Dry Magnetic Developer Containing a Non-Pulverizing Agglumerate of Cubic Magnetite Particles

1. Field of the Invention

The present invention relates to an improvement in the magnetic developer. More particularly, the present invention relates to a one-component type magnetic developer for electrophotography, which is excellent in the image sharpness, the resolving power and the half tone-reproducing property.

2. Description of the Prior Art

As the developer capable of developing an electrostatic latent image without using a particular carrier, there is known a so-called one-component type magnetic developer comprising a powder of a magnetic material contained in developer particles.

As one type of this one-component magnetic developer, there is known a so-called conductive magnetic developer in which a fine powder of a magnetic material is incorporated in developer particles to impart a property of being magnetically attracted and a conducting agent such as carbon black is distributed on the surface of the particles to impart them electrically conductive (see, for example, the specifications of U.S. Pat. Nos. 3,639,245 and 3,965,022). When this conductive magnetic developer is brought in the form of a so-called magnetic brush into contact with an electrostatic latent image-carrying substrate to effect development of the latent image, there can be obtained an excellent visible image free of a so-called edge effect or fog. However, as is well known, when the developer image is transferred to an ordinary transfer sheet from the substrate, a serious problem arises. More specifically, as described in Japanese Patent Application Laid-Open Specification No. 117435/75, when the inherent electric resistance of a transfer sheet used is lower than 3.times.10.sup.13 .OMEGA.-cm as in case of plain paper, broadening of contour or reduction of the transfer efficiency is caused by scattering of developer particles at the transfer step. This disadvantage is moderated to some extent by coating the toner-receiving surface of the transfer sheet with a resin, wax or oil having a high electric resistance. This improvement, however, is reduced under a high-humidity condition. Furthermore, the cost of the transfer sheet is increased by coating with a resin or the like and the feel of the transfer sheet is reduced.

As another type of the one-component magnetic developer, there is known a non-conductive magnetic developer comprising an intimate particulate mixture of a fine powder of a magnetic material and an electricity-detecting binder. For example, the specification of U.S. Pat. No. 3,645,770 discloses an electrostatic photographic reproduction process in which a magnetic brush (layer) of the above-mentioned non-conductive magnetic developer is charged with a polarity opposite to the polarity of the charge of an electrostatic latent image to be developed by means of corona discharge, the charged developer is brought into contact with a latent image-carrying substrate to develop the latent image and the developer image is transferred onto a transfer sheet. This electrostatic photographic reproduction process is advantageous in that a transfer image can be formed even on plain paper as the transfer sheet. However, this process is still disadvantageous in that it is difficult to uniformly charge the magnetic brush of the non-conductive magnetic developer even to the base portion thereof, it is generally difficult to form an image having a sufficient density and the apparatus become complicated because a corona discharge mechanism should be disposed in the developing zone.

Recently, there have been proposed a process in which an electrostatic latent image is developed by frictional charging of a non-conductive magnetic developer by frictional contact of the developer with the surface of a latent image-carrying substrate (see Japanese Patent Application Laid-Open Specification No. 62638/75) and a process in which development is effected by utilizing dielectric polarization of a non-conductive magnetic developer (see Japanese Patent Application Laid-Open Specification No. 133026/76). In the former process, however, if development conditions are not strictly controlled, fogging is readily caused (especially when the degree of the content of the tip of the spike of magnetic toner particles with the surface of the photosensitive material is high) or fixing or blocking of the magnetic toner particles onto the developing sleeve is caused, and this undesirable phenomenon is especially conspicuous when the copying operation is conducted continuously. In the latter process, there does not arise the problem of fogging, but since a visible image is formed by developing a latent image by utilizing the dielectric polarizing effect induced in the magnetic toner, the low-potential area of the latent image is not effectively developed. Accordingly, in the resulting print, a low-density portion of an original is hardly reproduced and reproduction of a half tone is difficult. Moreover, prints obtained according to these two processes are poor in the image sharpness, and when a p-type photosensitive material such as selenium is used as the photosensitive plate and a positively charged image is developed, it is very difficult to obtain an image having a sufficient density according to any of the foregoing two processes.

Furthermore, the specification of U.S. Pat. No. 4,102,305 discloses a process in which a one-component type magnetic developer, the electric resistance of which changes depending on the intensity of the electric field, namely a one-component type magnetic developer which becomes substantially conductive in a high electric field but has a high electric resistance in a low electric field, is used, a high voltage is applied between a magnetic brush-forming sleeve and a photosensitive plate to effect development under such conditions that the developer particles become conductive and transfer of the developer particles to a transfer sheet is carried out in a low electric field or in an electric field-free state to obtain an excellent transferred image. This specification teaches that the above-mentioned developer having a high electric field dependency of the electric resistance is prepared by spray-granulating 50% by weight of stearate-coated magnetite and 50% by weight of a styrene/n-butyl methacrylate copolymer. This process is excellent in the above idea of obtaining a good transferred image, but this process is disadvantageous in that a peculiar high voltage apparatus is necessary for the development and though the formed image has a high density, the image sharpness is still insufficient.

Moreover, the specification of U.S. Pat. No. 4,121,931 discloses a process in which an electrically insulating one-component type magnetic developer is used, a magnetic brush-forming sleeve is used as an electrode and a voltage is applied between this electrode and a photosensitive plate to cause a turbulent agitation in the developer on the sleeve, whereby the developer particles are uniformly charged. This process, however, is disadvantageous in that a high voltage apparatus should be disposed in the developing zone and special means should be disposed to agitate the developer particles on the sleeve.

As will be apparent from the foregoing description, the conventional researches made on one-component type magnetic developers and developing processes using these developers are concentrated to the composition of the developer, the developer-preparing process and the process for charging developer particles, but properties of magnetite to be incorporated into the developer have hardly been studied.

Ordinarily, when a magnetic brush of a one-component type developer is brought into contact with the surface of an electrostatic latent image-carrying substrate, the individual developer particles receive an electrostatic attracting force (Coulomb force) acting between the developer particles and the electrostatic latent image and a magnetic attracting force acting between the developer particles and a magnetic brush-forming magnet. The developer particles on which the Coulomb force is larger are attracted to the electrostatic latent image, while the developer particles on which the magnetic attracting force is larger are attracted to the magnetic sleeve, with the result that development is effected according to the electrostatic latent image on the substrate. Therefore, it is required for the one-component type magnetic developer that a certain balance should be maintained between magnetic characteristics and charging characteristics at the development step. Accordingly, it will readily be understood that the characteristics of the magnetic material powder used for the one-component type magnetic developer have important influences on the characteristics of an image which will be formed.

In accordance with the present invention, there is provided a dry magnetic developer consisting essentially of a particulate shaped article of a composition comprising a binder resin medium and a powdery magnetic material dispersed in the binder resin medium, wherein said composition is composed of a non-pulverizing agglomerate of cubic particles, and particles having a number average particle size of 1 to 10 microns, as measured by an electron microscope, are incorporated as the powdery magnetic material.

FIG. 1 is an electron microscope photograph of magnetite consisting of a non-pulverizing agglomerate of cubic particles, which is used in the present invention.

FIG. 2 shows an X-ray diffraction pattern of the agglomerate shown in FIG. 1.

When the above-mentioned non-pulverizing agglomerate particles are used as the magnetite of the one-component type magnetic developer according to the present invention, the image sharpness and resolving power can highly be improved over the conventional one-component type magnetic developers including magnetite of the needle or cubic crystal form or amorphous magnetite, and furthermore, the reproducibility of a half tone can also be improved.

As is seen from the electron microscope photograph of FIG. 1 and the X-ray diffraction pattern of FIG. 2, the powdery magnetic material used in the present invention is magnetite consisting of a non-pulverizing agglomerate of cubic particles.

By the term "non-pulverizing agglomerate" used in the instant specification and appended claims is meant an agglomerate of fine particles which are densely aggregated with one another and in which the particle size distribution is not substantially changed even by an ordinary pulverizing treatment, for example, 5 hours' ball-milling treatment.

This non-pulverizing agglomerate has a number average particle size of 1 to 10 microns, especially 2 to 7 microns, as measured by an electron microscope. Namely, it has a particle size larger than the particle size of ordinary magnetite particles.

Since the magnetic material used in the present invention has the above-mentioned dense aggregate structure and a relatively coarse particle size, the volume per unit weight, namely the bulk, is smaller than that of particles of magnetite of the cubic or needle crystal form or amorphous magnetite heretofore used for one-component magnetic developers. Accordingly, in the one-component type magnetic developer of the present invention, the resin/magnetite volume ratio can be made higher than that in the conventional one-component type magnetic developers when the comparison is made based on the same weight ratio of magnetite. Accordingly, as will readily be understood, in the one-component type magnetic developer of the present invention, much higher inherent charging characteristics can be given to the resin.

It has been known that a polymeric material having a larger dielectric constant is more readily positively charged (see The Society of Photographic Scientists and Engineers, 2nd Int. Conf., 1974, pages 95 to 100). It has been found by us that in a magnetic developer comprising a powdery magnetic material dispersed in a binder medium, if the dielectric constant of the magnetic developer is small, it is likely to be negatively charged by friction, and that if the dielectric constant is large, the magnetic material is likely to be positively charged by friction. More practically, developer particles comprising magnetite in an amount of 55% by weight based on the total developer have a dielectric constant of 3.85 to 4.05, whereas magnetic developer particles comprising 55% by weight of the above-mentioned non-pulverizing agglomerate of cubic particles have a dielectric constant of 3.79. Accordingly, it has been confirmed that the magnetic developer of the present invention is more readily negatively charged.

As pointed out hereinbefore, the powdery magnetic material used in the present invention has a smaller bulk, that is, a larger apparent density, than ordinary magnetite. More specifically, the powdery magnetic material has an apparent density of 0.5 to 1.5 g/ml, especially 0.7 to 1.3 g/ml, as determined according to the method of JIS K-5101.

The non-pulverizing agglomerate of cubic particles has magnetic characteristics of a saturation magnetization of 75 to 88 emu/g, a residual magnetization of 3 to 12 emu/g and a coercive force of 40 to 150 Oe.

The non-pulverizing agglomerate used in the present invention is prepared according to the following method, though an applicable method is not limited to this method.

A weakly alkaline aqueous solution, for example, aqueous ammonia, is added to an aqueous solution of iron (III) sulfate to form precipitates of iron (III) hydroxide. The precipitates are subjected to a hydrothermal treatment under pressure while maintaining the pH value of the mother liquor at 3 to 9, whereby gel-like precipitates of iron hydroxide are changed to cubic particles of alpha-Fe.sub.2 O.sub.3 (hematite). If the weakly alkaline aqueous solution is used to maintain the pH valve of the mother liquor to a level close to the acidic side, fine cubic particles which tend to aggregate are formed, and the so-obtained particles are aged by carrying out the hydrothermal treatment at 150.degree. to 230.degree. C. for a long time, for example, more than 50 hours, whereby alpha-diiron trioxide having the configuration specified in the present invention can be obtained. If this alpha-diiron trioxide is reduced under known conditions, for example, by heating it at 400.degree. C. with hydrogen in a reducing furnace, triiron tetroxide (Fe.sub.3 O.sub.4) having the configuration specified in the present invention can be obtained. The reducing treatment is ordinarily carried out so that the Fe.sup.2+ /Fe.sup.3+ atomic ratio is in the range of from 0.9/1.0 to 1.1/1.0. Thus, triiron tetroxide having the above-mentioned specific micro-structure can be obtained.

The X-ray diffraction pattern of the magnetite used in the present invention is the same as that of ordinary magnetite of the cubic crystal form and in view of the height of the diffraction peak, it has been confirmed that the magnetite used in the present invention is not substantially different from ordinary magnetite of the cubic crystal form in the degree of crystallization.

As the binder medium for dispersing this non-pulverizing agglomerate of cubic particles, there can be used resins, waxy materials or rubbers which show a fixing property under application of heat or pressure. These binder medium may be used singly or in the form of a mixture of two or more of them. It is preferred that the volume resistivity of the binder medium be at least 1.times.10.sup.15 .OMEGA.-cm as measured in the state where magnetite is not incorporated.

As the binder medium, there are used homopolymers and copolymers of mono- and di-ethylenically unsaturated monomers, especially (a) vinyl aromatic monomers and (b) acrylic monomers.

As the vinyl aromatic monomer, there can be mentioned monomers represented by the following formula: ##STR1## wherein R.sub.1 stands for a hydrogen atom, a lower alkyl group (having up to 4 carbon atoms) or a halogen atom, R.sub.2 stands for a substituent such as a lower alkyl group or a halogen atom, and n is an integer of up to 2 inclusive of zero,

such as styrene, vinyl toluene, alpha-methylstyrene, alpha-chlorostyrene, vinyl xylene and vinyl naphthalene. Among these vinyl aromatic monomers, styrene and vinyl toluene are especially preferred.

As the acrylic monomer, there can be mentioned monomers represented by the following formula: ##STR2## wherein R.sub.3 stands for a hydrogen atom or a lower alkyl group, and R.sub.4 stands for a hydroxyl group, an alkoxy group, a hydroxyalkoxy group, amino group or an aminoalkoxy group, such as acrylic acid, methacrylic acid, ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-aminopropylacrylate, 3-N,N-diethylaminopropyl acrylate and acrylamide.

As another monomer to be used singly or in combination with the above-mentioned monomer (a) or (b), there can be mentioned, for example, conjugate diolefin monomers represented by the following formula: ##STR3## wherein R.sub.5 stands for a hydrogen atom, a lower alkyl group or a chlorine atom, such as butadiene, isoprene and chloroprene.

As still another monomer, there can be mentioned ethylenically unsaturated carboxylic acids and esters thereof such as maleic anhydride, fumaric acid, crotonic acid and itaconic acid, vinyl esters such as vinyl acetate, and vinyl pyridine, vinyl pyrrolidone, vinyl ethers, acrylonitrile, vinyl chloride and vinylidene chloride.

It is preferred that the molecular weight of such vinyl type polymer be 3,000 to 300,000, especially 5,000 to 20,000.

In the present invention, it is preferred that the above-mentioned agglomerate be used in an amount of 40 to 70% by weight, especially 45 to 65% by weight, based on the sum of the amounts of the binder medium and the magnetic material. Magnetite is uniformly and homogeneously kneaded with the binder medium and the kneaded composition is granulated, whereby the intended one-component type magnetic developer is obtained.

Known auxiliary components for developers may be added according to known recipes prior to the above-mentioned kneading and granulating steps. For example, pigments such as carbon black and dyes such as Acid Violet may be added singly or in combination in amounts of 0.5 to 5% by weight based on the total composition so as to improve the hue of the developer. Furthermore, a filler such as calcium carbonate or powdery silica may be added in an amount of up to 20% by weight based on the total composition to obtain a bulking effect. In the case where fixing is effected by a hot roll, an offset-preventing agent such as a silicone oil, a low-molecular-weight olefin resin or a wax may be used in an amount of 2 to 15% by weight based on the total composition. In the case where fixing is effected by means of a pressure roll, a pressure fixability-improving agent such as paraffin wax, an animal or vegetable wax or a fatty acid amide may be used in an amount of 5 to 30% by weight based on the total composition. Furthermore, in order to prevent cohesion or agglomeration of developer particles and improve the flowability thereof, a flowability-improving agent such as a fine powder of polytetrafluoroethylene or finely divided silica may be added in an amount of 0.1 to 1.5% by weight based on the total composition.

Shaping of the developer can be accomplished by cooling the above-mentioned kneaded composition, pulverizing the composition and, if necessary, classifying the pulverization product. Mechanical high-speed stirring may be conducted so as to remove corners of indeterminate-shaped particles.

It is ordinarily preferred that the number average particle size of the developer particles be in the range of 5 to 35 microns and be at least 2 times the number average particle size of the agglomerate particles, though the particle size of the developer particles is changed to some extent according to the intended resolving power. The developer comprising indeterminate-shape particles formed by kneading and pulverization according to the present invention exerts enhanced effects of increasing the transfer efficiency and elevating the image sharpness.

In the the electrostatic photographic reproduction process using the developer according to the present invention, formation of an electrostatic latent image can be performed according to any of the known methods. For example, an electrostatic latent image can be formed by uniformly charging a photoconductive layer formed on a conductive substrate and subjecting the photoconductive layer to imagewise exposure.

A visible image of the developer is formed by bringing a magnetic brush of the above-mentioned one-component type magnetic developer into contact with the electrostatic latent image-carrying surface of the substrate. Development of the electrostatic latent image with the developer of the present invention can be accomplished, for example, according to the following procedures. The above-mentioned one-component type magnetic developer is charged in a developer hopper. A non-magnetic sleeve is rotatably mounted on a lower end opening of the hopper, and a magnet is disposed in the interior of the sleeve so that the magnet turns in a direction opposite to the rotation direction of the sleeve. When the sleeve and magnet are rotated, a brush layer of the magnetic developer is formed on the sleeve, and this brush layer is cut into an appropriate length by a spike-cutting plate. Then, the brush layer of the developer is lightly contacted with a selenium drum which is rotated in the same direction as the rotation direction of the sleeve to develop an electrostatic latent image on the selenium drum with the magnetic developer.

Then, the developer image on the substrate is brought into contact with a transfer sheet, and corona charging is effected from the back surface of the transfer sheet with the same polarity as that of the electrostatic latent image, whereby the developer image is transferred onto the transfer sheet.

In the present invention, fixation of the transferred image may be carried out according to any of a hot roller fixation method, a flash lamp fixation method and a pressure roller fixation method, and an appropriate fixation method is selected according to the kind of the developer.

The developer of the present invention is especially effective for a p-type photosensitive plate on which a positively charged latent image is formed, for example, a selenium photosensitive plate or a photosensitive plate comprising an organic photoconductive material layer. The conventional one-component magnetic developer of the frictional charging type can be applied to a photosensitive plate having a negatively charged latent image, but if this developer is used for developing a positively charged latent image formed on the above-mentioned p-type photosensitive plate, no satisfactory results can be obtained. In contrast, when the developer of the present invention is used, excellent results can be obtained in development and transfer of positively charged latent images.

The present invention will now be described in detail with reference to the following Examples that by no means limit the scope of the invention. All of "parts" and "%" are by weight unless otherwise indicated.

A composition comprising 55 parts of magnetite (Fe.sub.3 O.sub.4) shown in Table 1, 37 parts of a vinyl toluene/2-ethylhexyl acrylate copolymer (molar ratio=17/3, weight average molecular weight=83,000), 8 parts of low-molecular-weight polypropylene (average molecular weight=4,000) 0.5 part of zinc stearate was kneaded and molten at 150.degree. C. for 25 minutes by a two-roll kneading device. The kneaded composition was naturally cooled and roughly pulverized to a size of 0.5 to 2 mm by a cutting mill. Then, the roughly pulverized composition was finely pulverized by a jet mill and classified by a zigzag classifying machine to obtain a magnetic toner having a particle size within the range of from 5 to 35 microns. The classification was carried out so that the lower limit of the particle size range was at least 2 times the particle size of magnetite.

The following copying test was carried out by using the so-prepared magnetic toners.

In a copying machine comprising a selenium drum (outer diameter=150 mm) as a photosensitive material, the intensity of a magnetic field on a developing sleeve (outer diameter=33 mm) having a magnet disposed therein through a non-magnetic member was adjusted to about 900 gauss, and the magnetic toner was applied to a developing roller of the so-called two-rotation system capable of rotating the magnet and the sleeve independently, while adjusting the distance between a spike-cutting plate and the sleeve to 0.3 mm. An arrangement was made so that the magnetic toner was supplied to the developing roller zone from a hopper. The distance between the surface of the photosensitive material and the developing roller was adjusted to 0.5 mm. The developing sleeve and photosensitive material were rotated in the same direction, and the magnet was rotated in the opposite direction. Under the foregoing conditions, charging (+6.7 KV), exposure, development, transfer (+6.3 KV), heater roller fixation and fur brush cleaning were performed. High-quality paper having a thickness of 80 microns was used as a transfer sheet. The results in the copying test are shown in Table 2. The image density was measured on a solid black portion by using a commercially available reflective densitometer (supplied by Konishiroku Shashin Kogyo). A Copia test pattern supplied by Data Quest Co. was used as a copying test chart, and the gradient characteristic and resolving power were determined from a copy thereof.

The magnetic toner of the present invention can directly be applied to developing apparatuses where conventional electrically conductive magnetic toners are used. Furthermore, plain paper is used as a transfer sheet in this case, and a clear print can be obtained without broadening of the image contour or scattering or the toner, which is often observed at the transfer step when the conventional electrically conductive toners are used. In the transferred images obtained by using the above-mentioned magnetic toners of the present invention, the image density was high and a half tone was reproduced in a good condition.

These magnetic toners were characterized by a volume resistivity of 1.2.times.10.sup.14 .OMEGA.-cm to 4.6.times.10.sup.14 .OMEGA.-cm and a dielectric constant of 3.59 to 3.79 as measured under conditions of an electrode spacing of 0.65 mm, an electrode sectional area of 1.43 cm.sup.2 and an interelectrode load of 105 g/cm.sup.2.

An electron microscope photograph of the agglomerate magnetite B is shown in FIG. 1, and an X-ray diffraction pattern thereof is shown in FIG. 2.

A composition comprising agglomerate magnetite of the present invention (apparent density=0.735 g/ml, number average particle size=2.8 microns, coercive force=58 Oe, saturation magnetization=87.2 emu/g, residual magnetization=5.1 emu/g), a thermoplastic resin (styrene/butyl methacrylate copolymer, weight average molecular weight=27,000) and high density polyethylene at a mixing ratio shown in Table 3 was treated in the same manner as described in Example 1 to form a magnetic toner having a particle size within a range of from 6 to 20 microns.

The following copying test was carried out by using the so-obtained 5 magnetic toners.

In a copying machine comprising a selenium drum as a photosensitive material, the magnetic toner was applied to a developing roller having a magnet disposed therein through a non-magnetic member while adjusting the distance between a spike-cutting plate and the developing roller to 0.3 mm. The distance between the surface of the photosensitive material and the developing roller was adjusted to 0.5 mm. The developing roller and photosensitive material were rotated in the same direction, but the moving speed of the developing roller was 2 times as high as the moving speed of the photosensitive material. Under the foregoing conditions, charging, exposure, development and heat fixation were performed. High-quality paper having a thickness of 80 microns was used as a transfer sheet. The results of the copying test and the properties of the magnetic toners are shown in Table 4. The image density was measured on a solid black portion.

From the results shown in Table 4, it is seen that if the agglomerate magnetite of the present invention is incorporated in an amount of 40 to 70% by weight based on the sum of the amounts of the binder resin medium and agglomerate magnetite, there can be obtained a magnetic developer having excellent properties.