JP2010008454A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method and toner for attaining development stability extending to both the environments of low temperature and low humidity, and high temperature and high humidity. <P>SOLUTION: In the image forming method having an electrostatic charge step, an exposure step, a toner supply step, a toner regulation step, a development step for performing development with the toner, and a toner image transfer step, a toner carrier 14 is ≥4.0 μm to 20.0 μm, in ten point average surface roughness. The toner has at least toner particles and fatty acid metal salt particulates of ≥0.15 μm to 1.00 μm median diameter (D5Os), based on volume. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an image forming method and a toner used in a recording method represented by electrophotography.

  As electrophotographic technology used in copying machines, printers, facsimile receivers, etc., the demands from users have become stricter year by year as the devices have been developed. In recent years, there is a strong demand to provide stable image quality that does not depend on the environment because it is possible to print a large number of sheets and the environment used by the expansion of the market has expanded. .

  In order to satisfy the above requirements, an image forming method having high durability and high image quality is required more than before, and many improvements have been made to solve the above problems.

  For example, it is known that the inclusion of a fatty acid metal salt in the toner can provide an effect of preventing filming on a cleaning aid or an electrostatic latent image carrier. However, on the other hand, the fatty acid metal salt causes fogging and a decrease in image density, and high image quality cannot be obtained. Therefore, it has been disclosed to improve fogging while improving filming and voiding in an electrostatic latent image carrier by using a fatty acid metal salt and a titanic acid compound in combination (for example, Patent Document 1).

  In addition, by defining the particle size of toner particles having a certain storage modulus or the relationship between the particle size distribution of the toner particles and the particle size and distribution of the fatty acid metal salt, the image quality, fog, and fill to the electrostatic latent image carrier It is disclosed to improve the ming (for example, Patent Documents 2 and 3).

  Further, it is disclosed that fog, toner scattering and toner leakage are suppressed by containing an additive (alumina and titanium oxide) that defines the work function relationship with the base particles and a fatty acid metal salt (for example, Patent Document 4).

  Furthermore, it is disclosed that the image stability can be improved while coating a toner particle with a fatty acid metal salt to suppress the liberation rate while serving as an anti-filming agent for the electrostatic latent image carrier. For example, Patent Document 5).

  Certainly, such measures can reduce fogging, toner scattering, and toner leakage while suppressing toner filming on the latent electrostatic image bearing member, resulting in high durability and high image quality stability. It came to be obtained. However, as a result of intensive studies by the present inventors, the toner described in Patent Documents 1 and 2 has an effect on initial fogging because the particle size of the fatty acid metal salt used is too large. It has been found that there is a problem that when a large number of sheets are printed, the change in chargeability increases and fogging occurs. It has been found that the toners described in Patent Documents 3 and 4 have a problem of fogging due to a decrease in chargeability when the number of printed sheets increases in a severe environment of low temperature and low humidity and high temperature and high humidity.

  Further, in the toner described in Patent Document 5, it is necessary to coat the toner particles with a fatty acid metal salt, and the toner particles are easily mechanically damaged in the coating process, and the toner machine tax member is easily contaminated. It was found that it has the problem.

  Further, improvement of the properties of the toner carrier is one of means for achieving high durability with no deterioration in image quality. For example, in order to improve toner carrying performance and durability, techniques for devising conditions for rough particles and additives contained in the toner carrier surface layer are disclosed (for example, Patent Document 6, Patent Document 7, (See Patent Document 8 and Patent Document 9). Furthermore, a technique for maintaining durability even with a flexible toner has been proposed by devising the degree of unevenness of the surface layer of the toner carrier when pressure is applied (see, for example, Patent Document 10).

  Furthermore, several techniques for improving various performances by devising a toner carrier for a toner containing a fatty acid metal salt as described above have been disclosed. For example, in order to improve waste toner recyclability, a fatty acid metal salt and positively charged inorganic fine particles are externally added to the toner, and a developing roller (toner carrier) made of silicone resin or urethane resin and a toner supply roller made of urethane resin are provided. An example of use is given (for example, see Patent Document 11). Alternatively, a technique that defines work functions of toner particles, metal soap (fatty acid metal salt), and a developing roller (toner carrier) to prevent adhesion of external additives to the toner carrier is also disclosed (for example, Patent Documents). 12).

  However, it has been found that there is still a problem in terms of contamination of members such as a toner carrying member and a toner supply member that generate a large amount of rubbing in response to higher speeds. In particular, when printing a large number of sheets at high speed in a low-humidity environment, it has been found that image defects due to toner filming on the member occur. In other words, there is still a need for improved means to achieve the recently demanded high speed and long life printing.

JP-A-8-272132 Japanese Patent Laid-Open No. 9-311499 JP 2002-296829 A JP 2007-148198 A JP 2007-108622 A JP 2005-121728 A JP 2002-304053 A JP 2006-251342 A JP-A-2005-258201 JP 2006-178084 A JP 2002-014488 A JP 2005-274818 A

  In view of the above problems, the present invention is to provide an image forming method and a toner excellent in high speed and long life in both low temperature and low humidity and high temperature and high humidity environments.

  The present invention for achieving the above object includes a charging step of charging the electrostatic latent image carrier with a charging means, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, A step of supplying toner to the toner carrier by the toner supply member, a step of regulating the toner on the toner carrier by the toner layer regulating member, a developing step of developing the electrostatic latent image carrier by the toner on the toner carrier, In an image forming method having a transfer step of transferring a toner image to a transfer material with or without an intermediate transfer member, the toner carrier has a ten-point average surface roughness (Rz) of 4.0 μm or more and 20. An image forming method, wherein the toner has at least toner base particles and fatty acid metal salt fine particles having a volume-based median diameter (D50s) of 0.15 μm or more and 1.00 μm or less; About the donor.

  According to the present invention, it is possible to obtain a high-quality, highly stable image forming method and toner that are less dependent on the environment even in high-speed printing. That is, an image forming method that suppresses toner filming on a toner carrier, a toner regulating member, etc. even in high-speed and long-term printing in a low-temperature and low-humidity environment, and further suppresses fogging in a high-temperature and high-humidity environment. And toner can be obtained.

  The ability to print at high speed for a long period of time without depending on temperature and humidity is one of the most important issues in meeting market demands. As a result of intensive studies by the present inventors, it is possible to add a fatty acid metal salt having a certain particle size to the toner, and to regulate the surface roughness of the toner carrier within a certain range, which is good for the above problem. It was found that a good result was obtained.

  Specifically, a charging step of charging the electrostatic latent image carrier with a charging unit, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and toner carrying by a toner supply member A step of supplying toner to the body, a step of regulating the toner on the toner carrier with a toner layer regulating member, a development step of developing the electrostatic latent image carrier with the toner on the toner carrier, and a toner image as an intermediate transfer member In the image forming method including a transfer step of transferring to a transfer material with or without the toner, the toner carrier has a ten-point average surface roughness (Rz) of 4.0 μm or more and 20.0 μm or less, The toner is an image forming method characterized by having at least toner particles and fatty acid metal salt fine particles having a volume-based median diameter (D50s) of 0.15 μm or more and 1.00 μm or less.

  The guess about the effect expression of this invention is described below.

  As an example, consider a process cartridge using non-magnetic one-component toner as shown in FIG. The toner is supplied to the toner carrier 14 by the toner supply member 15, and the toner amount on the toner carrier is controlled by the toner regulating member 16. At this time, there is not a little mechanical damage due to the friction with the toner supply member 15, the electrostatic latent image carrier 10 or the toner regulating member 16. In particular, if the process speed is increased in a low-temperature and low-humidity environment for high-speed printing, it is inevitable that the rubbing becomes strong, and the damage to the toner becomes significant. As a result, many cases of toner filming on the toner carrier were observed. This filming is further exacerbated by increasing the number of printed sheets. When filming of toner occurs on the toner carrier or the like, uneven charging of the toner becomes remarkable, and an image detrimental effect such as density unevenness occurs on the image.

  However, the ten-point average surface roughness (Rz) of the toner carrier is 4.0 μm or more and 20.0 μm or less, and the volume-based median diameter (D50s) is 0.15 μm or more and 1.00 μm or less. By using a toner having fine particles, the above problem is greatly improved. Conventionally, it is known that fatty acid metal salts are materials that have the effect of preventing component contamination, but the effect is insufficient in terms of high-speed response in a low-temperature and low-humidity environment, or otherwise in response to high-speed and long-life. As described above, harmful effects are likely to occur. Presumably, there is a very important correlation between the fine fatty acid metal salt and the surface property of the toner carrier.

  First, D50s of the fatty acid metal salt of the toner needs to be 0.15 μm or more and 1.00 μm or less. In the present invention, when the D50 of the fatty acid metal salt is smaller than 0.15 μm, the particle size is too small, so that the function as a lubricant is lowered, and it is difficult to obtain the effect of suppressing toner filming on the toner carrier. On the other hand, if it exceeds 1.00 μm, the fatty acid metal salt tends to be unevenly present on the surface of the toner particles, so that a charge distribution occurs in the toner particles and the toner of reverse polarity increases. For this reason, fog and image stability due to the fatty acid metal salt are likely to occur in a high temperature and high humidity environment. In addition, release in the toner tends to occur more easily when the particle size becomes larger, and when a large number of prints are made, the fatty acid metal salt is released from the toner and the effect of suppressing filming is reduced. This is likely to cause image damage.

  After the volume-based median diameter (D50s) of the fatty acid metal salt contained in the toner is controlled as described above, the ten-point average surface roughness (Rz) of the toner carrier is 4.0 μm or more and 20.0 μm or less. Further, a large filming suppressing effect was obtained. On the contrary, when Rz is smaller than 4.0 μm, or when Rz is larger than 20.0 μm, the filming suppressing effect is decreased. Further, such a phenomenon that the effect of suppressing filming fades becomes more prominent as the printing speed is increased. That Rz is smaller than 4.0 μm is basically a direction in which the surface of the toner carrying member is rubbed more uniformly. Although it seems that filming on the toner carrier is more advantageous, it is considered that the entire surface of the toner carrier is always rubbed and adhesion of the toner component gradually proceeds as a whole. On the other hand, it was found that when Rz exceeds 20.0 μm, the contamination of the concaves and convexes on the surface of the toner carrying member proceeds when the high-speed operation is supported. That is, when a fine fatty acid metal salt is used, there is a surface roughness shape that can maximize the lubrication effect. Rz can be controlled, for example, by incorporating particles on the surface of the toner carrier and changing the particle size of the particles.

  In the present invention, the effect is further enhanced by satisfying the following conditions. First, when the volume-based 5% integrated diameter of the fatty acid metal salt is D5s, the 95% integrated diameter is D95s, and the span value B = (D95s−D5s) / D50s, the span value B satisfies 1.75 or less. That is. In the present invention, when the fatty acid metal salt having a fine and uniform particle size distribution is included in the toner, the span value B can be uniformly present in the toner. It is presumed that this is a condition in which filming suppression is exerted more strongly. Further, when the 10% cumulative diameter based on the number of toners is D10t, the 90% cumulative diameter is D90t, the median diameter based on the number is D50t, and a span value A = (D90t−D10t) / D50t, 0.25 ≦ It is also important to satisfy (A / B) ≦ 0.75. Under these conditions, it is possible to obtain a high-development high-quality image with a balance between fog and density stability while maintaining a large filming suppression effect. When A / B is smaller than 0.25, the particle size distribution of the fatty acid metal salt is broader than the toner particle size distribution, and the charge becomes non-uniform. Become. Conversely, if it exceeds 0.75, the particle size distribution of the fatty acid metal salt is too sharp with respect to the particle size distribution of the toner, which is effective in suppressing fogging, but the reason is not clear, but if high-speed printing is continued many times, A slight decrease in density is likely to occur. The presence of a certain particle size distribution in the fatty acid metal salt may cause some functional separation with respect to anti-fusing and charging characteristics between large and small particles. In consideration of the balance between fog and concentration stability, 0.40 ≦ (A / B) ≦ 0.70 is more preferable.

  The toner has a number-based median diameter (D50t) of not less than 3.0 μm and not more than 7.0 μm because the relative relationship between the surface roughness of the toner carrier and the particle size of the fatty acid metal salt is optimized. The filming suppression effect is further increased, which is preferable. When D50t is less than 3.0 μm, the toner particles are relatively small with respect to the surface roughness of the toner carrying member, so that the filming suppression effect of the fatty acid metal salt is diminished. In the present invention, when D50t is more than 7.0 μm, relatively small particles in the toner particles tend to collect on the surface of the toner carrying member, and the damage to the toner is biased and the effect of suppressing filming is reduced. is there. A ratio of 2.0 μm or less in the number average particle size distribution of the toner is preferably 1.0% by number or more and 15.0% by number or less, which is a preferable condition in terms of enhancing the filming suppressing effect. Toner particles having a particle size of 2.0 μm or less are particles that have a small particle size and thus have increased adhesion to the surface of the toner carrying member and facilitate filming. In the present invention, if it exceeds 15.0% by number, the effect of suppressing filming is slightly reduced. However, by including a fine fatty acid metal salt in the toner, a result suggesting that toner particles of 2.0 μm or less may be interposed between the toner and the toner carrier and serve as a spacer. It has been. In fact, when the number was less than 1.0%, a phenomenon suggesting that the damage to the toner is greater when printing a large number of sheets at a high speed than when the number is 1.0% or more and 15.0% or less. It is estimated that the region where a moderate synergistic effect is exhibited is 1.0% by number or more and 15.0% by number or less.

  Moreover, as for the preferable conditions of the fatty acid metal salt which improves the effect of this invention further, the said D50s is 0.30 micrometer or more and 0.60 micrometer or less, and the said span value B is 1.40 or less.

  Examples of fatty acid metal salts that can be used in the present invention include zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, lithium stearate, and zinc laurate. Zinc stearate or calcium stearate is preferred in that the effect is easily obtained.

  A preferred toner carrier for obtaining the effects of the present invention is a toner carrier having an elastic layer on the outer periphery of the shaft core and a surface layer containing at least a binder resin and resin particles on the outer periphery of the elastic layer. is there. At this time, the film thickness of the surface layer is particularly preferably 5.0 μm or more and 20.0 μm or less. The film thickness of the toner carrier surface layer here is a thickness depending on the binder resin constituting the surface layer (detailed definition and measurement method will be described later). By controlling the unevenness (Rz) of the surface layer of the toner carrier by adding particles to the surface layer, the unevenness becomes smooth and the filming suppression effect of the present invention is further exhibited, and at the same time a high temperature and high humidity environment The development characteristics in the process are also good. The film thickness of 5.0 μm or more and 20.0 μm or less is probably an effective range in which the elasticity of the toner carrier elastic layer has a moderate influence, and as a result, the effect of the present invention can be further obtained. It is presumed that this is one of the conditions for enhancing the lubricating effect of the fatty acid metal salt contained in the toner when the toner and the toner carrier are rubbed. In addition, as for the said elastic layer, it is preferable conditions that the above-mentioned synergistic effect increases more that Asker C hardness is 50 degrees or more and 60 degrees or less. Moreover, it is a more preferable range that the film thickness is 8.0 μm or more and 15.0 μm or less.

  Further, the preferable condition of the particles contained in the surface layer is that the volume average particle diameter (Dvp) is 3.0 μm or more and 20.0 μm or less, and 30 masses with respect to 100 mass parts of the binder resin of the surface layer. It is to mix | blend in the ratio of 100 to 100 mass parts. This is one of the factors that determine the surface roughness Rz when the surface layer of the toner carrier is composed of at least a binder resin and particles. Since it almost coincides with the Rz range (4.0 μm or more and 20.0 μm or less), which is an essential requirement of the present invention, it is possible to obtain the Rz of the present invention by appropriately dispersing particles with little deviation. It is assumed that is a condition that is drawn more. What is more important in the present invention is the blending amount of the particles. By blending the particles at a ratio of 30 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin of the surface layer, an extremely large filming suppressing effect is obtained. And good development characteristics in high humidity environment. The blending amount of the particles affects the surface unevenness, particularly the recess characteristics. Although the detailed reason is unknown, when the fine fatty acid metal salt, which is one of the features of the present invention, is used, there is a surface recess property that provides a greater effect, and the preferred amount of particles added is the surface layer. It is thought that it is 30 to 100 parts by mass with respect to 100 parts by mass of the binder resin.

  When the amount is less than 30 parts by mass, the filming suppression effect of the present invention is slightly diminished, but this is because there are few particles and there is a smooth part, and the synergistic effect with the fine fatty acid metal salt is diminished in that part. I guess that. When the amount is more than 100 parts by mass, the fatty acid metal salt is easily released from the toner particles during the rubbing of the toner regulating member or toner supply member with the toner carrier, and fog is likely to occur. A more preferable condition from the above viewpoint is that the addition amount of the particles with respect to 100 parts by mass of the binder resin of the surface layer is 40 parts by mass or more and 85 parts by mass or less.

  Furthermore, the elastic modulus of the particles contained in the toner carrier surface layer also has an effective range for more exerting the effects of the present invention. Specifically, particles having an elastic modulus of 0.02 MPa or more and 3.60 MPa or less are used. The particles on the surface layer of the toner carrier are basic elements constituting the convex portions of the surface irregularities. At this time, it was found that when the elastic modulus of the particles is 0.02 MPa or more and 3.60 MPa or less, damage to the toner is suppressed even when high-speed printing is performed. The convex part is the most pressure-applying part. In the present invention in which a fine fatty acid metal salt is contained in the toner, if the elastic modulus is satisfied, the lubricating effect of the fatty acid metal salt at the moment when the toner is rubbed by the convex part And the toner carrier is hardly contaminated. When the pressure is less than 0.02 MPa, the increase in the lubricating effect of the fatty acid metal salt is weakened due to the large deformation of the convex portion when contacting the toner regulating member. When it is higher than 3.60 MPa, the rubbing property between the binder resin on the toner surface layer and the toner particles increases, and this also tends to weaken the increase in the lubricating effect of the fatty acid metal salt. From such a viewpoint, a more preferable condition in the present invention is to use resin particles having an elastic modulus of the particles of 0.10 MPa to 1.90 MPa.

  In addition to the preferable conditions as described above, the microrubber hardness of the surface of the toner carrying member is set to 30 degrees or more and 43 degrees or less to achieve filming resistance and good developability due to toner lubrication at a higher level. This is a preferable condition. If it is less than 30 degrees, the adhesion force of the toner particles to the toner carrier is increased, and accordingly, the excellent lubricating effect of the fatty acid metal salt in the present invention is slightly weakened. When it exceeds 43 degrees, the damage from the toner carrying member received by the toner at the time of rubbing is increased, and the life is slightly shortened when a large number of sheets are printed at high speed printing.

  It is preferable that the toner supply member that supplies toner to the toner carrier has a surface layer of a foamed elastic body because a longer number of sheets can be printed during high-speed printing. Since the surface of the toner supply member is a foamed elastic body, the lubricating action of the fine metal salt-containing toner contained in the foamed portion effectively works against the rubbing that occurs during toner supply, so a large filming suppression effect is obtained. I guess it will be.

  Next, a toner manufacturing method will be described.

  The toner particles used in the present invention may be produced by any method, but a production method of granulating in an aqueous medium such as a suspension polymerization method, an emulsion polymerization method, or a suspension granulation method. It is preferable to obtain by.

  Hereinafter, the most preferable suspension polymerization method for obtaining the toner particles used in the present invention will be described as an example to describe the method for producing the toner.

  The binder resin, colorant, wax component and other additives as required are uniformly dissolved or dispersed by a disperser such as a homogenizer, ball mill, colloid mill, ultrasonic disperser, etc. Is dissolved to prepare a polymerizable monomer composition. Next, toner particles are produced by suspending the polymerizable monomer composition in an aqueous medium containing a dispersion stabilizer and performing polymerization.

  The polymerization initiator may be added simultaneously with the addition of other additives to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.

  Examples of the binder resin for the toner include commonly used styrene-acrylic copolymers, styrene-methacrylic copolymers, epoxy resins, and styrene-butadiene copolymers. As the polymerizable monomer, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  The following are mentioned as a polymerizable monomer for producing | generating a binder resin. Styrene; Styrenic monomers such as o- (m-, p-) methylstyrene, m- (p-) ethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, Acrylic acid ester monomers such as 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, Ether-based monomers; butadiene, isoprene, cyclohexene, acrylonitrile, methacrylonitrile, acrylic acid amide, such as ene-based monomers methacrylamide.

  These polymerizable monomers are used alone or in general, and have a theoretical glass transition temperature (Tg) of 40 to 75 described in Publication Polymer Handbook 2nd edition III-p139-192 (manufactured by John Wiley & Sons). A polymerizable monomer is appropriately mixed and used so as to indicate ° C. If the theoretical glass transition temperature is less than 40 ° C., problems are likely to occur from the viewpoint of storage stability and durability stability of the toner, while if it exceeds 75 ° C., the fixability is lowered.

  In the case of producing toner particles, it is a preferable example to add a low molecular weight polymer so that the THF soluble content of the toner has a preferable molecular weight distribution. The low molecular weight polymer can be added to the polymerizable monomer composition when toner particles are produced by suspension polymerization. The low molecular weight polymer has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) in the range of 2,000 to 5,000, and Mw / Mn of less than 4.5, preferably Those of less than 3.0 are preferred in terms of fixability and developability.

Examples of the low molecular weight polymer include low molecular weight polystyrene, low molecular weight styrene-acrylic acid ester copolymer, and low molecular weight styrene-acrylic copolymer.
It is preferable to use together with the above-mentioned binder resin a polar resin having a carboxyl group such as a polyester resin or a polycarbonate resin.

  For example, in the case of directly producing toner particles by a suspension polymerization method, if a polar resin is added from the dispersion step to the polymerization step, the polarities exhibited by the polymerizable monomer composition that becomes the toner particles and the aqueous dispersion medium can be obtained. Depending on the balance, the presence state of the polar resin can be controlled so that the added polar resin forms a thin layer on the surface of the toner particles or exists with a gradient toward the center from the toner particle surface. That is, the addition of the polar resin can reinforce the shell part of the core-shell structure, so that it becomes easy to optimize the micro compression hardness, and the toner of the present invention can achieve both developability and fixability. It becomes easy to do.

  A preferable addition amount of the polar resin is 1 to 25 parts by mass, and more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 1 part by mass, the presence state of the polar resin in the toner particles tends to be non-uniform. On the other hand, if it exceeds 25 parts by mass, the layer of the polar resin formed on the surface of the toner particles becomes thick.

  Examples of the polar resin include polyester resin, epoxy resin, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, and styrene-maleic acid copolymer. A polyester resin is particularly preferable, and the acid value is preferably in the range of 4 to 20 mgKOH / g. When the acid value is less than 4 mgKOH / g, it is difficult to form a shell structure, and the rise of charging is slow, which tends to cause problems such as a decrease in image density and fogging. When the acid value exceeds 20 mgKOH / g, the chargeability is affected and the developability tends to deteriorate. The molecular weight of 3,000 to 30,000 is preferably a main peak molecular weight because the fluidity and negative frictional charging characteristics of the toner particles can be improved.

  In order to increase the mechanical strength of the toner particles and control the molecular weight of the THF soluble component of the toner, a crosslinking agent may be used when the binder resin is synthesized.

  Examples of the bifunctional crosslinking agent include the following. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-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-type diacrylate (MANDA Nippon Kayaku), and diacrylate above instead of diacrylate Thing.

  The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and methacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate and triallyl trimellitate. The addition amount of these crosslinking agents is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  The following are mentioned as a polymerization initiator. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxide-based polymerization initiators such as peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.

  The amount of these polymerization initiators to be used varies depending on the target degree of polymerization, but is generally 3 to 20 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer. The kind of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  The toner of the present invention contains a colorant as an essential component in order to impart coloring power. Examples of the colorant preferably used in the present invention include the following organic pigments, organic dyes, and inorganic pigments.

  Examples of organic pigments or organic dyes as cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue.

  Examples of the organic pigment or organic dye as the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  Examples of the organic pigment or organic dye as the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

Examples of the black colorant include carbon black and those prepared by using the above yellow colorant / magenta colorant / cyan colorant to black.
These colorants can be used alone or in combination and further in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  The colorant is preferably used by adding 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin.

  When obtaining toner particles using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and water phase transferability of the colorant, and preferably, the colorant is subjected to a hydrophobic treatment with a substance that does not inhibit polymerization. It is better to leave it. In particular, since dye-based colorants and carbon black have many polymerization inhibiting properties, care must be taken when using them. A preferable method for treating the dye-based colorant includes a method of polymerizing a polymerizable monomer in the presence of these dyes in advance, and the obtained colored polymer is added to the polymerizable monomer composition.

  Moreover, about carbon black, you may process with the substance (for example, polyorganosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

  As the dispersion stabilizer used when preparing the aqueous medium, known inorganic and organic dispersion stabilizers can be used.

  Specifically, the following are mentioned as an example of an inorganic dispersion stabilizer. Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina . Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch.

Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.
As the dispersion stabilizer used at the time of preparing the aqueous medium, an inorganic poorly water-soluble dispersion stabilizer is preferable, and it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in an acid.

  Further, when preparing an aqueous medium using a hardly water-soluble inorganic dispersion stabilizer, the amount of these dispersion stabilizers used is 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is preferable that In the present invention, it is preferable to prepare an aqueous medium using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.

  When preparing an aqueous medium in which the poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is. In order to obtain particles of a dispersion stabilizer having a fine uniform particle size, an aqueous medium may be prepared by generating a poorly water-soluble inorganic dispersion stabilizer in a liquid medium such as water under high-speed stirring. For example, when tricalcium phosphate is used as a dispersion stabilizer, a preferred dispersion stabilizer can be obtained by mixing sodium phosphate aqueous solution and calcium chloride aqueous solution under high speed stirring to form fine particles of tricalcium phosphate. Can do.

  In the toner, if necessary, a charge control agent can be mixed with toner particles and used. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.

  As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is particularly preferable.

  Examples of the charge control agent that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.

  Examples of the charge control agent that controls the toner to be positively charged include the following. Nigrosine-modified products such as nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, Gallic acid, ferricyanide, ferrocyanide, etc.); metal salt of higher fatty acid; resin charge control agent.

  These charge control agents can be contained alone or in combination of two or more.

  Among these charge control agents, a metal-containing salicylic acid-based compound is preferable in order to sufficiently exhibit the effects of the present invention, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.

  A preferable blending amount of the charge control agent is 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin. However, it is not essential to add a charge control agent to the toner of the present invention, and the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

  As a mixer used for the additive mixing step, an existing high-speed stirring mixer such as a Henschel mixer or a super mixer can be used.

  It is essential that the toner of the present invention contains a fatty acid metal salt having a volume-based median diameter (D50s) of 0.15 μm or more and 1.00 μm or less. However, even if other additives are added. Good. Examples of the additive include fine powder such as silica fine powder, titanium oxide fine powder, or double oxide fine powder thereof. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.

Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside the silica fine powder and less Na ₂ O and SO ₃ ²⁻ is preferable. The dry silica may be a composite fine powder of silica and another metal oxide by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process.

  The inorganic fine powder is added to the toner particles in order to improve the fluidity of the toner and make the toner particles uniformly charged. By hydrophobizing the inorganic fine powder, it is possible to adjust the charge amount of the toner, improve the environmental stability, and improve the characteristics in a high-humidity environment. It is preferable to use it. When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner is reduced, and the developability and transferability are easily lowered.

  Treatment agents for hydrophobizing inorganic fine powder include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, organic A titanium compound is mentioned. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, when the inorganic fine powder is hydrophobized with a coupling agent or simultaneously with or after the treatment, the hydrophobized inorganic fine powder treated with silicone oil maintains a high toner particle charge amount even in a high humidity environment, and is selected. It is good for reducing developability.

  The total amount of the inorganic fine powder is preferably 1.5 to 5.0 parts by mass with respect to 100 parts by mass of the toner particles. In addition, the fatty acid metal salt of the present invention is preferably contained in a ratio of 0.02 parts by mass or more and 0.50 parts by mass or less with respect to 100 parts by mass of the toner base particles.

  Next, an example of the toner carrier in the present invention will be described. First, the shaft core used for the toner carrier in the present invention functions as a support member for the toner carrier. In addition, it is a preferable function that the surface of the toner carrying member can be an electrode for making the toner carrying member appropriately conductive so that the toner attached to the surface of the toner carrying member can be electrostatically developed with an electrostatic latent image. For example, a metal or alloy such as aluminum, copper alloy, stainless steel, or the like; iron that has been plated with chromium, nickel, or the like, or a conductive material such as a synthetic resin having conductivity is preferable.

It is preferable that such an elastic layer provided on the outer periphery of the shaft core body can also serve as an electrode for making the surface of the toner carrying member suitable conductivity. Examples of the material of the elastic layer that can be used include ethylene-propylene-diene copolymer rubber (EPDM), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), natural rubber (NR), isoprene rubber (IR ), Rubber materials such as styrene-butadiene rubber (SBR), fluorine rubber, silicone rubber, epichlorohydrin rubber, hydride of NBR, polysulfide rubber, urethane rubber, or a mixture of two or more of them. Can do. In particular, silicone rubber is preferably used because of its unique properties of low hardness and high resilience. In order to impart conductivity to these materials, for example, conductive carbon such as ketjen black EC and acetylene black, carbon for rubber such as SAF, ISAF, HAF, FEF, GPF, SRF, FT and MT, oxidation treatment, etc. The applied color (ink) carbon, copper, silver, germanium and other metals and metal oxides are blended. Among these, carbon black is preferable because the conductivity can be controlled with a small amount. These conductive powders are usually suitably used in the range of 0.5 to 50 parts by mass, particularly 1 to 30 parts by mass with respect to 100 parts by mass of the base material. Examples of ionic conductive materials used as conductive materials include inorganic ionic conductive materials such as sodium perchlorate, lithium perchlorate, calcium perchlorate and lithium chloride, and modified aliphatic dimethylammonium ethosulphate. An organic ionic conductive material such as stearyl ammonium acetate is used. At this time, a resistance region adjusted to 10 ^{3 to} 10 ¹⁰ Ωcm, preferably 10 ^{4 to} 10 ⁸ Ωcm is suitable.

  In addition, the rubber material used for the production of the elastic layer can appropriately contain various additives such as a non-conductive filler, a crosslinking agent, and a catalyst within a range not impairing these functions. For example, diatomaceous earth Non-conductive filler such as silica, quartz powder, titanium oxide, zinc oxide, aluminosilicate, calcium carbonate, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide Cross-linking agents such as oxy) hexane, dicumyl peroxide, and t-butylperoxybenzoate can be included.

  The thickness of the elastic layer is preferably in the range of 2.0 to 6.0 mm, and more preferably in the range of 3.0 to 5.0 mm.

  On the surface of the toner carrier, it is preferable to have a surface layer having a structure different from that of the elastic layer above the elastic layer. Further, the toner carrier surface layer preferably includes a conductive agent imparting conductivity and particles in the binder resin. Such a binder resin may contain any resin, but from the viewpoint of film strength, toner chargeability, etc., urethane resin, polyester resin, amino resin, polyether resin, and the like are preferable. One or more of them can be appropriately selected and used so that a toner charge amount corresponding to the developing system to be used can be obtained. Of these resins, urethane resins are particularly preferable. As such a urethane resin, a urethanized polyol obtained by extending a chain of a bifunctional polyether polyol and a bifunctional isocyanate component is preferable.

  Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. In addition, these polyol components may be prepolymers that are chain-extended with an isocyanate such as 2,4-tolylene diisocyanate (TDI), 1,4 diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) as necessary.

  Isocyanate compounds to be reacted with these polyol components are not particularly limited, but aliphatic polyisocyanates such as ethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclohexane 1,3 -Arocyclic polyisocyanates such as diisocyanate, cyclohexane 1,4-diisocyanate, aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and these A modified product, a copolymer, or a block body thereof can be used.

Moreover, the material example for providing moderate electroconductivity to this surface layer is the same as that of what is used with the said elastic layer. The resistance region is also preferably adjusted to 10 ^{3 to} 10 ¹⁰ Ωcm, preferably 10 ^{4 to} 10 ⁸ Ωcm.

  Various particles can be used in the toner carrier surface layer, but resin particles are particularly preferable because of having an appropriate elastic modulus. Examples include acrylic resin, urethane resin, silicon resin, amino resin, polyester resin, polyamide resin, polycarbonate resin, epoxy resin, phenol resin, and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples as long as the gist thereof is not exceeded.

  The physical properties relating to the fatty acid metal salt, toner and toner carrier in the present invention were measured using the following methods.

<Particle size and particle size distribution of fatty acid metal salt>
The volume-based median diameter (D50) of the fatty acid metal salt used in the present invention is measured according to JIS Z8825-2 (2001), and is specifically as follows.

  As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used. The dedicated software “HORIBA LA-920 for Windows (registered trademark) WET (LA-920) Ver. 2.02” attached to LA-920 is used for setting measurement conditions and analyzing measurement data. As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used.

The measurement procedure is as follows.
(1) A batch type cell holder is attached to LA-920.
(2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.
(3) The inside of the batch cell is stirred using a dedicated stirrer chip.
(4) Press the “refractive index” button on the “display condition setting” screen and select the file “110A000I” (relative refractive index 1.10).
(5) In the “display condition setting” screen, the particle diameter reference is set as the volume reference.
(6) After performing warm-up operation for 1 hour or more, the optical axis is adjusted, the optical axis is finely adjusted, and blank measurement is performed.
(7) Put about 60 ml of ion-exchanged water in a glass 100 ml flat bottom beaker. Among them, as a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting the product (manufactured) with ion exchange water about 3 times by mass is added.
(8) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(9) The beaker of (7) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the aqueous solution in a beaker may become the maximum.
(10) In a state where the aqueous solution in the beaker of (9) is irradiated with ultrasonic waves, about 1 mg of a fatty acid metal salt is added to the aqueous solution in the beaker little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In this case, the fatty acid metal salt may solidify and float on the liquid surface. In this case, ultrasonic dispersion is performed for 60 seconds after the mass is submerged by shaking the beaker. Moreover, in ultrasonic dispersion, it adjusts suitably so that the water temperature of a water tank may become 10 to 40 degreeC.
(11) The aqueous solution in which the fatty acid metal salt prepared in the above (10) is dispersed is immediately added little by little to a batch type cell, taking care not to enter bubbles, and the transmittance of the tungsten lamp is 90% to 95%. Adjust so that Then, the particle size distribution is measured. The volume-based median diameter (D50) is calculated based on the obtained volume-based particle size distribution data.

  For the obtained volume-based particle size distribution, the diameter corresponding to 5% integrated from the smaller side is Dv5, and the diameter corresponding to 95% is Dv95.

<Measurement of Toner Number Average Particle Size (D1) and Number-Based Variation Coefficient>
The number average particle diameter (D1) of the toner is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, dedicated software was set up as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and the Kd value is “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water is placed in a water tank of an ultrasonic disperser, and about 2 ml of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the number average particle diameter (D1) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / number% is set in the dedicated software is the number average particle diameter (D1).

  In addition, with respect to the obtained particle size distribution based on the number, the diameter corresponding to 5% by integrating from the smaller side is Dt5, and the diameter corresponding to 95% is Dt95.

<Measurement method of ratio of 2.0 μm or less in number average particle size distribution>
The ratio of 2.0 μm or less in the number average particle size distribution of the toner is measured using a flow type particle image measuring device “FPIA-2100” (manufactured by Sysmex Corporation). A specific measurement method is as follows.

  First, about 10 ml of ion-exchanged water from which impure solids and the like are previously removed is put in a glass container. As a dispersant, “Contaminone N” (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH 7 precision measuring instrument cleaning, made of organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.1 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. As an ultrasonic disperser, two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispensing System Tetora 150 type” with an electrical output of 120 W (manufactured by Nikkei Bios) Is used. A predetermined amount of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of the contamination N is added to the water tank. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. Further, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the in-machine temperature of the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. In addition, automatic focus adjustment is performed using standard latex particles of 2 μm at regular intervals, preferably every 2 hours (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) is diluted with ion-exchanged water. Do.

  In the measurement, the flow type particle image measuring apparatus was used, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, and the concentration of the dispersion is readjusted and measured so that the toner particle concentration at the time of measurement is about 5000 particles / μl. After the measurement, a ratio (number%) of equivalent circle diameter of 2.00 μm or less is obtained.

  “FPIA-2100”, which is a measuring apparatus used in the present invention, has a thinner sheath flow (7 μm → 4 μm) than “FPIA-1000” which has been used for observing the shape of a conventional toner. ) And the magnification of the processed particle image. In addition, the processing resolution of the captured image is improved (256 × 256 → 512 × 512), and the accuracy of toner shape measurement is improved.

<Measurement of ten-point average surface roughness (Rz) of toner carrier>
For measuring the ten-point average surface roughness Rz (according to Japanese Industrial Standard (JIS) B0601: 2001) of the toner carrier, a contact-type surface roughness meter (manufactured by Kosaka Laboratory Ltd .: Surfcorder-SE-3300) Was used. The measurement conditions were set such that the cutoff value was 0.8 mm, the measurement length was 2.5 mm, the feed speed was 0.1 mm / second, and the magnification was 5000 times. As the number of measurement points, the surface of the developing roller in the developing region was arbitrarily measured at 10 points, and the average value was obtained. The results of Rzjis for each roller are shown in Table 2.

<Measurement of film thickness of toner carrier surface layer>
First, the case where the toner carrier has an elastic layer and a surface layer will be described. Using a sharp razor blade, the toner carrier surface layer is cut out into a semi-cylindrical shape with a sharp razor blade from the central part of the toner carrier and 30 mm from the both ends of the toner carrier. Thickness measurement samples (1), (2) and (3) are obtained. This cut surface was observed with a video microscope (manufactured by Keyence Co., Ltd., magnification 2000 times), and in each of the obtained samples (1), (2), (3), the measurement position was changed and the surface layer film thickness at 5 points was changed. The average value of the measurement results of a total of 15 points is taken as the film thickness of the toner carrier surface layer. Here, when the surface layer includes particles, the measurement position of the surface layer thickness is a portion that does not include particles present in the surface layer, and specifically, the adjacent particles and the midpoint of the particles ± 2. This is a suitable point within 0 μm (see FIG. 2). Further, the surface film thickness is a distance between the surface layer surface and the elastic layer surface at a perpendicular of the elastic layer surface passing through the point.

  When the toner carrier is essentially a single layer except for the shaft core, the distance from the surface to the surface of the shaft core is the film thickness referred to here.

<Measurement of Volume Average Particle Diameter (Dvp) of Particles Contained in Toner Carrier Surface Layer>
Dvp can be measured directly from the toner carrier. First, the surface layer is cut from the toner carrier, the cut surface layer is torn and broken by an appropriate method, and the broken surface is observed with an optical magnification observation means such as a video microscope. The observation magnification is preferably 2000 times.

  From the observed fractured surface, only 1000 resin particles for which all the contour lines of the resin particles can be observed are selected. For each of the selected resin particles, an area equivalent diameter (diameter of a circle having an area equal to the projected area): Rn (μm, where n is an integer of 1 to 1000) is obtained.

In the present invention, the resin particles are approximated to be spherical, and the volume of each resin particle: Vn (μm ³ ) is calculated by Equation 3.

  Furthermore, Dvp is calculated based on the following formula 4 for Rn and Vn obtained above.

<Measurement of Elastic Modulus of Particles Contained in Surface Layer of Toner Carrier>
First, the toner carrier is left in an environment of 23 ° C./55% Rh for 24 hours or more. Then, using a Nano Indenter (trade name, manufactured by MTS) in a measurement environment of 23 ° C./55% Rh, according to the operation manual of the apparatus, with a DCM head and a Berkovich indenter (CSM mode), from a depth of 10 nm Measure to 100 nm. Using a sharp razor blade from the center of the toner carrier, the sample is cut into a kamaboko shape with the elastic layer to obtain a surface layer thickness measurement sample. From this cut surface, only the resin particles from which all the contour lines of the resin particles can be observed are selected. At the time of measurement, a value is picked up for every 10 nm depth per particle, and the average of a total of 10 measured values up to 100 nm is taken as the elastic modulus of the measured particle. This operation is performed for 100 arbitrary particles, and the average value of the 100 particles is taken as the elastic modulus of the particles in the present invention.

<Measurement of micro rubber hardness of toner carrier surface layer>
A micro rubber hardness meter MD-1 type A (manufactured by Kobunshi Keiki Co., Ltd.) is used. In the present invention, the measurement was carried out only for the toner carrying member having a surface layer. First, the toner carrier is left in an environment of 23 ° C./55% Rh for 24 hours or more. Thereafter, in a measurement environment of 23 ° C./55% Rh, measurement positions were measured at a total of 12 locations of 3 in the axial direction × 4 in the circumferential direction as shown below. The average value of these 12 points is taken as the micro rubber hardness of the toner carrier surface layer.

(Measurement position)
Axial direction: development roller axial direction center, and 3 points circumferential direction at positions of 30 mm inward from both ends in the axial direction: with respect to each of the three axial directions, in increments of 90 ° in the circumferential direction Next, used in the present invention An example of toner production will be described.

<Toner particle production example 1>
With respect to 100 parts by mass of the styrene monomer, C.I. I. 16.5 parts by mass of Pigment Blue 15: 3 and 2.0 parts by mass of an aluminum compound of 3,5-di-tert-butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Co., Ltd.)] were prepared. These were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.) and stirred at 200 rpm at 25 ° C. for 180 minutes using zirconia beads (140 parts by mass) with a radius of 1.25 mm to prepare a master batch dispersion 1. .

On the other hand, 450 parts by mass of 0.1 M Na ₃ PO ₄ aqueous solution was added to 710 parts by mass of ion-exchanged water and heated to 60 ° C., and then 68 parts by mass of 1.0 M CaCl ₂ aqueous solution was gradually added to the calcium phosphate compound. An aqueous medium containing was obtained.

Master batch dispersion 1 40 parts by mass Styrene monomer 30 parts by mass n-butyl acrylate monomer 18 parts by mass Low molecular weight polystyrene 20 parts by mass (Mw = 3,000, Mn = 1,050, Tg = 55 ° C)
Hydrocarbon wax 9 parts by mass (Fischer-Tropsch wax, maximum endothermic peak = 78 ° C., Mw = 750)
Polyester resin 5 parts by mass (terephthalic acid: isophthalic acid: propylene oxide modified bisphenol A (2 mol adduct): ethylene oxide modified bisphenol A (2 mol adduct) = 30: 30: 30: 10 polycondensate, acid No. 11, Tg = 74 ° C., Mw = 11,000, Mn = 4,000)
The above material was heated to 65 ° C., and uniformly dissolved and dispersed at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). In this, 7.0 parts by mass of a 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition is charged into the aqueous medium, and stirred at 10,000 rpm for 10 minutes with a TK homomixer in a N ₂ atmosphere at a temperature of 65 ° C. to prepare a polymerizable monomer composition. Grained. Thereafter, the temperature was raised to 67 ° C. while stirring with a paddle stirring blade. When the polymerization conversion rate of the polymerizable vinyl monomer reached 90%, a 0.1 mol / liter sodium hydroxide aqueous solution was added. The pH of the aqueous dispersion medium was adjusted to 9. Furthermore, it heated up at 80 degreeC with the temperature increase rate of 40 degreeC / h, and was made to react for 4 hours. After completion of the polymerization reaction, the residual monomer in the toner particles was distilled off under reduced pressure. After cooling the aqueous medium, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 6 hours to dissolve the calcium phosphate salt. The toner particles were separated by filtration, washed with water, and then dried at a temperature of 40 ° C. for 48 hours to obtain cyan toner particles (1). Table 1 shows the physical properties of the obtained toner particles.

<Toner particle production example 2>
Toner particles 2 were obtained in the same manner as toner particles 1 except that the granulation of the polymerizable monomer composition by the TK homomixer was changed to stirring at 10,000 rpm for 15 minutes. The physical properties of the obtained toner particles 2 are shown in Table 1.

<Toner particle production example 3>
Toner particles 3 were obtained in the same manner as toner particles 1 except that the granulation of the polymerizable monomer composition by the TK homomixer was changed to stirring at 10,000 rpm for 20 minutes. The physical properties of the obtained toner particles 3 are shown in Table 1.

<Toner particle production example 4>
In the production of the toner particles 1, the cooling slurry after the residual monomer of the toner particles was distilled off under reduced pressure was subjected to centrifugal separation at 8,000 rpm for 5 minutes to perform individual liquid separation. With respect to the obtained solid content, ion-exchange water was added so that solid content might be 30 mass%, and it slurried once again. Hydrochloric acid was added to the slurry to adjust the pH to 1.4, and the calcium phosphate salt was dissolved by stirring for 6 hours. The toner particles were separated by filtration and washed with water, and then dried at a temperature of 40 ° C. for 48 hours to obtain toner particles 4. The physical properties of the obtained toner particles 4 are shown in Table 1.

<Toner particle production example 5>
In the production of toner particles 1, the cooling slurry after the residual monomer of the toner particles was distilled off under reduced pressure was centrifuged at 10,000 rpm for 5 minutes to perform individual liquid separation. With respect to the obtained solid content, ion-exchange water was added so that solid content might be 30 mass%, and it slurried once again. Hydrochloric acid was added to the slurry to adjust the pH to 1.4, and the calcium phosphate salt was dissolved by stirring for 6 hours. The toner particles were separated by filtration and washed with water, and then dried at a temperature of 40 ° C. for 48 hours to obtain toner particles 5. The physical properties of the obtained toner particles 5 are shown in Table 1.

<Toner particle production example 6>
In the production of toner particles 1, the amount of ion-exchanged water is changed from 710 parts by weight to 780 parts by weight, the amount of 0.1M-Na ₃ PO ₄ aqueous solution is 400 parts by weight, and 1.0M-CaCl ₂ aqueous solution The same operation as that of the toner particles 1 was performed except that the input amount was 60 parts by mass. The physical properties of the obtained toner particles 6 are shown in Table 1.

<Toner particle production example 7>
In the production of toner particles 1, the amount of ion-exchanged water is changed from 580 parts by mass to 770 parts by mass, the amount of 0.1 M Na ₃ PO ₄ aqueous solution is changed to 570 parts by mass, and 1.0 M CaCl ₂ aqueous solution is added. The same operation as that of the toner particles 1 was performed except that the input amount was 86 parts by mass. The physical properties of the obtained toner particles 7 are shown in Table 1.

<Toner particle production example 8>
Toner particles 1 were cut into fine powder and coarse powder on both sides by air classification to adjust the particle size distribution. The physical properties of the obtained toner particles 8 are shown in Table 1.

<Toner particle production example 9>
The following materials were mixed in advance, melt-kneaded with a biaxial extruder, the cooled kneaded product was roughly pulverized with a hammer mill, and the resulting finely pulverized product was classified to obtain toner particles 9. Table 1 shows the physical properties of the toner particles 9.
Binder resin 100 parts by mass [styrene-n-butyl acrylate copolymer resin (Mw = 30,000, Tg = 62 ° C.)]
・ C. I. Pigment Blue 15:35 parts by mass, aluminum compound of di-tertiary butylsalicylic acid 3 parts by mass [Orient Chemical Industries, Ltd .: Bontron E88]
Ester wax 6.0 parts by mass (behenyl behenate: maximum endothermic peak = 72 ° C., Mw = 700)
Next, production examples of fatty acid metal salts used in the present invention will be described.

<Production Example 1 of fatty acid metal salt>
A receiving container with a stirrer was prepared, and the stirrer was rotated at 350 rpm. 500 mass parts of 0.5 mass% sodium stearate aqueous solution was thrown into this receiving container, and liquid temperature was adjusted to 85 degreeC. Next, 525 mass parts of 0.2 mass% zinc sulfate aqueous solution was dripped at this receptacle over 15 minutes. After the completion of charging the whole amount, the reaction was terminated by aging for 10 minutes at the temperature during the reaction.

Next, the fatty acid metal salt slurry thus obtained was washed by filtration. The obtained washed fatty acid metal salt cake was roughly crushed and then dried at 105 ° C. using a continuous instantaneous air dryer. Then, after pulverizing with a nano grinding mill [NJ-300] (manufactured by Sanrex) under conditions of an air volume of 6.0 m ³ / min and a processing speed of 80 kg / h, reslurry and fine particles using a wet centrifugal classifier After removal of the coarse particles, the fatty acid metal salt 1 was obtained by drying at 80 ° C. using a continuous instantaneous air flow dryer. Table 2 shows the physical properties of the fatty acid metal salt 1 obtained.

<Production Example 2 of fatty acid metal salt>
In the metal soap fine particle 1, except that 0.5% by mass sodium stearate aqueous solution is changed to 0.25% by mass sodium stearate aqueous solution and 0.2% by mass zinc sulfate aqueous solution is changed to 0.15% by mass zinc sulfate aqueous solution. Fatty acid metal salt 2 was obtained in the same manner as in Production Example 1 of fatty acid metal salt. Table 2 shows the physical properties of the fatty acid metal salt 2 obtained.

<Production Example 3 of fatty acid metal salt>
In Production Example 1 of a fatty acid metal salt, a 0.5 mass% sodium stearate aqueous solution was changed to a 0.25 mass% sodium stearate aqueous solution, a 0.2 mass% zinc sulfate aqueous solution was changed to a 0.15 mass% zinc sulfate aqueous solution, The pulverization condition was changed to an air volume of 9.5 m ³ / min, and the pulverization process was performed three times. Table 2 shows the physical properties of the fatty acid metal salt 3 obtained.

<Production Example 4 of fatty acid metal salt>
In Production Example 1 of fatty acid metal salt, 0.5% by mass sodium stearate aqueous solution was changed to 0.7% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.3% by mass zinc sulfate aqueous solution. did. The pulverization conditions were an air volume of 4.0 m ³ / min and a processing speed of 50 kg / h. Table 2 shows the physical properties of the fatty acid metal salt 4 obtained.

<Production Example 5 of fatty acid metal salt>
In Production Example 1 of fatty acid metal salt, 0.5% by mass sodium stearate aqueous solution was changed to 1.0% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.4% by mass zinc sulfate aqueous solution. did. Further, the reaction was terminated by aging for 15 minutes. The pulverization condition was an air volume of 4.0 m ³ / min. Table 2 shows the physical properties of the fatty acid metal salt 5 obtained.

<Production Example 6 of fatty acid metal salt>
In Production Example 1 of fatty acid metal salt, the 0.5 mass% sodium stearate aqueous solution was changed to 1.0 mass% sodium stearate, and the 0.2 mass% zinc sulfate aqueous solution was changed to 0.7 calcium chloride aqueous solution. The reaction was terminated by aging for 5 minutes. The pulverization conditions were changed to an air volume of 5.0 m ³ / min, and after pulverization, fine coarse powder was removed with an air classifier to obtain fatty acid metal salt 6. Table 2 shows the physical properties of the fatty acid metal salt 6 obtained.

<Production Example 7 of fatty acid metal salt>
In Production Example 1 of a fatty acid metal salt, the 0.2% by mass zinc sulfate aqueous solution was changed to a 0.3% by mass lithium chloride aqueous solution. Otherwise, the fatty acid metal salt 7 was obtained in the same manner as in Production Example 1 of fatty acid metal salt. Table 2 shows the physical properties of the fatty acid metal salt 7 obtained.

<Production Example 8 of fatty acid metal salt>
In Production Example 1 of the fatty acid metal salt, the 0.5 mass% sodium stearate aqueous solution was changed to 0.5 mass% sodium laurate. Otherwise, the fatty acid metal salt 8 was obtained in the same manner as in Production Example 1 of fatty acid metal salt. Table 2 shows the physical properties of the fatty acid metal salt 8 obtained.

<Production Example 9 of fatty acid metal salt>
In Production Example 1 of fatty acid metal salt, 0.5% by mass sodium stearate aqueous solution was changed to 1.0% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.4% by mass zinc sulfate aqueous solution. did. Moreover, the classification process after performing the grinding | pulverization process was not performed. Table 2 shows the physical properties of the fatty acid metal salt 9 obtained.

<Production Example 10 of fatty acid metal salt>
A commercially available zinc stearate (MZ2 manufactured by NOF Corporation) was used to adjust the particle size by air classification to obtain a fatty acid metal salt 10. Table 2 shows the physical properties of the fatty acid metal salt 10 obtained.

<Production Example 11 of fatty acid metal salt>
In Production Example 1 of the fatty acid metal salt, the 0.5 mass% sodium stearate aqueous solution was changed to 0.05 mass% sodium stearate, and the 0.2 mass% zinc sulfate aqueous solution was changed to 0.02 mass% zinc sulfate aqueous solution. changed. Further, the pulverization condition was set to an air volume of 10.0 m ³ / min, and the pulverization step was performed three times. Thereafter, coarse particles were removed by meshing, and the particle size was adjusted by air classification to obtain fatty acid metal salt 11. Table 2 shows the physical properties of the fatty acid metal salt 11 obtained.

<Production Example 12 of fatty acid metal salt>
The particle size of the fatty acid metal salt 1 was adjusted by air classification. Table 2 shows the physical properties of the fatty acid metal salt 12 obtained.

<Production Example 13 of fatty acid metal salt>
Fatty acid metal salt powder was obtained in the same manner as in Production Example 1 of fatty acid metal salt, except that the air volume during pulverization was 5.0 m ³ / min. Further, the particle size of the obtained powder was adjusted by air classification. Table 2 shows the physical properties of the fatty acid metal salt 13 obtained.

<Toner Production Examples 1 to 21>
A combination of 100 parts by mass of toner particles and 0.10 parts by mass of a fatty acid metal salt shown in Table 3 and 1.5 parts by mass of hydrophobic silica fine powder surface-treated with hexamethyldisilazane (number average primary particles) (Diameter: 10 nm) is added, and a mixing process is performed for 150 seconds with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) (mixing process 1). Thereafter, a pause process for 120 seconds is taken (pause process 1). Immediately after the pause process for 120 seconds, the mixing process is restarted, and the mixing process for 150 seconds is performed (mixing process 2). Thereafter, a pause process of 120 seconds is taken (pause process 2). Immediately after 120 seconds, mixing was resumed and mixing was continued for 150 seconds (mixing step 3). Thereafter, a pause process of 120 seconds is taken (pause process 3). After 120 seconds, mixing was resumed immediately and mixing was continued for 150 seconds (mixing step 4). By repeating the mixing step and the pause step as described above, the maximum reached temperature in the tank was less than about 35 ° C. for each toner production example.

<Production Example 1 of Toner Carrier>
(Formation of elastic layer)
As a shaft core, a SUS 8 mm core metal made of SUS was nickel-plated, and a primer DY35-051 (trade name, manufactured by Toray Dow Corning Silicone) was applied and baked. Next, the shaft core is arranged concentrically with a cylindrical mold having an inner diameter of 16 mm, and carbon black talker is used for 100 parts by mass of liquid silicone rubber material SE6724A / B (trade name, manufactured by Toray Dow Corning Silicone). An addition type silicone rubber composition in which 35 parts by mass of black # 7360SB (trade name, manufactured by Tokai Carbon Co., Ltd.), 0.2 parts by mass of silica powder as a heat resistance imparting agent, and 0.1 parts by mass of platinum catalyst are mixed. Injection into a cavity formed in the mold. Subsequently, the mold was heated to vulcanize and cure the silicone rubber at 150 ° C. for 15 minutes, demolded, and further heated at 200 ° C. for 2 hours to complete the curing reaction, and the elastic layer having a thickness of 4 mm was formed into the shaft core body. It was provided on the outer periphery.

(Polyol synthesis)
As a binder resin component of the toner carrier surface layer, 100 parts by mass of polytetramethylene glycol PTG1000SN (trade name, manufactured by Hodogaya Chemical Co., Ltd.) and 20 parts by mass of isocyanate compound Millionate MT (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) A polyether polyol having a hydroxyl value of 20 was prepared by mixing stepwise in a MEK solvent and reacting at 80 ° C. for 7 hours in a nitrogen atmosphere.

(Synthesis of isocyanate)
Under a nitrogen atmosphere, with respect to 100 parts by mass of polypropylene glycol having a number average molecular weight of 500, 57 parts by mass of crude MDI was heated at 90 ° C. for 2 hours, and then butyl cellosolve was added to a solid content of 70%. Of 5.0% was obtained. Thereafter, 22 parts by mass of MEK oxime was added dropwise under a reaction temperature of 50 ° C. to obtain block polyisocyanate A.

(Preparation of surface layer paint)
Block polyisocyanate A is mixed with the polyol produced as described above so that the NCO / OH group ratio is 1.4, and carbon black (trade name: MA100 is used with respect to 100 parts by mass of the binder resin solid content. (Mitsubishi Chemical Co., Ph = 3.5) 20 parts by mass are mixed, dissolved and mixed in MEK so that the total solid content ratio is 35% by mass, and glass beads having a particle diameter of 1.5 mm are used. Dispersion 1 was prepared by dispersing for 4 hours using a sand mill. Thereafter, 75 parts by mass of a spherical urethane resin particle Art Pearl C800 transparent (trade name, manufactured by Negami Kogyo Co., Ltd.) adjusted in particle size by wind classification in the same amount of MEK as the solid content of the binder resin component in the dispersion. A spherical urethane resin particle dispersion was obtained by adding and ultrasonically dispersing. The obtained spherical urethane resin particle dispersion was added to dispersion 1 and further dispersed for 30 minutes using a sand mill to obtain a coating material for the surface layer.

(Formation of surface layer on elastic layer)
The surface layer paint obtained as described above is dip coated on the elastic layer using an overflow dip coating apparatus, dried, and heat-treated at 150 ° C. for 2 hours. A toner carrier surface layer was provided on the elastic layer. Table 4 shows the physical properties of Toner Carrier 1 thus obtained.

<Toner carrier production example 2>
In the production process of the surface layer coating material in Production Example 1 of the toner carrier, the classification condition of the spherical urethane resin particle Art Pearl C800 transparent (trade name, manufactured by Negami Kogyo Co., Ltd.) to be used was changed, and 75 parts by mass of the particle was added. Changed to be. Table 4 shows the physical properties of the toner carrier 2 obtained.

<Production Example 3 of Toner Carrier>
In the preparation process of the surface layer coating material in Production Example 1 of the toner carrier, the spherical urethane resin particles used are changed to spherical urethane resin particle Art Pearl C400 transparent (trade name, manufactured by Negami Kogyo Co., Ltd.), and the particle size is determined by air classification. Adjusted. The added amount of the obtained particles is 75 parts by mass, as in Production Example 1 of the toner carrier. Table 4 shows the physical properties of the toner carrier 3 obtained.

<Toner carrier production example 4>
In the production process of the surface layer coating material in Production Example 1 of the toner carrier, the same procedure as in Production Example 1 of the toner carrier is performed except that the addition amount of the spherical urethane resin particles is changed to 45 parts by mass. Body 4 was obtained. Table 4 shows the physical properties of the toner carrier 4 thus obtained.

<Manufacturing Example 5 of Toner Carrier>
In the production process of the surface layer coating material in Production Example 1 of the toner carrier, the same procedure as in Production Example 1 of the toner carrier is performed except that the addition amount of the spherical urethane resin particles is changed to 90 parts by mass. Body 5 was obtained. Table 4 shows the physical properties of the toner carrier 5 thus obtained.

<Manufacturing Example 6 of Toner Carrier>
In the production process of the surface layer coating material in Production Example 1 of the toner carrier, the same procedure as in Production Example 1 of the toner carrier is performed except that the addition amount of the spherical urethane resin particles is changed to 25 parts by mass. Body 6 was obtained. Table 4 shows the physical properties of the toner carrier 6 thus obtained.

<Production Example 7 of Toner Carrier>
In the production process of the surface layer coating material in toner carrier production example 1, the same operation as in toner carrier production example 1 was carried out except that the amount of spherical urethane resin particles added was changed to 105 parts by mass. Body 7 was obtained. Table 4 shows the physical properties of the toner carrier 7 obtained.

<Manufacturing Example 8 of Toner Carrier>
In the production process of the surface layer coating material in Production Example 1 of the toner carrier, the classification condition of the spherical urethane resin particle Art Pearl C800 transparent (trade name, manufactured by Negami Kogyo Co., Ltd.) to be used was changed, and 75 parts by mass of the particle was added. did. Table 4 shows the physical properties of Toner Carrier 8 thus obtained.

<Production Example 9 of Toner Carrier>
In the preparation process of the surface layer coating material in Production Example 1 of the toner carrier, the spherical urethane resin particles used are changed to spherical urethane resin particle Art Pearl C400 transparent (trade name, manufactured by Negami Kogyo Co., Ltd.), and the particle size is determined by air classification. Adjusted. The added amount of the obtained particles is 75 parts by mass, as in Production Example 1 of the toner carrier. Table 4 shows the physical properties of the toner carrier 9 obtained.

<Manufacturing Example 10 of Toner Carrier>
In the production process of the surface layer coating material in Production Example 1 of the toner carrier, the spherical urethane resin particles to be used were changed to ethylene propylene rubber (trade name: Mitsui 3045ETP, manufactured by Mitsui Chemicals). The ethylene propylene rubber was pulverized by a freeze pulverization method using liquid nitrogen, and then the particle size of the ethylene propylene comb particles was adjusted by an air classifier. The amount of the ethylene propylene rubber particles added was 75 parts by mass, and a toner carrier 10 was obtained in the same manner as in Production Example 1 of the toner carrier. Table 4 shows the physical properties of Toner Carrier 10 thus obtained.

<Manufacturing Example 11 of Toner Carrier>
In the production process of the surface layer coating material in Production Example 1 of the toner carrier, the spherical urethane resin particles used were changed to spherical silicone rubber having a volume average particle size of 10.1 μm, and the addition amount was 75 parts by mass. Table 4 shows the physical properties of the toner carrier 11 obtained.

<Toner carrier production example 12>
In the production process of the coating material for the surface layer in Production Example 1 of the toner carrier, the spherical urethane resin particles to be used were changed to phenol resin particles obtained by classification operation of phenol resin (trade name: Universex C10, manufactured by Unitika). The amount added was 75 parts by mass. Table 4 shows the physical properties of the toner carrier 12 obtained.

<Manufacturing Example 13 of Toner Carrier>
In the production process of the surface layer coating material in Production Example 1 of the toner carrier, the spherical urethane resin particles used were adjusted in particle size by air classification of spherical silica particles (trade name: Pyrossphere C-1510, manufactured by Fuji Silysia). The amount added was changed to 75 parts by mass. Table 4 shows the physical properties of the toner carrier 13 obtained.

<Manufacturing Example 14 of Toner Carrier>
Conductive silicone rubber was affixed to the SUS surface of Φ11 mm so as to have a thickness of 1 mm. The Rz of the toner carrier 14 obtained after the polishing was 13.5 μm.

<Manufacturing Example 15 of Toner Carrier>
In Toner Carrier Production Example 14, the toner carrier 15 was obtained by changing the polishing conditions. Rz of the obtained toner carrier 15 was 3.0 μm.

<Manufacturing Example 16 of Toner Carrier>
In the production process of the surface layer coating material in Production Example 1 of the toner carrier, the classification condition of the spherical urethane resin particle Art Pearl C800 transparent (trade name, manufactured by Negami Kogyo Co., Ltd.) to be used was changed, and 75 parts by mass of the particle was added. did. Table 4 shows the physical properties of the obtained toner carrier 16.

<Manufacturing Example 17 of Toner Carrier>
In the preparation process of the surface layer coating material in Production Example 1 of the toner carrier, the spherical urethane resin particles used are changed to spherical urethane resin particle Art Pearl C400 transparent (trade name, manufactured by Negami Kogyo Co., Ltd.), and the particle size is determined by air classification. Adjusted. Moreover, the addition amount of the obtained particle | grains was changed into 65 mass parts. Table 4 shows the physical properties of the toner carrier 17 thus obtained.

<Image evaluation>
The image evaluation was performed by partially modifying a commercially available color laser printer HP Color LaserJet 4700dn (manufactured by HP). In the modification, the process speed was changed to 240 mm / sec. Furthermore, it has been improved so that it can operate even when only one color process cartridge is installed.

After removing the toner contained in the black cartridge for commercially available HP Color LaserJet 4700dn (manufactured by HP) and cleaning the inside by air blow, the test toner (315 g) and the test toner carrier are mounted on the cartridge. The developing property and durability of this cartridge were evaluated in both low temperature and low humidity environments (15 ° C., 10% RH) and high temperature and high humidity environments (32.5 ° C., 80% RH). The image evaluation items are as follows. At the time of durability, an image having a printing rate of 1% was printed. The image evaluation was performed at the end of printing 20,000 sheets and 40,000 sheets. During durability, LETTER size XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) was used.

(Image density stability)
All three solid images were printed in succession and evaluated by the difference in image density between the first and third sheets. The image density was measured using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth). As evaluation paper, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
A: Less than 0.03 B: 0.03 or more, less than 0.05 C: 0.05 or more, less than 0.10 D: 0.10 or more

[Fog]
The reflectance (%) of the non-image portion of the printout image is measured with “REFLECTOMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.). The obtained reflectance was evaluated using a numerical value (%) subtracted from the reflectance (%) of unused printout paper (standard paper) measured in the same manner. The smaller the numerical value, the more image fog is suppressed. As evaluation paper, LETTER size XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) was used.
A: Less than 0.5 B: 0.5 or more, less than 1.0 C: 1.0 or more, less than 3.0 D: 3.0 or more

[Development stripe]
A halftone image (toner loading: 0.6 mg / cm ² ) was printed out and evaluated by the number of development stripes. As evaluation paper, LETTER size XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) was used.
A: Not generated B: 1 or more, 3 or less C: 4 or more, 6 or less D: 7 or more, or a line having a width of 0.5 mm or more

[Filming]
The filming of the toner carrier was evaluated by visual observation and image of the surface of the toner carrier.

In the initial halftone image after printing 20,000 sheets and 40,000 sheets, it was visually evaluated whether or not unevenness in density occurred between the 1% printed image portion and the non-printed image portion. As evaluation paper, LETTER size XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) was used. Thereafter, the toner on the surface of the toner carrier was blown with air, and the surface of the toner carrier was observed.
A: There is no occurrence of uneven density on the image and the surface of the toner carrier is good. B: No unevenness of density is generated on the image, but some filming is confirmed on the surface of the toner carrier.
C: Mild shading unevenness on the image D: Slight shading unevenness on the image

<Examples 1 to 32>
Evaluation was carried out according to the above-mentioned image evaluation by the combination of the toner and the toner carrier shown in Table 5. In addition, the evaluation results are attached in Table 5.

<Example 33>
The toner contained therein was extracted from a commercially available black cartridge for HP Color LaserJet 4700dn (manufactured by HP), the interior was cleaned by air blow, and the toner (315 g) of Toner Production Example 1 was filled. Next, a non-foamed urethane resin-coated toner supply roller was mounted, and further a toner carrier 1 was mounted. Evaluation was performed according to the image evaluation. The evaluation results are shown in Table 5.

<Comparative Examples 1 to 5>
Evaluation was carried out according to the above-mentioned image evaluation by the combination of the toner and the toner carrier shown in Table 6. In addition, the evaluation results are attached in Table 6. None of these were outside the scope of the present invention, and various problems occurred under high-speed printing.

It is sectional drawing of a process cartridge. It is a schematic diagram of a toner carrier surface film thickness.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Latent image carrier 11 Charging roller 14 Toner carrier 15 Toner supply member 16 Toner regulating member 17 Toner 23 Toner container 25 Stirrer

Claims (22)

A charging process for charging the electrostatic latent image carrier with charging means, an exposure process for exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and supplying toner to the toner carrier with a toner supply member A step of regulating the toner on the toner carrier with the toner layer regulating member, a developing step of developing the electrostatic latent image carrier with the toner on the toner carrier, the toner image via the intermediate transfer member, or In an image forming method having a transfer step of transferring to a transfer material without intervention,
The toner carrier has a ten-point average surface roughness (Rz) of 4.0 μm or more and 20.0 μm or less,
The toner comprises at least toner particles and fatty acid metal salt fine particles having a volume-based median diameter (D50s) of 0.15 μm or more and 1.00 μm or less. The image forming method according to claim 1, wherein a span value B defined by the following formula (1) of the fatty acid metal salt is 1.75 or less.
Span value B = (D95s−D5s) / D50s (1) Formula D5s: 5% integrated diameter on the volume basis of fatty acid metal salt D50s: Median diameter on the volume basis of fatty acid metal salt D95s: 95% on the volume basis of fatty acid metal salt Integrated diameter 3. The image forming method according to claim 1, wherein a span value A defined by the following formula (2) of the toner and a span value B of the fatty acid metal salt satisfy the following formula (3): 3.
Span value A = (D90t−D10t) / D50t (2) Formula D10t: 10% integrated diameter based on number D50t: Median diameter based on number (D50)
D90t: 90% integrated diameter based on number 0.25 ≦ (A / B) ≦ 0.75 Equation (3)   4. The volume-based median diameter (D50s) of the fatty acid metal salt is 0.30 μm or more and 0.60 μm or less, and the B is 1.40 or less. 5. Image forming method.   The image forming method according to claim 1, wherein the fatty acid metal salt is zinc stearate or calcium stearate.   The toner carrier is a toner carrier having an elastic layer on the outer periphery of the shaft core and a surface layer containing at least a binder resin and particles on the outer periphery of the elastic layer, and the film thickness of the surface layer 6. The image forming method according to claim 1, wherein the image forming method is 5.0 μm or more and 20.0 μm or less.   The particles contained in the surface layer have a volume average particle diameter (Dvp) of 3.0 μm or more and 20.0 μm or less, and a ratio of 30 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin. The image forming method according to claim 6, wherein the image forming method is blended.   The image forming method according to claim 6 or 7, wherein the particles contained in the surface layer have an elastic modulus of 0.02 MPa to 3.60 MPa.   9. The image forming method according to claim 6, wherein the particles contained in the surface layer are resin particles having an elastic modulus of 0.10 MPa to 1.90 MPa.   10. The image forming method according to claim 6, wherein the toner bearing member has a micro rubber hardness of 30 degrees or more and 43 degrees or less.   The image forming method according to claim 1, wherein the toner supply member that supplies toner to the toner carrier has a surface layer of a foamed elastic body. A charging step of charging the electrostatic latent image carrier with charging means, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and supplying toner to the toner carrier by a toner supply member A step of regulating the toner on the toner carrier with the toner layer regulating member, a developing step of developing the electrostatic latent image carrier with the toner on the toner carrier, the toner image via the intermediate transfer member, or An image forming method having a transfer step of transferring to a transfer material without intervention, wherein the toner carrier has a ten-point average surface roughness (Rz) of 4.0 μm or more and 20.0 μm or less. In the toner to be used
The toner includes at least toner particles and fatty acid metal salt fine particles having a volume-based median diameter (D50s) of 0.15 μm or more and 1.00 μm or less. The toner according to claim 12, wherein a span value B defined by the following formula (1) of the fatty acid metal salt is 1.75 or less.
Span value B = (D95s−D5s) / D50s (1) Formula D5s: 5% integrated diameter on the volume basis of fatty acid metal salt D50s: Median diameter on the volume basis of fatty acid metal salt D95s: 95% on the volume basis of fatty acid metal salt Integrated diameter The toner according to claim 12 or 13, wherein a span value A defined by the following formula (2) of the toner and a span value B of the fatty acid metal salt satisfy the following formula (3).
Span value A = (D90t−D10t) / D50t (2) Formula D10t: 10% integrated diameter based on number D50t: Median diameter based on number (D50)
D90t: 90% integrated diameter based on number 0.25 ≦ (A / B) ≦ 0.75 Equation (3)   15. The volume-based median diameter (D50s) of the fatty acid metal salt is 0.30 μm or more and 0.60 μm or less, and the B is 1.40 or less, according to claim 12. toner.   The toner according to claim 12, wherein the fatty acid metal salt is zinc stearate or calcium stearate.   The toner carrier is a toner carrier having an elastic layer on the outer periphery of the shaft core and a surface layer containing at least a binder resin and resin particles on the outer periphery of the elastic layer, and the film of the surface layer The toner according to claim 12, wherein the toner has a thickness of 5.0 μm to 20.0 μm.   The particles contained in the surface layer have a volume average particle diameter (Dvp) of 3.0 μm or more and 20.0 μm or less, and a ratio of 30 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin. The toner according to claim 17, wherein the toner is blended.   The toner according to claim 17, wherein the particles contained in the surface layer have an elastic modulus of 0.02 MPa to 3.60 MPa.   The toner according to claim 17, wherein the particles contained in the surface layer are resin particles having an elastic modulus of 0.10 MPa to 1.90 MPa.   21. The toner according to claim 17, wherein the toner carrying member has a micro rubber hardness of 30 degrees or more and 43 degrees or less.   The toner according to claim 12, wherein the toner supply member that supplies toner to the toner carrier has a surface layer of a foamed elastic body.

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