JP4438075B2 - Toner production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner capable of preventing the degradation in cleanability due to excessive electrostatic charging of the transfer residue toner by appropriately controlling the electrostatic charging amount of the developing toner on a photoreceptor. <P>SOLUTION: The toner has a binder resin, toner particles at least containing specific carbon black and a specific azo-base iron compound and inorganic micro-powder. The toner particles are produced by polymerizing a polymerizable monomer composition at least containing the polymerizable monomer, the carbon black and the azo-base iron compound in an aqueous medium. The polymerizable monomer composition is prepared by mixing a dispersion liquid dispersed with the carbon black and the azo-base iron compound in a first polymerizable monomer with at least a second polymerizable monomer. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

The present invention relates to a toner used in an image forming method using an electrophotographic method, an electrostatic recording method, or a magnetic recording method, and a toner manufacturing method. Specifically, the present invention is, after forming a toner image on a photosensitive member, and transferring the toner image onto the transfer material to the image forming, copying machines, printers, production of belt toner used in such an image forming apparatus fax Regarding the method.

  Conventionally, a number of methods are known as electrophotographic methods. In general, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the electric latent image is converted into a toner. The image is developed with a visible image, and if necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat or pressure to obtain a fixed image. is there. At this time, the toner remaining on the photoreceptor without being transferred to the transfer material after the transfer is cleaned by various methods.

  As a method for visualizing an electric latent image, a cascade development method, a magnetic brush development method, a nonmagnetic one-component development method, and a pressure development method are known. Furthermore, a magnetic one-component developing method is also used in which a magnetic toner is used and a rotating sleeve having a magnetic pole at the center is used to fly between the photosensitive member and the sleeve by an electric field.

  LED and LBP printers have become the mainstream in the recent market, and the direction of technology is higher resolution, that is, what is conventionally 240 dpi or 300 dpi is 400 dpi, 600 dpi, or 1200 dpi. Accordingly, the development method is also required to have higher definition. Copiers are also becoming more sophisticated, and are therefore moving toward digitalization. Since the method of forming an electrostatic charge image with a laser is mainly used in the digital method, the resolution is still high, and thus a high-resolution and high-definition developing method is required as in the case of a printer.

  For this reason, the reduction in the particle size of the toner is progressing, and Patent Documents 1 to 6 propose a toner having a specific particle size distribution and a small particle size.

  In recent years, a so-called contact one-component development method has been proposed in which development is performed by using a semiconductive development roller or a development roller having a dielectric layer formed on the surface thereof and pressing it against the surface layer of the photoreceptor.

  In the one-component development method, if the photosensitive member and the toner carrier have a distance, the electric force lines concentrate on the edge portion of the electrostatic latent image on the photosensitive member, and the toner is developed along the electric force lines. Image quality is likely to deteriorate due to an edge effect in which toner is biased and developed at the edge portion of the image.

  This edge effect is prevented by bringing the photosensitive member and the toner carrier very close to each other, but the gap between the photosensitive member and the toner carrier is mechanically set, that is, the gap is larger than the thickness of the toner layer on the toner carrier. Is difficult to set small.

  Therefore, the edge effect is prevented by using a contact one-component developing method in which the toner carrying member is pressed against the photosensitive member for development. However, if the toner carrying member surface moving speed is the same as the photosensitive member surface moving speed, a satisfactory image cannot be obtained when the latent image on the photosensitive member is visualized. Therefore, in the contact one-component developing method, by making a difference in the toner carrier surface moving speed with respect to the photosensitive member surface moving speed, a part of the toner on the toner carrier is made to the latent image on the photosensitive member surface. It is developed and some other toner is stripped off, resulting in a developed image without edge effects that is very faithful to the latent image.

  In such a contact one-component developing method, it is essential to rub the surface of the photosensitive member with toner and a toner carrier. For this reason, toner deterioration, toner carrier surface deterioration, photosensitive member surface deterioration or abrasion due to long-term use is essential. Since deterioration of durability characteristics remains a problem, this improvement method has been desired. Therefore, in the contact one-component developing method, it is necessary to improve the durability characteristics of the apparatus for the above reasons, and further, there is an essential problem that it is difficult to increase the speed at which a load is applied by the apparatus.

  Non-Patent Document 1 discusses a contact type one-component nonmagnetic development method. However, the durability characteristics are not mentioned.

  Non-Patent Document 2 reports an outline of a printer using a one-component contact development method. However, the durability characteristics are not sufficient and there is room for further improvement.

  Patent Documents 7 and 8 disclose a technique related to a one-component contact development method, but do not disclose a technique for improving durability.

  In recent years, from the viewpoint of environmental protection, in a conventional primary charging process and transfer process using corona discharge, a contact charging method in which charging is performed by bringing a charging member into contact with the surface of the photoreceptor, and transfer to the surface of the photoreceptor A contact transfer method in which transfer is performed by bringing a transfer member into contact with each other through a material is becoming mainstream.

  As such a contact charging method and a contact transfer method, for example, Patent Documents 9 and 10 have been proposed. In these methods, a conductive elastic roller is brought into contact with the photosensitive member, and the photosensitive member is uniformly charged while applying a voltage to the conductive roller, and then a toner image is obtained by an exposure and development process. A transfer material is passed while pressing another conductive roller to which a voltage is applied, and a toner image on the photoreceptor is transferred to the transfer material, and then a copy image is obtained through a fixing step.

  However, in such a contact transfer method, the transfer member is brought into contact with the photoconductor via the transfer material at the time of transfer, so that the toner image is formed when the toner image formed on the photoconductor is transferred to the transfer material. There arises a problem of partial transfer failure, which is referred to as a so-called “transfer dropout”.

  Further, as the diameter of the toner is reduced, the adhesion force (mirror image force, van der Waals force, etc.) of the toner particles to the photosensitive member becomes larger than the Coulomb force applied to the toner particles during the transfer, resulting in a residual transfer. There was a tendency for toner to increase.

  Therefore, the toner and the photoreceptor used in such an image forming method are required to have excellent releasability.

  Patent Document 11 discloses that a toner having a nearly spherical shape manufactured by a suspension polymerization method is used in order to improve the releasability of the toner from the photoreceptor and improve the transferability of the toner. Toners produced by suspension polymerization have been proposed for a long time. (For example, patent document 12). In this suspension polymerization method, a monomer composition is prepared by uniformly dissolving or decomposing a polymerizable monomer and a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives). After adjusting the monomer composition, the monomer composition is dispersed in a continuous layer (for example, an aqueous phase) containing a dispersion stabilizer using an appropriate stirrer, and a polymerization reaction is performed, so that a toner having a desired particle size is obtained. Particles are obtained.

  In this suspension polymerization method, droplets of the monomer composition are generated in a dispersion medium having a large polarity such as water. Therefore, the component having a polar group contained in the monomer composition is an interface with the aqueous phase. Thus, it is possible to produce a spherical toner having a so-called core / shell structure or sea-island structure in which a non-polar component does not exist in the surface layer portion.

  The toner by the polymerization method has been able to satisfy both the low-temperature fixing property and the anti-blocking property and the high-temperature offset-resistant property by embedding the wax component as a release agent.

  When such a toner is used, it is difficult to expose the colorant to the surface, and there is an advantage that the toner has uniform triboelectric chargeability. Furthermore, since the classification process can be omitted, the manufacturing cost reduction effect such as energy saving, time reduction, and process yield improvement is great.

  However, since the shape of the toner obtained by this method is substantially spherical, a cleaning failure occurs due to toner particle abrasion during cleaning in the above-described electrophotographic process, particularly blade cleaning, and a copy image is generated. The quality of the product may be significantly impaired.

  In particular, in non-magnetic one-component contact development, the charge amount of the toner developed on the photoconductor is high, and the adhesion force (mirror image force) of the toner particles to the photoconductor increases, resulting in an increase in the residual toner. Tend. There is also a tendency that the charge amount of the transfer residual toner tends to be high, and the adhesion force of the toner particles to the photosensitive member is increased, so that a cleaning failure is likely to occur during cleaning.

  It is also widely known that carbon black is contained as a black colorant in a toner. Carbon black is known to have a significant influence on its dispersibility due to its physical properties such as primary particle size, specific surface area, structure structure, and surface properties (functional groups on the surface, etc.). It is also known that the selection greatly affects the toner characteristics.

  For example, carbon black is very difficult to disperse because it has a small primary particle size, a large specific surface area, and a structure structure compared to other pigments. If the dispersibility of the carbon black in the toner particles is insufficient, the chargeability of the toner is impaired, and fogging occurs at the time of development. In addition, an image for reducing the coloring power of the toner particles Other adverse effects such as low density or increased toner consumption also occur.

  When the toner is prepared using carbon black as a pigment in the polymerization method, a further problem occurs.

  First, carbon black has a functional group that inhibits the polymerizability of the monomer, such as a quinone group, on the surface. Therefore, when a toner is produced by a polymerization method, the polymerization rate becomes slow and the degree of polymerization does not increase. Particles become unstable at the time of granulation, causing aggregation and coalescence, making it difficult to take out as particles.

  Secondly, a monomer composition is prepared by uniformly dissolving or dispersing a polymerizable monomer and carbon black (further, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives). At this time, carbon black is difficult to disperse in the monomer composition, and when the toner composition is produced by suspending and dispersing the monomer composition in a hydrogen medium, carbon black is unevenly distributed in the toner particle, Toner particles not containing black are easily generated.

  Third, since carbon black is conductive, the charge on the surface of the toner is likely to leak, greatly affecting the chargeability of the toner. Variation in the carbon black content, dispersibility, and presence / absence of aggregation for each toner particle results in variation in chargeability of the toner particles, which causes a decrease in development efficiency and an increase in fog.

  Such carbon black content between each toner particle, dispersion of dispersion and aggregation, uneven distribution within the particle, toner particles having a much higher charge amount and toner particles having a lower charge amount than the desired charge amount. As a result, toner chargeability becomes unstable. In particular, in non-magnetic one-component contact development, when toner particles having a low charge amount increase, the toner particles electrostatically adhere to the toner carrier and are scattered without being held, so that the inside of the apparatus and the image are stained, so-called toner scattering, Or fog on the image is likely to occur. Unnecessary toner particles with a higher charge amount have a larger adhesion force (mirror power) to the photoconductor, which increases the amount of residual toner and tends to increase the charge amount of the residual toner. Defects are likely to occur. Further, charging of other toner particles is inhibited to reduce the charge amount of the toner as a whole, which easily causes toner scattering and fogging.

  It is also known to contain an azo-based iron complex compound as a charge control agent in the toner.

In Patent Document 13, a proposal is made to use a suspension-polymerized toner in which a specific azo-based iron complex compound is contained in a toner and the chargeability is improved by a nonmagnetic one-component development method. However, carbon black that greatly affects the polymerizability and chargeability of the toner has not been studied.
Japanese Patent Laid-Open No. 1-112253 JP-A-1-191156 JP-A-2-214156 JP-A-2-284158 Japanese Patent Laid-Open No. 3-181952 JP-A-4-162048 JP-A-5-188765 JP-A-5-188752 JP-A 63-149669 JP-A-2-123385 JP 7-209952 A (corresponding US Pat. No. 5,659,857) Japanese Patent Publication No. 36-10231 JP-A-7-281485 Japan Hardcopy '89 Proceedings 25-28 FUJITSU Sci. Tech. J. et al. , 28, 4, pp. 473-480 (December 1992)

  Accordingly, an object of the present invention is to form an electrostatic latent image on the photosensitive member, and in the developing process of the electrostatic latent image, the surface of the photosensitive member and the toner layer on the toner carrying member are in contact with each other. To disclose a technique for improving toner deterioration in an image forming method using a contact one-component development method in which development of an electrostatic latent image is achieved by the movement of the surface of the toner and the surface of the toner carrier. is there.

  An object of the present invention is to disclose a technique for improving toner carrier surface deterioration.

  An object of the present invention is to provide a toner that does not cause a cleaning failure even in blade cleaning.

  An object of the present invention is to provide a toner capable of increasing the speed of an apparatus.

  An object of the present invention is to provide a toner that has improved durability and anti-offset properties, and has both durability for stably realizing a high-quality image over a long period of time.

  It is another object of the present invention to provide a toner that can provide a stable image over a long period of time without causing a charging failure even in a charging method using a contact charging member.

  The above object is achieved by the following configurations of the present invention.

The present invention relates to a method for producing a toner having toner particles containing at least a binder resin, carbon black and an azo-based iron compound, and an inorganic fine powder, wherein the carbon black has an average primary particle size of 25 to 80 nm. The azo-based iron compound has the following general formula (1)

[Wherein, X ₁ and X ₂ represent a member selected from the group consisting of a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group and a halogen atom, and X ₁ and X ₂ are the same or different, m And m ′ represents an integer of 1 to 3, R ₁ and R ₃ are a hydrogen atom, a C _{1 to} C ₁₈ alkyl group, a C _{2 to} C ₁₈ alkenyl group, a sulfonamide group, a mesyl group, a sulfonic acid group, carboxy ester group, hydroxy group, an alkoxy group of C ₁ -C _18, shows a member selected acetylamino group, from the group consisting of benzoylamino group and a halogen atom, R ₁ and R ₃ are the same or different, n and n 'is an integer of 1 to 3, _{R 2} and _{R 4} represents a hydrogen atom or a nitro group, ^{a +} is an ammonium ion, hydrogen ion, sodium Lee Down, it shows the cation ion selected from the group consisting of potassium ions and their mixtures ions. The toner particles are obtained by polymerizing a polymerizable monomer composition containing at least a polymerizable monomer, the carbon black, and the azo iron compound in an aqueous medium. produced by, the polymerizable monomer composition includes at least a second polymerizable monomer dispersion liquid obtained by dispersing the carbon black and the azo type iron compound in a first polymerizable monomer The present invention relates to a toner manufacturing method characterized by being prepared by mixing.

  According to the present invention, by applying a toner using a specific azo-based iron compound and carbon black having a specific physical property as a toner composition to an image forming method having a one-component contact development system, The image forming method using the pre-development cleaning method in which the cleaning process for removing the transfer residual toner from the surface of the image carrier is performed before the development process can be performed quickly and high quality images can be obtained. In this case, a stable cleaning property can be obtained.

  The synergy of the charge control effect due to the good dispersion of carbon black and the charge control effect that suppresses excessive charging of the azo iron complex compound itself by combining the specific carbon black of the present invention and the specific azo iron complex compound. Due to the effect, it is possible to obtain excellent development characteristics even in contact one-component development due to good charge controllability of the toner on the toner carrying member in which excessive charging is suppressed.

  Therefore, it is possible to appropriately control the charge amount of the developing toner on the photosensitive member and prevent deterioration of the cleaning property due to excessive charging of the transfer residual toner. As described above, the cleaning property of toner having a high sphericity is greatly improved.

  As an example of the developing device used in the image forming method of the present invention, an elastic roller is used as a toner carrying member for carrying toner as a one-component developer, and the toner is coated on the surface of the elastic roller to form a toner layer. And a developing device employing a method in which the toner layer is brought into contact with the surface of the photoreceptor as an image carrier. At this time, the toner may be either magnetic or non-magnetic, and it is important that the toner layer is in contact with the surface of the photoreceptor. It is preferable that the toner carrier is substantially in contact with the surface of the photosensitive member, which means that the toner carrier is in contact with the surface of the photosensitive member when the toner layer is removed from the toner carrier. means. At this time, in order to obtain an image having no edge effect by an electric field acting between the photosensitive member and the elastic roller facing the surface of the photosensitive member via the toner, the elastic roller surface or the vicinity of the surface has a potential, An electric field needs to be formed between the surfaces of the toner carrier. For this reason, the elastic layer formed of elastic rubber on the surface of the low resistance core material of the elastic roller is controlled in resistance to the middle resistance region to prevent electric conduction with the surface of the photoconductor, or the low resistance conductive It is also possible to use a thin dielectric layer on the surface layer of the conductive roller. Furthermore, a configuration in which the surface side facing the surface of the photoreceptor is coated with an insulating material on a conductive roller, or a configuration in which a conductive layer is provided on the inner surface side not facing the photoreceptor with an insulating sleeve is also possible.

  When the one-component contact development method is used, the surface of the developing roller as the toner carrying member for carrying the toner and the surface of the photosensitive member may be rotated in the same direction or in the opposite direction. Good. When the rotation direction is the same direction, the peripheral speed on the surface of the developing roller is preferably larger than 100% in terms of the peripheral speed ratio with respect to the peripheral speed of the photosensitive member. If it is 100% or less, there is a problem in image quality such as poor line cut. The higher the peripheral speed ratio, the more toner is supplied to the development site, the more frequent the toner is desorbed from the latent image, and the unnecessary parts are scraped off and applied to the necessary parts. Thus, an image faithful to the latent image can be obtained.

  The present invention does not include an image forming method using a two-component developing method using a magnetic brush composed of toner and carrier.

  In the present invention, it is preferable to have a cleaning step for removing the transfer residual toner which is not transferred in the transfer step and exists on the surface of the image carrier. This cleaning process uses a pre-development cleaning system in which a cleaning member is brought into contact with the surface of the image carrier after the transfer process and before the development process.

  In this pre-development cleaning system, a cleaning unit is provided between the transfer unit and the charging unit, which is in contact with the surface of the image carrier and removes transfer residual toner existing on the surface of the image carrier. It is preferable to provide it because the influence of the transfer residual toner on the charging member can be reduced.

  In the present invention, a blade, a roller, a fur brush, or a magnetic brush can be used as the cleaning member used in the pre-development cleaning method. Two or more of these cleaning members may be used in combination.

  When applying a toner containing carbon black to an image forming method using a one-component contact development method, the present inventors use a specific carbon black and a specific azo-based iron compound, thereby developing toner on a photoreceptor. It has been found that the charge amount of the toner can be controlled appropriately to prevent deterioration of the cleaning property due to excessive charging of the transfer residual toner.

  That is, if the transfer residual toner is excessively charged, the adhesion of the transfer residual toner to the photosensitive member is high, so that the cleaning property tends to be deteriorated. In particular, when the shape of the toner particles is nearly spherical, such as a toner prepared by a polymerization method such as a suspension polymerization method, the scraping property in the cleaning process is likely to be deteriorated and slipping out of the cleaning member may occur, which is disadvantageous for cleaning. Furthermore, excessive charge of the transfer residual toner significantly reduces the cleaning performance.

  The charge of the untransferred toner varies greatly depending on the transfer bias condition and the resistance of the transfer material. In general, a voltage having a polarity opposite to the charging polarity of the toner is applied to the transfer bias. However, when the development is normal development (the toner charging polarity and the photosensitive member charging polarity are reversed), the transfer material is a thick paper, an OHT film or the like. If it has a high resistance, toner particles having a high charge will not be transferred due to strong adhesion to the photoreceptor, and will proceed to the cleaning step with the same charge polarity, so that it will be difficult to complete cleaning.

  Therefore, as the toner, it is preferable that the charge amount of the developed toner on the photoconductor is appropriately controlled, and the toner having the originally high charge amount is not developed on the photoconductor.

  In order to prevent a high charge amount toner from being developed on the photosensitive member, it is necessary to prevent the toner from being charged or to prevent the toner from being charged. Detrimental effects such as reduction are likely to occur.

  By using a toner in which the specific carbon black of the present invention and a specific azo-based iron compound are used in combination, it is possible to suppress the generation of excessively charged toner particles and to give the toner an appropriate charge amount. became. As a result, stable performance excellent in durability is exhibited even in the development process. This is because of the charge control effect due to the good dispersion of the carbon black of the toner in which the specific carbon black of the present invention and the specific azo iron compound are used together, and the charge control effect that suppresses excessive charging of the azo iron compound itself. It is considered a synergistic effect.

  When the development is reversal development (the toner charging polarity and the photosensitive member charging polarity are the same polarity), if the transfer material is easy to pass an electric field like thin paper, toner particles that are strongly charged to the reverse polarity by the transfer bias can be formed. The toner particles that are strongly charged with the opposite polarity still have a strong adhesion to the photoconductor and cannot be easily cleaned.

  On the other hand, it is possible to suppress the generation of toner particles that are excessively charged with a reverse polarity by using the toner in which the specific carbon black of the present invention and the specific azo-based iron compound are used in combination.

  The toner charging control by the transfer bias also includes the charge control effect by the good dispersion of the carbon black due to the combination of the specific carbon black of the present invention and the specific azo iron compound, and the excessive charging of the azo iron compound itself. It is thought to be brought about by the synergistic effect of the charge control effect to suppress.

  Although these reasons are not necessarily clear, according to the knowledge of the present inventors, the specific azo-based iron compound used in the present invention causes the toner to have an excessively high charge amount (so-called charge-up phenomenon). In addition to making it difficult for the toner particles to retain excessive reverse charge even when a toner polarity and a reverse electric field are applied in the transfer process, the azo-based iron compound also functions as a dispersant. As a result of the improved dispersibility of carbon black, it is considered that the triboelectric charge amount of each toner particle becomes uniform.

  One of the features of the image forming method of the present invention is that a toner using a combination of carbon black having a particle size of 25 to 80 nm and a specific azo-based iron compound is used.

  The present inventors have used toner containing a specific carbon black and a specific azo-based iron compound in an image forming method using a one-component contact development system, so that toner particles that are excessively charged in the development process can be obtained. It has been found that there are fewer toner particles that are strongly charged with a reverse polarity due to the transfer bias in the transfer step, and therefore, good cleaning can be performed in the cleaning step.

  The reason for this is not necessarily clear, but according to the knowledge of the present inventors, the specific azo-based iron compound used in the present invention has an abnormally high charge amount (so-called charge-up phenomenon). Due to the effect of preventing the toner polarity and the reverse electric field from being applied in the transfer process, it is difficult for the toner to retain an excessive reverse charge, and the azo-based iron complex compound also functions as a dispersant. The effect of improving the dispersibility of the toner is considered to be due to a combination of improving the charging uniformity for each toner particle.

  When the average primary particle size of carbon black is smaller than 25 nm, when used in combination with the azo-based iron compound used in the present invention, the primary particle size is fine, so that it is difficult to obtain sufficient dispersion and the effects of the present invention can be obtained. Absent. Furthermore, when toner particles are produced by a suspension polymerization method, the toner particle size tends to become coarser and difficult to use.

  When the average primary particle size of carbon black is larger than 80 nm, there is a disadvantage that only low density images can be obtained or toner consumption increases due to insufficient coloring power as a toner even when dispersed well. Arise.

  In the present invention, the average primary particle size of carbon black is preferably 25 to 55 nm, and more preferably 35 to 55 nm. When used in combination with the specific azo iron compound of the present invention, if the particle size of the carbon black is within this range, the charge polarity and charge amount of the transfer residual toner by the charging member can be controlled more reliably and uniformly. It is more advantageous in terms of the stability of the charge amount and the toner coloring power.

  The average primary particle size of carbon black in the toner in the present invention can be measured by taking a photograph enlarged with a transmission electron microscope.

  The carbon black used in the present invention preferably has a DBP oil absorption of 40 to 150 ml / 100 g, more preferably 50 to 140 ml / 100 g.

  When a short carbon black structure with a DBP oil absorption of less than 40 ml / 100 g is used, the charge amount of the toner tends to be too low, and when the DBP oil absorption exceeds 150 ml / 100 g, the carbon has a strong long structure. It is difficult to obtain a fine dispersion of black.

  The DBP oil absorption of carbon black is measured according to “ASTM method D2414-79”.

The carbon black used in the present invention has a specific surface area by nitrogen adsorption of 100 m ² / g or less, preferably 30 to 90 m ² / g, more preferably 40 to 90 m ² / g, and a volatile content of 2 % Or less, preferably 0.1 to 1.8%, more preferably 0.1 to 1.7%. The carbon black according to the present invention has a smaller specific surface area and a smaller volatile content than the carbon black commonly used in toners.

  Carbon black having a small specific surface area and a small amount of volatile matter has the advantage of low polymerization inhibition because it has few functional groups having polymerization inhibition, and is also advantageous for uniform dispersion of carbon black in the toner.

When the specific surface area due to nitrogen adsorption of carbon black is greater than 100 m ² / g, polymerization inhibition tends to occur. If the volatile content of carbon black exceeds 2%, a large number of polymerization-inhibiting functional groups are present on the surface, which is not preferable.

  The measurement of the specific surface area by nitrogen adsorption of carbon black is performed according to “ASTM method D3037-78”.

  The volatile content of carbon black is measured in accordance with “JIS K 6221-1982”. Specifically, carbon black used as a measurement sample is first struck into a platinum crucible or a porcelain crucible with the same shape and capacity as a drop lid so as not to exceed 2 mm below the lid, and its mass is measured. Cover it, put it in an electric furnace, heat it at 950 ± 25 ° C for exactly 7 minutes, take it out, let it cool to room temperature in a desiccator, measure the mass after heating, and calculate the volatile content by the following formula. Ask.

V: Volatile content (%)
W _D : mass of dry sample (g)
W _R : Mass of the sample after heating (g)
When the toner is produced by a polymerization method, it is possible to disperse the carbon black at a higher concentration by performing a master batch process of pre-dispersing the carbon black according to the present invention and the azo-based iron complex compound in the polymerizable monomer. Therefore, it is preferable because shearing force is easily applied and the effect of improving dispersibility is increased.

  FIG. 6 shows the viscosity change of the dispersion when the carbon black and the azo iron compound according to the present invention are dispersed in a styrene monomer. As is clear from the figure, the addition of the azo-based iron compound dramatically increases the viscosity of the dispersion, indicating that the carbon black is stably dispersed with a high shear force.

  FIG. 7 shows the relationship between the oil absorption of carbon black and the viscosity of the dispersion when a certain amount of azo-based iron compound is added and dispersed in a styrene monomer in carbon black having a particle size of 25 to 80 nm. From this figure, it is shown that carbon oil having a high oil absorption of 40 ml / 100 g or higher has a higher dispersion viscosity and better dispersibility. However, when the oil absorption of carbon black exceeds 150 ml / 100 g, the viscosity of the dispersion becomes too high, and the granulation property during polymerization tends to be impaired.

According to the study by the present inventors, the content A [wt%] of the carbon black and the azo-based iron complex compound B [wt%] with respect to the weight of the toner particles are preferably the following conditions 2 ≦ A / B ≦ 35
It is good to satisfy | fill, More preferably, the following conditions 3 <= A / B <= 35
Good to meet.

  If the content of the azo-based iron compound is too small with respect to the content of carbon black, the viscosity does not increase as is apparent from FIG. 7, and the carbon black is not stably dispersed. In this case, carbon black precipitates with the passage of time, and when a toner is produced using this dispersion, the coloring power does not increase.

  If the content of the azo-based iron compound is too large with respect to the carbon black content, the azo-based iron compound causes secondary aggregation, dispersibility decreases, and this secondary aggregate causes polymerization inhibition, resulting in toner. It becomes difficult to produce the particles well.

  In the present invention, the carbon black content of the toner particles is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, and still more preferably 3 to 15% by weight.

  In the present invention, the content of the azo iron compound in the toner particles is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.1 to 3.0% by weight. It is good to be.

  When the content of carbon black in the toner particles is less than 0.1% by weight, the coloring power as a toner is low, and it is difficult to obtain a high image density. It is not preferable. On the other hand, if it exceeds 30% by weight, even if the azo-based iron compound used in the present invention is used, the dispersibility of the carbon black is not sufficiently uniform, and fog and toner scattering tend to occur.

  When the content of the azo-based iron compound in the toner particles is less than 0.01% by weight, the dispersion viscosity is likely to increase, and the effect of improving the dispersibility of the carbon black is not sufficiently exhibited. On the contrary, the viscosity of the dispersion liquid is lowered, and the effect of improving the dispersibility of carbon black is lowered.

  As described above, the present inventors can transfer carbon black with a specific azo-based iron complex compound in combination with a specific azo-based iron complex compound having an appropriate structure in a specific oil absorption range, a small specific surface area, and a small volatile content. It has been found that the toner can be improved in charge control characteristics when the toner passes through the charging member.

  By applying the toner thus obtained to an image forming method of a one-component contact development system, the presence ratio of excessively charged toner particles in the transfer residual toner or the excessively charged amount of reverse polarity Since the toner particles are present in a small proportion, the transfer residual toner can be satisfactorily removed from the surface of the photoreceptor in the cleaning step, and a high-quality image can be formed.

  The azo-based iron compound used in the present invention has a structure represented by the following formula (1).

[Wherein, X ₁ and X ₂ represent a member selected from the group consisting of a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group and a halogen atom, and X ₁ and X ₂ are the same or different, m And m ′ represents an integer of 1 to 3, R ₁ and R ₃ are a hydrogen atom, a C _{1 to} C ₁₈ alkyl group, a C _{2 to} C ₁₈ alkenyl group, a sulfonamide group, a mesyl group, a sulfonic acid group, carboxy ester group, hydroxy group, an alkoxy group of C ₁ -C _18, shows a member selected acetylamino group, from the group consisting of benzoylamino group and a halogen atom, R ₁ and R ₃ are the same or different, n and n 'is an integer of 1 to 3, _{R 2} and _{R 4} represents a hydrogen atom or a Niroto group, ^{a +} is an ammonium ion, hydrogen ion, sodium Ion, showing a cation ion selected from the group consisting of potassium ions and their mixtures ions. ]
In the present invention, “lower” means 1 to 6 carbon atoms.

  Typical examples of the azo-type iron complex compound of the general formula include the following compounds.

  The azo-based iron complex compound is also used as a negative charge control agent. The compound can be synthesized by a known method.

  In the present invention, the shape of the toner is preferably a shape close to a sphere from the viewpoint of improving toner fusion on the toner carrier and contamination of the surface of the charging member when a large number of images are printed. The shape factors SF-1 and SF-2 indicating the shape of the toner are preferably such that the value of SF-1 is 100 <SF-1 ≦ 160 and the value of SF-2 is 100 <SF-2 ≦ 140. More preferably, the value of SF-1 is 100 <SF-1 ≦ 140 and the value of SF-2 is 100 <SF-2 ≦ 120 in order to improve transferability while maintaining developability. Is preferable.

  In the present invention, SF-1 and SF-2 indicating shape factors are randomly sampled 100 toner images of 2 μm or more magnified 1000 times using, for example, FE-SEM (S-800) manufactured by Hitachi, The image information is introduced into, for example, an image analysis apparatus (Luzex III) manufactured by Nicole via an interface, analyzed, and values obtained from the following equations are defined as shape factors SF-1 and SF-2.

(In the formula, MXLNG represents the absolute maximum length of the particle, PERI represents the perimeter of the particle, and AREA represents the projected area of the particle.)
The shape factor SF-1 indicates the degree of roundness of the toner particles, and the shape factor SF-2 indicates the degree of unevenness of the toner particles.

  When the toner shape factor SF-1 exceeds 160, the toner moves away from the spherical shape and approaches an indeterminate shape, so that the toner is easily crushed in the developing device, the particle size distribution is fluctuated, and the charge amount distribution is likely to be broad. Inverted fog is likely to occur. When the toner shape factor SF-2 exceeds 140, the transfer efficiency of the toner image at the time of transfer from the photosensitive member to the transfer material is decreased, and the transfer of characters and line images is lost.

  In order to develop fine latent image dots faithfully for higher image quality, the toner particles have a weight average diameter of 3 μm to 9 μm, preferably 4 μm to 8 μm, and a coefficient of variation in number distribution of 35% or less, preferably Is preferably 25% or less. In toner particles having a weight average diameter of less than 3 μm, there are many toner particles remaining on the photosensitive member or intermediate transfer member due to a decrease in transfer efficiency, and this tends to cause uneven image unevenness due to fogging or transfer defects. . When the weight average diameter of the toner particles exceeds 9 μm, fusion to a member such as the surface of the photoreceptor or an intermediate transfer material tends to occur. This tendency is further enhanced when the coefficient of variation in the number distribution of toner particles exceeds 35%.

The variation coefficient A in the toner particle number distribution is calculated from the following equation.
Coefficient of variation = [S / D ₁ ] × 100
[In the formula, S represents a standard deviation value in the number distribution of toner particles, and D ₁ represents the number average particle diameter (μm) of toner particles. ]
For the average particle size and particle size distribution of the toner particles, a Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Co., Ltd.) is used. ) And 1% NaCl aqueous solution is prepared using 1st grade sodium chloride as the electrolyte. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample was suspended was subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toners of 2 μm or more were measured using the Coulter counter TA-II with a 100 μm aperture as an aperture. Volume distribution and number distribution were calculated. Then, the volume-based weight average particle diameter (D4) obtained from the volume distribution according to the present invention and the number-based number average particle diameter (D1) obtained from the number distribution were obtained.

  In the present invention, it is preferable to add a release agent to the toner particles in order to improve the fixing property and offset resistance of the toner.

  As a mold release agent used in the present invention, a compound having a main endothermic maximum peak value (melting point) in a DSC curve measured in accordance with ASTM D3418-8 is in the range of 30 to 120 ° C, more preferably 40 to 90 ° C. Is preferred. When the maximum peak value (melting point) of the wax is less than 30 ° C., the self-cohesive force of the release agent becomes weak, and as a result, the high temperature offset resistance becomes weak, which is not preferable. When the maximum peak value (melting point) of the wax exceeds 120 ° C., the fixing temperature becomes high, and it becomes difficult to appropriately smooth the surface of the fixed image, which is not preferable from the viewpoint of lowering the color mixing property.

  Further, when toner particles are obtained by a polymerization method, since granulation and polymerization are performed in an aqueous medium, a high endothermic maximum peak value (melting point) is preferable because a release agent is mainly precipitated during granulation. Absent.

  For example, DSC-7 manufactured by Perkin Elmer is used to measure the temperature (melting point) of the maximum peak value of the release agent. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. For the sample, an aluminum pan is used and an empty pan is set as a control, and the temperature is measured from 20 ° C. to 180 ° C. at a heating rate of 10 ° C./min.

  Release agents include polymethylene waxes such as paraffin wax, polyolefin wax and Fischer tropish wax, amide waxes, higher fatty acids, higher fatty acid metal salts, long chain alkyl alcohols, ester waxes and derivatives thereof (for example, grafts thereof). Compound or block compound). In particular, ester wax is more preferable in that it can improve fixability because it acts as a plasticizer for a binder resin of a toner such as a styrene acrylic copolymer at the time of heat fixing of a toner image.

  In the present invention, a toner having a core / shell structure in the toner, the shell portion being formed by a polymer synthesized by polymerization, and the core portion being composed of wax as a release agent is used for the image forming method of the present invention. By using the toner, it is possible to prevent deterioration of toner particles and contamination of the image forming apparatus, so that good chargeability is maintained and a toner image excellent in reproducing a latent dot image can be formed over a long period of time. It becomes. Further, since the wax acts efficiently at the time of heat and pressure fixing, the low temperature fixing property and the high temperature offset resistance can be improved.

  In the present invention, the toner having a core / shell structure is such that the surface of the core portion made of wax as a releasing agent is covered with a shell portion formed by a polymer synthesized by polymerization of a polymerizable monomer. Means toner in state.

  In the present invention, the core / shell structure of the toner can be confirmed by observing the tomographic plane of the toner particles.

  As a specific method for observing the tomographic plane of the toner particles, the toner particles are sufficiently dispersed in a room temperature curable epoxy resin and then cured in an atmosphere at 40 ° C. for 2 days. After staining with ruthenium oxide and, if necessary, osmium tetroxide, a flaky sample is cut out using a microtome equipped with diamond teeth, and the tomographic morphology of the toner particles is observed using a transmission electron microscope (TEM). It is preferable to use a ruthenium tetroxide dyeing method in order to provide contrast between materials by utilizing a slight difference in crystallinity between the wax and the resin constituting the outer shell. A typical example is shown in FIG.

  In the present invention, the content of the release agent in the toner particles is preferably 2 to 30% by weight, and more preferably 2 to 25% by weight. When the content of the release agent is less than 2% by weight, the fixing property is insufficiently improved. When the content exceeds 30% by weight, the toner particles are likely to coalesce during granulation even in the production by the polymerization method. Those having a wide distribution are likely to be generated and are not suitable for the present invention.

  In the present invention, when a toner having a core / shell structure is produced, it is particularly preferable to add a polar resin to the resin constituting the shell portion because the shell portion is encapsulated by the wax as a release agent. .

  As the polar resin used in the present invention, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a saturated polyester resin, and an epoxy resin are preferably used.

  The content of the polar resin in the toner particles is preferably 1 to 20% by weight, more preferably 2 to 16% by weight (based on the weight of the toner particles).

  When the content of the polar resin is less than 1% by weight, the effect of addition is not sufficiently exhibited. When the content exceeds 20% by weight, the charging characteristics of the toner are often affected, particularly at high temperatures and high temperatures. This is not preferable because it tends to lower the chargeability of the toner in a wet environment.

  In the present invention, an outermost shell resin layer may be further provided on the toner surface.

  The glass transition temperature of the outermost shell resin layer is preferably designed to be higher than the glass transition temperature of the outer shell resin layer in order to further improve the blocking resistance, and is preferably crosslinked to such an extent that the fixing property is not impaired. . The outermost shell resin layer preferably contains a polar resin or a charge control agent in order to improve chargeability.

The method for providing the outermost shell layer is not particularly limited, and examples thereof include the following methods.
1. In the latter half of the polymerization reaction or after completion, if necessary, a polar resin, a charge control agent, and a crosslinking agent are dissolved and dispersed in the reaction system, added to the polymerized particles, adsorbed onto the polymerized particles, and then added with a polymerization initiator for polymerization. Method.
2. If necessary, emulsion polymer particles or soap-free polymer particles composed of monomers containing a polar resin, a charge control agent, and a cross-linking agent are added to the reaction system and aggregated on the surface of the polymer particles, and if necessary, fixed by heat. Method.
3. A method in which emulsion-polymerized particles or soap-free polymerized particles comprising a monomer containing a polar resin, a charge control agent, and a cross-linking agent are mechanically fixed to the toner particle surface in a dry manner, if necessary.

  In the present invention, by a polymerization method for producing toner particles by polymerizing a monomer composition containing a wax and a polar resin as a release agent together with a colorant and a polymerizable monomer in an aqueous medium, the wax and In the case of producing toner particles containing a polar function, the produced toner particles have a core part made of wax and a shell part made of a polymer synthesized by polymerization of a polymerizable monomer and a polar resin. It has a core / shell structure, and a polar resin is located in the outermost shell resin layer of the shell portion. Therefore, in the case of toner particles having such a form, since a polar group exists on the surface of carbon black used as a colorant, carbon black does not enter non-polar wax and enters the shell portion. The coloring power tends to be lower than that of toner particles in which carbon black is uniformly dispersed in the toner particles, and polar resin is located in the outermost shell layer of the shell portion. Therefore, since the ratio of carbon black located on the surface portion of the toner particles is reduced, the triboelectric chargeability of the toner tends to be lower than that of toner particles not containing a polar resin.

  However, in the present invention, since the toner particles contain carbon black and a specific azo iron compound as described above, the coloring power of the toner is improved by the effect of improving the dispersibility of carbon black by the azo iron compound. It is possible to suppress the decrease in the triboelectric chargeability of the toner by suppressing the decrease, and by the effect of improving the dispersibility of carbon black and the high charge control effect of the azo-based iron compound.

  In the one-component contact development type image forming method of the present invention, since the toner on the toner carrier contacts the surface of the image carrier during development, the durability of the toner and the surface of the toner carrier and the image carrier It is preferable that the toner has anti-fusing property to the surface.

  Therefore, the toner used in the one-component contact development method is required to have higher mechanical characteristics than the toner used in the one-component non-contact development method and the two-component development method having a toner and a carrier.

  The resin component of the toner particles used in the present invention has a C component insoluble in THF (tetrahydrofuran) and a component soluble in THF. The component soluble in THF is a gel permeation chromatogram (GPC). In the molecular weight distribution measured in (1), it has an A component having a molecular weight of less than 1 million and a B component having a molecular weight of 1 million or more, and these A component, B component and insoluble C component preferably satisfy the following conditions. .

  The component (corresponding to the A component and B component) soluble in THF of the resin component of the toner particles according to the present invention preferably has a number average molecular weight (Mn) of 9000 to 1000000 in the molecular weight distribution of GPC, more preferably Various properties required for the toner to be 10,000 to 500,000, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 5 to 500, more preferably 7 to 400. Can be achieved in a well-balanced manner.

The resin component of these toner particles is (1) the content (W _A ) of component _A is preferably 30 to 95% by weight, more preferably 50 to 90% by weight based on the weight of the resin component. The content of the component (W _B ) is preferably 0 to 20% by weight, more preferably 1 to 20% by weight, and (3) the content of the C component (W _C ) is preferably 0 to 70% by weight, More preferably, it is 1 to 70% by weight, and (4) the total content of components B and C (W _B + W _C ) is preferably 5 to 70% by weight, more preferably 10 to 50% by weight. The image forming method of the present invention can be preferably used.

The resin component of the toner particles used in the present invention has a molecular weight of 3000 to 50,000, more preferably a molecular weight, in the molecular weight distribution of GPC which is a component soluble in THF, the aforementioned component A (THF soluble component having a molecular weight of less than 1 million). Having a main peak in the region of 5000 to 22000 is preferable because matching with the image forming apparatus is good. When the main peak has a molecular weight of less than 3000, it tends to cause deterioration of the charging characteristics of the toner, fusion at the contact portion with the image forming apparatus, and deterioration of high temperature offset resistance and blocking resistance. When the main peak exceeds the molecular weight of 50,000, the contact portion with the image forming apparatus is likely to be damaged or the low-temperature fixability is likely to be significantly reduced.
When the content of component _A (W _A ) is less than 30% by weight, the low-temperature fixability tends to decrease, and when it exceeds 95% by weight, the matching with the image forming apparatus deteriorates, and the toner Fusing and image quality degradation are likely to occur.
If the content of component _B (W _B ) exceeds 20% by weight, the high temperature offset resistance is improved, but the low temperature fixability is deteriorated.
When the content of the C component (W _C ) is more than 70% by weight, it is not preferable because matching with the image forming apparatus is hindered and low-temperature fixing is difficult. Even if there is no C component, it is possible to maintain developability and fixability if the B component is preferably contained in an amount of 5 to 20% by weight, more preferably 10 to 20% by weight. On the other hand, even if there is no B component, the C component is preferably contained in an amount of 5 to 70% by weight, more preferably 10 to 70% by weight, so that developability and fixability can be maintained.

Furthermore, the total content (W _B + W _C ) of the B component and the C component is preferably 5 to 70% by weight, more preferably 10 to 50% by weight. When the total content (W _B + W _C ) of the B component and the C component is less than 5% by weight, the charging characteristics of the toner, the high-temperature offset resistance, and the matching with the image forming apparatus deteriorate, and the toner is fused. If the amount exceeds 70% by weight, the low-temperature fixability is lowered, which is not preferable.

In the present invention, the molecular weight and content (W _A , W _B and W _C ) of each resin component (AC components) in the toner particles are measured and calculated by the following method.

  In the present invention, the C component insoluble in THF refers to a resin component insoluble in THF (tetrahydrofuran) as a resin component in toner particles, and the content thereof is the degree of crosslinking of the resin composition containing a crosslinking component. However, even if the THF-insoluble content is 0% by weight, it does not necessarily mean that it is not crosslinked. The content of component C insoluble in THF is defined by the values measured as follows.

First, the content of additives in toner particles such as pigment is measured in advance by a known method. Next, a certain amount of developer 0.5 to 1.0 g is weighed (W ₁ g), put into a cylindrical filter paper (No. 86R, manufactured by Toyo Roshi), subjected to a Soxhlet extractor, and 100 to 200 ml of THF is used as a solvent. After extracting for 20 hours and evaporating the soluble component extracted by the solvent, the solution is vacuum dried at 100 ° C. for several hours, and the amount of the THF-soluble resin component is weighed (W ₂ g). Of the additives such as pigments contained in a fixed amount of the developer, the weight of the component soluble in THF is W ₃ g, and the weight of the component insoluble in THF is W ₄ g. According to the formula, the THF-insoluble content (the C component) in the resin component is calculated.

On the other hand, the main peak position and content (W _A ) of the A component having a molecular weight of less than 1 million in the molecular weight distribution of GPC, which is a component soluble in THF, and the content (W _B ) of the B component of 1 million or more, (resin component (Weight basis) is obtained from the molecular weight distribution obtained using the THF-soluble resin component obtained in the above-described Soxhlet extraction as a GPC measurement sample. It is assumed that the area% of the region having a molecular weight of less than 1,000,000 (component A) and the region having a molecular weight of 1,000,000 or more (component B) are equal to the weight percent, and converted to the weight basis of the resin component. The weight percentage (W _A and W _B ) of the component is determined.

  In the present invention, the resin component includes a wax component in addition to the binder resin.

In the present invention, the molecular weight distribution of the resin component in the toner particles is measured under the following conditions by GPC (gel permeation chromatography). The material used is a material that has been previously dispersed / dissolved in a solvent and then filtered through a solvent-resistant membrane filter (pore diameter: 0.3 μm).
Apparatus: GPC-150C (manufactured by Waters)
Column: 7 series of KF801-7 (manufactured by Shodex) Temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 ml / min
Sample: 0.1 ml of a sample having a concentration of 0.05 to 0.6% by weight is measured under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used in calculating the molecular weight of the sample.

  As the binder resin for the toner used in the present invention, generally used styrene- (meth) acrylic copolymers, polyester resins, epoxy resins, and styrene-butadiene copolymers can be used. In the method of obtaining toner particles by a polymerization method, those monomers are preferably used. Specifically, styrene monomers such as styrene, o (m-, p-)-methylstyrene, m (p-)-ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, ( Meth) propyl acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; ene monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile and acrylamide Is preferably used. These monomers are used singly or appropriately mixed so that the theoretical glass transition temperature (Tg) described in Polymer Handbook 2nd edition-P139-192 (John Wiley & Sons) is 40-75 ° C. Used. When the theoretical glass transition temperature is less than 40 ° C., problems arise from the viewpoint of storage stability of the toner and durability of the developer, and when it exceeds 75 ° C., the fixing point increases.

  Furthermore, in the present invention, it is preferable to use a crosslinking agent during the synthesis of the binder resin in order to generate the above THF-insoluble component and / or to generate a component having a molecular weight of 1,000,000 or more.

  Examples of the crosslinking agent used in the toner of the present invention include divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1, bifunctional crosslinking agent. 4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester diacrylate (MAN It includes those changing the A Nippon Kayaku) and the above diacrylate dimethacrylate.

  Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy, polyethoxy) Phenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate.

  These crosslinking agents are preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of other vinyl monomers.

  When the amount of the crosslinking agent used is less than 0.05 parts by weight, the crosslinking reaction of the binder resin is not sufficiently performed, and when it exceeds 10 parts by weight, the crosslinking reaction of the binder resin proceeds excessively. In either case, it becomes difficult to control the content of the THF-insoluble matter in the toner particles within the range of 5 to 70% by weight.

  The azo-based iron complex compound used in the present invention also has a function as a charge control agent, but another charge control agent may be used in combination. As another charge control agent, a known one can be used, but a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, in the case of producing toner particles by the polymerization method in the present invention, a charge control agent having no polymerization inhibition and no solubilized product in an aqueous system is particularly preferable.

  Specific examples of the other charge control agent include negative compounds such as salicylic acid, naphthoic acid, dicarboxylic acid or its derivative metal compound, azo pigment or its derivative metal compound, sulfonic acid or carboxylic acid in the side chain. Molecular type compounds, boron compounds, urea compounds, silicon compounds, and calixarenes can be used. As the Hoji system, nigrosine, triphenylmethane compound, quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound are preferably used.

  Another charge control agent is preferably contained in the toner particles in an amount of preferably 0.2 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the binder resin. However, in the present invention, it is not essential to add another charge control agent. Even when the non-magnetic-component blade coating development method is used, the triboelectric charge with the blade member or sleeve member is positively used in the toner. It is not always necessary to include another charge control agent.

  When toner particles are produced by the polymerization method in the present invention, examples of the polymerization initiator include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, Azo polymerization initiators such as 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide Peroxide-based polymerization initiators such as methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide are used.

  The addition amount of the polymerization initiator varies depending on the desired degree of polymerization, but generally 0.5 to 20% by weight is added to the monomer. The kind of the initiator is slightly different depending on the polymerization method, but can be used alone or mixed with reference to the 10-hour half-life temperature.

  In order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, or polymerization inhibitor may be further added and used.

  When suspension polymerization is used as the toner production method according to the present invention, the dispersant used is, for example, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, carbonic acid as an inorganic oxide. Examples thereof include magnesium, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina, magnetic substance, and ferrite. As the organic compound, for example, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch are used dispersed in an aqueous phase. These dispersants are preferably used in an amount of 0.2 to 10.0 parts by weight with respect to 100 parts by weight of the polymerizable monomer.

  As these dispersants, commercially available ones may be used as they are, but in order to obtain dispersed particles having a fine uniform particle size, the inorganic compound may be generated and used in a dispersion medium under high-speed stirring. I can do it. For example, in the case of tricalcium phosphate, a preferred dispersant for the suspension polymerization method can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution under high-speed stirring. You may use together 0.001-0.1 weight part of surfactant for refinement | miniaturization of these dispersing agents. Specifically, commercially available nonionic, anionic and cationic surfactants can be used, such as sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, olein. Calcium acid is preferably used.

  When the polymerization method is used in the toner manufacturing method according to the present invention, the toner can be specifically manufactured by the following manufacturing method.

  Carbon black and azo-based iron compound in the polymerizable monomer, and if necessary, charge control agent, polymerization initiator, and other additives are added, and dissolved or mixed uniformly with a mixing device such as a homogenizer or an ultrasonic disperser. A polymerizable monomer composition is prepared by dispersing. The prepared polymerizable monomer composition is dispersed in an aqueous phase containing a dispersion stabilizer by a usual stirrer or a mixing device such as a homomixer or a homogenizer. Preferably, granulation is performed by adjusting the stirring speed and time so that droplets of the polymerizable monomer composition have a desired toner particle size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. Polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. The temperature may be raised in the latter half of the polymerization reaction, and for the purpose of improving durability in the image forming method using the toner of the present invention, the polymerization reaction is performed to remove unreacted polymerizable monomers and by-products. A part of the aqueous medium may be distilled off in the latter half or after completion of the polymerization reaction. After completion of the polymerization reaction, the produced toner particles are washed, collected by filtration, and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.

  In the present invention, as described above, a polymerizable monomer composition is prepared through a master batch process in order to improve the dispersibility of carbon black in the toner particles.

  Specifically, with respect to 100 parts by weight of the first polymerizable monomer, preferably 4 to 40 parts by weight, more preferably 5 to 25 parts by weight of carbon black and preferably 0.2 to 5 parts by weight, More preferably, by mixing and dispersing 0.5 to 3 parts by weight of an azo-based iron compound, carbon black can be mixed at a very high concentration with respect to the polymerizable monomer. Since the share at the time of mixing is sufficiently increased, the dispersibility of carbon black can be drastically improved in combination with the dispersion effect of the azo-based iron compound.

  When the amount of carbon black mixed is less than 4 parts by weight, even if an azo-based iron compound is used, the viscosity of the dispersion is small and sufficient dispersion is difficult to achieve. On the other hand, when it exceeds 40 parts by weight, it is difficult to control the viscosity of the dispersion, and as a result, dispersion tends to be non-uniform.

  When the amount of the azo-based iron compound is less than 0.2 parts by weight, the effect of increasing the viscosity of the dispersion is insufficient. On the other hand, when the amount exceeds 5 parts by weight, the viscosity is decreased again. The dispersion tends to be uneven.

  The viscosity of this first polymerizable monomer, carbon black and azo-based iron compound, and optionally a wax component and / or a charge control agent (masterbatch) dispersion preferably has a viscosity of 100 to 2000 centipoise. More preferably, it is 150 to 1600 centimeters voice.

  When the viscosity of this dispersion is less than 100 centipoise, the viscosity is too low to take a share of dispersion, and it becomes difficult to uniformly disperse carbon black. On the other hand, when the viscosity exceeds 2000 centipoise, the viscosity is too high and it is difficult to maintain a uniform dispersion state, and at the same time, the discharge from the manufacturing apparatus is deteriorated, resulting in a decrease in productivity. This dispersion is mixed with a second polymerizable monomer and, if necessary, a wax component, a polymer containing a polar functional period, a charge control agent, a polymerization initiator, and other additives to form a polymerizable monomer. A meter composition is prepared.

  The mixing amount of the second polymerizable monomer with respect to 100 parts by weight of the dispersion is preferably 20 to 100 parts by weight, more preferably 30 to 70 parts by weight. From the viewpoint of uniform dispersibility in the monomer.

  When the mixing amount of the second polymerizable monomer is less than 20 parts by weight, it takes time to uniformly disperse, and when it exceeds 100 parts by weight, re-aggregation of carbon black occurs. It becomes easy, and it takes time for uniform dispersion.

  The carbon black content in the polymerizable monomer composition is preferably 1 to 20% by weight, more preferably 3 to 15% by weight based on the weight of the polymerizable monomer composition. This is good in terms of coloring power and toner charge stabilization.

  When the content ratio of carbon black in the polymerizable monomer composition is less than 1% by weight, it becomes difficult to achieve a high image density, and when it exceeds 20% by weight, particularly under high humidity. The toner charge tends to be low.

  The content ratio of the azo-based iron compound with respect to the weight of the polymerizable monomer composition in the polymerizable monomer composition is preferably 0.1 to 3.0% by weight, more preferably 0.2 to 2%. It is good that the dispersion viscosity is maintained in an appropriate state and the uniform dispersibility of carbon black is improved.

  When the content ratio of the azo-based iron compound in the polymerizable monomer composition is less than 0.1% by weight, the dispersion viscosity does not increase, and the effect of improving the dispersibility of carbon black is not exhibited. If it exceeds 0.0% by weight, the viscosity of the dispersion is lowered, and the effect of improving the dispersibility of carbon black is lost.

  In the present invention, the surface of the toner particles is coated with an external additive to impart appropriate fluidity and chargeability to the toner particles, as well as improving cleaning properties and stress from a contact member such as a photosensitive member charging member. It is desirable that the electric member can be relaxed, and the external additive coverage on the toner surface is preferably 5 to 99%, more preferably 10 to 99%. Further, by having inorganic fine powder as an external additive on the surface of the toner particles, the transfer efficiency is improved and the omission of transfer of characters and line images is improved.

  As for the external additive coverage on the surface of the toner particles, 100 toner images were randomly sampled using FE-SEM (S-800) manufactured by Hitachi, Ltd. It introduced into the analysis apparatus (Luzex3), and it analyzed and calculated.

  The external additive used in the present invention preferably has an average particle diameter of 1/10 or less of the weight average diameter of the toner particles from the viewpoint of durability when added to the toner. The average particle diameter of the additive means the average particle diameter obtained by observing the surface of the toner particles with an electron microscope.

  Examples of external additives include metal oxides (aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, and zinc oxide), nitrides (silicon nitride, carbide (silicon carbide), Examples thereof include metal salts (calcium sulfate, barium sulfate and calcium carbonate), fatty acid metal salts (zinc stearate and calcium stearate), carbon black and silica, and these external additives are preferably 0 with respect to 100 parts by weight of toner particles. 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and these external additives may be used alone or in combination. Is more preferable.

As the inorganic fine powder used in the present invention, at least one kind is fine particles selected from silica, alumina, titania, or a double oxide thereof in order to improve charging stability, developability, fluidity, and storage stability. Preferably there is. Further, silica is more preferable. For example, as the silica, both a so-called dry method produced by vapor phase oxidation of silicon halide or alkoxide or dry silica called fumed silica, and so-called wet silica produced from alkoxide water glass can be used. . Dry silica having less silanol groups on the surface and fine silica powder and less production residue such as Na ₂ O and SO ₃ ²⁻ is more preferable. In dry silica, it is possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. Is also included.

Inorganic fine powder used in the present invention has a specific surface area according to the measured nitrogen adsorption by the BET method is ^{30 m} 2 / g or more, particularly in the range of 50 to 400 m ² / g give good results. The inorganic fine powder is preferably 0.1 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, and still more preferably more than 1.0 part by weight to 3.0 parts by weight with respect to 100 parts by weight of the toner particles. It is good to use until. The inorganic fine powder used in the present invention is a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, a silane coupling agent, and a silane having a functional period, if necessary, for the purpose of hydrophobization and chargeability control. Treatments such as coupling agents, other organic silicon compounds, and organic titanium compounds may be used alone or in combination.

  In order to maintain a high charge amount and achieve low consumption and high transfer rate, the inorganic fine powder is more preferably treated with at least silicone oil.

In order to improve transferability and / or cleaning properties, it is one of preferred modes to further add inorganic or organic spherical fine particles having a primary particle size of 50 nm or more (preferably a specific surface area of less than 30 m ² / g). As the spherical fine particles, for example, spherical silica particles, spherical polymethylsilsesquioxane particles, and spherical resin particles are preferably used.

  The toner used in the present invention may further contain other additives, for example, a lubricant powder such as Teflon (registered trademark) powder, zinc stearate powder, polyvinylidene fluoride powder; Polishing agents such as cerium powder, silicon carbide powder, strontium titanate powder; fluidity imparting agents such as acid value titanium powder and acid value aluminum powder; anti-caking agents; such as carbon black powder, zinc oxide powder and acid value tin powder A small amount of a conductivity imparting agent such as: organic fine particles having opposite polarity; and inorganic fine particles;

  In order to prepare the toner particles used in the present invention, in addition to the polymerization method described above, for example, a binder resin, an azo-based iron complex compound, carbon black, a release agent, a pressure kneader, an extruder, or a media dispersion After being uniformly dispersed using a machine, it is collided with a target under a mechanical or jet stream, finely pulverized to a desired toner particle size, and further subjected to a classification process to sharpen the particle size distribution and make a toner. A method for producing toner by a pulverization method; a method for obtaining a spherical toner by atomizing a molten mixture into air using a disk or a multi-fluid nozzle described in Japanese Patent Publication No. 56-13945; A dispersion polymerization method in which a toner is directly formed by polymerization of a polymerizable monomer using an organic solvent in which the polymer is insoluble; or a toner that is directly polymerized in the presence of a water-soluble polar polymerization initiator Emulsion polymerization method as typified by generate soap-free polymerization process; and the like.

  In the present invention, it is preferable to impart releasability to the surface of the photoconductor, and the contact angle of water on the surface of the photoconductor is preferably 85 degrees or more. More preferably, the contact angle of the photoreceptor surface with water is 90 degrees or more.

  A high contact angle on the surface of the photoconductor indicates that the surface of the photoconductor has a high releasability. This effect can significantly reduce the amount of toner remaining on the transfer, greatly increasing the load on the cleaning process. This can reduce the occurrence of defective cleaning more reliably.

  Further, since the surface of the photoconductor has a high releasability, the amount of residual toner can be significantly reduced, there is almost no light shielding by the residual toner, and a negative ghost image can be essentially prevented and the residual transfer can be prevented during development. The recovery efficiency of the toner in the development area is also improved, and positive ghost images are prevented.

  Here, the generation mechanism of the ghost image will be described.

  The problem of light shielding by the transfer residual toner is particularly problematic when the surface of the photoreceptor is repeatedly used for one transfer material, that is, when the length of the entire circumference of the photoreceptor is shorter than the length of the transfer material in the traveling direction, Since the transfer residual toner must be charged, exposed and developed in the state where the residual toner is present on the photosensitive member, the potential on the surface of the photosensitive member where the residual toner is present does not drop sufficiently and the development contrast becomes insufficient. As for development, it appears on the image as a negative ghost having a lower density than the surroundings.

  On the other hand, if the cleaning effect of the transfer residual toner is insufficient at the time of development, the toner is developed on the surface of the photoreceptor where the transfer residual toner is present, so that the density is higher than the surroundings and a positive ghost is generated.

  With the configuration of the present invention, the ghost image described above can be essentially prevented.

The image forming method of the present invention is effective when the surface of the photoreceptor is mainly composed of a polymer binder. For example, (i) when a protective film mainly composed of a resin is provided on an inorganic photoconductor such as selenium or amorphous silicon; (ii) a charge transport material and a resin as a charge transport layer of the function-separated organic photoconductor (Iii) In some cases, a protective layer as described above may be provided on the surface layer. As a means for imparting releasability to such a surface layer,
[1] A resin having a low surface energy is used as the resin constituting the film.
[2] Add additives that impart water repellency and lipophilicity.
[3] A material having high releasability is dispersed in powder form.
Is mentioned. [1] is achieved by introducing a fluorine-containing group or a silicone-containing group into the resin structure. As [2], a surfactant may be added as an additive. [3] includes using a compound containing a fluorine atom such as polytetrafluoroethylene, polyvinylidene fluoride, and carbon fluoride.

  By these means, the contact angle with respect to water on the surface of the photoreceptor can be set to 85 degrees or more. When the contact angle of water on the surface of the photoreceptor is less than 85 degrees, the toner and the toner carrier are likely to deteriorate due to durability.

  Of these, fluorine-containing resins such as polytetrafluoroethylene and polyvinylidene fluoride are particularly suitable. In the present invention, when a fluorine-containing resin is used as the third powder as the releasable powder, dispersion to the outermost surface layer is preferable.

  In order to contain these powders on the surface, a layer in which the powder is dispersed in a binder resin is provided on the outermost surface of the photoreceptor, or an organic photoreceptor that is originally composed mainly of a resin. For example, the powder may be dispersed in the outermost surface layer without providing a new surface layer.

  The amount of the powder added to the surface layer is preferably 1 to 60% by weight, more preferably 2 to 50% by weight, based on the total weight of the surface layer. If the amount is less than 1% by weight, the residual toner is not sufficiently reduced, the cleaning efficiency of the residual toner is not sufficient, and the ghost prevention effect is insufficient. If the amount exceeds 60% by weight, the strength of the film decreases. This is not preferable because the amount of light incident on the photosensitive member is significantly reduced. The particle size of the powder is 1 μm or less, preferably 0.5 μm or less from the viewpoint of image quality. When it is larger than 1 μm, the line breakage is deteriorated due to scattering of incident light, and it cannot be put into practical use.

  The present invention is particularly effective in the case of the contact charging method in which the charging means makes the charging member contact the photoconductor. That is, if there is a large amount of residual toner after cleaning, it adheres to the direct charging member, which is a subsequent process, and causes charging failure. Therefore, compared to corona discharge in which the charging means does not contact the photoconductor, the amount of residual toner is smaller and it is necessary to make it difficult to adhere.

  One preferred embodiment of the photoreceptor used in the present invention will be described below.

  As a conductive substrate, a cylinder of a metal such as aluminum or stainless steel; a plastic having a coating layer of an aluminum alloy or an indium oxide-tin oxide alloy; paper or plastic impregnated with conductive particles; a plastic having a conductive polymer; Cylinder and film are used.

  On these conductive substrates, for the purpose of improving the adhesion of the photosensitive layer, improving the coating property, protecting the substrate, coating defects on the substrate, improving the charge injection from the substrate, and protecting the photosensitive layer from electrical breakdown. An undercoat layer may be provided.

  Undercoat layer is polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, phenol resin, casein, polyamide, copolymer nylon, glue, gelatin, polyurethane Alternatively, it is formed of an aluminum oxide material. The thickness of the undercoat layer is usually 0.1 to 10 μm, preferably 0.1 to 3 μm.

  The charge generation layer is composed of azo pigments, phthalocyanine pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, squarylium dyes, pyrylium salts, thiopyrylium salts, triphenylmethane dyes or selenium or amorphous silicon. An inorganic charge generating material is dispersed in a suitable binder and coated, or formed by vapor deposition. Of these, phthalocyanine pigments are preferred for adjusting the sensitivity of the photoreceptor to a sensitivity suitable for the present invention. The binder can be selected from a wide range of binder resins such as polycarbonate resin, polyester resin, polyvinyl butyral resin, polystyrene resin, acrylic resin, methacrylic resin, phenol resin, silicone resin, epoxy resin, vinyl acetate resin. Can be mentioned. The amount of the binder contained in the charge generation layer is 80% by weight or less, preferably 0 to 40% by weight. The thickness of the charge generation layer is preferably 5 μm or less, particularly preferably 0.05 to 2 μm.

  The charge transport layer has a function of receiving charge carriers from the charge generation layer in the presence of an electric field and transporting them. The charge transport layer is formed by dissolving a charge transport material in a solvent together with a binder resin as required, and coating, and the film thickness is generally 5 to 40 μm. Examples of charge transport layer materials include polycyclic aromatic compounds such as biphenylene, anthracene, pyrene and phenanthrene in the main chain or side chain; nitrogen-containing cyclic compounds such as indole, carbazole, oxadiazole and pyrazoline; hydrazone compounds; styryl compounds Selenium; selenium-tellurium; amorphous silicon; cadmium sulfide.

  Examples of binder resins for decomposing these charge transport materials include polycarbonate resins, polyester resins, polymethacrylate esters, polystyrene resins, acrylic resins and polyamide resins; organic photoconductive materials such as poly-N-vinylcarbazole and polyvinylanthracene. A functional polymer.

  A protective layer may be provided as the surface layer. As the resin for the protective layer, polyester, polycarbonate, acrylic resin, epoxy resin, phenol resin, or curing agents for these resins are used alone or in combination of two or more.

  Conductive fine particles may be dispersed in the resin of the protective layer. Examples of the conductive fine particles include metals and metal oxides. Preferably, there are ultrafine particles of zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin oxide-coated titanium oxide, tin-coated indium oxide, antimony-coated tin oxide or zirconium oxide. These may be used alone or in combination of two or more. In general, when particles are dispersed in a protective layer, it is necessary that the particle size of the particles is smaller than the wavelength of the incident light in order to prevent scattering of incident light by the dispersed particles. The particle diameter of the insulating particles is preferably 0.5 μm or less. The content in the protective layer is preferably 2 to 90% by weight, more preferably 5 to 80% by weight, based on the total weight of the protective layer. The thickness of the protective layer is preferably from 0.1 to 10 μm, more preferably from 1 to 7 μm.

  The surface layer can be applied by spray coating, beam coating or penetration (dipping) coating of the resin dispersion.

  The condition of the development process used in the present invention is that the toner layer on the toner carrier and the surface of the photoreceptor are in contact with each other.

In the case of a one-component developer, a method in which an elastic roller is used as a toner carrier and a toner layer formed by coating toner on the surface of the elastic roller is brought into contact with the surface of the photoreceptor. At this time, the toner may be either magnetic or non-magnetic, and it is important that the toner layer is in contact with the surface of the photoreceptor. The toner carrier is substantially in contact with the surface of the photoreceptor, which means that the toner carrier is in contact with the surface of the photoreceptor when the toner layer is removed from the toner carrier. At this time, the surface of the elastic roller or the vicinity of the surface has a potential in order to obtain an image having no edge effect by the electric field acting between the surface of the photoconductor and the elastic roller facing the surface of the photoconductor through the toner layer. There is a need to have an electric field between the photoreceptor surface and the toner carrying surface. Therefore, it is possible to use a method in which the elastic rubber of the elastic roller is resistance-controlled in the middle resistance region to keep the electric field while preventing conduction with the surface of the photoreceptor, or a method of providing a thin insulating layer on the surface layer of the conductive roller. . Furthermore, a conductive resin sleeve in which the outer surface facing the photosensitive member surface of the conductive roller is coated with an insulating material, or a conductive layer is provided on the inner surface side of the insulating sleeve not facing the photosensitive member surface is also possible. It is. A configuration in which a rigid roller is used as the toner carrying member and the photosensitive member is flexible like a belt is also possible. The electric resistance of the developing roller as the toner carrier is preferably in the range of 10 ² to 10 ⁹ Ω.

The electric resistance of the developing roller is measured by the following method. That is, as shown in FIG. 9, the aluminum roller 102 having a diameter of 16 mm and the developing roller 101 are brought into contact with a contact load of 4.9 N (500 g), and the aluminum roller 102 is rotated at 2 rps. Next, a DC voltage of V ₁ = 400 V is applied to the developing roller 101.

The variable resistor R is disposed on the ground side, while adjusting the resistance value of the variable resistor R in accordance with the developing roller 101, to measure the voltage V ₂ at both ends thereof, by calculating the current value of the developing roller 101 Calculate the electrical resistance.

  When the one-component contact development method is used, the surface of the developing roller carrying the toner may be rotated in the same direction as the movement direction of the photosensitive member surface, or may be rotated in the opposite direction. When the rotation is in the same direction, it is desirable that the peripheral speed ratio is faster than 100% with respect to the peripheral speed of the photoreceptor. If it is 100% or less, the image quality is poor. The higher the peripheral speed ratio, the more toner is supplied to the development site, the more frequently the toner is desorbed from the latent image, and the unnecessary parts are scraped off and applied to the necessary parts. Thus, an image faithful to the latent image can be obtained. Specifically, it is preferable that the moving speed of the toner carrying member surface is 1.05 to 3.0 times the moving speed of the photosensitive member surface.

  Hereinafter, the transfer process applicable to the image forming method of the present invention will be specifically described.

  In the transfer step, it is preferable to use a contact transfer system in which the toner image is electrostatically transferred to the transfer material while the transfer means is brought into contact with the surface of the photoreceptor via the transfer material. The contact pressure of the transfer unit with respect to the photosensitive member surface is preferably 2.9 N / m (3 g / cm) or more, more preferably 9.8 to 490 N / m (10 to 500 g / cm). ) Is good. If the linear pressure as the contact pressure is less than 2.9 N / m (3 g / cm), it is not preferable because transfer of the transfer material and transfer failure are likely to occur. When the contact pressure is too high, the surface of the photoconductor is deteriorated and the toner adheres, and as a result, toner fusion on the surface of the photoconductor occurs.

As the transfer means in the contact transfer process, an apparatus having a transfer roller or a transfer belt is used. The transfer roller has at least a metal core and a conductive elastic layer covering the metal core, and the conductive elastic layer has a volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm such as urethane or EPDM in which conductive fine particles such as carbon are dispersed. Made of elastic material.

  The present invention is particularly effectively used in an image forming apparatus in which the surface of the photoreceptor is an organic compound. That is, when the organic compound forms the surface layer of the photoreceptor, transferability is higher because the adhesion to the binder resin contained in the toner particles is higher than other photoreceptors using inorganic materials. It has a technical problem that it tends to decrease. Therefore, the effect of high transferability by the toner used in the present invention becomes more remarkable.

  Examples of the surface material of the photoreceptor according to the present invention include, but are not limited to, silicone resin, vinylidene chloride, ethylene-vinyl chloride, styrene-acrylonitrile, styrene-methyl methacrylate, styrene, polyethylene terephthalate, and polycarbonate. However, other monomers or copolymers and blends between the aforementioned binder resins can also be used.

  In the present invention, the present invention is particularly effective for an image forming apparatus having a small drum-shaped photosensitive member having a diameter of 50 mm or less. That is, in the case of a small-diameter photosensitive drum, pressure concentration tends to occur at the contact portion of the contact member with the same linear pressure. Although it is considered that the same phenomenon occurs in the belt photoreceptor, the present invention is also effective for an image forming apparatus using a photoreceptor belt having a radius of curvature of 25 mm or less at the contact portion.

  Furthermore, in the present invention, it is desirable to control the total charge amount of the toner when developing the toner. Therefore, the surface of the toner carrier according to the present invention is preferably coated with a resin layer in which conductive fine particles and / or a lubricant are dispersed.

  As a charging method, a known corona charging method called corotron or scorotron is used, and a method using a pin electrode can also be used. Further, a contact charging method in which charging is performed by bringing a charging member into contact with the surface of the photoreceptor can be used in the same manner.

  In the present invention, the charging means is particularly effective in the case of the contact charging method in which the charging member is brought into contact with the surface of the photoreceptor. That is, compared to non-contact corona discharge in which the charging means does not contact the surface of the photoreceptor, the contact charging method is liable to cause deterioration of the surface of the photoreceptor, and from the viewpoint of durability, the transfer residual toner increases due to a decrease in transferability. It has a technical problem that it is in a strict direction for cleaning performance. Therefore, the effect of the high transferability used in the present invention becomes more remarkable.

  As a preferable process condition when a charging roller is used as the contact charging member, the contact pressure of the charging roller is 4.9 to 490 N / m (5 to 500 g / cm), more preferably 9.8 to 392 N / m ( Furthermore, in order to make the polarity of the transfer residual toner the same as that of the photosensitive member charging polarity and to facilitate recovery during development, it is preferable to apply a DC voltage. When a voltage is superimposed, it is preferable to superimpose an AC voltage having a peak-to-peak voltage less than 2 × Vth (V) [Vth; discharge start voltage (V) in DC application] on the DC voltage.

  Other contact charging members include a method using a charging blade and a method using a conductive brush. These contact charging means are effective in that a high voltage is not required and generation of ozone is reduced.

  As the contact charging member, in the case of a roller or a blade, a conductive metal such as iron, copper or stainless steel; a carbon dispersion resin; a metal or a metal oxide dispersion resin is used as a conductive substrate. In the case of a blade, a rod shape or a plate shape can be used. As the structure of the elastic roller, a structure in which an elastic layer, a conductive layer and a low resistance layer are provided on a conductive substrate is used.

  Examples of the elastic layer include chloroprene rubber, isoprene rubber, EPDM rubber, polyurethane rubber, sponge such as rubber foam or rubber foam such as butyl rubber; styrene-butadiene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester thermoplastic. It can be formed of an elastomer, a thermoplastic elastomer such as an ethylene-vinegar thermoplastic elastomer.

The conductive layer preferably has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ¹ to 10 ⁶ Ω · cm. As the conductive layer, for example, a metal vapor deposition film, a conductive particle-dispersed resin, a conductive resin, or the like is used. Specific examples include vapor-deposited films of conductive metals such as aluminum, indium, nickel, copper and iron; conductive particles such as carbon, aluminum, nickel and titanium oxide with urethane, polyester, vinyl acetate-vinyl chloride copolymer and Examples thereof include conductive particle-dispersed resins dispersed in a resin such as polymethyl methacrylate; conductive resins such as quaternary ammonium salt-containing polymethyl methacrylate, polyvinyl aniline, polyvinyl pyrrole, polydiacetylene and polyethylene imine.

The resistance layer is preferably a layer having a volume resistivity of 10 ⁶ to 10 ¹² Ω · cm. As the resistance layer, a semiconductive resin or a conductive particle-dispersed insulating resin can be used. As the semiconductive resin, for example, ethyl cellulose, nitrocellulose, methoxymethylated nylon, ethoxymethylated nylon, copolymer nylon, polyvinyl hydrin, or casein is used. Examples of the conductive particle dispersion resin include a small amount of conductive particles such as carbon, aluminum, indium oxide, and titanium oxide in an insulating resin such as urethane, polyester, vinyl acetate-vinyl chloride copolymer, and polymethyl methacrylate. Dispersed ones are mentioned.

  As the conductive brush as the contact charging member, a conductive brush whose resistance is adjusted by dispersing a conductive material in commonly used fibers is used. As the fiber, a generally known fiber can be used, and examples thereof include nylon, acrylic, rayon, polycarbonate, and polyester. As the conductive material, generally known conductive materials can be used. For example, conductive metals such as copper, nickel, iron, aluminum, gold and silver; iron oxide, zinc oxide, tin oxide, antimony oxide, titanium oxide Or conductive powders such as carbon black. These conductive materials may be subjected to surface treatment for the purpose of hydrophobization and resistance adjustment as necessary. In use, it is selected in consideration of dispersibility with fibers and productivity.

As for the shape of the conductive brush, the fiber thickness is 1 to 20 denier (fiber diameter of about 10 to 500 μm), the length of the brush fiber is 1 to 15 mm, and the brush density is 10,000 to 300,000 per square inch. Those (about 1.5 × 10 ^{7 to} 4.5 × 10 ⁸ per square meter) are preferably used.

  The image forming method of the present invention will be described with reference to the accompanying drawings.

  FIG. 1 is a diagram schematically showing an image forming apparatus having a process cartridge as an example of an embodiment of the image forming method of the present invention.

  The photosensitive member 36 is charged by a charging roller 31 as a contact charging unit, and an image portion is exposed with a laser beam 40 to form an electrostatic latent image. The toner 30 accommodated in the developing device 32 is applied onto the toner carrier 34 by the toner application roller 35 and the application blade 33, and the toner layer on the toner carrier 34 is brought into contact with the surface of the photoconductor 36 so as to contact the photoconductor 36. The upper electrostatic latent image is developed by a reversal developing method to form a toner image on the photoreceptor 36. At least a DC bias is applied to the toner carrier 34 by the bias applying means 41. The toner image on the photosensitive member 36 is transferred onto a recording material 38 as a transfer material being conveyed by a transfer roller 37 which is a transfer means to which a bias is applied by a bias applying means 42 and transferred onto the recording material. The toner image is fixed by a heat and pressure fixing means 43 having a heat roller and a pressure roller.

  The image forming apparatus includes a blade-shaped cleaning member 39 that abuts on the surface of the photoreceptor 36 between a transfer portion by the transfer roller 37 and a charging portion by the charging roller 31. The transfer residual toner on the sightseeing spot 36 after the transfer process is scraped off by the cleaning member 39 and collected by the cleaner. The photosensitive member 36 from which the transfer residual toner has been removed is charged again by the charging roller 31, and an electrostatic latent image is formed by exposure with the laser beam 40 after charging. The electrostatic latent image on the photoreceptor 36 is developed with toner on the toner carrier 34. The toner image on the photoreceptor 36 after the development process is transferred onto the recording material 38 being conveyed by the transfer roller 37. After the transfer process, after the transfer residual toner is removed by the cleaning member, the photosensitive member 36 is charged again by the charging roller 31, and thereafter the same process is repeatedly performed.

  FIG. 2 shows another example of an image forming apparatus that can more smoothly remove toner contributed to development from the developing sleeve in addition to supplying toner to the developing sleeve as a toner carrier.

  In FIG. 2, reference numeral 1 denotes a photosensitive drum, around which a primary charging roller 2 as a contact charging unit, a developing device 8 as a developing unit, a transfer charging roller 21 as a contact and transfer unit, and a register roller 19 are provided. . The photosensitive drum 1 is charged to, for example, −700 V by the primary charging roller 2. The voltage applied by the bias applying means 5 is, for example, −1350V DC voltage. And it exposes by irradiating the photosensitive drum 1 with the laser beam 7 by the laser generator 6, and a digital electrostatic latent image is formed. The electrostatic latent image on the photosensitive drum 1 is developed with a non-magnetic one-component toner 15 by the developing unit 8, and a bias voltage is applied by a bias applying unit 24 that is in contact with the photosensitive drum 1 via a recording material 20 as a transfer material. The image is transferred onto the recording material 20 by the applied transfer roller 21. The recording material 20 on which the toner image 26 is placed is conveyed by the conveying belt 25 to a heating and pressure fixing device 27 having a heating roller 38 and a pressure roller 29 and fixed on the recording material 20. Reference numeral 82 denotes a cleaner having a cleaning member 81. Transfer residual toner on the photosensitive drum after the transfer process is scraped off by the cleaning member 81 and collected by the cleaner 82.

  The charging roller 2 is basically composed of a central cored bar 4 and a conductive elastic layer 3 formed on the outer periphery thereof.

  As shown in FIGS. 3 and 4, the developing unit 8 is configured such that the toner layer on the developing sleeve 9 as a toner carrying member is in contact with the photosensitive drum 1 and the bias is applied by the bias applying unit 18 and the elastic layer 10. A developing sleeve serving as a toner carrier comprising an elastic roller 9 having 11 is disposed. A toner application roller 13 having a metal core 13 and an elastic layer 14 to which a bias is applied by a bias applying means 17 is disposed in the developing device 8. A toner regulating blade 16 is provided as a member for regulating the amount of toner that adheres to the developing sleeve 9 and is conveyed, and the amount of toner (toner layer) conveyed to the developing region by the contact pressure of the toner regulating blade 16 against the developing sleeve 9 Thickness) is controlled. In the development area, at least a DC development bias is applied to the development sleeve 9, and the toner layer on the development sleeve comes into contact with the surface of the photosensitive drum 1 and is transferred onto the photosensitive drum 1 in accordance with the electrostatic latent image to form a toner image. Form.

  When the light portion potential of the photosensitive drum 1 is 0 to 250 V and the dark portion potential is 300 to 1000 V, the supply bias voltage applied by the bias applying unit 17 is 100 to 900 V, and is applied by the bias applying unit 18. The developing bias voltage is preferably 100 to 900V. Further, the supply bias voltage applied by the bias applying unit 17 is larger by 10 to 400 V in absolute value than the developing bias voltage applied by the bias applying unit 18, and the supply of the nonmagnetic toner 15 to the developing sleeve 9 and The nonmagnetic toner is preferably peeled off from the developing sleeve 9 smoothly.

  It is preferable in terms of supplying and stripping non-magnetic toner that the surfaces of the toner application roller 12 move in the counter direction as indicated by the arrows with respect to the rotation direction of the developing sleeve 9 (the rotation direction is the same). .

  The image forming apparatus shown in FIG. 1 or 2 employs an image forming method in which a toner image formed on an image carrier is directly transferred to a recording material without using an intermediate transfer member.

  Next, the toner image formed on the image carrier is subjected to a first transfer to an intermediate transfer member as a transfer material, and the toner image transferred onto the intermediate transfer member is subjected to a second transfer to a recording material. A forming method will be described using the image forming apparatus shown in FIG.

In FIG. 4, an electrostatic latent image is formed by the exposure means 53 by applying a surface potential on the photosensitive drum 51 by a charging roller 52 that rotates in contact with the photosensitive drum 51 as an image carrier. The electrostatic latent image is developed by the four-component toners magenta toner, cyan toner, yellow toner, and black toner by the one-component contact developing type developing devices 54, 55, 56, and 57 to form a full-color toner image. At the time of development, any one of the developing devices 54, 55, 56, and 57 is moved so that the toner carrier of the developing device comes into contact with the surface of the photosensitive drum 51 and development is performed. When the developing device moves to the position, the toner carrier is separated from the surface of the photosensitive drum 51. This operation is repeated four times for each developing device. The toner image is transferred onto the intermediate transfer member 58 for each color, and is repeated a plurality of times to form a multiple toner image.

  The intermediate transfer member 58 is in the form of a drum, and has a holding member stretched on the outer peripheral surface, and a conductive member such as carbon black, zinc oxide, tin oxide, silicon carbide, or titanium oxide is sufficient on the substrate. A material having a dispersed elastic layer (for example, nitrile butadiene rubber) is used. A belt-like intermediate transfer member may be used.

  The intermediate transfer member 58 is a drum-shaped member having an elastic layer 60 having a hardness of 10 to 50 degrees (JIS K-6301) formed on the surface of the support member 59, or a transfer material (recording material) in the case of a transfer belt. It is preferable that the transfer portion is composed of a support member having an elastic layer 150 having this hardness.

  In the transfer from the photosensitive drum 51 to the intermediate transfer member 58, a bias current is applied to the metal core 59 as a support member of the intermediate transfer member 58 from the power source 66, whereby a transfer current is obtained and the toner image is transferred. Corona discharge or roller charging from the back of the holding member or belt may be used.

  The multiple toner images on the intermediate transfer body 58 are collectively transferred onto the recording material S by the transfer means 61. As the transfer means, a contact electrostatic transfer means using a corona charger, a transfer roller, or a transfer belt is used.

  The recording material S having a toner image includes a fixing roller 68 as a fixing member having a heating body 67 therein, and a pressure roller 69 of a heat fixing device 70 having a pressure roller 69 in pressure contact with the fixing roller 68. As the recording material S passes through the abutting nip portion with respect to 69, the toner image is fixed on the recording material S.

  The toner containing carbon black used in the present invention is used as a black toner in one developing device selected from the developing devices 54, 55, 56 and 57 of the image forming apparatus described above, and the remaining three developments. The container uses three chromatic color toners. The black toner used in the present invention is used for forming a color image or a full-color image in combination with a chromatic color toner, or for forming a monochrome image using only the black toner.

  In FIG. 4, reference numeral 63 denotes a cleaner (first cleaning means) having a cleaning member 62 for removing toner remaining on the surface of the photosensitive drum 51 after the first transfer. It is in contact with the surface of the body drum 51. Reference numeral 65 denotes a cleaner (second cleaning means) having a cleaning member 64 for removing toner remaining on the surface of the intermediate transfer body 58 after the second transfer.

  Hereinafter, the present invention will be described in more detail with specific methods for manufacturing toners and photosensitive drums, examples, and comparative examples.

  Carbon black shown in Table 1 was prepared.

(Preparation of master batch dispersions 1-19)
As shown in Table 2 below, a combination of carbon blacks a to l and a dispersant in the types and addition amounts shown in Table 2 is added to Atlite 1S (Mitsui Mining Co., Ltd.) with respect to 2000 g of styrene monomer. Then, using 2 mm zirconia beads, stirring was performed at 200 rpm at a temperature of 25 ° C. for 180 minutes to prepare master batch dispersions 1 to 19 in which carbon black and a dispersant were dispersed in a styrene monomer. Table 2 shows the viscosities of the obtained master batch dispersions 1 to 19.

[Production Example A of Polymerized Toner]
To 700 g of ion-exchanged water in a 2 liter four-necked flask, 500 g of 0.1M Na ₃ PO ₄ aqueous solution was added and heated to 60 ° C., and then a high-speed stirring device TK homomixer (manufactured by Special Machine Industries) ) And stirred at 12000 rpm. To this, 76 g of 1.0 M CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing a minute hardly water-soluble dispersion stabilizer.
(Pre-dispersion) Master batch dispersion 1 100g
(Monomer) Styrene 66g
34 g of n-butyl acrylate (n-BA)
(Polar resin) saturated polyester (condensation product of propoxylated bisphenol and terephthalic acid, acid value 14, peak molecular weight 7000) 8 g
(Release agent) Ester wax (melting point 65 ° C) 30g
The above formulation was heated to 60 ° C., uniformly dissolved and dispersed. Into this, 10 g of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was put into the aqueous medium and stirred at 12,000 rpm for 10 minutes with a TK homomixer at 60 ° C. in an N ₂ atmosphere to granulate the polymerizable monomer composition. . Thereafter, while stirring with a paddle stirring blade (50 rpm), the mixture was reacted at the same temperature for 5 hours, then heated to 80 ° C. and further reacted for 5 hours. After completion of the polymerization reaction, the residual monomer is distilled off under reduced pressure, and after cooling, hydrochloric acid is added to dissolve calcium phosphate, followed by filtration, washing with water, and drying, sharp black polymerized particles having a weight average particle size of about 6.9 μm (Black toner particles) were obtained.

To 100 parts by weight of the obtained black toner particles, 1.6 parts by weight of hydrophobic silica having a specific surface area by the BET method of 140 m ² / g was externally added to obtain polymerized toner A. Table 4 shows the physical properties of the obtained toner.

[Production Examples B to F of Polymerized Toner]
Polymerized toner B was prepared in the same manner as in [Polymerized toner production example A], except that master batch dispersion 2-6 in which the addition amount of the azo-based iron complex compound (1) was changed as shown in Table 2 was used. -F was produced. Table 4 shows the physical properties of the obtained toner.

[Production Example G of Polymerized Toner]
A polymerized toner G was produced in the same manner as in [Polymerized toner production example A] except that the master batch dispersion 7 using carbon black b shown in Table 1 was used instead of carbon black a. Table 4 shows the physical properties of the obtained toner.

[Production Examples H and I of Polymerized Toner]
_0.1M-Na 3 PO ₄ aqueous solution and 1.0 M-CaCl ₂ by adjusting the amount of the aqueous solution toners having different particle sizes in the same manner as in Production Example G polymerized toner] polymerized toner H, was prepared I. Table 4 shows the physical properties of the obtained toner.

[Production Examples J to R of Polymerized Toner]
Polymerized toners J to R were prepared in the same manner as in [Production example A of polymerized toner] except that master batch dispersion 8-17 using carbon blacks c to l shown in Table 1 was used instead of carbon black a. Was made. The master batch dispersion 16 was too viscous to be taken out, and toner could not be obtained. Table 4 shows the physical properties of the obtained toner.

[Production Examples S and T of Polymerized Toner]
[Production Example A of Polymerized Toner A] except that master batch dispersions 18 and 19 using an azo chromium compound and a zinc compound of ditertiary butylsalicylic acid, respectively, were used instead of the azo iron compound (1). Similarly, polymerization toners S and T were produced. Table 4 shows the physical properties of the obtained toner.

[Production Examples U and V for Polymerized Toner]
Polymerized toners U and V were produced in the same manner as in [Polymerized toner production example A] except that the formulation of the polymerizable monomer composition was changed as shown in Table 3. Table 4 shows the physical properties of the obtained toner.

[Production Examples of Polymerized Toner WZ]
Polymerized toners W to Z were produced in the same manner as in [Polymerized toner production example A] except that a part of the styrene monomer contained in the polymerizable monomer composition was changed to divinylbenzene.

  Table 4 shows the physical properties of the obtained toner.

[Production Examples AA and BB of Polymerized Toner]
Polymerized toners AA and BB were prepared in the same manner as in [Polymerized toner production example A] except that the amount of polymerization initiator added and the temperature conditions during the polymerization reaction were changed. Table 4 shows the physical properties of the obtained toner.

  Table 3 shows the formulations of the polymerized toners A to Z, AA, and BB.

(Photoreceptor Production Example 1)
An aluminum cylinder having a diameter of 30 mm and a length of 254 mm was used as a substrate. On this substrate, layers having the following constitutions were sequentially laminated by dip coating to produce a photoreceptor 1.
(1) Conductive coating layer: Mainly composed of a powder of tin oxide and titanium oxide dispersed in a phenolic resin. Film thickness 15 μm.
(2) Undercoat layer: Mainly composed of modified nylon and copolymer nylon. Film thickness 0.6 μm.
(3) Charge generation layer: Mainly composed of an azo pigment having absorption in a long wavelength region dispersed in a butyral resin. Film thickness 0.6 μm.
(4) Charge transport layer: Mainly composed of a hole-transporting triphenylamine compound dissolved in a polycarbonate resin (molecular weight of 20,000 by the Ostwald viscosity method) at a weight ratio of 8:10, and polytetrafluoroethylene powder ( 10% by weight with respect to the total solid content was added and dispersed uniformly. Film thickness 25 μm.

  The contact angle of water on the surface of the obtained photoreceptor 1 with respect to water was 95 degrees.

  The contact angle was measured using pure water, and the device used was Kyowa Interface Science Co., Ltd., contact angle meter CA-DS type.

(Photoreceptor Production Example 2)
A charge transport layer having a film thickness of 25 μm was formed in the same manner as in Photoconductor Production Example 1 except that no polytetrafluoroethylene powder (particle size 0.2 μm) was added to the charge transport layer. 2 was produced.

  The contact angle of water on the surface of the obtained photoreceptor 2 with respect to water was 79 degrees.

<Example 1>
A 600 dpi laser beam printer (manufactured by Canon: LBP-8Mark IV) was prepared as an image forming apparatus. This apparatus was modified to print 12 sheets per minute with LTR size paper at a process speed of 80 mm / s (variable toner carrier speed). As shown in FIG. 2, this apparatus uniformly charges a photoreceptor 36 (30φ) using a charging roller 32 to which a direct current and an alternating current component are applied. At this time, the DC component is controlled to a constant voltage, and the AC component is controlled to a constant current. After charging, an image portion is exposed with a laser beam 40 to form an electrostatic latent image, and a toner image is formed as a visible image with the toner 30. Then, the toner image is transferred to a transfer material 38 by a transfer roller 37 to which a voltage is applied. With the process of transcribing.

  Next, the developing container 32 in the process cartridge was modified. A medium resistance rubber roller (16φ) made of silicone rubber having a resistance adjusted by dispersing carbon black was used as a toner carrier 34 instead of an aluminum sleeve containing a magnet as a toner supply body, and was in contact with the photoreceptor 36. The moving direction and the rotational peripheral speed of the surface of the toner carrying member 34 are the same in the contact portion with the surface of the photosensitive member, and are driven so as to be 150% with respect to the rotational peripheral speed of the photosensitive member. That is, the peripheral speed of the toner carrier is 120 mm / s, and the relative speed with respect to the surface of the photoreceptor is 80 mm / s.

  As a means for applying the toner to the toner carrier, an application roller 35 is provided at the developing portion and brought into contact with the toner carrier. At the contact portion, the toner was applied onto the toner carrier by rotating so that the moving direction of the surface of the coating roller 35 was moved in the direction opposite to the moving direction of the toner carrier. Further, a stainless steel blade 33 coated with resin was attached to control the coat layer of the toner on the toner carrier. A blade made of urethane rubber is used as the cleaning member 39.

As the photoreceptor, the photoreceptor 1 produced in (Photoreceptor Production Example 1) was used, toner A was used as the toner, and process conditions were set so as to satisfy the following development conditions.
Photoreceptor dark part potential -700V
Photoreceptor bright part potential -150V
Development bias -450V (DC component only)
The image was evaluated by performing a continuous image output test of 1000 sheets while replenishing the toner, but the image density, scattering suppression, fog suppression, and transferability are good, and no cleaning failure occurs. Got image quality. Although both the photoreceptor and the developing roller were observed, it was not necessary to replace them without fusing.

(Evaluation methods)
(1) Image density A square solid black image having a side of 5 mm was formed, and the image density of the solid black image was measured using an image density measuring machine RD918 manufactured by Macbeth.

(2) Scattering Scattering evaluation is a splatter evaluation with fine fine lines related to the image quality of graphical images as follows, and is a line when printing out a 1-dot line image that is more likely to scatter than character lines. The reproducibility of the toner and the scattering of toner around the line were visually evaluated.
A: Almost no scattering occurs and shows good line reproducibility B: Slight scattering is observed C: Scattering is observed but there is little influence on the line reproducibility D: Remarkable scattering is observed and line reproducibility is improved (3) Transferability Transferability is the transfer residual toner on the photoconductor when solid black image is formed by taping with Mylar tape and stripping Mylar tape on the paper. Evaluation was made by subtracting the Macbeth concentration of the material pasted on the paper. Therefore, the smaller the numerical value, the better the transferability.

(4) Fogging Fogging removes the transfer residual toner on the photoconductor when solid white image is formed by taping with Mylar tape and sticking only Mylar tape on the paper from the Macbeth density of the stripped Mylar tape on the paper. The value was calculated by subtracting the Macbeth concentration of the fish. Therefore, the smaller the value, the better the fog suppression.

(5) Resolution The resolving power was evaluated by the reproducibility of a 600 dpi 50 μm small-diameter isolated dot as shown in FIG.
A: 5 or less defects in 100 B: 6 to 10 defects in 100 C: 11 to 20 defects in 100 D: 20 or more defects in 100 (6) Roller Matching with development After completion of the printout test, the appearance of residual toner adhering to the surface of the developing roller and the effect on the printout image were visually evaluated.
A: Very good (not generated)
B: Good (almost no occurrence)
C: Normal (there is sticking, but there is little influence on the image)
D: Poor (much sticking and causes image unevenness)
(7) Matching with Photosensitive Drum After completion of the printout test, the occurrence of scratches on the surface of the photoconductive drum and the sticking of residual toner and the influence on the printout image were visually evaluated.
A: Very good (not generated)
B: Good (slight scratches are seen but there is no effect on the image)
C: Normal (there is sticking or scratching, but there is little effect on the image)
D: Poor (there is much sticking and causes vertical stripe-like image defects)
(8) Matching with fixing device After completion of the printout test, the surface of the fixing roller was scratched and the residual toner was fixed visually.
A: Very good (not generated)
B: Good (although slight fixation is observed, there is no influence on the image)
C: Normal (there is sticking or scratching, but there is little effect on the image)
D: Poor (much sticking and causes image defects)
The evaluation results are shown in Table 5.

<Example 2>
The same procedure as in Example 1 was performed except for the following.

  The toner carrying member was driven so that the moving direction of the surface of the toner carrier was the same in the contact portion with the surface of the photosensitive member, and was 200% with respect to the rotational speed of the photosensitive member. The peripheral speed of the toner carrier is 160 mm / s, and the relative speed with respect to the surface of the photoreceptor is 80 mm / s.

Toner B was used as the toner, and process conditions were set so as to satisfy the following development conditions.
Development bias -500V (DC component only)
A durability test of 1000 sheets was performed while replenishing the toner, but the image density, fog suppression, and transferability were good, and no poor cleaning occurred, and an image quality equivalent to the initial one was obtained. Further, although both the photoconductor and the developing roller were observed, it was not necessary to replace them without fusing. The evaluation results are shown in Table 5.

<Examples 3 to 6>
Evaluation was performed in the same manner as in Example 1 except that polymerized toners B to E were used as toners. As shown in Table 5, the results were generally good.

<Comparative example 1>
In Example 1, the same test was performed except that the polymerized toner F and the photoreceptor 2 of the photoreceptor production example 2 were used.

Process conditions were set to satisfy the following development conditions.
Development bias -350V (DC component only)
Cleaning failure occurred at 500 sheets. When the cleaning blade was cleaned and the durability was continued every time a cleaning failure occurred, white spots caused by toner fusion were generated in a part of the solid black image in the period of the photoconductor at 1000 sheets.

  When the photoconductor was replaced, the white spots disappeared, but the image density did not recover to the initial level. The reproduction of isolated dots of 50 μm was insufficient, and the line image was conspicuous. The results are shown in Table 5.

<Examples 7 to 14>
Evaluation was performed in the same manner as in Example 1 except that polymerized toners G and J to P were used as toners. As shown in Table 5, the results were generally good.

<Comparative Examples 2 and 3>
Evaluation was performed in the same manner as in Example 1 except that polymerized toners Q and R were used as toners. As shown in Table 5, since the carbon black used in the toner is not the specific carbon black in the present invention, good results were not obtained.

  In the case of the polymerization toner Q, noticeable image staining due to poor cleaning occurred, and in the case of the polymerization toner R, a slight cleaning failure occurred at 1000 sheets and the image density was low.

<Comparative Examples 4 and 5>
Evaluation was performed in the same manner as in Example 1 except that polymer toners S and T were used as toners. As shown in Table 5, since the dispersant used for the toner was not the specific azo-based iron compound in the present invention, a good result was not obtained. Polymerized toner S was good at the initial stage, but caused a decrease in image density at 1000 sheets. Further, the polymer toner T has a low image density, and other characteristics are not sufficient.

<Examples 15 to 22>
Evaluation was performed in the same manner as in Example 1 except that polymerized toners U to Z, AA, and BB were used as toners. The results are shown in Table 5.

<Examples 23 to 31>
Polymerized toners G to I are used as toners, and the amount of each external additive (hydrophobic silica having a specific surface area of 140 m <2> / g according to the BET method) added is 0.5%, 1.8%, 3.0%. The evaluation was performed in the same manner as in Example 1 except that the values were changed. As shown in Table 6, when the amount of external additive added is 0.5%, the amount of residual toner after transfer increases slightly, and when it is 3.0%, the fixability is slightly inferior. Got.

<Example 32>
In the electrophotographic apparatus used in Example 1, a single-layer sponge roller is used as the toner application roller 35 in the developing container 32, and a bias voltage is applied to the toner application roller 35 from a bias application unit (not shown). Except for such changes, image formation was performed in the same manner as in Example 1 and evaluated.

  In this development, the developing roller 34 was applied with only a DC component of −300 V as a developing bias voltage, and the toner application roller 35 was applied with only a DC component of −450 V as an application bias voltage.

  When evaluated in the same manner as in Example 1, the image density and fog suppression were both stable and good, and no defective cleaning occurred, and an excellent image quality was obtained. Matching with the image forming apparatus was also good.

<Example 33>
An image was formed using the polymerized toner A produced in polymerized toner production example A in the developing device 57 of the image forming apparatus shown in FIG.

  As shown in FIG. 4, the image forming apparatus includes a cleaner having a cleaning member that comes into contact with the surface of the photoconductor as a first cleaning unit for removing toner remaining on the surface of the photoconductor after the first transfer step. As a second cleaning means provided between the first transfer portion and the charging portion for charging the photosensitive member, and further for removing toner remaining on the surface of the intermediate transfer member after the second transfer step. A cleaner having a cleaning member in contact with the surface of the intermediate transfer member is provided downstream of the second transfer unit and downstream of the first transfer unit.

  As the developing device 57, the one having the configuration of the developing device 8 shown in FIGS. 2 and 3 was used.

  A medium resistance rubber roller (16φ) made of silicone rubber, the resistance of which is adjusted by dispersing carbon black, is used as the toner carrier 9 and is in contact with the photoreceptor. The moving direction and the rotational peripheral speed of the surface of the toner carrying member 9 are the same in the contact portion with the surface of the photosensitive member, and are driven so as to be 150% of the photosensitive member rotational peripheral speed. That is, the peripheral speed of the toner carrier is 120 mm / s, and the relative speed with respect to the surface of the photoreceptor is 80 mm / s.

  As a means for applying toner to the toner carrier, a sponge roller having a single layer structure was provided as the application roller 12 and brought into contact with the toner carrier. At the contact portion, the toner was applied onto the toner carrier by rotating so that the movement direction of the surface of the application roller was moved in the direction opposite to the movement direction of the toner carrier. Further, a stainless steel blade 16 coated with resin was attached to control the coat layer of the toner on the toner carrier.

As the photoreceptor, the photoreceptor 1 produced in (Photoreceptor Production Example 1) was used, and toner A was used as the toner. Image forming conditions were set so as to satisfy the following development conditions and transfer body.
Photoconductor dark part potential: -700V
Photoreceptor bright part potential: -150V
Development bias applied to the development roller: -450V (DC component only)
Bias applied to toner application roller: -300V (DC component only)
Transfer bias applied to the intermediate transfer property in the first transfer process: 300 V (DC component only)
Transfer bias applied to the transfer roller in the second transfer step: 1000 V (DC component only)
The toner image transferred onto the recording material under the above image forming conditions was heat-fixed on the recording material by the following heat fixing device.

  As the heat fixing device 70, a heat roll type fixing device having no oil application function was used. At this time, both the upper roller 68 and the lower roller 69 had a fluororesin surface layer, and the roller diameter was 55 mm. The fixing temperature was set to 140 ° C. and the nip width was set to 7 mm.

  Using the image forming apparatus having the above configuration, 2000 continuous image output tests were performed while replenishing toner, and image evaluation was performed. However, the image density, scattering suppression, fog suppression, and transferability were good, and the cleaning was poor. The image quality equivalent to the initial image was obtained. Although the photoreceptor, developing roller, and intermediate transfer member were observed, no replacement was required without fusing.

1 is a diagram schematically illustrating an image forming method using a contact one-component developing device used as an example of an embodiment of an image forming method of the present invention. It is the figure which showed the image forming method using the contact one-component developing apparatus used as another example of the image forming method of this invention in the schematic diagram. FIG. 3 is an enlarged view of a developing device of the image forming apparatus shown in FIG. 2. FIG. 2 is a diagram schematically illustrating an image forming apparatus using an intermediate transfer member. It is explanatory drawing of the isolated dot pattern for evaluating resolution. It is a figure which shows a viscosity change when the carbon black concerning this invention and an azo type iron complex compound are disperse | distributed in styrene. In the carbon black concerning this invention, it is a figure which shows the relationship between the oil absorption amount of a carbon black, and a viscosity when a fixed quantity of azo type iron complex compound is added and disperse | distributed in styrene. FIG. 4 is a schematic diagram illustrating an example of a cross section of toner particles containing a wax component. It is a schematic explanatory drawing of the measuring apparatus for measuring the electrical resistance value of a developing roller.

Explanation of symbols

30 Toner 31 Charging roller 32 Developing container 33 Toner regulating blade 34 Toner carrier (elastic roller)
35 toner application roller 36 photoconductor (image carrier)
37 Transfer roller 38 Transfer material 39 Cleaning member 40 Laser light (exposure)
41 Bias applying means 43 Fixing device

Claims (6)

A method for producing a toner comprising toner particles containing at least a binder resin, carbon black, and an azo-based iron compound and an inorganic fine powder,
The carbon black has an average primary particle size of 25-80 nm,
The azo-based iron compound has the following general formula (1)

[Wherein, X ₁ and X ₂ represent a member selected from the group consisting of a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group and a halogen atom, and X ₁ and X ₂ are the same or different, m And m ′ represents an integer of 1 to 3, R ₁ and R ₃ are a hydrogen atom, a C _{1 to} C ₁₈ alkyl group, a C _{2 to} C ₁₈ alkenyl group, a sulfonamide group, a mesyl group, a sulfonic acid group, carboxy ester group, hydroxy group, an alkoxy group of C ₁ -C _18, shows a member selected acetylamino group, from the group consisting of benzoylamino group and a halogen atom, R ₁ and R ₃ are the same or different, n and n 'is an integer of 1 to 3, _{R 2} and _{R 4} represents a hydrogen atom or a nitro group, ^{a +} is an ammonium ion, hydrogen ion, sodium Lee Down, it shows the cation ion selected from the group consisting of potassium ions and their mixtures ions. And a compound represented by
The toner particles are produced by polymerizing a polymerizable monomer composition containing at least a polymerizable monomer, the carbon black, and the azo-based iron compound in an aqueous medium ,
The polymerizable monomer composition is prepared by mixing a dispersion in which the carbon black and the azo-based iron compound are dispersed in a first polymerizable monomer with at least a second polymerizable monomer. And a toner production method . The method for producing a toner according to claim 1, wherein the carbon black has an average primary particle size of 25 to 55 nm. 3. The toner production method according to claim 1, wherein the carbon black has a DBP oil absorption of 40 to 150 ml / 100 g. The method for producing a toner according to any one of claims 1 to 3, wherein the carbon black has a specific surface area by nitrogen adsorption of 100 m ² / g or less and a volatile content of 2% or less. The toner particles have a carbon black content A weight% and an azo-based iron compound content B weight% under the following condition 2 ≦ A / B ≦ 35.
The toner production method according to claim 1, wherein: In the toner, the shape factors SF-1 and SF-2 have the following relationship 100 <SF-1 ≦ 160.
100 <SF-2 ≦ 140
The toner production method according to claim 1, wherein: