density of 2.4 to 3.0 g/cm³ is used. According to another preferred embodiment of the present invention, a magnetic carrier having such a particle size distribution that the amount of particles having a particle size up to 0.5 time as large as the average particle is smaller than 0.1% by weight based on the entire carrier and the amount of particles having a particle size 0.7 to 1.4 times as large as the average particle size is at least 90% by weight based on the entire carrier is used. According to still another embodiment of the present invention, the surface of the magnetic carrier is covered with a resin. If the surface of the magnetic carrier is covered with a resin, an optimum state of the magnetic brush can be produced repeatedly for a long time, and the number of obtainable copies can be drastically increased. As the resin to be used for covering the surface of the magnetic carrier, there can be mentioned an acrylic resin, a styrene/acrylic resin, an acrylic-modified silicone resin, a silicone resin, an epoxy resin, a resin-modified phenolic resin, a formalin resin, a cellulose resin, a polyether resin, a polyvinyl butyral resin, a polyester resin, a styrene/butadiene resin, a polyurethane resin, a polyvinyl formal resin, a melamine resin, a polycarbonate resin and a fluorine resin such as a tetrafluoroethylene resin. These resins can be used singly or in the form of a mixture of two or more of them. If a resin formed by curing and reacting a melamine resin and a thermoplastic resin having an unreacted hydroxyl group or alkoxyl group is used, the mechanical strength of the covering is further improved and the life of the carrier can be prolonged, and an optimum image can be obtained for a long time. As the thermoplastic resin having a hydroxyl group or alkoxyl group, there can be mentioned, for example, an epoxy resin, a hydroxyl or alkoxyl group-containing acrylic resin, a hydroxyl or alkoxyl group-containing styrene/acrylic resin, an acrylic-modified silicone resin, a phenoxy resin, a polyester resin, a butyral resin, a formal resin, a silicone resin and a hydroxyl or alkoxyl group-containing fluorine resin. It is preferred that the covering resin be used in an amount of 0.1 to 10 parts by weight, especially 0.2 to 5 parts by weight, per 100 parts by weight of the carrier core. In the above-mentioned toner, the toner concentration is adjusted so that the specific surface area ratio of the carrier to the toner is from 1/0.7 to 1/1.3, especially from 1/0.9 to 1/1.1. Electrophotographic Apparatus Referring to Fig. 1 illustrating an electrophotographic apparatus suitable for use in working the magnetic brush development process of the present invention, a photoconductive layer 2 is formed on the surface of a metal drum 1 driven and rotated. The photoconductive layer 2 is composed of, for example, Se, ZnO, CdS, amorphous silicon or a function-separated organic photoconductor. Around the circumference of this drum, there are disposed a corona charger 3 for main charging, an imagewise light exposure mechanism comprising a lamp 4, an original-supporting transparent plate 5 and an optical system 6, a developing mechanism 8 having a developer 7, a corona charger 9 for transfer of the toner, a paper-separating corona charger 10, an electricity-removing lamp 11, and a cleaning mechanism 12 in the recited order. The image-forming process using this electrophotographic apparatus will now be described in brief. At first, the photoconductive layer 2 is charged with a certain polarity by the corona charger 3. Then, an original 13 to be copied is illuminated by the lamp 4 and the photoconductive layer 2 is exposed to the light image of the original through the optical system 6 to form an electrostatic latent image corresponding to the image of the original. This electrostatic latent image is visualized by the developing mechanism 8 to form a toner image. A transfer paper 14 is supplied so that the transfer paper 14 is brought into contact with the surface of the drum at the position of the charger 9 for transfer of the toner, and corona charging with the same polarity as that of the electrostatic latent image is effected from the back surface of the transfer paper 14 to transfer the toner image to the transfer paper 14. The transfer paper 14 having the toner image transferred thereon is electrostatically peeled from the drum by removal of electricity by the paper-separating corona charger 10 and is fed to a processing zone such as a fixing zone (not shown). After the transfer of the toner image, residual charges on the photoconductive layer 2 are erased by the entire surface light exposure by the electricity-removing lamp 11, and then, the residual toner is removed by the cleaning mechanism 12. Development Appartaus and Development Process Fig. 2 is an enlarged view showing the development apparatus 8 in the above-mentioned electrophotographic apparatus. The development apparatus 8 comprises a developer delivery sleeve 21 having a cylindrical shape, in which a magnet 20 having N poles and S poles arranged alternately is arranged. The development process of the present invention is applied to the type where the magnet 20 is fixed and the sleeve 21 is rotated in the same direction as the rotation direction of the drum to deliver a magnetic brush 7 of the developer. The magnetic intensity of the main pole of the magnet 20 is set at 600 to 1000 G, and the angle between the line connecting the center of the main pole and the center of the drum and the line connecting the center of the main pole and the center of the sleeve is adjusted to 0 to 10°. The distance ℓ between the photoconductive layer 2 and the sleeve 21 is adjusted to 0.8 to 1.5 mm. A brush-cutting mechanism 22 is arranged upstream of the developing zone and the magnetic brush 7 is fed to the developing zone in the state cut into a length of 0.8 to 1.2 mm, whereby the development is carried out. In the present invention, as pointed out hereinbefore, the development is carried out under such conditions that the peripheral speed ratio K of the sleeve to the drum 1 satisfies the requirement represented by the following formula (1): wherein d represents the average particle size (µm) of the magnetic carrier, x represents the saturation magnetization (emu/g) of the magnetic carrier as measured at 50 KOe, and R represents the electric resistance value (Ω-cm) of the magnetic carrier, whereby an image having a high image density and an excellent resolution can be obtained. According to the present invention, an optimum image can be obtained only by appropriately adjusting the peripheral speed ratio between the photosensitive material drum and the magnet sleeve according to the electric resistance value, average particle size, and saturation magnetization of the magnetic carrier, which can be independently measured. Accordingly, optimum development conditions can be very easily set without changing mechanical conditions such as the drum-sleeve distance, the position of the magnetic pole and the brush-cutting length according to the toner used. The present invention is especially advantageously applied to the case where the mechanical development conditions are drastically changed as in case of high-speed reproduction. The present invention will now be described in detail with reference to the following examples. Example 1 By using a commercially available copying machine (Model DC-112C supplied by Mita), the copying operation was carried out under developing conditions described below while changing the physical properties (electric resistance value, particle size and saturation magnetization) of the carrier of the two-component type developer, and the image quality was evaluated. Development Conditions Cut brush length: 1.0 mm Drum-sleeve distance: 1.1 mm Sleeve: main pole position = +3.5°, main pole intensity = 800 G Surface potential: +700 V Bias voltage: +180 V Photosensitive material drum: selenium drum Developer: carrier = ferrite carrier, toner = toner for negative charging, having an average particle size of 11 µm, the toner concentration being set so that the specific surface area ratio between the carrier and toner was 1/1 The results of the evaluation are shown in Table 1. In the evaluation of the image quality, when ID (reflection density) of the first copy was at least 1.3 and the resolution of the second copy was at least 2.8 lines/mm in either the longitudinal direction or the lateral direction, the image quality was judged to be good and indicated by mark "O", and other case was indicated by mark "X". In Table 1, A represents (1.25d/x)(logR/9) and B represents (2d/x)(logR/9). Example 2 In the same manner as descried in Example 1, the copying test was carried out by using the carrier used in Run 1 of Example 1 while changing the peripheral speed ratio K of the sleeve to the drum. The evaluation results are shown in Table 2. Example 3 By using a commercially available electrophotographic copying machine (Model DC-112C supplied by Mita) and a black toner for negative charging, having an average particle size of 11 µm, the copying operation was carried out under development conditions shown below while changing the physical properties (average particle size and saturation magnetization and electric resistance value) of the magnetic carrier, and the image quality was evaluated. Development Conditions Cut brush length: 1.0 mm Drum-sleeve distance: 1.1 mm Sleeve: main pole position = +3.5°, main pole intensity = 800 G Drum/sleeve peripheral speed ratio: 2.9 Surface potential: +700 V Bias Voltage: +180 V Photosensitive material: selenium Developer: carrier = ferrite carrier having an electric resistance of 10⁹ Ω-cm, toner = toner for negative charging, having an average particle size of 11 µm, the toner concentration being set so that the specific surface area ratio between the carrier and toner was 1/1 The results of the evaluation are shown in Table 3. In the evaluation of the image quality, when ID (reflection density) of the first copy was at least 1.3 and the resolution of the second copy was at least 2.8 lines/mm in either the longitudinal direction or the lateral direction, the image quality was judged to be good and indicated by mark "O", and other case was indicated by mark "X". In Table 3, A represents (1.25d/x)(logR)/9 and B represents (2d/x)(logR)/9. Example 4 In the same manner as described in Example 3, the copying test was carried out by using the carrier used in Run 13 of Example 3 while changing the peripheral speed ratio K of the sleeve to the drum. The evaluation results are shown in Table 4. Example 5 To 100 parts by weight of a toner for negative charging having average particle size of 11 µm was added 0.03 part by weight, per 100 parts by weight of the toner, of a fine powder of a PMMA polymer having a particle size of 0.5 µm, and the polymer particle was uniformly dispersed on the surfaces of the toner particles. Then, 0.03 part of hydrophobic silica having an average primary particle size of 0.03 µm was mixed in the above toner particles to obtain a toner composition (hereinafter referred to as "toner composition A"). A toner composition B was prepared by adding only 0.03 part of the fine powder of the PMMA polymer to the toner, a toner composition C was prepared by adding only 0.03 part by weight of the hydrfophobic silica to the toner, and a toner composition D was prepared by adding 0.03 part by weight of aluminum oxide having a paticle size of 0.02 µm and 0.03 part by weight of the hydrophobic silica to the toner. The copying test was carried out by using these toner compositions under the development conditions adopted in Example 3 by using the carrier used in Run 8 of Example 3 and setting the peripheral speed ratio K of the sleeve to the drum to 3.3 [(1.25d/x)(logR/9) = 2.5, (2d/x)(logR/9) = 4.0]. The evaluation of images was carried out in the same manner as described in Example 3, and the number of copies in which the evaluation result was "0" was counted as the printable copy number. The obtained results are shown in Table 5. From the results shown in Table 5, it is seen that if a developer comprising a toner composition formed by incorporating a fine powder of an acrylic polymer and a fine powder of silica is used, the copying property (printability) is drastically improved. Example 6 The copying test was carried out at a high temperature and a high relative humidity (35°C and 85%) under conditions adopted in Example 5 by using a toner composition formed by adding 0.04 part by weight, per 100 parts by weight of the toner, of the fine powder of the RMMA polymer while changing the amount added of the hydrophobic silica as shown in Table 6. The obtained results are shown in Table 6. From the results shown in Table 6, it is seen that a toner composition formed by adding silica in an amount 1 to 5 times the amount of a fine powder of an acrylic polymer gives good results. Example 7 By using a commercially available electrophotographic copying machine (Model DC-112C supplied by Mita) and a black toner for negative charging, having an average particle size of 11 µm, the copying operation was carried out under development conditions shown below while changing the physical properties (average particle size and saturation magnetization and electric resistance value) of a magnetic carrier, and the image quality was evaluated. Development Conditions Cut brush length: 1.0 mm Drum-sleeve distance: 1.1 mm Sleeve: main pole position = +3.5°, main pole intensity = 800 G Drum/sleeve peripheral speed ratio: 2.9 Surface potential: +700 V Bias voltage: +180 V Developer: carrier = ferrite carrier having an electric resistance of 10⁹ Ω-cm, toner = toner for negative charging, having an average particle size of 11 µm, the toner concentration being set so that the specific surface area ratio between the carrier and toner was 1/1. The result of the evaluation are shown in Table 7. In the evaluation of the image quality, when ID (reflection density) of the first copy was at least 1.3 and the resolution of the second copy was at least 2.8 lines/mm in either the longitudinal direction or the lateral direction, the image quality was judged to be good and indicated by mark "O", and other case was indicated by mark "X". In Table 7, A represents (1.25d/x)(logR/9) and B represents (2d/x)(logR/9). Example 8 In the same manner as described in Example 7, the copying test was carried out by using the carrier used in Run 1 of Example 7 while changing the peripheral speed ratio K of the sleeve to the drum. The evaluation results are shown in Table 8. From the results shown in Tables 7 and 8, it is seen that a good image is obtained only when the requirement of (1.25d/x)·(logR/9)≦K≦(2d/x)·(logR/9) is satisfied. Example 9 The copying test was carried out under the same development conditions as described in Example 7 by using the carrier used in Run 8 in Example 7 while changing the apparent density as shown in Table 9. The image quality was evaluated in the same manner as described in Example 7, and the number of copies in which the image quality was "O" was counted as the printable copy number. The obtained results are shown in Table 9. From the results shown in Table 9, it is seen that when a carrier A having an apparent density of 2.4 to 3.0 g/cm³ is used, the printable copy number is drastically increased and good images can be obtained over a long period, as compared with the case where a carrier B or C failing to satisfy the above requirement of the apparent density is used. Example 10 By using a commercially available electrophotographic copying machine (Model DC-112C supplied by Mita) and a black toner for negative charging, having an average particle size of 11 µm, the copying operation was carried out under development conditions shown below while changing the physical properties (average particle size, saturation magnetization and electric resistance) of the magnetic carrier, and the image quality was evaluated. Development Conditions Cut brush length: 1.0 mm Drum-sleeve distance: 1.1 mm Sleeve: main pole position = +3.5°, main pole intensity = 800 G Drum/sleeve peripheral speed ratio: 2.9 Surface potential: +700 V Bias voltage: +180 V Photosensitive material: selenium Developer: carrier = ferrite carrier having an electric resistance of 10⁹ Ω-cm, toner = toner for negative charging, having an average particle size of 11 µm, the toner concentration being set so that the specific surface area ratio between the carrier and toner was 1/1. The results of the evaluation are shown in Table 10. In the evaluation of the image quality, when ID (reflection density) of the first copy was at least 1.3 and the resolution of the second copy was at least 2.8 lines/mm in either the longitudinal direction or the lateral direction, the image quality was judged to be good and indicated by mark "O", and other case was indicated by mark "X". In Table 10, A represents (1.25d/x)(logR/9) and B represents (2d/x)(logR/9). Example 11 In the same manner as described in Example 10, the copying test was carried out by using the carrier used in Run 1 of Example 10 while changing the peripheral speed ratio K of the sleeve to the drum. The evaluation results are shown in Table 11. From the results shown in Tables 10 and 11, it is seen that a good image is obtained only when the requirement of (1.25d/x)·(logR/9)≦K≦(2d/x)·(logR/9) is satisfied. Example 12 The copying test was carried out under the same development conditions as described in Example 10 by using the carrier (having an average particle size of 80 µm) used in Run 8 in Example 10 while changing the particle size distribution. The image quality was evaluated in the same manner as described in Example 10. The number of copies in which the image quality was judged to be "O" was counted as the printable copy number. The obtained results are shown in Table 12. From the results shown in Table 12, it is seen that when a carrier A satisfying the requirement that the amount of particles having a particle size up to 0.5 time as large as the average particle size is smaller than 0.1% by weight and the average particle size is smaller than 0.1% by weight and the amount of particles having a particle size 0.7 to 1.4 times as large as the average particle size is at least 90% by weight is used, the printable copy number is much increased over the printable copy numbers attained when the carriers B, C and D failing to satisfy this requirement of the particle size distribution are used, and copies having a good image quality can be stably obtained for a long time when the carrier A is used. Example 13 By using a commercially available electrophotographic copying machine (Model DC-112C supplied by Mita) and a black toner for negative charging, having an average particle size of 11 µm, the copying operation was carried out under development conditions shown below while changing the physical properties (average particle size, saturation magnetization and electric resistance value) of the magnetic carrier, and the image quality was evaluated. Development Conditions Cut brush length: 1.0 mm Drum-sleeve distance: 1.1 mm Sleeve: main pole position = +3.5°, main pole intensity = 800 G Drum/sleeve peripheral speed ratio: 2.9 Surface potential: +700 V Bias voltage: +180 V Photosensitive material: selenium Developer: carrier = ferrite carrier having an electric resistance of 10⁹ Ω-cm, toner = toner for negative charging, having an average particle size of 11 µm, the toner concentration being set so that the specific surface area ratio between the carrier and toner was 1/1. The results of the evaluation are shown in Table 13. In the evaluation of the image quality, when ID (reflection density) of the first copy was at least 1.3 and the resolution of the second copy was at least 2.8 lines/mm in either the longitudinal direction or the lateral direction, the image quality was judged to be good and indicated by mark "O", and other case was indicated by mark "X". In Table 13, A represents (1.25d/x)(logR/9) and B represents (2d/x)(logR/9). Example 14 In the same manner as described in Example 13, the copying test was carried out by using the carrier used in Run 1 of Example 13 while changing the peripheral speed ratio K of the sleeve to the drum. The evaluation results are shown in Table 14. From the results shown in Tables 13 and 14, it is seen that a good image is obtained only when the requirement of (1.25d/x)·(logR/9)≦K≦(2d/x)·(logR/9) is satisfied. Example 15 The copying test was carried out under the same development conditions as described in Example 14 except that a covered carrier formed by covering the surface of the carrier used in Run 8 of Example 14 with a resin under conditions A through F shown in Table 15 was used as the magnetic carrier. The image quality was evaluated in the same manner as described in Example 14, and the number of copies where the image quality was judged to be "O" was counted as the printable copy number. The obtained results are shown in Table 16. From the results shown in Table 16, it is seen that when the resin-covered carriers A through E are used, the printable copy number is drastically increased and good images can be obtained over a long period, as compared with the case where the uncovered carrier F is used.

Claims: A magnetic brush development process for obtaining a high-quality image in the electrophotography, which a two-component type developer comprising an electroscopic toner and a magnetic carrier onto a magnet sleeve to form a magnetic brush and bringing the magnetic brush into sliding contact with the surface of a photosensitive material drum on which an electrostatic latent image is formed, to effect development, characterized in that a developer formed by mixing the toner and the magnetic carrier at a specific surface area ratio of from 0.7/1 to 1.3/1 is used, and the development is carried out under such conditions that the peripheral speed ratio K of the magnet sleeve to the photosensitive material drum satisfies the following requirement: wherein d represents the average particle size (µm) of the magnetic carrier, x represents the saturation magnetization (emu/g) of the magnetic carrier as measured at 50 KOe, and R represents the electric resistance value (Ω-cm) of the magnetic carrier. A development process according to claim 1, wherein the two-component type developer comprises the toner and carrier at such a ratio that the specific surface area ratio of the toner to the carrier is from 0.9/1 to 1.1/1. A development process according to claim 1 or 2, wherein the magnetic carrier has an average particle size of 20 to 200 µm and a saturation magnetization of 30 to 70 emu/g. A development process according to claim 1,2 or 3, wherein the electroscopic toner is one formed by adding a fine powder of an acrylic polymer and a fine powder of silica to an electroscopic toner. A development process according to claim 4, wherein the fine powder of the acrylic polymer has a primary particle size of 0.01 to 1 µm and the fine powder of silica has a primary particle size of 0.01 to 1 µm. A development process according to claim 4 or 5, wherein the fine powder of the acrylic polymer is present in an amount of 0.01 to 0.2 part by weight per 100 parts by weight of the electroscopic toner and the fine powder of silica is present in such an amount that the weight ratio of the fine powder of silica to the fine powder of the acrylic polymer is from 1/1 to 1/5. A development process according to any preceding claim, wherein the magnetic carrier has an apparent density of 2.4 to 3.0 g/cm³. A development process according to any preceding claim, wherein the magnetic carrier has such a particle size distribution that the amount of particles having a particle size up to 0.5 times as large as the average particle size is smaller than 0.1% by weight based on the entire carrier and the amount of particles having a particle size 0.7 to 1.4 times as large as the average particle size is at least 90% by weight based on the entire carrier. A development process according to any preceding claim, wherein the magnetic carrier is one covered with a resin. A development process according to claim 9, wherein the covering resin is a composition comprising a melamine resin and a thermoplastic resin containing a hydroxyl group or an alkoxyl group. A development process according to claim 9 or 10, wherein the covering resin is present in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the core of the magnetic carrier.

Inventors: HIGASHIGUCHI TERUAKI, MIZUNO JUNKO, HIGASHIGUCHI, TERUAKI, MIZUNO, JUNKO
Applicants: MITA INDUSTRIAL CO LTD, MITA INDUSTRIAL CO., LTD.
Application year: 1989
Main classification: G03G13
IPC codes: G03G13