JP5142847B2 - toner - Google Patents

Description

  The present invention relates to a toner used in electrophotography, electrostatic recording, and magnetic recording. Specifically, the present invention relates to an electrostatic charge image developing toner (hereinafter abbreviated as toner) used in an image recording apparatus that can be used in a copying machine, a printer, a facsimile, a plotter, and the like.

  In recent years, the electrophotographic technology used for copying machines, printers, and the like has expanded with the development. For this reason, demands from the market are becoming stricter year by year, and it is strongly demanded to provide a product with a long life, a small size and a low price while satisfying performance such as high speed and high image quality.

  In order to satisfy the above requirements, the demand for toner as an electrophotographic developer is becoming strict.

  Electrophotographic developers are classified into two-component developers and one-component developers. One-component developers are classified into magnetic one-component developers and non-magnetic one-component developers.

  In recent years, a one-component developing system has been widely adopted as an electrophotographic developer. In this method, the toner is charged by rubbing between the toner carrier and the regulating member. By adopting such a charging method, it is easy to achieve a reduction in price and size of the printer.

  In addition, the two-component developer is more advantageous in terms of stabilizing the chargeability of the toner. Accordingly, the electrophotographic developer employs both one-component and two-component toners.

  The present invention can be used in both one-component and two-component development systems.

  On the other hand, there has been a strong demand for lower power consumption as prices and size are reduced. In particular, in many of the electrophotographic development methods, the developer transferred onto the recording medium is fixed through a fixing step, so that it is necessary to lower the fixing temperature. For this reason, the toner particle size, which is advantageous for low-temperature fixing, has been reduced. Further, with the increase in image quality and definition, the toner particle size is being reduced.

  However, it has become difficult to maintain the charging stability of the toner as the particle size of the toner is reduced. As a result, image defects due to “selective coating” in which minute toner particles are selectively carried on the toner carrying member are likely to occur. Excessive minute toner causes poor regulation of the toner carrier. As a result, spotted streaks, toner clumps, and the like are generated on the image. Furthermore, fogging occurs, and when a large number of sheets are printed, the particle size distribution changes, so that the fluidity is deteriorated and the image density stability is lowered.

  In addition, there are strong demands from the market for higher speed and longer service life. In order to satisfy these requirements, a much higher toner charging stability is required over a long period of time.

  Therefore, a method for stabilizing the charging of the toner by applying a voltage between the toner carrier and the toner regulating member and between the toner carrier and the toner supply member has become common (for example, patents). References 1, 2). Furthermore, it is disclosed that the charge of the toner is stabilized by including a charge control resin in the toner particles (for example, Patent Documents 3 and 4).

  In recent years, attempts have been made to control charging with fatty acid metal salts (Patent Document 5). According to Patent Document 5, it is disclosed that toner particles are coated with a fatty acid metal salt, and a charge control agent is adhered and fixed on the surface of the toner particles to provide excellent environmental stability and stabilize charging.

  Certainly, when the toner described in Patent Document 5 is used, it is possible to obtain a high-quality image with increased environmental stability and less fog. However, as a result of intensive studies by the present inventors, the selective coating on the toner carrier was not improved, and when a large number of sheets were printed, the image density decreased and fogging deteriorated.

  Such a phenomenon appears remarkably in a low temperature and low humidity environment. This is because the charge of the toner tends to be high when the temperature is low and the humidity is low. In addition, since it is caused by insufficient charge and non-uniform charge amount distribution, it appears most noticeably when printing is performed while taking a long intermittent time.

  Therefore, various characteristics need to be improved in order to satisfy the high demands currently required in the conventional technology as described above.

JP 2004-117733 A JP 2004-198877 A JP 2007-156456 A JP 2007-156457 A JP 2007-241166 A

  As a result of extensive studies by the present inventors, it has been found that there is a problem in the charging stability of the small particle size toner. That is, since the chargeability of the small particle size toner is unstable, the charge amount distribution of the entire toner becomes non-uniform so that a selective coat is developed.

  An object of the present invention is to provide a toner that can solve the above-mentioned problems and can obtain a high-quality image over a long period of time by stabilizing the charging property of a small particle size toner and suppressing selective coating.

  The said subject can be achieved by the following this invention.

That is, in a toner having at least a toner particle containing a binder resin, a colorant, and a release agent, and at least a fatty acid metal salt,
The toner has a number average particle diameter (D1) of Dt (μm), the number of particles having a particle diameter of 2/3 or less of Dt in the toner particles is P (number%), and is based on the volume basis of the fatty acid metal salt. A toner satisfying the following formulas (1) to (5) where the median diameter (D50) is Ds (μm) and the amount of the fatty acid metal salt added to the toner is V (mass%). is there.
4.0 ≦ Dt ≦ 8.5 (1)
0.10 ≦ Ds ≦ 0.65 (2)
5.0 ≦ P ≦ 25.0 (3)
8.0 ≦ Dt / Ds ≦ 40.0 (4)
0.0005 ≦ V / P ≦ 0.0500 (5)

  By using the toner of the present invention, the chargeability of a minute toner is stabilized. As a result, the charge distribution of the entire toner becomes uniform, the selective coating is suppressed, and there is little selective development occurring during printing. As a result, fog is reduced, and the occurrence of poor regulation on the toner carrier is suppressed. Further, even when a large number of sheets are printed, the change in the particle size distribution is small, so that the fluidity can be maintained, the density stability is high, and the toner can be provided.

  Further, by using the toner of the present invention, it is possible to suppress contamination of the charging member and the toner regulating member due to the external additive in the toner. As a result, transfer loss is extremely small and development streaks can be suppressed.

  The ability to print over a long period of time without depending on temperature and humidity is an essential issue in order to satisfy market needs. Therefore, the present inventors have intensively studied the performance.

  As a result, by defining the particle size of the toner particles, the amount of toner particles smaller than the central particle size of the toner particles, the particle size of the fatty acid metal salt added to the toner particles and the addition amount, the above performance can be achieved. It turned out to be good.

That is, in a toner particle containing at least a binder resin, a colorant and a release agent, and a toner having at least a fatty acid metal salt,
The toner has a number average particle diameter (D1) of Dt (μm), the number of particles having a particle diameter of 2/3 or less of Dt in the toner particles is P (number%), and is based on the volume basis of the fatty acid metal salt. When the median diameter (D50) is Ds (μm) and the addition amount of the fatty acid metal salt to the toner is V (mass%), satisfying the following formulas (1) to (3) solves the above problem. It is essential to do.
4.0 ≦ Dt ≦ 8.5 (1)
0.10 ≦ Ds ≦ 0.65 (2)
5.0 ≦ P ≦ 25.0 (3)
8.0 ≦ Dt / Ds ≦ 40.0 (4)
0.0005 ≦ V / P ≦ 0.0500 (5)

  Although the detailed reason is unknown, the present inventors guess as follows.

  In the process cartridge as shown in FIG. 1, the toner on the toner carrier 14 is charged between the toner carrier 14 and the regulating blade 16 and between the toner carrier 14 and the supply roller 15. The particle size of the toner 14 on the toner carrier 14 is extremely smaller than the central particle size of the toner 17 in the container, and the selective coating is caused.

  Further, the toner that is a non-conductive substance is largely charged on the surface. For this reason, it is considered that the smaller the toner particle size, the larger the charge amount per unit mass.

  On the other hand, a potential for holding the toner is applied to the toner carrier, and it is considered that a toner having a larger charge amount is easily held selectively.

  Furthermore, in order to stabilize charging between the toner carrier and the regulating blade and between the toner carrier and the supply roller, this tendency is strong by applying a regulation bias and a supply bias. Was significantly reduced, and the selective coatability was found to increase.

  It is considered that such a selective coat is caused by unstable charging of a minute toner. That is, the charge of a minute toner that can easily have high charge rises rapidly. As a result, the toner charge amount distribution becomes non-uniform, and a selective coat is developed.

  That is, in order to suppress the selective coating on the toner carrying member, it is necessary to suppress the rising of excessive charging of a minute toner and to have a uniform charge amount distribution throughout the toner.

  According to the present invention, it is possible to suppress the rapid charging of the minute toner in the toner, and as a result, it is possible to suppress the selective coating on the toner carrier.

  With the toner of the present invention, when the toner number average diameter (D1) is Dt (μm) and the volume-based median diameter (D50) of the fatty acid metal salt is Ds (μm), the ratio Dt / Ds is Dt / Ds. By setting the value to 8.0 to 40.0, the charge amount distribution of the toner can be made uniform.

  It is considered that electrostatic adhesion force is dominant over physical force in adhesion between particles having a small particle diameter. When Dt / Ds is in the above range, the fatty acid metal salt is sufficiently small with respect to the toner particles, and the adhesion between the fine toner particles and the fatty acid metal salt is improved. I think that the rise was suppressed.

  On the other hand, when Dt / Ds is smaller than 8.0, since the fatty acid metal salt is too large for the toner particles, the adhesion of the fatty acid metal salt to the minute toner particles is weak, and the charging of the minute toner is started. I think that it is not able to suppress enough.

  On the other hand, when Dt / Ds is larger than 40.0, the adhesion force with the toner having a smaller particle diameter is high, the rising of charging of the minute toner is suppressed, and the selective coating is strongly suppressed. As a result, the fluidity on the toner carrier tends to deteriorate and development streaks are likely to occur. In addition, a minute toner that is not sufficiently charged is likely to be present as a transfer residual toner on the electrostatic latent image carrier, and contamination of the charging roller is likely to occur.

  Further, the amount of toner selectively coated on the toner-carrying pair increased rapidly from the vicinity of a particle size (2/3 Dt) that is two-thirds or less of Dt. Therefore, it is considered that selective developability can also be suppressed by reducing the amount of 2 / 3Dt. However, assuming that the number of toner particles having a particle diameter of 2/3 or less of Dt is P (number%), if P is less than 5 number%, the toner having a small particle diameter is too small, and the fluidity is low. Is difficult to maintain, and the concentration stability cannot be satisfied. Furthermore, since toner stays between the toner carrier and the regulating blade becomes longer, toner adhesion to the regulating blade member is likely to occur, and development streaks are likely to occur. When P is more than 25% by number, the amount of minute toner is too large, and toner slippage between the toner carrier and the regulating blade is likely to cause poor regulation. Furthermore, even when the fatty acid metal salt was added, the selective coating was not sufficiently suppressed, and fogging and charging contamination occurred. Detailed examination of the toner and the fog component on the toner carrier revealed that these toners have reverse polarity. This is considered to be caused by unevenness in the amount of fatty acid metal salt deposited when there is a lot of fine toner. That is, when there are many minute toners, it is considered that electrostatic aggregation occurs between the minute toners and the surface of the minute toner particles cannot be uniformly covered.

  Therefore, it is essential that the number P (number%) of particles having a particle size of 2/3 or less of Dt in the toner is 5 to 25 number%.

  Next, when the addition amount of the fatty acid metal salt to the toner is V (mass%), it is essential that the ratio V / P of V to P is in an appropriate range 0.0005 ≦ V / P ≦ 0.0500. . That is, when V / P is less than 0.0005, sufficient performance cannot be exhibited because the amount of fatty acid metal salt relative to the amount of minute toner particles is insufficient.

  On the other hand, when V / P is larger than 0.0500, the amount of fatty acid metal salt is too much relative to the amount of minute toner particles, so Aggregation occurs and adhesion to the toner particles is considered to decrease. As a result, when a large number of sheets are printed, the fatty acid metal salt is easily released from the toner particles, and the charging roller is contaminated.

  Therefore, it is essential that V / P is 0.0005 to 0.0500, and preferably 0.0025 to 0.0250.

  When the number average particle diameter (D1) of the toner is Dt, it is essential that the appropriate range of Dt is 4.0 μm or more and 8.5 μm or less, preferably 4.5 μm or more and 7.0 μm or less.

  When the particle size is too small, toner having a reversal polarity is likely to be generated, and the fog is deteriorated. Furthermore, the selective coating property is further enhanced, and an excessive amount of minute toner is carried on the toner carrying member, so that it is easy to cause poor regulation. When the fatty acid metal zinc is added to the toner having such a particle size, the selective coating is relaxed, but in the end, the above problem cannot be solved.

  On the other hand, when the particle size is too large, no extreme selective coating is generated, but the concentration stability is lowered due to low fluidity. In addition, it is difficult for the toner to slip between the toner carrier and the regulating blade, and toner fusing easily occurs on the regulating blade, so that development streaks occur.

  When the volume-based median diameter (D50) of the fatty acid metal salt is Ds, an appropriate range of Ds is 0.10 to 0.65 μm. If the particle size of the fatty acid metal zinc is in the above range, the electrostatic aggregation of the extreme fatty acid metal salt does not occur, and the fatty acid metal salt is hardly destroyed by passing through a mechanical attachment step. As a result, it is considered that the charging property of the minute toner particles can be stabilized by uniformly adhering to the surface of the toner particles.

  When Ds is smaller than 0.10 μm, it is considered that electrostatic aggregation of fatty acid metal salts occurs before adhering to the minute toner, and uniform adhesion to the minute toner is less likely to occur. Therefore, the toner to which the fatty acid metal zinc having such a small particle diameter is added has little suppression of selective coating.

  Moreover, when Ds is larger than 0.65 μm, it is considered that the fatty acid metal zinc is likely to be destroyed when the mechanical adhesion process is performed. Therefore, the particle size distribution of the fatty acid metal salt is widened, the adhesion of the fatty acid metal salt to a minute toner becomes insufficient, and the selective coating cannot be suppressed. Further, since the particle size distribution of the fatty acid metal salt is widened, the charge amount distribution as the toner is also deteriorated, and the fog suppression effect is reduced.

  In the toner, the effect of the present invention can be more easily obtained by adding a charge control resin, which is a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group, to the toner particles.

  The charge of the toner containing the charge control resin is excellent in rising, and by adding the fatty acid metal salt of the present invention, the charge amount distribution of the toner can be made uniform more quickly.

  The fatty acid metal salt suitably used for the toner is preferably a salt of a higher fatty acid having a fatty acid species of 12 to 22 carbon atoms and a metal selected from zinc, calcium, magnesium, aluminum and lithium, more preferably. Is a salt of zinc or calcium. When the metal species is zinc or calcium, the effects of the present invention are more easily obtained.

  Moreover, generation | occurrence | production of a free fatty acid is easy to be suppressed when a C12 or more fatty acid is used. The free fatty acid is preferably 0.20% or less, and if it is more than 0.20%, fog is likely to occur. Further, when a fatty acid metal salt having 22 or less carbon atoms is used, the melting point of the fatty acid metal salt is not too high, and it is difficult to affect the fixing property.

  Examples of the fatty acid metal salt include zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, lithium stearate, and zinc laurate.

  Next, a toner manufacturing method will be described.

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

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

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

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

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

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

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

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

  Examples of the low molecular weight polymer include low molecular weight polystyrene, low molecular weight styrene-acrylic acid ester copolymer, and low molecular weight styrene-acrylic copolymer.

  It is preferable to use together with the above-mentioned binder resin a polar resin having a carboxyl group such as a polyester resin or a polycarbonate resin.

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

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

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

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

  Examples of the bifunctional crosslinking agent include the following. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and diacrylate above instead of diacrylate Thing.

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

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

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

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

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

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

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

  Examples of the black colorant include carbon black and those prepared by using the above yellow colorant / magenta colorant / cyan colorant to black.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  The colorant is preferably used in an amount of 1 to 20% by mass added to 100% by mass of the polymerizable monomer or binder resin.

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

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

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

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

  Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.

  As the dispersion stabilizer used at the time of preparing the aqueous medium, an inorganic poorly water-soluble dispersion stabilizer is preferable, and it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in an acid.

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

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

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

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

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

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

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

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

  A preferable blending amount of the charge control agent is 0.01 to 20% by mass, more preferably 0.5 to 10% by mass with respect to 100% 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 the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

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

  Moreover, the other additive may be added. Examples of the additive include fine powder such as silica fine powder, titanium oxide fine powder, or double oxide fine powder thereof. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.

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

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

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

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

  The total amount of the inorganic fine powder is preferably 1.0 to 5.0% by mass with respect to 100% by mass of the toner particles.

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

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

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

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

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

<Number% (P) of toner particles having a particle diameter of 2/3 or less of Dt, where Dt is the number average particle diameter (D1) of toner particles>
The number average particle diameter (D1) of the toner is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.

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

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

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

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

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

[Production of resin having sulfonic acid or sulfonate group or sulfonic acid ester]
In a 2 L flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 100% by mass of toluene, 350 parts by mass of methanol, 470 parts by mass of styrene, 40 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid- 70 parts by mass of 2-ethylhexyl, 20 parts by mass of benzyl methacrylate, and 10 parts by mass of lauryl peroxide were charged, and the solution was polymerized at 65 ° C. for 10 hours with stirring and nitrogen introduction. The contents were taken out from the flask, washed with isopropyl alcohol, After drying under reduced pressure at 40 ° C. for 96 hours, the mixture was roughly crushed with a hammer mill, and the crushed product was further dried under reduced pressure at 40 ° C. for 48 hours. A resin having a sulfonic acid or a sulfonic acid base and a sulfonic acid ester (hereinafter referred to as CCR) was produced.

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

On the other hand, after adding 420 parts by mass of 0.1 M Na ₃ PO ₄ aqueous solution to 400 parts by mass of ion-exchanged water and heating to 60 ° C., 60 parts by mass of 1.0 M CaCl ₂ aqueous solution was gradually added to the calcium phosphate compound. An aqueous medium containing was obtained.
Master batch dispersion 1 36 parts by mass Styrene monomer 30 parts by mass n-butyl acrylate monomer 20 parts by mass Low molecular weight polystyrene 20 parts by mass (Mw = 3,000, Mn = 1,050, Tg = 55 ° C)
Hydrocarbon wax 9 parts by mass (Fischer-Tropsch wax, maximum endothermic peak = 78 ° C., Mw = 750)
Polyester resin 5 parts by mass (terephthalic acid: isophthalic acid: propylene oxide modified bisphenol A (2 mol adduct): ethylene oxide modified bisphenol A (2 mol adduct) = 30: 30: 30: 10 polycondensate, acid No. 11, Tg = 74 ° C., Mw = 11,000, Mn = 4,000)
2 parts by mass of CCR (Mw = 24000, Tg = 67 ° C., residual monomer = 350 ppm)
The above material was heated to 65 ° C., and uniformly dissolved and dispersed at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). In this, 7.5 parts by mass of a 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate was dissolved to prepare a polymerizable monomer composition.

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

<Manufacture of toner particles 2>
Toner particles 2 were obtained in the same manner as toner particles 1 except that the rotational speed of the TK homomixer was changed to 10,000 rpm to 15,000 rpm. Table 1 shows the production conditions of the toner particles 2 obtained.

<Manufacture of toner particles 3>
Toner particles 3 were obtained in the same manner as toner particles 1, except that the polymerizable monomers were polymerized by stirring for 10 minutes, but the polymerizable monomers were polymerized by stirring for 15 minutes. . The production conditions of the toner particles 3 obtained are shown in Table 1.

<Manufacture of toner particles 4>
The ion-exchanged water used to obtain the aqueous medium containing the calcium phosphate compound is 373 parts by mass, the input amount of the 0.1M-Na ₃ PO ₄ aqueous solution is 450 parts by mass, and the input amount of the 1.0M-CaCl ₂ aqueous solution is 68 Toner particles 4 were obtained in the same manner as toner particles 1 except that the parts were in parts by mass and the rotational speed of the TK homomixer was 10,000 rpm. The production conditions of the toner particles 4 obtained are shown in Table 1.

<Manufacture of toner particles 5>
The ion-exchanged water used for obtaining the aqueous medium containing the calcium phosphate compound is 137 parts by mass, the input amount of the 0.1M-Na ₃ PO ₄ aqueous solution is 650 parts by mass, and the input amount of the 1.0M-CaCl ₂ aqueous solution is 93 Toner particles 5 were obtained in the same manner as toner particles 1 except that the amount was changed to part by mass. The production conditions of the obtained toner particles 5 are shown in Table 1.

<Manufacture of toner particles 6>
The amount of ion-exchanged water used to obtain an aqueous medium containing a calcium phosphate compound is 206 parts by mass, the amount of 0.1M-Na ₃ PO ₄ aqueous solution is 590 parts by mass, and the amount of 1.0M-CaCl ₂ aqueous solution is 84 Toner particles 6 were obtained in the same manner as toner particles 1 except that the amount was changed to part by mass. The production conditions for the obtained toner particles 6 are shown in Table 1.

<Manufacture of toner particles 7>
The ion-exchanged water used to obtain the aqueous medium containing the calcium phosphate compound is 446 parts by mass, the input amount of the 0.1M-Na ₃ PO ₄ aqueous solution is 380 parts by mass, and the input amount of the 1.0M-CaCl ₂ aqueous solution is 54 Toner particles 7 were obtained in the same manner as toner particles 1 except that the amount was changed to part by mass. Table 1 shows the production conditions of the toner particles 7 obtained.

<Manufacture of toner particles 8>
The ion-exchanged water used to obtain the aqueous medium containing the calcium phosphate compound is 514 parts by mass, the input amount of the 0.1M-Na ₃ PO ₄ aqueous solution is 320 parts by mass, and the input amount of the 1.0M-CaCl ₂ aqueous solution is 46 Toner particles 8 were obtained in the same manner as toner particles 1 except that the amount was changed to part by mass. The production conditions for the obtained toner particles 8 are shown in Table 1.

<Manufacture of toner particles 9 to 16>
Toner particles 9 to 16 were obtained by air classifying toner particles 1 to 8. The production conditions for the obtained toner particles 9 to 16 are shown in Table 1.

<Manufacture of toner particles 17>
Toner particles 17 were obtained by air classification to remove only the coarse powder side of the toner particles 2. The production conditions for the obtained toner particles 17 are shown in Table 1.

<Manufacture of toner particles 18>
Toner particles 18 were obtained by air-classifying the toner particles 12 again. The production conditions for the obtained toner particles 18 are shown in Table 1.

<Manufacture of toner particles 19>
In the production of toner particles 1, toner particles 19 were obtained in the same manner as in the production of toner particles 1 except that CCR was not added. Table 1 shows the formulation of the toner particles 19 obtained.

  Next, one production example of the fatty acid metal salt used in the present invention will be described.

<Production of fatty acid metal salt particles 1>
A receiving container with a stirrer was prepared, and the stirrer was rotated at 450 rpm. 450 mass parts of 0.5 mass parts sodium stearate aqueous solution was thrown into this receiving container, and liquid temperature was adjusted to 85 degreeC. Next, 550 mass parts of 0.15 mass parts zinc sulfate aqueous solution was dripped at this receptacle over 20 minutes. After the entire amount was charged, the reaction was terminated by aging for 15 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 110 ° C. using a continuous instantaneous air dryer. Then, after crushing with a nanogrinding mill [NJ-300] (manufactured by Sanrex) under conditions of an air volume of 5.0 m ³ / min and a processing speed of 80 kg / h, reslurry and fine particles using a wet centrifugal classifier After removal of the coarse particles, the fatty acid metal salt particles 1 were obtained by drying at 80 ° C. using a continuous instantaneous air flow dryer. The volume-based median diameter Ds of the obtained fatty acid metal salt particles 1 was 0.42 μm. The production conditions of the fatty acid metal salt particles 1 are shown in Table 2.

<Production of fatty acid metal salt particles 2>
In fatty acid metal salt particles 1, except that 0.5 parts by mass of sodium stearate aqueous solution is changed to 0.1 parts by mass of sodium stearate aqueous solution, and 0.15 parts by mass of zinc sulfate aqueous solution is changed to 0.05 parts by mass of zinc sulfate aqueous solution. Obtained fatty acid metal salt particles 2 in the same manner as fatty acid metal salt particles 1. The volume-based median diameter Ds of the fatty acid metal salt particles 2 was 0.12 μm. The production conditions for the fatty acid metal salt particles 2 are shown in Table 2.

<Production of fatty acid metal salt 3>
In the fatty acid metal salt particles 1, fatty acid metal salt particles 3 were obtained in the same manner as the fatty acid metal salt particles 1 except that the 0.15 part by mass zinc sulfate aqueous solution was changed to a 0.5 part by mass zinc sulfate aqueous solution. The volume-based median diameter Ds of the fatty acid metal salt particles 3 was 0.64 μm. The production conditions for the fatty acid metal salt particles 3 are shown in Table 2.

<Production of fatty acid metal salt 4>
In the fatty acid metal salt particles 2, fatty acid metal salt particles 4 were obtained in the same manner as in the fatty acid metal salt particles 2 except that the pulverization conditions were an air volume of 4.0 m ³ / min and a treatment speed of 50 kg / h. The volume-based median diameter Ds of the fatty acid metal salt particles 4 was 0.16 μm. The production conditions for the fatty acid metal salt particles 4 are shown in Table 2.

<Production of fatty acid metal salt 5>
In fatty acid metal salt particles 1, except that 0.5 parts by mass of sodium stearate aqueous solution is changed to 0.8 parts by mass of sodium stearate aqueous solution and 0.15 parts by mass of zinc sulfate aqueous solution is changed to 0.5 parts by mass of calcium chloride aqueous solution. Obtained fatty acid metal salt particles 7 in the same manner as fatty acid metal salt particles 1. The volume-based median diameter Ds of the fatty acid metal salt particles 5 was 0.49 μm. The production conditions for the fatty acid metal salt particles 5 are shown in Table 2.

<Production of fatty acid metal salt 6>
In fatty acid metal salt particles 1, except that 0.5 parts by mass of sodium stearate aqueous solution is changed to 0.8 parts by mass of sodium stearate aqueous solution, and 0.15 parts by mass of zinc sulfate aqueous solution is changed to 0.7 parts by mass of magnesium chloride aqueous solution. Obtained fatty acid metal salt particles 6 in the same manner as fatty acid metal salt particles 1. The volume-based median diameter Ds of the fatty acid metal salt particles 6 was 0.55 μm. The production conditions for the fatty acid metal salt particles 6 are shown in Table 2.

<Production of fatty acid metal salt 7>
In fatty acid metal salt particles 1, except that 0.5 parts by mass of sodium stearate aqueous solution is changed to 0.7 parts by mass of sodium laurate aqueous solution, and 0.15 parts by mass of zinc sulfate aqueous solution is changed to 0.3 parts by mass of zinc sulfate aqueous solution. Obtained fatty acid metal salt particles 7 in the same manner as fatty acid metal salt particles 1. The volume-based median diameter Ds of the fatty acid metal salt particles 7 was 0.47 μm. The production conditions for the fatty acid metal salt particles 7 are shown in Table 2.

<Production of fatty acid metal salt 8>
In the fatty acid metal salt particles 1, fatty acid metal salt particles 8 were obtained in the same manner as in the fatty acid metal salt particles 1 except that the rotation speed of stirring was 250 rpm. The volume-based median diameter Ds of the fatty acid metal salt particles 8 was 0.66 μm. The production conditions for the fatty acid metal salt particles 8 are shown in Table 2.

<Production of fatty acid metal salt 9>
In the fatty acid metal salt particles 2, fatty acid metal salt particles 9 were obtained in the same manner as in the fatty acid metal salt particles 2 except that the pulverization process was changed three times. The volume-based median diameter Ds of the fatty acid metal salt particles 9 was 0.08 μm. The production conditions for the fatty acid metal salt particles 9 are shown in Table 2.

<Toner Production Example 1>
To toner particles 1, 0.20% by mass of fatty acid metal salt 1 and 1.5% by mass of hydrophobic silica fine powder surface-treated with hexamethyldisilazane were added at an average primary particle size: 10 nm, and Henschel mixer Mitsui A mixing process was performed for 300 seconds by Mining Co., and toner A was obtained. Table 3 shows the physical properties of Toner A thus obtained.

<Toner Production Example 2>
Toner B was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 14 in Toner Production Example 1. Table 3 shows the physical properties of Toner B thus obtained.

<Toner Production Example 3>
Toner C was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 15 in Toner Production Example 1. Table 3 shows the physical properties of Toner C thus obtained.

<Toner Production Example 4>
In Toner Production Example 1, Toner D was obtained in the same manner as in Toner Production Example 1 except that toner particles 1 were changed to toner particles 11 and the amount of fatty acid metal salt 1 added was 0.03% by mass. Table 3 shows the physical properties of Toner D thus obtained.

<Toner Production Example 5>
Toner E was obtained in the same manner as in Toner Production Example 1 except that the amount of fatty acid metal salt 1 added was 0.30% by mass in Toner Production Example 1. Table 3 shows the physical properties of Toner E thus obtained.

<Toner Production Example 6>
In Toner Production Example 1, Toner F was obtained in the same manner as in Toner Production Example 1 except that the amount of fatty acid metal salt 1 added was 0.03% by mass. Table 3 shows the physical properties of Toner F thus obtained.

<Toner Production Example 7>
In Toner Production Example 1, Toner G was obtained in the same manner as in Toner Production Example 1 except that toner particles 1 were changed to toner particles 11 and the amount of fatty acid metal salt 1 added was 0.30 mass%. Table 3 shows the physical properties of Toner G thus obtained.

<Toner Production Example 8>
A toner H was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 7 in Toner Production Example 1. Table 3 shows the physical properties of Toner H thus obtained.

<Toner Production Example 9>
Toner I was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 8 in Toner Production Example 1. Table 3 shows the physical properties of Toner I thus obtained.

<Toner Production Example 10>
In Toner Production Example 1, Toner J was obtained in the same manner as in Toner Production Example 1 except that toner particles 1 were changed to toner particles 18 and the amount of fatty acid metal salt 1 added was 0.50 mass%. Table 3 shows the physical properties of Toner J thus obtained.

<Toner Production Example 11>
Toner K was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 6 in Toner Production Example 1. Table 3 shows the physical properties of Toner K thus obtained.

<Toner Production Example 12>
Toner L was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 4 in Toner Production Example 1. Table 3 shows the physical properties of Toner L thus obtained.

<Toner Production Example 13>
A toner M was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 2 in Toner Production Example 1. Table 3 shows the physical properties of Toner M thus obtained.

<Toner Production Example 14>
In Toner Production Example 1, Toner N was obtained in the same manner as in Toner Production Example 1 except that toner particles 1 were changed to toner particles 10 and the amount of fatty acid metal salt 1 added was 0.01% by mass. Table 3 shows the physical properties of Toner N thus obtained.

<Toner Production Example 15>
Toner O was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 13 in Toner Production Example 1. Table 3 shows the physical properties of Toner O obtained.

<Toner Production Example 16>
In the toner production example 1, a toner P was obtained in the same manner as in the toner production example 1 except that the toner particles 1 were the toner particles 6 and the fatty acid metal salt 1 was the fatty acid metal salt 2. Table 3 shows the physical properties of Toner P thus obtained.

<Toner Production Example 17>
In the toner production example 1, a toner Q was obtained in the same manner as in the toner production example 1 except that the toner particles 1 were the toner particles 3 and the fatty acid metal salt 1 was the fatty acid metal salt 3. Table 3 shows the physical properties of Toner Q thus obtained.

<Toner Production Example 18>
In the toner production example 1, a toner R was obtained in the same manner as in the toner production example 1 except that the toner particles 1 were the toner particles 2 and the fatty acid metal salt 1 was the fatty acid metal salt 3. Table 3 shows the physical properties of Toner R obtained.

<Toner Production Example 19>
In the toner production example 1, a toner S was obtained in the same manner as in the toner production example 1 except that the toner particles 1 were the toner particles 3 and the fatty acid metal salt 1 was the fatty acid metal salt 4. Table 3 shows the physical properties of Toner S thus obtained.

<Toner Production Example 20>
A toner T was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 19 in Toner Production Example 1. Table 3 shows the physical properties of Toner T thus obtained.

<Toner Production Example 21>
Toner U was obtained in the same manner as in Toner Production Example 1 except that Fatty Acid Metal Salt 1 was changed to Fatty Acid Metal Salt 5 in Toner Production Example 1. Table 3 shows the physical properties of the obtained toner U.

<Toner Production Example 22>
Comparative toner V was obtained in the same manner as in Toner Production Example 1 except that Fatty Acid Metal Salt 1 was changed to Fatty Acid Metal Salt 6 in Toner Production Example 1. Table 3 shows the physical properties of Comparative toner V thus obtained.

<Toner Production Example 23>
Toner W was obtained in the same manner as in Toner Production Example 1 except that Fatty Acid Metal Salt 1 was changed to Fatty Acid Metal Salt 7 in Toner Production Example 1. Table 3 shows the physical properties of Comparative Toner W obtained.

<Toner Comparative Production Example 1>
In Toner Production Example 1, Comparative Example Toner B was obtained in the same manner as in Toner Production Example 1 except that toner particle 1 was changed to toner particle 9 and the amount of fatty acid metal salt 1 added was 0.50 mass%. . Table 3 shows the physical properties of Comparative Toner B obtained.

<Toner Comparative Production Example 3>
Comparative toner C was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 6 in Toner Production Example 1. Table 3 shows the physical properties of Comparative Toner C obtained.

<Toner Comparative Production Example 4>
Comparative toner D was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 12 in Toner Production Example 1. Table 3 shows the physical properties of Comparative Toner D obtained.

<Toner Comparative Production Example 5>
Comparative toner E was obtained in the same manner as in Toner Production Example 1 except that Toner Production Example 1 was replaced with Toner Particles 14 and Toner Fatty Acid Metal Salt 1 to Fatty Acid Metal Salt 3. Table 3 shows the physical properties of Comparative Toner E obtained.

<Toner Comparative Production Example 6>
Comparative Example Toner F was obtained in the same manner as in Toner Production Example 1 except that Toner Production Example 1 was replaced with Toner Particle 18 as Toner Particle 18 and Fatty Acid Metal Salt 1 to Fatty Acid Metal Salt 4. Table 3 shows the physical properties of Comparative Toner F obtained.

<Toner Comparative Production Example 7>
Comparative toner G was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 16 in Toner Production Example 1. Table 3 shows the physical properties of Comparative Toner G obtained.

<Toner Comparative Production Example 8>
Comparative toner H was obtained in the same manner as in Toner Production Example 1 except that Toner Particle 1 was replaced with Toner Particle 5 in Toner Production Example 1. Table 3 shows the physical properties of Comparative Toner H obtained.

<Toner Comparative Production Example 9>
Comparative toner I was obtained in the same manner as in Toner Production Example 1 except that Toner Production Example 1 was replaced with Toner Particles 1 and Toner Fatty Acid Metal Salt 1 to Fatty Acid Metal Salt 8. Table 3 shows the physical properties of Comparative Toner I obtained.

<Toner Comparative Production Example 10>
Comparative toner J was obtained in the same manner as in toner production example 1 except that toner particle 1 was changed to toner particle 6 and fatty acid metal salt 1 was changed to fatty acid metal salt 9 in toner production example 1. Table 3 shows the physical properties of Comparative Toner J thus obtained.

(Image evaluation)
The image evaluation was performed by partially modifying a commercially available color laser printer HP Color LaserJet 4700dn (manufactured by HP). In the modification, the process speed was changed to 200 mm / sec so that the fixing temperature could be set to an arbitrary temperature. Furthermore, it has been improved so that it can operate even when only one color process cartridge is installed.

  After removing the toner contained in the commercially available black cartridge and cleaning the inside by air blow, the test toner (225 g) and the toner carrier are mounted on the cartridge, and this cartridge is placed in a low temperature and low humidity environment (15 ° C.). 10% RH), developability and durability were evaluated. The image evaluation items are as follows, and the image evaluation was performed after printing 500, 15,000, and 30,000 images with a printing rate of 1% with horizontal lines as shown in FIG.

  Further, every 500 image prints were performed while taking an intermittent time of 8 hours to 12 hours.

LETTER size XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) was used as the transfer material.

[Fog]
After the printout test of 500 sheets, 15,000 sheets, and 30,000 sheets, the reflectance (%) of the non-image part of the printout image is measured with “REFLECTOMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku). did. The obtained reflectance was evaluated using a numerical value (%) subtracted from the reflectance (%) of unused printout paper (standard paper) measured in the same manner. The smaller the numerical value, the more image fog is suppressed. As a transfer material, LETTER size XEROX 4200 paper (manufactured by XEROX, 75 g / m ² ) was used.
A: Less than 0.5 B: 0.5 or more, less than 1.0 C: 1.0 or more, less than 3.0 D: 3.0 or more

[Poor regulation]
After the printout test of 500 sheets, 15,000 sheets, and 30,000 sheets, a halftone image (toner loading: 0.6 mg / cm ² ) is formed on transfer paper (75 g / m ² , A4 size paper). Printed out and evaluated by the amount of speckled streaks and toner clumps appearing on the image.
A: Not generated B: No spot-like streaks, but there are a few small toner clumps C: There are some speckled streaks at the end, or four, five small toner clumps D: Full surface There are spot-like streaks, or there are 5 or more small toner clusters or obvious toner clusters.

[Development stripe]
After the printout test of 500 sheets, 15,000 sheets, and 30,000 sheets, a halftone image (toner loading: 0.6 mg / cm ² ) is formed on transfer paper (75 g / m ² , A4 size paper). Printed out and evaluated by the number of development lines.
A: Not generated B: 1 or more, 3 or less C: 4 or more, 6 or less D: 7 or more, or a line having a width of 0.5 mm or more

[Charged contamination]
After the printout test of 500 sheets, 15,000 sheets, and 30,000 sheets, a halftone image (toner loading: 0.6 mg / cm ² ) is formed on transfer paper (75 g / m ² , A4 size paper). After printing out, the degree of transfer omission and the charging roller were directly observed visually, and the degree of contamination was evaluated.
A: There is no contamination on the charging roller and there is no problem in the image. B: Although the contamination on the charging roller can be confirmed slightly, there is almost no influence on the image. C: The contamination on the charging roller can be confirmed and transfer omission is slightly observed. Although there is almost no problem on the image D: Contamination to the charging roller is significant and there is an image defect

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

After the printout test of 500 sheets, 15,000 sheets, and 30,000 sheets, in the halftone image, it was visually evaluated whether or not uneven density occurred between the 1% printed image portion and the non-printed image portion. . Thereafter, the toner on the surface of the toner carrier was blown with air, and the surface of the toner carrier was observed.
A: No shading unevenness on the image and the surface of the toner carrying member is good. B: No shading unevenness is produced on the image, but some filming is confirmed on the surface of the toner carrying member.
C: Mild shading unevenness on the image D: Slight shading unevenness on the image

(Image density stability)
After the printout test of 500 sheets, 15,000 sheets, and 30,000 sheets was completed, three solid images were printed continuously, and evaluation was performed based on the difference in image density between the first sheet and the third sheet. The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure a relative density with respect to a printout image of a white background portion having a document density of 0.00. As the transfer material, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
A: Less than 0.05 B: 0.05 or more, less than 0.10 C: 0.10 or more, less than 0.15 D: 0.15 or more

<Example 1>
Evaluation was performed using toner A. As a result, good results were obtained for each item. The evaluation results are shown in Table 4.

<Example 2>
Evaluation was performed using toner B. As a result, good results were obtained for each item. The evaluation results are shown in Table 4.

<Example 3>
Evaluation was performed using toner C. As a result, good results were obtained for each item. The evaluation results are shown in Table 4.

<Example 4>
Evaluation was performed using toner D. As a result, good results were obtained for each item. The evaluation results are shown in Table 4.

<Example 5>
Evaluation was performed using Toner E. As a result, good results were obtained for each item. The evaluation results are shown in Table 4.

<Example 6>
Evaluation was performed using toner F. As a result, although fog and filming were slightly deteriorated, it was not a problem level, but generally good results were obtained for each item. The evaluation results are shown in Table 4.

<Example 7>
Evaluation was performed using toner G. As a result, in addition to slight electrification contamination, the development streaks were slightly deteriorated, but not at a problem level, and generally good results were obtained for each item. The evaluation results are shown in Table 4.

<Example 8>
Evaluation was performed using toner H. As a result, the image density stability was slightly deteriorated, but it was not a problem level. The evaluation results are shown in Table 4. In general, good results were obtained for each item. The evaluation results are shown in Table 4.

<Example 9>
Evaluation was performed using Toner I. As a result, the development streaks were slightly deteriorated and the image density stability was deteriorated, but it was not a problem level. The evaluation results are shown in Table 4.

<Example 10>
Evaluation was performed using Toner J. As a result, charging contamination occurred but was not a problem level. The evaluation results are shown in Table 4.

<Example 11>
Evaluation was performed using toner K. As a result, slight fogging, minor regulation failure, slight electrification contamination, and slight filming occurred, but this was not a problem level.

<Example 12>
Evaluation was performed using toner L. As a result, some development streaks occurred and the density stability deteriorated, but this was not a problem level. The evaluation results are shown in Table 4.

<Example 13>
Evaluation was performed using toner M. As a result, some fogging, some poor regulation and slight filming occurred. In addition, charging contamination occurred and transfer was lost, but this was not a problem level. The evaluation results are shown in Table 4.

<Example 14>
Evaluation was performed using toner N. As a result, the occurrence of fog and minor regulation defects and the density stability were slightly deteriorated. Further, although filming occurred, it was not at a level causing a problem due to slight unevenness in the image. The evaluation results are shown in Table 4.

<Example 15>
Evaluation was performed using toner O. As a result, fog and minor charging failure occurred. In addition, although there were minor regulatory failures, it was at a level that would not be a major problem. Further, although filming occurred, it was not at a level causing a problem due to slight unevenness in the image. The evaluation results are shown in Table 4.

<Example 16>
Evaluation was performed using toner P. As a result, slight fogging, slight regulation failure and slight filming occurred. In addition, charging contamination occurred and transfer omission on the image occurred, but this was not a problem level. The evaluation results are shown in Table 4.

<Example 17>
Evaluation was performed using toner Q. As a result, the fog and concentration stability deteriorated, but the level was not problematic. The evaluation results are shown in Table 4.

<Example 18>
Evaluation was performed using toner R. As a result, there was a slight deterioration of fog, a slight regulation failure and a slight development streak. Further, although the concentration stability deteriorated, it was not a problem level. The evaluation results are shown in Table 4.

<Example 19>
Evaluation was performed using toner S. As a result, there was slight deterioration of fog, slight regulation failure, slight development streaks and slight filming, but this was not a problem level. The evaluation results are shown in Table 4.

<Example 20>
Evaluation was performed using toner T. As a result, some fog was generated. Further, development streaks occurred and the initial density stability deteriorated, but this was not a problem level. The evaluation results are shown in Table 4.

<Example 21>
Evaluation was performed using toner U. As a result, slight fogging, slight electrification contamination, and slight density stability deterioration occurred. Further, although development streaks occurred, it was not a problem level. The evaluation results are shown in Table 4.

<Example 22>
Evaluation was performed using toner V. As a result, slight fogging, slight development streaks, slight electrification contamination and slight filming occurred. Further, although the image density stability deteriorated, it was not a problem level. The evaluation results are shown in Table 4.

<Example 23>
Evaluation was performed using toner W. As a result, there was slight charge contamination and slight deterioration in image density stability. In addition, fogging deteriorated and filming occurred, but it was not a problem level. The evaluation results are shown in Table 4.

<Comparative Example 1>
Evaluation was performed using Comparative Example Toner A. As a result, the occurrence of clear fogging and remarkable regulation failure occurred, which was a big problem on the image. Moreover, density stability deteriorated and filming occurred. The evaluation results are shown in Table 4.

<Comparative example 2>
Evaluation was performed using Comparative Example Toner B. As a result, significant electrification contamination occurred and a large number of transfer defects occurred. In addition, a large number of development streaks occurred, which became a big problem on the image. The evaluation results are shown in Table 4.

<Comparative Example 3>
Evaluation was performed using Comparative Example Toner C. As a result, obvious fogging and significant regulatory failure occurred. In addition, a large number of transfer omissions due to the occurrence of significant charging defects and the occurrence of filming occurred, which became a serious problem on the image. The evaluation results are shown in Table 4.

<Comparative example 4>
Evaluation was performed using Comparative Example Toner D. As a result, the image density stability was significantly deteriorated and a large number of development streaks occurred, which caused a serious problem on the image. The evaluation results are shown in Table 4. The evaluation results are shown in Table 4.

<Comparative Example 5>
Evaluation was performed using Comparative Example Toner E. As a result, obvious fogging and remarkable regulation failure occurred, which became a big problem on the image. Further, the concentration stability was deteriorated. The evaluation results are shown in Table 4.

<Comparative Example 6>
Evaluation was performed using Comparative Example Toner F. As a result, a large number of transfer omissions due to a remarkable charging failure and a large number of development streaks occurred, which became a serious problem on the image. In addition, slight density unevenness occurred due to filming. The evaluation results are shown in Table 4.

<Comparative Example 7>
Evaluation was performed using the toner G of Comparative Example. As a result, the density stability is greatly deteriorated, a large number of development streaks are generated, and this is a serious problem on the image. The evaluation results are shown in Table 4.

<Comparative Example 8>
Evaluation was performed using Comparative Example Toner H. As a result, obvious fogging, remarkable regulation failure, transfer omission due to significant charging contamination, and filming occurred, resulting in a large image problem. The evaluation results are shown in Table 4.

<Comparative Example 9>
Evaluation was performed using Comparative Example Toner I. As a result, clear fog was generated. In addition, a large number of development streaks and image density stability are remarkably deteriorated, resulting in a large image problem. The evaluation results are shown in Table 4.

<Comparative Example 10>
Evaluation was performed using Comparative Example Toner J. As a result, significant deregulation, significant charging contamination, and significant filming occurred, which became a serious problem on images. In addition, fogging, deterioration of density stability, and development streaks were slightly generated. The evaluation results are shown in Table 4.

It is sectional drawing of a process cartridge. The horizontal line is an image with a printing rate of 1%.

Explanation of symbols

10: latent image carrier 11: charging roller 14: toner carrier 15: toner supply member 16: regulating blade 17: toner 23: toner container 25: stirring unit

Claims (6)

In a toner having toner particles containing at least a binder resin, a colorant, and a release agent, and at least a fatty acid metal salt,
The toner has a number average particle diameter (D1) of Dt (μm), the number of particles having a particle diameter of 2/3 or less of Dt in the toner particles is P (number%), and is based on the volume basis of the fatty acid metal salt. A toner satisfying the following formulas (1) to (5), where Ds is a median diameter (D50), and V (mass%) is an addition amount of the fatty acid metal salt to the toner.
4.0 ≦ Dt ≦ 8.5 (1)
0.10 ≦ Ds ≦ 0.65 (2)
5.0 ≦ P ≦ 25.0 (3)
8.0 ≦ Dt / Ds ≦ 40.0 (4)
0.0005 ≦ V / P ≦ 0.0500 (5)   The toner according to claim 1, wherein the Dt is 4.5 μm or more and 7.0 μm or less. The toner according to claim 1, wherein a ratio V / P of V and P satisfies the following formula (4).
0.0025 ≦ V / P ≦ 0.0250 (6)   The toner according to any one of claims 1 to 3, wherein the toner further contains a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group. The toner according to the fatty acid metal salt, any one of claims 1 to 4, wherein the carbon number of 12 to 22 of a metal salt of a fatty acid. Wherein the fatty acid metal salt, the toner according to any one of claims 1 to 5, characterized in that zinc stearate or calcium stearate.

Images