JP2010060608A - Image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of forming an image superior in endurance, development stability and charging stability in both of low-temperature and low-humidity, and high-temperature and high-humidity environments over a long term. <P>SOLUTION: In the image forming method, a toner carrier comprises a shaft body and a resin layer disposed around the shaft body, wherein the resin layer contains polyether silicone compound, toner comprises: toner particles containing binder resin, colorant and wax; and fatty acid metal salt, an isolation rate of the fatty acid metal salt to the toner is in the range of 1.0% to 25.0% and, when number average particle size D1 of the toner particle is Dt (μm) and median diameter in a volume reference of the fatty acid metal salt is Ds (μm), the following relations are satisfied: 3.00≤Dt≤9.00, 0.10≤Ds≤1.0 and 0.02≤Ds/Dt≤0.25. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an image forming method used in a recording method such as electrophotography.

  In recent years, with the development of computers and multimedia, there is a demand for means for outputting high-definition images in a wide range of fields from offices to homes. In particular, users are strongly demanded to provide stable image quality independent of the environment. In order to achieve the above requirements, a developer and an image forming method have been studied from various viewpoints.

  For example, in a toner carrier (developing roller), in order to solve the problem of fogging and photoconductor adhesion, it is necessary to use a conductive member in which the outermost resin layer is made of a resin material containing a urethane resin and a polysiloxane component. It has been reported (see Patent Document 1). However, there are cases where it is very difficult to achieve both image characteristics in extreme environments such as a high temperature and high humidity environment and a low temperature and low humidity environment.

  Further, when the toner supply roller and the developing roller are kept in contact at the same position for a long time, streaky unevenness (banding) may occur. In order to solve this problem, a developing roller containing a non-reactive silicone compound having a polyether portion has been reported (see Patent Document 2). However, it has been found that there is room for improvement in the problem of toner filming on the developing roller, particularly when a large number of sheets are printed in a low temperature and low humidity environment.

  On the other hand, for toner, it is disclosed that toner particles are coated with a fatty acid metal salt to suppress the release rate, thereby improving the image stability while serving as an anti-filming agent for the electrostatic latent image carrier. (See Patent Document 3). However, in this case, it is necessary to coat the toner particles with a fatty acid metal salt, and it has been found that the coating process has a problem that the toner particles are mechanically damaged and development streaks are likely to occur. .

  In addition to the problems described above, in order to obtain stable developability even in printing on a large number of sheets, which is required by the market, image formation that sufficiently satisfies high durability, environmental stability, and charging stability A method is awaited.

JP 2003-167398 A JP 2008-96947 A JP 2007-108622 A

  The present invention has been made in view of the above circumstances, and an object thereof is to provide an image forming method capable of forming a high-quality image even during durability. That is, it is to provide an image forming method excellent in durability, development stability, and charging stability in both low temperature and low humidity and high temperature and high humidity environments for a long period of time.

  As a result of intensive studies on the above problems, the present inventors have found that the above requirements are satisfied by using the following image forming method, and have come to invent the invention.

That is, 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 a toner layer regulating member on the toner carrier. In an image forming method including a step of regulating toner and a development step of developing the electrostatic latent image carrier with toner on the toner carrier,
The toner carrier has a shaft body and a resin layer provided on the outer periphery of the shaft body, and the resin layer contains a polyether silicone compound,
The toner has toner particles containing at least a binder resin, a colorant, and a wax, and a fatty acid metal salt, and the liberation ratio of the fatty acid metal salt to the toner is 1.0% or more and 25.0% or less. Yes,
The present invention relates to an image forming method characterized by satisfying the following relationship, wherein the number average particle diameter (D1) of the toner particles is Dt (μm) and the median diameter of the fatty acid metal salt is Ds (μm). Is.
3.00 ≦ Dt ≦ 9.00
0.10 ≦ Ds ≦ 1.00
0.02 ≦ Ds / Dt ≦ 0.25

  According to the present invention, it is possible to provide a high-quality and highly stable image forming method that does not depend on the environment even in long-term printing. In other words, even during long-term printing in a low-temperature and low-humidity environment, the toner filming on the toner carrier is suppressed, and even in both high-temperature and high-humidity environments, fogging is suppressed over long-term printing, resulting in stable image density. It is possible to provide an excellent image forming method.

  As a result of intensive studies on the resin layer of the toner carrier (developing roller), the particle diameters of the toner and the fatty acid metal salt, and the liberated amount of the fatty acid metal salt in the toner, the present inventors have solved the above-mentioned problems. The present inventors have found that a forming method can be obtained and have completed the present invention. The present invention is described in further detail below.

  An example of a cross-sectional structure of a toner carrier (developing roller) according to the present invention is shown in FIG. The developing roller 100 shown in FIG. 1 has a resin layer 2 on the outer periphery of a highly conductive shaft 1 (shaft 1), and the resin layer 2 contains a silicone compound having a polyether portion. .

  Since the polyether silicone compound according to the present invention has a polyether portion, the influence of exudates from the toner supply roller can be suppressed, and deterioration of banding can be suppressed. Further, it is possible to control the friction charging performance with respect to the toner and the influence of water on the surface of the developing roller.

  The form of copolymerization of the silicone part and the polyether part of the silicone compound may be any of a linear block polymer type, a branched block polymer type, and a graft polymer type of a silicone part and a polyether part. Preferably, it is a silicone compound represented by the following general formulas (A) to (D).

（式中、ｍ及びｎはそれぞれ正の整数を示す。）

(In the formula, m and n each represent a positive integer.)

  Further, the weight average molecular weight (Mw) of the polyether silicone compound is preferably in the range of 3,000 ≦ Mw ≦ 20,000. When the weight average molecular weight (Mw) is in the range of 3,000 ≦ Mw ≦ 20,000, the polyether silicone compound is more likely to be present on the surface of the developing roller.

  The polyether silicone compound is preferably added in an amount of 0.2 to 20.0 parts by mass with respect to 100 parts by mass of the resin (base material) forming the outermost surface layer. This makes it possible to control the proper frictional charging ability, the surface interface state of the developing roller, and the influence of water. A more preferable addition amount is 0.5 to 10.0 parts by mass.

  For the molecular structure of the polyether silicone compound and the structure of the silicone part and the polyether part, the polyether silicone compound is isolated from the surface layer by appropriate means, and methods such as pyrolysis GC / MS, NMR, IR, and elemental analysis are used. Can be identified. Further, the confirmation of the addition amount is judged based on the quantitative ratio when extracting from the surface layer.

  As the shaft having a good conductivity, any shaft can be used as long as it has good conductivity. Usually, a metal cylinder having an outer diameter of 4 to 10 mm formed of a material such as aluminum, iron, or SUS is used.

  Examples of the base material of the resin layer 2 formed on the outer periphery of the highly conductive shaft 1 include the following. Polyamide resin, urethane resin, urea resin, imide resin, melamine resin, fluorine resin, phenol resin, alkyd resin, polyester resin, polyether resin, acrylic resin, natural rubber, butyl rubber, acrylonitrile-butadiene rubber, polyisoprene rubber, polybutadiene rubber Silicone rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, chloroprene rubber, and mixtures thereof.

  Urethane resin is preferably used as a base material for the resin layer 2 because it has a large ability to charge the developer by friction and has wear resistance. Specifically, the raw material of the urethane resin is composed of a polyol and an isocyanate, and if necessary, a chain extender. The following are mentioned as a polyol which is a raw material of a urethane resin. Polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, and mixtures thereof. The following are mentioned as isocyanate which is a raw material of a urethane resin. Tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), phenylene diisocyanate (PPDI), xylylene diisocyanate (XDI) , Tetramethylxylylene diisocyanate (TMXDI), cyclohexane diisocyanate, and mixtures thereof. Examples of the chain extender that is a raw material of the urethane resin include the following. Bifunctional low molecular diols such as ethylene glycol, 1,4-butanediol, 3-methylpentanediol; trifunctional low molecular triols such as trimethylolpropane, and mixtures thereof.

  In particular, it is preferable to use a polyether polyurethane resin using a polyether polyol among urethane resins. In this case, the polyether silicone compound oozes out due to the affinity between the resin material and the polyether portion of the polyether silicone compound, and it is difficult to move to another member.

In the resin layer 2, a conductivity-imparting agent such as an electron conductive material or an ionic conductive material is blended with the base material, and an appropriate resistance region (volume resistivity) is preferably 10 ^{3 to} 10 ¹¹ Ω · cm. More preferably, it is formed of a material adjusted to 10 ^{4 to} 10 ¹⁰ Ω · cm. The thickness of the resin layer 2 can be preferably in the range of 0.3 to 10.0 mm. More preferably, it can be used in the range of 1.0 to 5.0 mm.

  Examples of the electronic conductive material used for imparting conductivity to the urethane resin layer 2 include the following. Conductive carbon such as ketjen black EC, acetylene black; carbon for rubber such as SAF, ISAF, HAF, FEF, GPF, SRF, FT, MT; carbon for color (ink) subjected to oxidation treatment; copper, silver, Metals such as germanium and metal oxides.

  Among these, carbon black [conductive carbon, carbon for rubber, carbon for color (ink)] is preferable because the conductivity can be easily controlled with a small amount.

  Examples of the ion conductive material used for imparting conductivity to the resin layer 2 include the following. Inorganic ionic conductive materials such as sodium perchlorate, lithium perchlorate, calcium perchlorate and lithium chloride; organic ionic conductive materials such as modified aliphatic dimethylammonium ethosulphate and stearylammonium acetate.

  These conductivity-imparting agents are used in an amount necessary for making the resin layer have an appropriate volume resistivity as described above, but usually in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the base material. Used.

  FIG. 2 is a schematic sectional view showing another embodiment of the developing roller according to the present invention. The developing roller 200 shown in FIG. 2 includes a shaft body 1, a resin layer 201 that covers the periphery of the shaft body 1, and a resin layer 202 that covers the periphery of the resin layer 201 and forms a surface layer. Yes.

  The resin layer 202 corresponds to the resin layer 2 of the developing roller 100. Therefore, for the details of the resin layer 202, the description about the resin layer 2 is used.

  Next, the resin layer 201 forming the lower layer preferably has a high elasticity among the resins in order to ensure a nip width with a stable drum and to continue to output a uniform image and a stable image for a long time, The following are suitable. Natural rubber, butyl rubber, acrylonitrile-butadiene rubber, polyisoprene rubber, polybutadiene rubber, silicone rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, chloroprene rubber, and mixtures thereof. Among these, silicone rubber and ethylene-propylene-diene rubber are particularly preferable.

The resin layer 201 is preferably adjusted to a suitable resistance region (volume resistivity) by containing a conductive substance. The preferable volume resistivity is 10 ^{3 to} 10 ¹⁰ Ω · cm, particularly 10 ^{4 to} 10 ⁸ Ω · cm.

  As said electroconductive substance, the thing similar to the electroconductive substance which can be added to the said resin layer 2 is mentioned. Further, the amount of addition is the same as in the case of the resin layer 2.

  Further, the hardness of the resin layer 201 is preferably 25 to 70 degrees, preferably 35 to 50 degrees in terms of ASKER-C hardness.

  Furthermore, the thickness of the resin layer 201 is usually in the range of 0.3 to 10.0 mm, particularly 1.0 to 5.0 mm. The thickness of the resin layer 202 is preferably 0.5 to 100.0 μm so as not to impair the elasticity of the lower resin layer.

  The thickness of the resin layer was determined by cutting the developing roller on which the resin layer was formed, measuring the cross section with nine calipers, and measuring the average value. When the thickness was thin (1.0 mm or less), the cross section was measured with a video microscope (magnification 5 to 3000 times) at nine points, and the average value was taken.

  The developing roller according to the present invention can be produced as follows.

  The developing roller shown in FIG. 1 is added when forming the resin (base material), the conductivity imparting agent, and at least the outermost surface layer in a cavity of a molding die in which a shaft body is previously arranged. It can be prepared by injecting a composition in which the polyether silicone compound is kneaded. In addition, from a slab or block separately formed using the above composition in advance, by cutting, it is cut into a tube-shaped predetermined shape and dimensions, and a shaft body is press-fitted into this to form a resin that becomes the outermost layer on the shaft body A developing roller can be produced by forming a layer. If desired, the outer diameter may be further adjusted to a predetermined outer diameter by cutting or polishing treatment.

  Further, in the developing roller shown in FIG. 2, the resin layer 202 is applied to the outer peripheral surface of the resin layer 201 formed in advance on the outer periphery of the shaft body by a spraying or dipping method, followed by heat curing. Can be produced.

The resin layer 201 can be formed by the following method 1) or 2).
1) A method comprising a step of injecting a composition for forming the resin layer into a cavity of a molding die in which a shaft is previously disposed and heat-curing it;
2) A step of forming a slab or a block using a composition for forming a resin layer in advance, and a cutting process from the slab or block into a predetermined shape and size of a tube, and a shaft body is cut into this And press-fitting.

  In either case of the above methods 1) and 2), after the resin layer 201 is formed around the shaft body, it may be further adjusted to a predetermined outer diameter by cutting or polishing treatment as necessary. Good.

  The resin layer 202 is kneaded with the above-described resin (base material), a conductivity-imparting agent, and at least the polyether silicone compound added when forming the outermost surface layer. For kneading, use a machine such as a ball mill to add and disperse the rough particles for adjusting the surface roughness of the developing roller as needed, and then add the time-hardening agent or curing catalyst and stir. Can be performed. There is a method of applying the obtained composition by a coating method such as spraying or dipping. Examples of the coarse particles to be added include the following. EPDM, NBR, SBR, CR, rubber particles such as silicone rubber; particles of elastomer such as polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide-based thermoplastic elastomer (TPE); PMMA, urethane resin, fluororesin, Resin particles such as silicone resin, phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, polyacrylonitrile resin. These particles can be used alone or in combination. At this time, the surface roughness Rz of the developing roller is generally adjusted to 1 to 15 μm. The surface roughness of the developing roller is Rz according to JIS B0601: 2001.

  Next, the toner according to the present invention will be described.

The toner used in the image forming method of the present invention has toner particles containing at least a binder resin, a colorant and a wax, and a fatty acid metal salt, and the liberation ratio of the fatty acid metal salt to the toner is 1.0. % To 25.0%, the number average particle diameter (D1) of the toner particles is Dt (μm), and the median diameter on the volume basis of the fatty acid metal salt is Ds (μm).
3.00 ≦ Dt ≦ 9.00
(More preferably 3.00 ≦ Dt ≦ 8.00)
0.10 ≦ Ds ≦ 1.00
(More preferably 0.15 ≦ Ds ≦ 0.75)
(More preferably 0.15 ≦ Ds ≦ 0.65)
0.02 ≦ Ds / Dt ≦ 0.25
(More preferably 0.03 ≦ Ds / Dt ≦ 0.20)
(More preferably 0.03 ≦ Ds / Dt ≦ 0.15)
It is characterized by satisfying the relationship.

  The fatty acid metal salt used in the present invention has a smaller particle size than the conventional one. It has been found that by using such a fatty acid metal salt, filming on the toner carrier can be suppressed and a high-quality image can be obtained over a long period of time. In particular, in the case of the developing roller according to the present invention, since the fatty acid metal salt used in the present invention has a small adhesion to the polyether portion on the surface of the developing roller, the effect of suppressing filming is further obtained.

  In the present invention, the liberation rate of the fatty acid metal salt to the toner needs to be 1.0% or more and 25.0% or less. When the liberation rate is in the range of 1.0% to 25.0%, a certain amount of the fatty acid metal salt is present on the surface of the toner particles even after printing a large number of sheets. Due to this effect, toner filming on the developing roller can be suppressed. If the liberation rate is less than 1.0%, it means that the fatty acid metal salt is embedded in the toner particles. In such a case, it is difficult to obtain the effect of the fatty acid metal salt as a lubricant, and image defects due to filming on the developing roller are likely to occur. On the contrary, when the liberation rate exceeds 25.0%, when printing a large number of sheets, the fatty acid metal salt is excessively liberated from the toner, and the effect as a lubricant is diminished. Filming will occur. A more preferable range of the liberation rate is 2.0% or more and 20.0% or less.

  Further, when the number average particle diameter (D1) of the toner particles is Dt (μm) and the median diameter on the volume basis of the fatty acid metal salt is Ds (μm), 3.00 ≦ Dt ≦ 9.00, 0.10 It is necessary to satisfy the relationship of ≦ Ds ≦ 1.00 and 0.02 ≦ Ds / Dt ≦ 0.25. When the number average particle diameter of the toner particles is in the range of 3.00 μm or more and 9.00 μm or less, finer latent image dots can be faithfully developed, which is advantageous for high image quality. If it is less than 3.00 μm, the transferability of the toner is deteriorated, so that the density stability of the image is lowered. On the other hand, if it exceeds 9.00 μm, toner having a large particle diameter that is difficult to develop in the second half of the durability tends to remain, and the image density decreases. A more preferable range of the number average particle diameter of the toner particles is 4.00 μm or more and 8.00 μm or less.

  When the median diameter on the volume basis of the fatty acid metal salt is in the range of 0.10 μm or more and 1.00 μm or less, the effect as a lubricant is easily obtained. In the case of less than 0.10 μm, the particle size of the fatty acid metal salt is too small, so that it is difficult to obtain an effect as a lubricant. On the other hand, when it exceeds 1.00 μm, the fatty acid metal salt tends to be biased to the surface of the toner particles, so that it is difficult to obtain an effect as a lubricant. A more preferable range of the median diameter on the volume basis of the fatty acid metal salt is 0.15 μm or more and 0.75 μm or less, and a more preferable range is 0.15 μm or more and 0.65 μm or less.

  When the number average particle diameter of the toner particles is Dt (μm) and the median diameter of the fatty acid metal salt is Ds (μm) satisfying 0.02 ≦ Ds / Dt ≦ 0.25, the particles of the fatty acid metal salt It shows that the diameter has a certain ratio to the particle diameter of the toner. That is, when the toner is carried on the developing roller, the toner particle surface and the developing roller surface have a certain distance. Thereby, the interaction between the polyether portion of the polyether silicone compound on the surface of the developing roller and the toner particles becomes appropriate. When Ds / Dt is less than 0.02, the distance between the developing roller surface and the toner particle surface is too short with respect to the toner particle diameter, so that the interaction between the polyether portion and the toner particles becomes too strong. As a result, the toner easily adheres to the developing roller, and filming to the developing roller is likely to occur. On the contrary, when Ds / Dt exceeds 0.25, the fatty acid metal salt tends to be liberated from the surface of the toner particles from the viewpoint of curvature with respect to stress during printing. For this reason, filming on the toner carrier occurs. A more preferable range of Ds / Dt is 0.03 or more and 0.20 or less, and a more preferable range is 0.03 or more and 0.15 or less.

  In the fatty acid metal salt used in the present invention, the metal species is preferably zinc or calcium. In the case of zinc or calcium, charging stability in a low-temperature and low-humidity environment is improved, and fogging can be suppressed. Further, stearic acid is preferable as the fatty acid, and it is easy to suppress the generation of free fatty acid. When there are many free fatty acids, it will become easy to generate | occur | produce the fog in a high temperature, high humidity environment.

  The fatty acid metal salt preferably has a span value A of 1.75 or less, which is an index of particle size distribution.

Formula (1) Span value A = (D95s-D5s) / Ds
Ds: median diameter of fatty acid metal salt based on volume D5s: 5% integrated diameter based on volume of fatty acid metal salt D95s: 95% integrated diameter based on volume of fatty acid metal salt

  When the span value A exceeds 1.75, the charging becomes unstable due to variations in the particle diameter of the fatty acid metal salt present in the toner, and fogging in the latter half of the durability tends to occur. The span value A is more preferably 1.50 or less.

  The addition amount of the fatty acid metal salt is preferably 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 particles. More preferably, they are 0.05 mass part or more and 0.30 mass part or less. When the amount is less than 0.02 parts by mass, development streaks are likely to occur in a low temperature and low humidity environment, and when the amount is more than 0.50 parts by mass, development streaks are likely to occur in a high temperature and high humidity environment.

  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 that it is manufactured by. In the case of toner particles produced by a general pulverization method, it is very difficult to add a large amount of the wax component to the toner particles. In the production method of granulating toner particles in an aqueous medium, even if a large amount of wax component is added to the toner particles, the wax component does not exist on the surface of the toner particles and can be encapsulated. Therefore, in the fixing process, it is possible to prevent the toner from being offset to the fixing member and contaminating the heating source as much as possible. As a result, a stable and high-definition image can be obtained over a long period of time. Among these production methods, the suspension polymerization method is optimal because the wax component is encapsulated in toner particles to form a capsule structure, and is suitable for dramatically improving developability and durability. In the present invention, the average circularity of the toner particles is preferably 0.960 or more and 0.990 or less, and a suitable circularity can be easily obtained by the suspension polymerization method. When the average circularity is less than 0.960, a large amount of the added fatty acid metal salt is present in the concave portion of the toner surface, the charge distribution in the particles is deteriorated, and fog is likely to occur. Further, when the average circularity is larger than 0.990, the cleaning property is inferior.

  Hereinafter, a method for producing toner particles will be described by exemplifying a suspension polymerization method suitable for obtaining toner particles used in the present invention. Binder resin, colorant, wax and other additives as required are uniformly dissolved or dispersed by a disperser such as a homogenizer, ball mill, colloid mill, or ultrasonic disperser. Dissolve to prepare a polymerizable monomer composition. Next, toner particles are manufactured 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 used in the present invention 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.

  In order to satisfy the high glossiness of the image, a low molecular weight polymer may be added when the toner particles are produced. 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 Is preferably less than 3.0.

  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.

  A preferable addition amount of the low molecular weight polymer is 1 part by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or the binder resin.

  Examples of the wax that can be used in the toner of the present invention include the following. Paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof according to Fischer-Tropsch method, polyolefin wax and derivatives thereof such as polyethylene and polypropylene, carnauba wax, candelilla Natural waxes such as waxes and derivatives thereof (the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products), ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, Animal wax, silicone wax. These waxes may be used alone or in combination of two or more.

  Among these, when the hydrocarbon wax or the paraffin wax by the Fischer-Tropsch method is used, it is possible to maintain good developability over a long period of time and to maintain good offset resistance to the fixing member. These waxes may contain an antioxidant within a range that does not affect the chargeability of the toner.

  The content of the wax used in the present invention is preferably 2.0 parts by mass or more and 17.0 parts by mass or less, more preferably 5.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer or the binder resin. It is not less than 16.0 parts by mass. If the wax content is less than 2.0 parts by mass, even if a fixing member having good releasability is used, the releasability effect at the time of fixing cannot be sufficiently exerted, and a part of the toner becomes a fixing member. There may be an offset. On the other hand, if it is larger than 17.0 parts by mass, the wax tends to be unevenly distributed on the surface of the toner particles when subjected to mechanical stress such as excessive friction in the developing device, and this tends to cause problems such as fogging and fusing.

  Further, the wax preferably has a maximum endothermic peak temperature of 60 ° C. or higher and 120 ° C. or lower, more preferably 62 ° C. or higher and 110 ° C. or lower, in a DSC curve measured with a differential scanning calorimetry (DSC) apparatus. Preferably it is 65 to 90 degreeC. When the maximum endothermic peak temperature is less than 60 ° C., the storage stability of the toner and the developability such as fogging are lowered. On the other hand, when the maximum endothermic peak temperature exceeds 120 ° C., the plastic effect imparted to the toner is small, and a part of the toner tends to be offset to the fixing member during fixing.

  In the present invention, a polar resin having a carboxyl group such as a polyester resin or a polycarbonate resin can be used in combination with the above-described binder resin.

  For example, when producing toner particles by a suspension polymerization method, if a polar resin is added from the dispersion step to the polymerization step, the polar resin forms a thin layer on the surface of the toner particles, or from the toner particle surface. The existence state can be controlled, for example, having a tilt toward the center. That is, adding a polar resin can reinforce the shell portion of the core-shell structure.

  A preferable addition amount of the polar resin is 1.0 part by mass or more and 30.0 parts by mass or less, more preferably 1.5 parts by mass or more and 20.20 parts by mass with respect to 100 parts by mass of the polymerizable monomer or the binder resin. 0 parts by mass or less. If the amount is less than 1.0 part by mass, the presence state of the polar resin in the toner particles tends to be non-uniform. On the other hand, if the amount exceeds 20.0 parts by mass, the shell formed on the surface of the toner particles becomes thick. .

  Examples of the polar resin used in the present invention include polyester resins, epoxy resins, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-maleic acid copolymers. In particular, as a polar resin, a polyester resin having a molecular weight of 3,000 to 10,000 and having a main peak molecular weight is preferable because the fluidity and negative triboelectric charging characteristics of toner particles can be improved.

  In the present invention, in order to increase the stress resistance of the toner particles, 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 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

  In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. 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.

  The toner of the present invention can contain these charge control agents alone or in combination of two or more.

  A preferable blending amount of the charge control agent is 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or the binder resin. . However, it is not essential to add a charge control agent to the toner of the present invention, and it is not always necessary to include the charge control agent in the toner by actively utilizing frictional charging with the toner regulating member or the toner carrier. Absent.

  The following are mentioned as a polymerization initiator used for the toner of the present invention. 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.

  Although the usage-amount of these polymerization initiators changes with the target degree of polymerization, generally it is 3 to 20 mass parts with respect to 100 mass parts of polymerizable monomers. 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. Specifically, the following are mentioned. 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. Specifically, the following are mentioned. 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. Specifically, the following are mentioned. 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 a solid solution state. 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.

  In the present invention, when toner particles are obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and water phase migration property of the colorant, and preferably a hydrophobic treatment with a substance that does not inhibit polymerization is performed. It is better to apply it to the colorant. In particular, since dye-based colorants and carbon black have many polymerization inhibiting properties, care must be taken when using them.

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

  In the present invention, as the dispersion stabilizer used at the time of 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.

  In the present invention, the dispersion stabilizer used in preparing the aqueous medium is preferably an inorganic poorly water-soluble dispersion stabilizer, and more preferably, a poorly water-soluble inorganic dispersion stabilizer that is soluble in an acid.

  In the present invention, when preparing an aqueous medium using a hardly water-soluble inorganic dispersion stabilizer, the amount of these dispersion stabilizers used is 0.2 mass relative to 100 parts by mass of the polymerizable monomer. It is preferable that it is at least 2.0 parts by mass. Moreover, in this invention, it is preferable to prepare an aqueous medium using 300 to 3000 mass parts of water with respect to 100 mass parts of polymerizable monomer compositions.

  In the present invention, when preparing an aqueous medium in which the above 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 of the present invention, it is essential to contain a fatty acid metal salt having a median diameter (D50) of 0.10 μm or more and 1.00 μm or less on a volume basis, and further, an inorganic fine powder as a fluidity improver. May be added.

  Examples of the inorganic fine powder externally added to the toner particles of the present invention include fine powder such as silica fine powder, titanium oxide fine powder, alumina 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 external additives other than inorganic fine powders include various resin particles and fatty acid metal salts. These are preferably used alone or in combination.

Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, wet silica produced from water glass, and sol-gel silica produced by a sol-gel method. 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 produced by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process.

  In addition, the hydrophobic treatment of the inorganic fine powder makes it possible to adjust the charge amount of the toner, improve the environmental stability, and improve the characteristics in a high-humidity environment. The body may be used.

  As treatment agents for the hydrophobic treatment of inorganic fine powder, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, organotitanium Compounds. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the hydrophobicity-treated inorganic fine powder treated with silicone oil treated with silicone oil simultaneously or after the hydrophobic treatment of the inorganic fine powder with a coupling agent increases the charge amount of the toner particles even in a high humidity environment. It is good for maintaining high and reducing selective developability.

  The addition amount of the inorganic fine powder is preferably 1.0 part by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

  The physical properties of the fatty acid metal salt and toner in the present invention were measured using the following method.

<Measurement of median diameter (D50) and span value A 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 longer, 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 that 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 introduce bubbles, and the transmittance of the tungsten lamp is 90 to 95%. Adjust so that Then, the particle size distribution is measured. Based on the obtained volume-based particle size distribution data, a median diameter (D50), a 5% integrated diameter and a 95% integrated diameter are calculated to obtain a span value A.

<Rate of fatty acid metal salt>
The liberation rate of the fatty acid metal salt in the toner according to the present invention is determined using a powder tester (manufactured by Hosokawa Micron Corporation) having a digital vibrometer (Digivibro Model 1332), an X-ray fluorescence analyzer Axios (manufactured by PANallytical), measurement condition setting, and Using the attached dedicated software “SuperQ ver. 4.0F” (manufactured by PANalytical) for analyzing the measurement data, the liberation rate of the fatty acid metal salt was determined from the intensity difference of the fluorescent X-rays.

  As a specific measuring method, a sieve having a mesh size of 25 μm (635 mesh) is set on a vibrating table of a powder tester. 5 g of a sample accurately weighed is added to the sieve having a mesh size of 25 μm (635 mesh), the amplitude of the digital vibrometer is adjusted to about 0.60 mm, and vibration is applied for about 2 minutes. The above operation is further repeated twice, and the sample is passed through a 25 μm (635 mesh) sieve three times in total. Next, about 4 g of the obtained sample is placed on an aluminum ring having a diameter of 40 mm, and compressed by a press machine at 150 kN to prepare a sample. The obtained sample was measured with a fluorescent X-ray analyzer (Axios). Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).

The liberation rate of the fatty acid metal salt was determined from the following formula by measuring the Kα ray net intensity (KCPS) of the metal element of the fatty acid metal salt before and after the sieve.
{(Kα ray net intensity of metal element of fatty acid metal salt in toner before sieve) − (Kα ray net intensity of metal element of fatty acid metal salt in toner passed through sieve)} / (Fatty acid metal salt in toner before sieve) (Kα line net intensity of metallic elements)

<Method for Measuring Number Average Particle Size (D1) of Toner Particles>
The number average particle diameter (D1) of the toner particles 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. 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, the dedicated software was set 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 solution is placed 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 rpm. 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. 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.
(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 particles are 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 (1) installed in the sample stand, the electrolyte solution (5) in which the toner particles are dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. 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 / number statistical value (arithmetic average)” screen when the graph / number% is set in the dedicated software is the number average particle diameter (D1).

<Measuring method of average circularity of toner particles>
The average circularity of the toner particles is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation. The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is subjected to image processing at an image processing resolution of 512 × 512 (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted, The projected area S, the peripheral length L, and the like are measured.

  Next, the equivalent circle diameter and the circularity are obtained using the area S and the peripheral length L. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is a value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. And is calculated by the following formula.

Circularity C = 2 × (π × S) ^1/2 / L
When the particle image is circular, the degree of circularity is 1, and the degree of unevenness on the outer periphery of the particle image increases, and the degree of circularity decreases. After calculating the circularity of each particle, the range of the circularity of 0.200 to 1.000 is divided into 800, the arithmetic average value of the obtained circularity is calculated, and the value is defined as the average circularity.

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. 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 0.2 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. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  For the measurement, the above-mentioned flow type particle image analyzer equipped with “UPlanApro” (magnification 10 times, numerical aperture 0.40) as an objective lens is used, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. It was used. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle size was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

  Next, an image forming apparatus using the image forming method of the present invention will be described.

  FIG. 3 is a cross-sectional view showing a schematic configuration of the electrophotographic image forming apparatus of the present invention.

  Exposure means for writing the electrostatic latent image on the photosensitive member 21 by rotating the photosensitive member 21 as an electrostatic latent image carrier in the direction of arrow A, being uniformly charged by the charging member 22 for charging the photosensitive member 21. An electrostatic latent image is formed on the surface of the laser beam 23. The toner is applied by a developing device 24 held in a process cartridge that can be attached to and detached from the image forming apparatus main body, whereby the electrostatic latent image is developed and visualized as a toner image.

  In the development, reversal development is performed to form a toner image on the exposed portion. The developer image on the photosensitive member 21 is transferred to a paper 33 as a transfer material by a transfer roller 29. The paper 33 to which the toner image has been transferred is subjected to a fixing process by the fixing device 32, discharged outside the device, and the printing operation is completed.

  The developing device 24 includes a developing container 34 that contains toner, and a developing roller 25 that serves as a toner carrying member that is positioned in an opening extending in the longitudinal direction in the developing container 34 and that is opposed to the photosensitive member 21. The electrostatic latent image on the photoconductor 21 is developed and visualized. The electrophotographic process cartridge includes a developing device and at least one of an electrostatic latent image carrier, a charging member, a cleaning member, and a transfer member, and these are integrally held, and an image forming apparatus Is detachably provided.

  Further, the developing roller 25 is in contact with the photoreceptor 21 with a contact width. In the developing device 24, the toner supply roller 26 is in contact with the contact portion of the developing blade 27, which is a toner layer regulating member, with the surface of the developing roller 25 in the developing container 34 on the upstream side in the rotation direction of the developing roller 25. And is rotatably supported. In the present invention, SUS is preferable as the material used for the toner regulating member.

  Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this does not limit the present invention in any way.

<Production Example of Toner Particle 1>
With respect to 102 parts by mass of the styrene monomer, C.I. I. 15.6 parts by mass of Pigment Blue 15: 3 and 2.4 parts by mass of di-tertiary butylsalicylic acid aluminum compound [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 for 180 minutes at 200 rpm using zirconia beads (140 parts by mass) with a radius of 1.25 mm to prepare a master batch dispersion.

On the other hand, 432.0 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 65.0 parts by mass of 1.0 M CaCl ₂ aqueous solution was gradually added. Thus, an aqueous medium containing a calcium phosphate compound was obtained.

-Masterbatch dispersion 50.0 parts by mass-Styrene monomer 37.5 parts by mass-N-butyl acrylate monomer 20.0 parts by mass-Hydrocarbon wax 10.0 parts by mass (Fischer-Tropsch wax, maximum endotherm (Peak = 78 ° C., Mw = 750)
Polyester resin 5.0 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 value 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, 9.0 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 at a temperature of 65 ° C. and in an N ₂ atmosphere. After granulation, the temperature was raised to 70 ° C. while stirring with a paddle stirring blade. When the polymerization conversion of the polymerizable vinyl monomer reached 90%, a 0.1 mol / liter sodium hydroxide aqueous solution was added to adjust the pH of the aqueous dispersion medium to 9.0. Further, the temperature was raised to 80 ° C. and reacted for 3 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 and washed with water, and then dried at a temperature of 40 ° C. for 48 hours to obtain cyan toner particles 1. The obtained toner particles 1 had a number average particle diameter (D1) of 5.00 μm and an average circularity of 0.984.

<Production Example of Toner Particle 2>
In the production example of the toner particle 1, except that the addition amount of the 0.1M-Na ₃ PO ₄ aqueous solution is changed to 324.9 parts by mass and the addition amount of the 1.0M-CaCl ₂ aqueous solution is changed to 48.9 parts by mass. In the same manner as in the production example of toner particles 1, toner particles 2 of the present invention were obtained. The toner particles 2 obtained had a number average particle diameter (D1) of 8.00 μm and an average circularity of 0.972.

<Production Example of Toner Particle 3>
In the production example of the toner particle 1, the addition amount of the 0.1M-Na ₃ PO ₄ aqueous solution is changed to 289.1 parts by mass, and the addition amount of the 1.0M-CaCl ₂ aqueous solution is changed to 43.5 parts by mass. In the same manner as in the production example of toner particles 1, toner particles 3 of the present invention were obtained. The obtained toner particles 3 had a number average particle diameter (D1) of 9.00 μm and an average circularity of 0.960.

<Production Example of Toner Particle 4>
In the production example of the toner particle 1, the addition amount of the 0.1M-Na ₃ PO ₄ aqueous solution is changed to 467.7 parts by mass, and the addition amount of the 1.0M-CaCl ₂ aqueous solution is changed to 70.4 parts by mass. In the same manner as in the production example of toner particles 1, toner particles 4 of the present invention were obtained. The obtained toner particles 4 had a number average particle diameter (D1) of 4.00 μm and an average circularity of 0.987.

<Production Example of Toner Particle 5>
In the production example of the toner particle 1, the addition amount of the 0.1M-Na ₃ PO ₄ aqueous solution is changed to 494.5 parts by mass, and the addition amount of the 1.0M-CaCl ₂ aqueous solution is changed to 74.4 parts by mass. In the same manner as in the production example of toner particles 1, toner particles 5 of the present invention were obtained. The obtained toner particles 5 had a number average particle diameter (D1) of 3.25 μm and an average circularity of 0.989.

<Production Example of Toner Particle 6>
In the production example of the toner particle 1, the addition amount of the 0.1M-Na ₃ PO ₄ aqueous solution is changed to 503.4 parts by mass, and the addition amount of the 1.0M-CaCl ₂ aqueous solution is changed to 75.7 parts by mass. In the same manner as in the production example of toner particles 1, toner particles 6 of the present invention were obtained. The obtained toner particles 6 had a number average particle diameter (D1) of 3.00 μm and an average circularity of 0.990.

<Production Example of Toner Particle 7>
In the production example of the toner particle 1, the addition amount of the 0.1M-Na ₃ PO ₄ aqueous solution is changed to 516.3 parts by mass, and the addition amount of the 1.0M-CaCl ₂ aqueous solution is changed to 77.7 parts by mass. In the same manner as in the production example of toner particles 1, toner particles 7 of the present invention were obtained. The obtained toner particles 7 had a number average particle diameter (D1) of 2.64 μm and an average circularity of 0.990.

<Production Example of Toner Particle 8>
In the production example of the toner particle 1, the addition amount of the 0.1M-Na ₃ PO ₄ aqueous solution is changed to 257.0 parts by mass, and the addition amount of the 1.0M-CaCl ₂ aqueous solution is changed to 38.7 parts by mass. In the same manner as in the production example of toner particles 1, toner particles 8 of the present invention were obtained. The obtained toner particles 8 had a number average particle diameter (D1) of 9.90 μm and an average circularity of 0.961.

<Production Example of Toner Particle 9>
Styrene / n-butyl acrylate copolymer 100.0 parts by mass (mass ratio 80/20, Mw = 28,500, Tg = 62 ° C.)
・ C. I. Pigment Blue 15: 3 6.5 parts by mass Aluminum compound of di-tertiary butylsalicylic acid 1.0 part by mass (Bontron E88: manufactured by Orient Chemical Co., Ltd.)
Hydrocarbon wax 10.0 parts by mass (Fischer-Tropsch wax, maximum endothermic peak = 78 ° C., Mw = 750)
Polyester resin 5.0 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 value 11, Tg = 74 ° C., Mw = 11,000, Mn = 4,000)
The above materials were mixed in a blender, melt kneaded with a biaxial extruder heated to 110 ° C., and the cooled kneaded product was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a jet mill collision type jet mill (manufactured by Nippon Pneumatic Industry Co., Ltd.), and the resulting finely pulverized product was classified by wind to obtain toner particles 9. The obtained toner particles 9 had a number average particle diameter (D1) of 5.00 μm and an average circularity of 0.945.

<Production example of fatty acid metal salt 1>
A receiving container with a stirrer was prepared, and the stirrer was rotated at 350 rpm. 500 parts by mass of a 0.50 mass% sodium stearate aqueous solution was put into this receiving container, and the liquid temperature was adjusted to 85 ° C. Next, 525 mass parts of 0.20 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, it grind | pulverized on the conditions of the air volume of 6.5 m < ³ > / min and the process speed of 80 kg / h with the nano grinding mill [NJ-300] (made by a Sanrex company). After pulverization, reslurry, fine particles and coarse particles were removed using a wet centrifugal classifier, and then dried at 80 ° C. using a continuous instantaneous air dryer to obtain fatty acid metal salt 1. The resulting fatty acid metal salt 1 had a volume-based median diameter (D50) of 0.40 μm and a span value A of 1.05.

<Production example of fatty acid metal salt 2>
In the production example of the fatty acid metal salt 1, the fatty acid metal salt 2 was obtained in the same manner as in the production example of the fatty acid metal salt 1 except that the aging time was changed to 5 minutes. The volume-based median diameter (D50) of the obtained fatty acid metal salt 2 was 0.40 μm, and the span value A was 1.50.

<Production example of fatty acid metal salt 3>
In the production example of the fatty acid metal salt 1, the aging time was changed to 5 minutes, classification after pulverization was not performed, and the coarse particles were removed by passing through a mesh. Metal salt 3 was obtained. The volume-based median diameter (D50) of the obtained fatty acid metal salt 3 was 0.42 μm, and the span value A was 1.75.

<Production example of fatty acid metal salt 4>
The fatty acid metal salt 4 was obtained in the same manner as in the production example of the fatty acid metal salt 1 except that in the production example of the fatty acid metal salt 1, the aging time was changed to 5 minutes and the classification step after pulverization was not performed. The volume-based median diameter (D50) of the obtained fatty acid metal salt 4 was 0.39 μm, and the span value A was 1.84.

<Production example of fatty acid metal salt 5>
In the production example of fatty acid metal salt 1, 0.50 mass% sodium stearate aqueous solution was aged in 0.80 mass% sodium stearate aqueous solution, 0.20 mass% zinc sulfate aqueous solution was aged in 0.30 mass% zinc sulfate aqueous solution. The fatty acid metal salt 5 was obtained in the same manner as in the production example of the fatty acid metal salt 1 except that the time was changed to 5 minutes and the air volume in the pulverization step was changed to 5.5 m ³ / min. The obtained fatty acid metal salt 5 had a volume-based median diameter (D50) of 0.65 μm and a span value A of 1.50.

<Production example of fatty acid metal salt 6>
In the production example of fatty acid metal salt 1, 0.50 mass% sodium stearate aqueous solution was aged to 0.90 mass% sodium stearate aqueous solution, 0.20 mass% zinc sulfate aqueous solution was aged to 0.35 mass% zinc sulfate aqueous solution. The fatty acid metal salt 6 was obtained in the same manner as in the production example of the fatty acid metal salt 1 except that the time was changed to 5 minutes and the air volume in the pulverization step was changed to 5.0 m ³ / min. The obtained fatty acid metal salt 6 had a volume-based median diameter (D50) of 0.75 μm and a span value A of 1.49.

<Production example of fatty acid metal salt 7>
In the production example of fatty acid metal salt 1, 0.50% by mass sodium stearate aqueous solution was pulverized to 0.20% by mass sodium stearate aqueous solution, and 0.20% by mass zinc sulfate aqueous solution to 0.10% by mass zinc sulfate aqueous solution. The fatty acid metal salt 7 was obtained in the same manner as in the production example of the fatty acid metal salt 1 except that the air volume in the process was changed to 11.0 m ³ / min. The resulting fatty acid metal salt 7 had a volume-based median diameter (D50) of 0.15 μm and a span value A of 1.11.

<Production example of fatty acid metal salt 8>
In the production example of the fatty acid metal salt 1, the fatty acid metal salt 8 is the same as the production example of the fatty acid metal salt 1 except that the 0.50 mass% sodium stearate aqueous solution is changed to a 0.45 mass% sodium laurate aqueous solution. Got. The resulting fatty acid metal salt 8 had a volume-based median diameter (D50) of 0.42 μm and a span value A of 1.07.

<Production example of fatty acid metal salt 9>
In the production example of the fatty acid metal salt 1, a fatty acid metal salt 9 is obtained in the same manner as in the production example of the fatty acid metal salt 1 except that the 0.20 mass% zinc sulfate aqueous solution is changed to a 0.35 mass% calcium chloride aqueous solution. It was. The resulting fatty acid metal salt 9 had a median diameter (D50) based on volume of 0.41 μm and a span value A of 1.09.

<Production example of fatty acid metal salt 10>
In the production example of the fatty acid metal salt 1, the fatty acid metal salt 10 is obtained in the same manner as in the production example of the fatty acid metal salt 1 except that the 0.20 mass% zinc sulfate aqueous solution is changed to a 0.35 mass% lithium chloride aqueous solution. It was. The resulting fatty acid metal salt 10 had a volume-based median diameter (D50) of 0.41 μm and a span value A of 1.04.

<Production example of fatty acid metal salt 11>
In the production example of fatty acid metal salt 1, 0.50% by mass sodium stearate aqueous solution was changed to 0.15% by mass sodium stearate aqueous solution, and 0.20% by mass zinc sulfate aqueous solution was changed to 0.05% by mass zinc sulfate aqueous solution. The fatty acid metal salt 11 was obtained in the same manner as in the production example of the fatty acid metal salt 1 except that the pulverization step was performed twice at an air volume of 11.0 m ³ / min in the pulverization step. The volume-based median diameter (D50) of the obtained fatty acid metal salt 11 was 0.10 μm, and the span value A was 1.10.

<Production example of fatty acid metal salt 12>
In the production example of fatty acid metal salt 1, 0.50 mass% sodium stearate aqueous solution was pulverized into 1.20 mass% sodium stearate aqueous solution, and 0.20 mass% zinc sulfate aqueous solution was pulverized into 0.50 mass% zinc sulfate aqueous solution. A fatty acid metal salt 12 was obtained in the same manner as in the production example of the fatty acid metal salt 1 except that the air volume in the process was changed to 4.5 m ³ / min. The resulting fatty acid metal salt 12 had a median diameter (D50) based on volume of 1.00 μm and a span value A of 1.06.

<Production example of fatty acid metal salt 13>
In the production example of fatty acid metal salt 1, 0.50 mass% sodium stearate aqueous solution was aged in 1.10 mass% sodium laurate aqueous solution, and 0.20 mass% zinc sulfate aqueous solution was aged in 0.85 mass% lithium chloride aqueous solution. The fatty acid metal salt 13 was prepared in the same manner as in the production example of the fatty acid metal salt 1 except that the time was changed to 5 minutes, the air volume in the pulverization step was changed to 4.5 m ³ / min, and the classification step after pulverization was not performed. Obtained. The obtained fatty acid metal salt 13 had a volume-based median diameter (D50) of 1.00 μm and a span value A of 1.81.

<Production example of fatty acid metal salt 14>
In the production example of fatty acid metal salt 1, a 0.50% by mass sodium stearate aqueous solution was aged in a 0.15% by mass sodium laurate aqueous solution and a 0.20% by mass zinc sulfate aqueous solution in an 0.10% by mass lithium chloride aqueous solution. Similar to the production example of fatty acid metal salt 1 except that the time was changed to 5 minutes, the pulverization step was performed twice at 11.0 m ³ / min, and the classification step after pulverization was not performed. Thus, fatty acid metal salt 14 was obtained. The resulting fatty acid metal salt 14 had a volume-based median diameter (D50) of 0.10 μm and a span value A of 1.83.

<Example of production of fatty acid metal salt 15>
In the production example of fatty acid metal salt 1, 0.50% by mass sodium stearate aqueous solution was aged in 1.30% by mass sodium laurate aqueous solution and 0.20% by mass zinc sulfate aqueous solution in 1.00% by mass lithium chloride aqueous solution. The fatty acid metal salt 15 was prepared in the same manner as in the production example of the fatty acid metal salt 1 except that the time was changed to 5 minutes, the air volume in the pulverization step was changed to 4.0 m ³ / min, and the classification step after pulverization was not performed. Obtained. The resulting fatty acid metal salt 15 had a median diameter (D50) based on volume of 1.20 μm and a span value A of 1.82.

<Production example of fatty acid metal salt 16>
In the production example of fatty acid metal salt 1, a 0.50 mass% sodium stearate aqueous solution was aged in a 0.10 mass% sodium laurate aqueous solution, and a 0.20 mass% zinc sulfate aqueous solution was aged in a 0.05 mass% lithium chloride aqueous solution. Except for changing the time to 5 minutes, performing the pulverization step three times at an air volume of 11.0 m ³ / min, and not performing the classification step after pulverization, the same as the production example of fatty acid metal salt 1 Thus, fatty acid metal salt 16 was obtained. The median diameter (D50) of the obtained fatty acid metal salt 16 on a volume basis was 0.06 μm, and the span value A was 1.81.

<Production Example of Toner 1>
0.10 parts by mass of fatty acid metal salt 1 and 1.5 parts by mass of hydrophobic silica fine powder surface-treated with dimethylsilicone oil (number average primary particle size: 16 nm) with respect to toner particles 1 (100 parts by mass) Toner 1 was obtained by dry mixing with a Henschel mixer (Mitsui Mining Co., Ltd.) for 10 minutes. Various physical properties of the toner 1 are shown in Table 1.

<Production Example of Toner 2>
A toner 2 was obtained in the same manner as in the production example of the toner 1 except that the toner particle 1 was changed to the toner particle 9 in the production example of the toner 1. Various physical properties of Toner 2 are shown in Table 1.

<Production Example of Toner 3>
A toner 3 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 2 in the production example of the toner 1. Various physical properties of the toner 3 are shown in Table 1.

<Production Example of Toner 4>
In the toner 1 production example, a toner 4 was obtained in the same manner as in the toner 1 production example, except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 3. Various physical properties of Toner 4 are shown in Table 1.

<Production Example of Toner 5>
A toner 5 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 4 in the production example of the toner 1. Various physical properties of the toner 5 are shown in Table 1.

<Production Example of Toner 6>
A toner 6 was obtained in the same manner as in the production example of the toner 1 except that the toner particles 1 were changed to the toner particles 2 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 5 in the production example of the toner 1. Various physical properties of Toner 6 are shown in Table 1.

<Production Example of Toner 7>
A toner 7 was obtained in the same manner as in the production example of the toner 1 except that the toner particles 1 were changed to the toner particles 2 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 6 in the production example of the toner 1. Various physical properties of the toner 7 are shown in Table 1.

<Production Example of Toner 8>
A toner 8 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 6 in the production example of the toner 1. Various physical properties of Toner 8 are shown in Table 1.

<Production Example of Toner 9>
A toner 9 was obtained in the same manner as in the production example of the toner 1 except that, in the production example of the toner 1, the toner particles 1 were changed to the toner particles 4 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 6. Various physical properties of Toner 9 are shown in Table 1.

<Production Example of Toner 10>
A toner 10 was obtained in the same manner as in the production example of the toner 1 except that the toner particles 1 were changed to the toner particles 6 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 7 in the production example of the toner 1. Various physical properties of the toner 10 are shown in Table 1.

<Production Example of Toner 11>
A toner 11 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 8 in the production example of the toner 1. Various physical properties of the toner 11 are shown in Table 1.

<Production Example of Toner 12>
A toner 12 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 9 in the production example of the toner 1. Various physical properties of the toner 12 are shown in Table 1.

<Production Example of Toner 13>
A toner 13 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 10 in the production example of the toner 1. Various physical properties of the toner 13 are shown in Table 1.

<Production Example of Toner 14>
In the toner 6 production example, a toner 14 was obtained in the same manner as in the toner 6 production example, except that the addition amount of the fatty acid metal salt 5 was changed to 0.50 parts by mass. Various physical properties of the toner 14 are shown in Table 1.

<Production Example of Toner 15>
In the toner 10 production example, a toner 15 was obtained in the same manner as in the toner 10 production example, except that the addition amount of the fatty acid metal salt 7 was changed to 0.02 parts by mass. Various physical properties of the toner 15 are shown in Table 1.

<Production Example of Toner 16>
In the toner 6 production example, a toner 16 was obtained in the same manner as in the toner 6 production example, except that the addition amount of the fatty acid metal salt 5 was changed to 0.56 parts by mass. Various physical properties of the toner 16 are shown in Table 1.

<Production Example of Toner 17>
In the toner 10 production example, a toner 17 was obtained in the same manner as in the toner 10 production example, except that the addition amount of the fatty acid metal salt 7 was changed to 0.01 parts by mass. Various physical properties of the toner 17 are shown in Table 1.

<Production Example of Toner 18>
Toner 18 was obtained in the same manner as in Toner 1 except that Toner 1 was changed to Toner Particle 5 and Fatty Acid Metal Salt 1 was changed to Fatty Acid Metal Salt 5. Various physical properties of the toner 18 are shown in Table 1.

<Production Example of Toner 19>
A toner 19 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 7 in the production example of the toner 1. Various physical properties of the toner 19 are shown in Table 1.

<Production Example of Toner 20>
A toner 20 was obtained in the same manner as in the production example of the toner 1 except that the toner particles 1 were changed to the toner particles 6 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 6 in the production example of the toner 1. Various physical properties of the toner 20 are shown in Table 1.

<Production Example of Toner 21>
A toner 21 was obtained in the same manner as in the production example of the toner 1 except that the toner particles 1 were changed to the toner particles 2 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 7 in the production example of the toner 1. Various physical properties of the toner 21 are shown in Table 1.

<Production Example of Toner 22>
A toner 22 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 11 in the production example of the toner 1. Various physical properties of the toner 22 are shown in Table 1.

<Production example of toner 23>
In the toner 1 production example, a toner 23 was obtained in the same manner as in the toner 1 production example except that the toner particles 1 were changed to the toner particles 6 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 11. Various physical properties of the toner 23 are shown in Table 1.

<Production Example of Toner 24>
In the toner 1 production example, a toner 24 was obtained in the same manner as in the toner 1 production example except that the toner particles 1 were changed to the toner particles 2 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 12. Various physical properties of the toner 24 are shown in Table 1.

<Production Example of Toner 25>
In the toner 1 production example, a toner 25 was obtained in the same manner as in the toner 1 production example except that the toner particles 1 were changed to the toner particles 3 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 12. Various physical properties of the toner 25 are shown in Table 1.

<Production Example of Toner 26>
In the toner 18 production example, a toner 26 was obtained in the same manner as in the toner 18 production example, except that the mixing time was changed to 5 minutes. Various physical properties of the toner 26 are shown in Table 1.

<Production Example of Toner 27>
In the toner 19 production example, a toner 27 was obtained in the same manner as in the toner 19 production example, except that the mixing time was changed to 15 minutes. Various physical properties of the toner 27 are shown in Table 1.

<Production Example of Toner 28>
0.52 parts by mass of fatty acid metal salt 13 and 1.5 parts by mass of hydrophobic silica fine powder surface-treated with dimethyl silicone oil (number average primary particle size: 16 nm) are added to toner particles 4 (100 parts by mass). Toner 28 was obtained by dry mixing with a Henschel mixer (Mitsui Mining Co., Ltd.) for 8 minutes. Various physical properties of the toner 28 are shown in Table 1.

<Production Example of Toner 29>
0.01 parts by mass of fatty acid metal salt 14 and 1.5 parts by mass of hydrophobic silica fine powder surface-treated with dimethyl silicone oil (number average primary particle size: 16 nm) are added to toner particle 1 (100 parts by mass). Toner 29 was obtained by dry mixing with a Henschel mixer (Mitsui Mining Co., Ltd.) for 15 minutes. Various physical properties of the toner 29 are shown in Table 1.

<Production Example of Toner 30>
In the production example of the toner 29, a toner 30 was obtained in the same manner as in the production example of the toner 29 except that the toner particles 1 were changed to the toner particles 9. Various physical properties of the toner 30 are shown in Table 1.

<Production Example of Toner 31>
In the production example of the toner 29, the mixing machine is the same as the production example of the toner 29 except that the mixing machine is a mechanohybrid (MH type, manufactured by Mitsui Mining Co., Ltd.) having stronger adhesion strength than the Henschel mixer and the mixing time is changed to 10 minutes. Thus, toner 31 was obtained. Various physical properties of the toner 31 are shown in Table 1.

<Production Example of Toner 32>
In the production example of the toner 28, a toner 32 was obtained in the same manner as in the production example of the toner 28 except that the mixing time was changed to 5 minutes. Various physical properties of the toner 32 are shown in Table 1.

<Production Example of Toner 33>
In the production example of the toner 29, the toner 33 was obtained in the same manner as in the production example of the toner 29 except that the toner particles 1 were changed to the toner particles 5 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 16. Various physical properties of the toner 33 are shown in Table 1.

<Production Example of Toner 34>
0.52 parts by mass of fatty acid metal salt 15 and 1.5 parts by mass of hydrophobic silica fine powder surface-treated with dimethyl silicone oil (number average primary particle size: 16 nm) are added to toner particle 1 (100 parts by mass). Toner 34 was obtained by dry mixing with a Henschel mixer (Mitsui Mining Co., Ltd.) for 10 minutes. Various physical properties of the toner 34 are shown in Table 1.

<Production Example of Toner 35>
In the production example of the toner 29, a toner 35 was obtained in the same manner as in the production example of the toner 29 except that the toner particles 1 were changed to the toner particles 3. Various physical properties of the toner 35 are shown in Table 1.

<Production Example of Toner 36>
0.52 parts by mass of fatty acid metal salt 13 and 1.5 parts by mass of hydrophobic silica fine powder surface-treated with dimethyl silicone oil (number average primary particle size: 16 nm) are added to toner particles 5 (100 parts by mass). Toner 36 was obtained by dry-mixing for 10 minutes with a Henschel mixer (Mitsui Mining Co., Ltd.). Various physical properties of the toner 36 are shown in Table 1.

<Production Example of Toner 37>
In the toner 1 production example, a toner 37 was obtained in the same manner as in the toner 1 production example except that the toner particles 1 were changed to the toner particles 7 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 11. Various physical properties of the toner 37 are shown in Table 1.

<Production Example of Toner 38>
In the toner 1 production example, a toner 38 was obtained in the same manner as in the toner 1 production example, except that the toner particles 1 were changed to the toner particles 8 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 12. Various physical properties of the toner 38 are shown in Table 1.

<Example of production of developing roller 1>
A core metal (shaft body) with an outer diameter of 6 mm is placed concentrically in a cylindrical mold with an inner diameter of 12 mm, and a liquid conductive silicone rubber (made by Toray Dow Corning Silicone Co., Ltd.) is used as a material for forming the lower resin layer. ASKER-C hardness 40 degrees, volume resistivity 1 × 10 ⁷ Ω · cm product) was cast. After casting, it was placed in an oven at a temperature of 130 ° C. and heat-molded for 20 minutes. After demolding, secondary vulcanization was performed in an oven at a temperature of 200 ° C. for 4 hours to form an elastic layer having a thickness of 3 mm.

  Next, 100 parts by mass of polytetramethylene glycol (trade name: PTG1000SN, manufactured by Hodogaya Chemical Co., Ltd.) and 18.7 parts by mass of isocyanate (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) in a methyl ethyl ketone solvent And a polyether polyol prepolymer having a weight average molecular weight (Mw) of 12,000 and a hydroxyl value of 17.2 was obtained.

-Polyether polyol prepolymer 100 parts by mass-Isocyanate 85 parts by mass (trade name: C2521, manufactured by Nippon Polyurethane Industry Co., Ltd.)
-Polyether silicone compound 5.0 parts by mass (trade name: TSF4460, manufactured by GE Toshiba Silicone)
A solution prepared by adding methyl ethyl ketone to the raw material mixture so as to have a solid content of 28 parts by mass was used as a raw material solution for forming a resin layer. 20 parts by mass of carbon black (trade name: MA100, manufactured by Mitsubishi Chemical Corporation) and 30 parts by mass of acrylic resin particles (trade name: MX-1000, manufactured by Soken Chemical Co., Ltd.) are added to the solid content of the raw material liquid. The coating liquid was stirred and dispersed with a ball mill. The obtained paint is applied on the previously molded resin layer to a thickness of 15 μm by dipping, dried in an oven at a temperature of 80 ° C. for 15 minutes, and then cured in an oven at a temperature of 140 ° C. for 4 hours. As a result, a developing roller 1 was obtained.

<Example 1>
A specific evaluation method for the toner 1 and the developing roller 1 will be described.

An LBP5050 (manufactured by Canon Inc.) was used as an evaluation machine, the toner 1 was refilled in the cyan cartridge, and the developing roller 1 was replaced. This cartridge is developable in three environments: low temperature and low humidity (15 ° C., 10% RH), normal temperature and normal humidity (23 ° C., 55% RH), and high temperature and high humidity (30 ° C., 80% RH). Durability was evaluated. The evaluation was performed after printing 3,000 images at the initial stage and a horizontal line as shown in FIG. A4 size CLC color copy paper (manufactured by Canon Inc., weighing 80 g / m ² ) was used as the recording material. The evaluation results are shown in Table 2.

(1) Evaluation of filming Filming evaluation of the developing roller was performed by visual observation and image of the surface of the developing roller.

After printing 3,000 sheets, in a halftone image in which the applied amount of toner is 0.3 mg / cm ² , it was visually evaluated whether or not uneven density occurred in the 1% printed image portion and the non-printed image portion. Thereafter, the toner on the surface of the developing roller was blown with air, and the surface of the developing roller was observed.
A: Density unevenness is not generated on the image, and the surface of the developing roller is not filmed (good).
B: There is no occurrence of uneven density on the image, but slight filming is confirmed on the surface of the developing roller (no problem in practical use).
C: Mild shading unevenness on the image (practical limit).
D: Occurrence of dark and light unevenness on the image (practical problem).

(2) Evaluation of image density stability The difference in density between the initial image and the solid image after printing 3,000 sheets was used as the evaluation standard. The image density was measured with a color reflection densitometer (X-RITE 404A: manufactured by X-Rite Co.).
A: Less than 0.10 (good)
B: 0.10 or more and less than 0.15 (no problem in practical use)
C: 0.15 or more and less than 0.20 (practical limit)
D: 0.20 or more (practical problem)

(3) Evaluation of development streaks After printing 3,000 sheets, a halftone image having a toner loading of 0.3 mg / cm ² was prepared, and the image and the developing roller were visually evaluated.
A: Vertical stripes are not seen on the developing roller or the halftone image. There is no problem in practical use.
B: Although there are 1 to 3 fine streaks in the circumferential direction on the developing roller, no vertical streaks are seen on the halftone image. There is no problem in practical use.
C: There are several fine streaks in the circumferential direction on the developing roller, and several fine streaks can be seen on the halftone image. However, it is a level that can be erased by image processing, and there is almost no problem in practical use.
D: Many streaks are observed on the developing roller and the halftone image, and cannot be erased even by image processing. A practically problematic level.

(4) Evaluation of fogging After the initial and 3,000 printing, an image having a white background is output, and the whiteness of the white background of the output image measured by “REFECTRECTER MODEL TC-6DS” (manufactured by Tokyo Denshoku) The fog density (%) was calculated from the difference in whiteness of the recording material, and the image fog was evaluated. An amberlite filter was used as the filter.
A: Less than 1.0% (good)
B: 1.0% or more and less than 2.0% (no problem in practical use)
C: 2.0% or more and less than 3.0% (practical limit)
D: 3.0% or more (practical problem)

<Examples 2 to 30 and Comparative Examples 1 to 8>
Using the toners listed in Table 2, the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2.

FIG. 3 is an axial sectional view showing an example of the developing roller of the present invention. FIG. 3 is an axial sectional view showing an example of the developing roller of the present invention. 1 is a cross-sectional view of an electrophotographic apparatus using a developing device of the present invention. The horizontal line is an image with a printing rate of 1%.

Explanation of symbols

1: Highly conductive shaft (shaft)
2: resin layer 21: photosensitive drum 22: charging member 23: laser beam 24: developing device 25: developing roller 26: toner supply roller 27: developing blade 28: toner 29: transfer roller 30: cleaning blade 31: waste developer container 32: fixing device 33: paper 34: developing container 100: developing roller 200: developing roller 201: resin layer 202: resin layer

Claims (9)

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; and toner on the toner carrier with a toner layer regulating member In the image forming method including the step of regulating, and the developing step of developing the electrostatic latent image carrier with the toner on the toner carrier,
The toner carrier has a shaft body and a resin layer provided on the outer periphery of the shaft body, and the resin layer contains a polyether silicone compound,
The toner has toner particles containing at least a binder resin, a colorant, and a wax, and a fatty acid metal salt, and the liberation ratio of the fatty acid metal salt to the toner is 1.0% or more and 25.0% or less. Yes,
An image forming method characterized by satisfying the following relationship, wherein the number average particle diameter (D1) of the toner particles is Dt (μm) and the median diameter of the fatty acid metal salt is Ds (μm).
3.00 ≦ Dt ≦ 9.00
0.10 ≦ Ds ≦ 1.00
0.02 ≦ Ds / Dt ≦ 0.25 2. The toner according to claim 1, wherein when the number average particle diameter (D1) of the toner particles is Dt (μm) and the median diameter of the fatty acid metal salt is Ds (μm), the following relationship is satisfied. The image forming method described.
3.00 ≦ Dt ≦ 9.00
0.15 ≦ Ds ≦ 0.75
0.03 ≦ Ds / Dt ≦ 0.20   The image forming method according to claim 1 or 2, wherein the addition amount of the fatty acid metal salt is 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 particles.   4. The image forming method according to claim 1, wherein the fatty acid metal salt is fatty acid zinc or fatty acid calcium.   The image forming method according to claim 1, wherein the fatty acid of the fatty acid metal salt is stearic acid. The following relationship is satisfied, where the number average particle diameter (D1) of the toner particles is Dt (μm) and the median diameter on the volume basis of the fatty acid metal salt is Ds (μm). 6. The image forming method according to any one of 5 above.
3.00 ≦ Dt ≦ 9.00
0.15 ≦ Ds ≦ 0.65
0.03 ≦ Ds / Dt ≦ 0.15 The image forming method according to claim 1, wherein the fatty acid metal salt has a span value A defined by the following formula (1) of 1.75 or less.
Formula (1) Span value A = (D95s-D5s) / Ds
Ds: median diameter of fatty acid metal salt based on volume D5s: 5% integrated diameter based on volume of fatty acid metal salt D95s: 95% integrated diameter based on volume of fatty acid metal salt The image forming method according to claim 1, wherein the fatty acid metal salt has a span value A defined by the following formula (1) of 1.50 or less.
Formula (1) Span value A = (D95s-D5s) / Ds
Ds: median diameter of fatty acid metal salt based on volume D5s: 5% integrated diameter based on volume of fatty acid metal salt D95s: 95% integrated diameter based on volume of fatty acid metal salt   9. The image forming method according to claim 1, wherein the toner particles are produced by a suspension polymerization method.

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