JP2011047988A - Toner - Google Patents

Abstract

An object of the present invention is to provide a toner which prevents start-up streaks and is excellent in initial fog characteristics and development stability in long-term use.
A toner having toner particles, a fatty acid metal salt and an inorganic fine powder,
The inorganic fine powder contains silica fine particles,
The silica fine particles are treated with at least one of alkoxysilane or alkoxysilazane, and are treated with silicone oil,
The silica fine particles have a release rate of silicone oil from the silica fine particles of 50% by mass or less based on the amount of carbon.
The fatty acid metal salt is characterized in that a median diameter (D50) on a volume basis is 0.15 μm or more and 0.65 μm or less.
[Selection figure] None

Description

  The present invention relates to a toner used in a recording method using electrophotography or the like.

  2. Description of the Related Art In recent years, image forming apparatuses such as copying machines and printers have been increasingly required to have higher speed, higher image quality, and higher stability as the purpose of use and usage environment have diversified. However, if the speed of the apparatus is increased, the temperature rise of the apparatus is promoted due to the high process speed, so that the image density and the image quality are easily deteriorated due to the toner deterioration. In addition, since the charging time for the toner tends to be shorter, an image defect (hereinafter referred to as fogging) is likely to occur in the initial state, for example, when the toner flies to the non-image area and the non-print area is colored. Become. In order to solve such a problem, a device has conventionally been devised such as external addition of a fluidity imparting agent such as silica fine particles or a microcarrier such as strontium titanate. However, these materials stagnate or accumulate on the photosensitive drum together with the transfer residual toner that has not been removed in the cleaning process, and grow each time through the development process, thereby causing various image defects. Among the image defects generated in this way, there is a strong demand for improvement of the starting stripe that appears in the image as a colored stripe. The startup stripe will be described below.

  Considering the behavior of the photosensitive drum and the cleaning blade when printing, an agglomerate composed of the transfer residual toner and the external additive is formed at the tip of the cleaning blade by superimposing a large number of prints. When such agglomerates are present, fusion is likely to occur by being pressed against the photosensitive drum by the pressure of the contact portion of the cleaning blade when printing is stopped. If printing is performed again in this state, the fused agglomerates will pass through the cleaning blade and reach the charging member, and a part of the agglomerate will move to the charging member, causing charging failure and disturbing the latent image on the photosensitive drum. . Then, every time the charging member rotates twice and three times, an image defect due to a charging failure occurs for each rotation period of the charging member due to the same cause. Since such a phenomenon occurs at the time of starting after printing is stopped, this image defect is called a starting stripe.

  As described above, there is a need for a toner that suppresses initial fogging even when the speed of the apparatus is increased, exhibits excellent development stability even during long-term use, and is less likely to cause startup streaks.

  In order to deal with such problems, a technique for preventing the occurrence of fogging on non-image areas and filming on a photoreceptor by treating polydimethylsiloxane on the surface of silica fine particles so as to minimize free components is disclosed. (See Patent Document 1). Further, a technique for improving fog and durable developability by treating silica fine particles with silicone oil and controlling the release amount of the silicone oil is disclosed (see Patent Documents 2 and 3). Furthermore, a technique for improving the environmental stability and the cleaning property by suppressing the liberation rate of the toner base particles and the fatty acid metal salt to a low level and preventing the occurrence of photoconductor filming is disclosed (see Patent Document 4).

  However, there is still room for improvement in the above-described technique in terms of preventing image defects caused by charging member contamination such as startup stripes.

JP 2000-066439 A JP 2004-212789 A JP 2004-102236 A JP 2007-108622 A

  The object of the present invention has been made in view of the above problems of the prior art. That is, it is an object of the present invention to provide a toner that prevents starting streaks and is excellent in initial fog characteristics and development stability in long-term use.

The present invention is a toner having toner particles containing at least a binder resin, a colorant and a wax, a fatty acid metal salt and an inorganic fine powder,
The inorganic fine powder contains silica fine particles,
The silica fine particles are treated with at least one of alkoxysilane or silazane, and are treated with silicone oil,
The silica fine particles have a release rate of silicone oil from the silica fine particles of 50% by mass or less based on the amount of carbon.
The fatty acid metal salt relates to a toner having a median diameter (D50) on a volume basis of 0.15 μm to 0.65 μm.

  According to the present invention, it is possible to provide a toner that prevents the occurrence of startup streaks and is excellent in initial fog characteristics and development stability in long-term use.

FIG. 2 is a schematic cross-sectional view illustrating an example of an image forming apparatus that can suitably use the toner of the present invention. It is explanatory drawing of the propeller-type blade of the powder fluidity | liquidity analyzer used for a measurement of Total Energy.

A toner having toner particles containing at least a binder resin, a colorant, and a wax, a fatty acid metal salt, and an inorganic fine powder,
The inorganic fine powder contains silica fine particles,
The silica fine particles are treated with at least one of alkoxysilane or silazane, and are treated with silicone oil,
The silica fine particles have a release rate of silicone oil from the silica fine particles of 50% by mass or less based on the amount of carbon.
The fatty acid metal salt is a toner having a volume-based median diameter (D50) of 0.15 μm or more and 0.65 μm or less.

  According to the earnest study of the present inventors, after combining silica fine particles and a fatty acid metal salt as an external additive of the toner, silicone oil is fixed on the surface of the silica fine particles, and the particle size of the fatty acid metal salt is adjusted. Thus, the inventors have found that the above problems can be solved, and have completed the present invention.

  Below, the effect acquired by this invention is demonstrated in detail.

  According to the study by the present inventors, it was effective to improve the releasability between the toner, the charging member, and the photosensitive drum in order to prevent the start stripe. Here, it is as follows when the mechanism of starting stripe generation is arranged.

  First, an agglomerate formed from the external additive and the transfer residual toner is generated at the contact portion between the cleaning blade and the photosensitive drum. Next, when printing is stopped, the aggregate is pressed against the photosensitive drum by the cleaning blade, and the aggregate is partially fused on the photosensitive drum. Thereafter, the agglomerates fused when printing again pass through the cleaning blade to reach the charging member, shift from the photosensitive drum to the charging member, and streak at the cycle of the charging member every time the charging member rotates (starting streak) Will occur.

  Therefore, in order to improve the starting stripe, it is necessary to first suppress the formation of agglomerates, then suppress the fusion to the photosensitive drum, and suppress the transition to the charging member. In order to suppress the formation of agglomerates, it is necessary to control the cohesive force between toners as a toner. In terms of suppressing the transfer to the charging member, it is important to make the toner easily peel off from the charging member.

  First, in order to reduce the cohesive force between toners, it is necessary to impart high fluidity and releasability between toners to the toner. With regard to fluidity, the effect of having silica fine particles present on the surface is large, and among them, a remarkable effect was obtained with the treatment with silicone oil in addition to the treatment with alkoxysilane or alkoxysilazane. This is because the surface of the silica fine particles is uniformly hydrophobized by the surface treatment, so that the adhesion state to the toner becomes uniform, the fluidity is improved, and the cohesive force between the toners can be reduced. Further, in order to improve the releasability between the toners, the effect of fixing an external additive acting as a lubricant on the toner surface is great, and the effect of the fatty acid metal salt is particularly great. In order to fix the fatty acid metal salt, it is necessary to reduce the particle size of the fatty acid metal salt to some extent. However, if the fatty acid metal salt is too small, it tends to be difficult to exhibit the releasability. Specifically, when the median diameter (D50) of the fatty acid metal salt is 0.15 μm or more and 0.65 μm or less, the adhesion between the toner surface and the releasability can be balanced, so that the cohesive force between toners is reduced. The startup streaks tended to improve significantly.

  Next, the point that the toner is easily peeled off from the charging member will be described. When attention is paid to the phenomenon in which the toner moves to the charging member, the adhesion force of the silica fine particles to the charging member is high, and the silica fine particles often adhere to the starting point. Therefore, it has been necessary to impart a releasing effect to the silica fine particles. According to the study by the present inventors, there was a tendency that a release effect was imparted to the silica fine particles by combining the silica fine particles with the silicone oil fixed on the surface and the fatty acid metal salt. This is because silica fine particles and fatty acid metal salts firmly covered with silicone oil have a structure in which alkyl groups are present at a high density on the outermost surface. I think. Further, when the polarity is high, the existence state and behavior on the toner surface are expected to be similar. Therefore, even if the silica fine particles on the toner surface come into contact with the charging member, the fatty acid metal salt is considered to behave together. At that time, the effect of releasing the fatty acid metal salt is imparted to the silica fine particles, and it is assumed that the starting stripe is improved because the fatty acid metal salt is easily peeled off from the charging member. Specifically, it is necessary to make the fatty acid metal salt present on the toner surface after controlling the carbon oil-based release rate of the silicone oil contained in the silica fine particles to 50 mass% or less.

  Regarding durable developability in long-term use, two points were important: uniform charging of the toner and improvement of charge rising property. Regarding uniform charging, the influence of silica fine particles is large, and it was particularly effective to make the silica surface uniform. Specifically, when the silica fine particles are treated with alkoxysilane or silazane and silicone oil, the surface of the silica fine particles becomes uniform and the chargeability tends to be uniform. As a result of investigating the rising property of charging after using such silica fine particles, a significant improvement effect was obtained by using a fatty acid metal salt. This is presumed to be because the fatty acid metal salt contributes as a microcarrier and, as described above, has a high affinity with the silica fine particles, whereby the entire toner surface can be uniformly charged.

  As described above, in order for the fatty acid metal salt to exert an effect as a microcarrier, it is necessary that the fatty acid metal salt behaves out of the toner to some extent. According to the study by the present inventors, when the median diameter (D50) of the fatty acid metal salt is 0.15 μm or more and 0.65 μm or less, both the component fixed to the toner surface and the free component exist. Thereby, the effect as a microcarrier was also acquired with the effect with respect to the above-mentioned starting stripe.

  The median diameter (D50) of the fatty acid metal salt of the present invention on a volume basis is 0.15 μm or more and 0.65 μm or less. If it is less than 0.15 μm, the effect of releasing from the charging member is reduced, so that the starting stripe is greatly deteriorated. In addition, since the effect as a microcarrier is reduced, image density and fog characteristics are greatly deteriorated. On the other hand, if it exceeds 0.65 μm, the fatty acid metal salt is difficult to adhere to the toner, and the starting stripe is greatly deteriorated.

  The volume median diameter (D50) of the fatty acid metal salt is preferably 0.30 μm or more and 0.60 μm or less. When it is 0.30 μm or more, the function as a microcarrier is increased, and thus the fog characteristic at the initial stage of durability evaluation tends to be improved. If it is 0.60 μm or less, it tends to adhere to the toner surface, and the starting stripe tends to be improved.

  The silica fine particles of the present invention have a surface treated with alkoxysilane or silazane and silicone oil, and the liberation rate of the silicone oil from the silica fine particles is 50% by mass or less based on the amount of carbon. When the carbon oil-based liberation rate of the silicone oil exceeds 50% by mass, there are many sites having polarities different from those of the fatty acid metal salt because the coverage of the silica fine particle surface is low. Therefore, the affinity with the fatty acid metal salt is lowered, and the starting stripe is greatly deteriorated. Further, since the surface of the silica fine particles is not uniformly treated, the charging becomes non-uniform and the development performance is deteriorated. Similarly, when the surface of the silica fine particles is not subjected to the above-described treatment, the charge is likely to be non-uniform and the start-up streak deteriorates.

  Sensitivity was also found in the effect of the toner of the present invention in the order of the above treatments. Specifically, the silica fine particles are preferably treated with silicone oil and then treated with at least one of alkoxysilane or silazane. When treated as described above, the release rate of the silicone oil from the silica fine particles tends to be controlled to be low, the affinity with the fatty acid metal salt is improved, and the start-up streak tends to be improved.

  Further, the treatment amount of the silicone oil is preferably 0.5 parts by mass or more and 11.0 parts by mass or less with respect to 100 parts by mass of the silica fine particle raw material. When the amount is 0.5 parts by mass or more, the affinity with the fatty acid metal salt is increased, and the effect of the fatty acid metal salt as a microcarrier is sufficiently exerted. . If the amount is 11.0 parts by mass or less, the amount of free silicone oil can be easily controlled to be low, and a tendency to maintain the image density even when used for a long time is observed.

  The toner of the present invention contains a fatty acid metal salt. The liberation rate of the fatty acid metal salt is preferably 10.0% by mass or more and 40.0% by mass or less. 10.0 mass% or more is preferable because the initial image density under high temperature and high humidity is increased due to the increased function as a microcarrier. When the content is 40.0% by mass or less, the ratio of the fatty acid metal salt adhering to the toner surface is high and the starting stripe tends to be improved, which is preferable. In order to control the release rate, it is necessary to adjust the surface composition and particle size of the toner particles and to optimize the mixing process conditions. In particular, the release rate is controlled to be low by increasing the time and frequency of the mixing process. I can do it.

In the toner of the present invention, the starting stripe is improved by suppressing the formation of agglomerates between the cleaning blade and the photosensitive drum. In order to suppress the formation of agglomerates, it was also important to control the toner compression rate low. The compression ratio is sensitive to the particle size and surface composition of the toner, as well as the amount of silica fine particles treated with silica oil. When the particle size is reduced, the compression rate of the toner tends to increase. With respect to the silica fine particles, when the amount of the silicone oil treated is reduced, the bulk increases, the apparent density of the toner increases, and the compression rate tends to increase. As for the surface composition, the compression ratio tends to be lowered by making the surface hard. For example, in the case of a toner having a core-shell structure, the compression rate can be lowered by increasing the thickness of the shell. The inventors adjusted by the above means and controlled to a desired compression rate. Specifically, it is preferable that the compression ratio obtained from the following formula (2) is 30 or less, since start-up streaks are improved by suppressing the formation of aggregates.
Compression rate = {1- (apparent density / tap density)} × 100 (2)

  It was also important to control the ease of unraveling the toner particles before adding the silica fine particles and the fatty acid metal salt. When the ease of toner particle dissolution is controlled, the ease of toner dissolution is also affected. Specifically, the total energy when the stirring speed measured by the powder flowability measuring device for toner particles is 100 revolutions is preferably 500 mJ or more and 1000 mJ or less. Total Energy has a large sensitivity to the particle size of the toner particles. When the particle size is decreased, Total Energy tends to increase, and when the particle size is increased, Total Energy tends to decrease. For example, when using a toner having a core-shell structure, the toner can be adjusted by the thickness of the shell portion. When the shell is thick, the toner particles tend not to aggregate, and the total energy tends to decrease. When the total energy is within the above range, the agglomerates are easily broken, so that the starting stripes tend to be improved.

  Examples of the fatty acid metal salt suitably used in the present invention include a metal salt selected from zinc, calcium, magnesium, aluminum, and lithium. Fatty acid zinc or fatty acid calcium is particularly preferred. Fatty acid zinc and fatty acid calcium are highly effective as microcarriers, and there is a tendency that fog in the initial stage of durability is improved.

  The fatty acid metal salt is preferably a stearic acid metal salt. When the metal stearate is fixed on the toner surface, the cohesive force between the toners is reduced, and the agglomerates generated between the cleaning blade and the photosensitive drum are easily broken, so that the starting stripe tends to be improved.

The fatty acid metal salt preferably has a span value B defined by the following formula (1) of 1.75 or less.
Span value = (D95−D5) / D50 (1)
D5: 5% cumulative diameter based on volume of fatty acid metal salt D50: 50% cumulative diameter based on volume of fatty acid metal salt D95: 95% cumulative diameter based on volume of fatty acid metal salt

  The span value is an index indicating the particle size distribution of the fatty acid metal salt. When the span value is 1.75 or less, the dispersion in the particle size of the fatty acid metal salt present in the toner is reduced, so that the charging stability is improved. There was a tendency for fogging at the initial stage of durability to improve. The span value is more preferably 1.50 or less, and if it is 1.50 or less, the concentration at the end of durability tends to increase. More preferably, it is 1.30 or less, and if it is 1.30 or less, the state of fixing to the toner surface becomes uniform, and it becomes difficult to be fused on the photosensitive drum even after being left for a long period of time. It was a trend.

  The materials that can be used in the toner of the present invention are described below.

  Examples of fatty acid metal salts that can be used in the present invention include zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, lithium stearate, and zinc laurate.

  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.

  The silica fine particles used in the present invention must be treated with silicone oil and at least one of alkoxysilane or silazane.

  The silica raw material used to obtain the silica fine particles of the present invention is produced from a dry process produced by vapor phase oxidation of a silicon halogen compound or dry silica called fumed silica, and water glass. Both wet silicas are mentioned. In the present invention, dry silica having less silanol groups on the surface and inside and no production residue is preferred.

  The silica fine particles used in the present invention have the highest average particle size in the particle size distribution on the basis of the number of 5 to 25 nm, and the highest peak particle size in the particle size distribution on the number basis is 20 nm or less, which is the highest for the toner. It is preferable because it can be charged and fluid.

  In the method of treatment with silicone oil necessary for obtaining the silica fine particles of the present invention, the silica raw material and the silicone oil may be directly mixed using a mixer such as a Henschel mixer. It is good also by the method of injecting. Alternatively, the silicone oil may be dissolved or dispersed in an appropriate solvent, and then mixed with the silica raw material to remove the solvent.

As the silicone oil, dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, and the like can be used. In particular, dimethyl silicone oil is preferable, and the viscosity of the oil is preferably 100 mm ² / s or less at 25 ° C.

  For the treatment with at least one of alkoxysilane and silazane necessary for obtaining the silica fine particles of the present invention, a generally known method can be used. For example, a dry treatment in which a vaporized alkoxysilane or silazane is reacted with a silica base that has been made into a cloud by stirring can be mentioned. Moreover, it can process by the wet method which disperse | distributes a silica raw material in a solvent, and makes alkoxysilane or a silazane drop-react.

  As the alkoxysilane or silazane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, dimethyldiethoxysilane, isobutyltrimethoxysilane, hexamethyldisilazane and the like can be used. In particular, isobutyltrimethoxysilane and hexamethyldisilazane are preferable. A preferable treatment amount of these alkoxysilanes or silazanes is 5 to 30 parts by mass per 100 parts by mass of silica.

  In the toner used in the present invention, other additives may be further used within a range that does not substantially adversely affect the toner. For example, a lubricant powder such as polyethylene fluoride powder and polyvinylidene fluoride powder, an abrasive such as cerium oxide powder, silicon carbide powder, and strontium titanate powder, or a fluidity imparting agent such as titanium oxide powder and aluminum oxide powder, and caking Inhibitors, and organic fine particles having opposite polarity and inorganic fine particles can also be used in small amounts as developability improvers. These additives can also be used after hydrophobizing the surface.

  The toner of the present invention can be used as a one-component developer by further mixing with other external additives (for example, a charge control agent, etc.) if necessary, and can also be used as a two-component developer in combination with a carrier. Can do. As the carrier for use in the two-component development method, all conventionally known carriers can be used. Specifically, surface oxidized or unoxidized iron, nickel, cobalt, manganese, chromium, rare earth, etc. Particles having an average particle size of 20 μm or more and 300 μm or less, such as metals and their alloys or oxides, are preferably used.

  Examples of the binder resin used in the toner of the present invention include styrene such as polystyrene and polyvinyltoluene, and homopolymers thereof and styrene-propylene copolymers, styrene-vinyltoluene copolymers, and styrene-vinylnaphthalene copolymers. Polymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene -Methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl Ether copolymer, styrene Styrene copolymers such as vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, polymethyl methacrylate, poly Butyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, and the like can be used, and these can be used alone or in combination. Among these, a styrene-acrylic resin made of a copolymer of styrene and an acrylic monomer is particularly preferable in terms of development characteristics.

  The toner of the present invention contains a colorant. Any colorant can be used, and examples of the colorant that can be preferably used include the following.

  Examples of organic pigments or organic dyes as cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds.

  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.

  Examples of the organic pigment or organic dye as the yellow colorant include compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.

  Examples of the black colorant include carbon black, those prepared by using the above yellow colorant / magenta colorant / cyan colorant, and a magnetic material.

  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. From such a viewpoint, a magnetic material that has been subjected to a hydrophobic treatment is preferred.

  Examples of the release agent that can be used in the toner of the present invention include aliphatic hydrocarbon waxes and ester waxes. In the present invention, the ester wax only needs to have at least one ester bond in one molecule, and either natural wax or synthetic wax may be used.

Below, the wax which can be used is illustrated.
-Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax.
-Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof.
-Waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanic acid ester wax.
・ Deoxidized part or all of fatty acid esters such as deoxidized carnauba wax.
・ Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid.
・ Unsaturated fatty acids such as brassic acid, eleostearic acid and valinalic acid, stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, melyl alcohol and other saturated alcohols, and polyhydric alcohols such as sorbitol .
-Fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide.
-Saturated fatty acid bisamides such as methylene bis stearamide, ethylene biscapric amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide.
Unsaturated fatty acid amides such as ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide.
-Aromatic bisamides such as m-xylenebisstearic acid amide and N, N'-distearylisophthalic acid amide.
-Aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metal soap).
-Waxes grafted to aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid.
-A methyl ester compound having a hydroxyl group, obtained by partial esterification of a fatty acid and a polyhydric alcohol, such as behenic acid monoglyceride, hydrogenation of vegetable oils and the like.
-Long chain alkyl alcohol or long chain alkyl carboxylic acid having 12 or more carbon atoms.

  It is preferable to add a charge control agent to the toner of the present invention as necessary in order to improve charging characteristics. As the charge control agent, a known one can be used, but a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Among the charge control agents, specific examples of negative charge control agents include metal compounds of aromatic carboxylic acids such as salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid, dicarboxylic acid, azo dyes or metal salts of azo pigments or Examples thereof include a metal complex, a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group, a boron compound, a urea compound, a silicon compound, and a calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, a nigrosine compound, and an imidazole compound.

  The toner of the present invention preferably has a core-shell structure in order to further improve the durability developability under high temperature and high humidity. This is because by having the shell layer, the surface property of the toner becomes uniform, the charging property becomes uniform, and the stress resistance increases. For this reason, it is preferable to use an amorphous high molecular weight body for the shell layer.

  The method for producing the toner of the present invention will be described below.

  The toner of the present invention is produced in an aqueous medium. As a production method in an aqueous medium, it is preferable to produce toner particles in an aqueous medium, such as a dispersion polymerization method, an association aggregation method, a dissolution suspension method, a suspension polymerization method, etc. The control of the diameter and the surface composition is easy and preferable.

  The suspension polymerization method is a polymerizable monomer in which a polymerizable monomer and a colorant (in addition, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives as necessary) are uniformly dissolved or dispersed. A composition is obtained. Thereafter, the polymerizable monomer composition is dispersed in a continuous layer (for example, an aqueous phase) containing a dispersion stabilizer by using a suitable stirrer, and simultaneously subjected to a polymerization reaction, whereby toner particles having a desired particle size are obtained. Is what you get. The toner particles obtained by this suspension polymerization method are expected to be improved in durable developability because the individual toner particle shapes are almost spherical, and the charge amount distribution is relatively uniform.

  In the production of toner particles according to the present invention, examples of the polymerizable monomer constituting the polymerizable monomer composition include the following.

  Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, ethyl acrylate, Acrylate esters such as n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate , Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, Methacrylic acid dimethyl aminoethyl, methacrylic acid esters such as diethylaminoethyl methacrylate and other acrylonitrile, methacrylonitrile, and the like monomers acrylamide. These monomers can be used alone or in combination. Among the above-mentioned monomers, styrene or a styrene derivative is preferably used alone or mixed with other monomers from the viewpoint of developing characteristics and durability of the toner.

  In the production of the toner particles of the present invention, a crosslinking agent can be added as necessary. A preferable addition amount is 0.01 parts by mass or more and 10.00 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

  Here, as the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, such as ethylene glycol diacrylate and ethylene glycol diacrylate. Carboxylic acid ester having two double bonds, such as methacrylate, 1,3-butanediol dimethacrylate, divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone, and three or more vinyl groups A compound is used alone or as a mixture of two or more.

  When the toner particles of the present invention are produced by the suspension polymerization method, the above-described toner composition or the like is added as appropriate, and the polymerizability is uniformly dissolved or dispersed by a dispersing machine such as a homogenizer, a ball mill, or an ultrasonic dispersing machine. The monomer composition is suspended in an aqueous medium containing a dispersion stabilizer. At this time, the particle size of the obtained toner particles becomes sharper by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired toner particle size at a stretch. The polymerization initiator may be added at the same time when other additives are added to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Moreover, a polymerizable monomer or a polymerization initiator can be added immediately after granulation and before starting the polymerization reaction.

  After granulation, stirring may be performed using a normal stirrer to such an extent that the particle state is maintained and particle floating and sedimentation are prevented.

  When the toner particles of the present invention are produced, known surfactants, organic dispersants and inorganic dispersants can be used as the dispersion stabilizer. Among these, inorganic dispersants can be preferably used because they are less likely to produce ultrafine powder, are less likely to lose stability even when the reaction temperature is changed, and are easy to wash. Examples of such inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, phosphate polyvalent metal salts such as hydroxyapatite, carbonates such as calcium carbonate and magnesium carbonate, calcium metasuccinate, calcium sulfate, Examples thereof include inorganic salts such as barium sulfate and inorganic compounds such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

  These inorganic dispersants are preferably used in an amount of 0.20 parts by mass or more and 20.00 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. Moreover, the said dispersion stabilizer may be used independently and may use multiple types together. Further, a surfactant may be used in combination.

  In the step of polymerizing the polymerizable monomer, the polymerization temperature is set to 40 ° C or higher, and generally 50 ° C to 90 ° C. As described above, in the present invention, it is desirable to control the molecular weight distribution of the binder resin formed by polymerizing the polymerizable monomer to be low and sharp. The polymerization temperature and the rate of temperature rise until reaching the polymerization temperature greatly contribute to the molecular weight distribution, and it is important to adjust these production conditions in order to control the molecular weight distribution.

  After completion of the above steps, toner particles are obtained by filtering, washing and drying the obtained polymer particles by a known method. The toner of the present invention can be obtained by mixing the toner particles with external additives including silica fine particles and fatty acid metal salts as described above, if necessary, and adhering them to the surface of the toner particles. It is also possible to insert a classification step in the manufacturing process (before mixing the inorganic fine powder) to cut coarse powder and fine powder contained in the toner particles. Details of the mixing step will be described later.

  In the mixing step of the toner particles and the external additive, the stirring blade disposed in the mixing unit moves, and the toner particles and the external additive receive energy from the stirring blade and collide with each other. Additives adhere to the particles.

  At the start of mixing of the toner particles and the external additive, a difference in the movement speed between the toner particles and the additive occurs due to the difference in particle diameter and specific gravity, and the chance of collision between the toner particles and the additive increases. Thereby, the uniformization of the external additive in the toner proceeds mainly. When mixing continues and the movement of the toner particles and the external additive reaches a steady state, the difference in relative motion speed between the particles becomes small, and the chance of collision between the toner particles and the external additive decreases. The adhesion of the external additive to the toner particles proceeds mainly by contact with the toner particles.

  In order to exert the effect of the present invention, it is important that the fatty acid metal salt is present more uniformly on the surface of the toner particles and efficiently adhered to the toner particles. As a technique for that purpose, there is a method in which a pause process is provided in the mixing process, the mixing process is divided into several times, and mixing, taking out, and mixing are repeated for the purpose of eliminating dead space.

  Next, an example of an image forming apparatus that can suitably use the toner of the present invention will be specifically described with reference to FIG. In FIG. 1, reference numeral 100 denotes an electrostatic latent image carrier (hereinafter also referred to as a photoconductor), which includes a charging roller 117, a developing device 140 having a toner carrier 102, a transfer charging roller 114, a cleaner 116, and a register roller. 124 etc. are provided. The electrostatic latent image carrier 100 is charged to, for example, −600 V by the charging roller 117 (applied voltages are, for example, an AC voltage of 1.85 kVpp and a DC voltage of −620 Vdc). Then, exposure is performed by irradiating the electrostatic latent image carrier 100 with the laser beam 123 by the laser generator 121, and an electrostatic latent image corresponding to the target image is formed. The electrostatic latent image on the electrostatic latent image carrier 100 is developed with a one-component toner by the developing device 140 to obtain a toner image, and the toner image is transferred in contact with the electrostatic latent image carrier via a transfer material. The image is transferred onto the transfer material by the roller 114. The transfer material on which the toner image is placed is conveyed to the fixing device 126 by the conveying belt 125 or the like and fixed on the transfer material. In addition, the toner remaining on the electrostatic latent image carrier is partially cleaned by the cleaner 116.

  Next, a method for measuring each physical property related to the toner of the present invention will be described.

<Measurement of median diameter and span value of fatty acid metal salt>
The volume-based median diameter 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, optical axis adjustment, optical axis fine adjustment, and blank measurement are 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 enter 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, 5% integrated diameter, 50% integrated diameter, and 95% integrated diameter are calculated. The obtained values are D5, D50, and D95, and the span value is obtained from these values.

<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 KM Shaker (manufactured by Iwaki Sangyo Co., Ltd.), X-ray fluorescence analyzer Axios (manufactured by PANalytical), and dedicated software for setting measurement conditions and analyzing measurement data Using “SuperQ ver. 4.0F” (manufactured by PANalytical), the liberation rate of the fatty acid metal salt is determined from the difference in the intensity of the fluorescent X-rays.

Specific measurement methods are as follows.
(1) About 1 g of toner is placed on a PVC ring having a ring diameter of 22 mm × 16 mm × 5 mm, and compressed with 100 kgf by a press machine to prepare a sample. The obtained sample is measured with a fluorescent X-ray analyzer (Axios) to obtain the net strength derived from the metal element of the fatty acid metal salt contained in the toner.
(2) The toner particles are also measured with a fluorescent X-ray analyzer (Axios) in the same manner as in (1), and the net intensity derived only from the toner particles is obtained for the metal element contained in the fatty acid metal salt.
(3) Precisely evaluate 1 g of toner and add 16 g of methanol to a 30 cc vial. The toner is put into the vial, and after standing for 30 seconds, it is shaken under the following conditions to separate the toner and methanol. At this time, for example, a toner containing a magnetic material is preferably separated by a magnetic force.

[Shaking device / conditions]
Device: KM Shaker (manufactured by Iwaki Sangyo Co., Ltd.)
model: V. SX
Shaking conditions: Speed is set to 50 and shaken for 10 seconds. The separated toner is dried overnight in a vacuum dryer, and about 1 g of the obtained sample is placed on the same vinyl ring as in (1), and then pressed. Compress with 100kgf to make a sample. The obtained sample is measured with a fluorescent X-ray analyzer (Axios), and the net intensity derived from the fatty acid metal salt contained in the sample after shaking in methanol is obtained.

  Note that Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 300 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 is 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 shaking with methanol.
Fatty acid metal salt liberation rate (%) = {(BT)-(AT)} / (BT) × 100
A: Net strength of metal element of fatty acid metal salt in toner after methanol shaking B: Net strength of metal element of fatty acid metal salt in toner before methanol shaking T: Net strength of toner particles

<Average particle size and particle size distribution of toner>
The toner according to the present invention has a weight average particle diameter (D4) of a precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for measurement condition setting and measurement data analysis, measurement was performed with 25,000 effective measurement channels. The measurement data was analyzed and calculated.

  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.

  In the “Standard Measurement Method (SOM) Change 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 The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash 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 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, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
[2] About 30 ml of the electrolytic aqueous solution was placed in a glass 100 ml flat bottom beaker, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder consisting of an organic builder as a dispersant was precisely measured. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
[3] Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios) with an electrical output of 120 W. A fixed amount of ion-exchanged water is added, and about 2 ml of the above-mentioned Contaminone N is added to this 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] The electrolyte solution of [5] in which the toner is dispersed is dropped using a pipette into the round bottom beaker of [1] installed in the sample stand, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
[7] The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4 is calculated. Note that the analysis / volume statistics (arithmetic value when graph / volume% is set with the dedicated software) The “average diameter” on the (average) screen is the weight average particle diameter (D4).

<Total Energy of Toner Particles>
The total energy when the stirring speed of the toner particles of the present invention is 100 revolutions is a powder rheometer RH-4 (manufactured by Freeman Technology) (hereinafter, sometimes abbreviated as FT-4). By measuring.

  Specifically, the measurement is performed by the following operation. In all operations, the propeller blade is a 48 mm diameter blade dedicated to FT-4 measurement (see FIG. 2; there is a rotational axis in the normal direction at the center of the 48 mm × 10 mm blade plate, The outer edge portion (24 mm from the rotation axis) is smoothly twisted counterclockwise such that the outer edge portion (24 mm from the rotation axis) is 70 °, and the 12 mm portion from the rotation axis is 35 °, and the material is made of SUS. May be abbreviated as blade).

  23 for a cylindrical split container (model number: C203, 82 mm in height from the bottom of the container to the split part. The material is glass. Hereinafter, it may be abbreviated as a container). A toner powder layer is formed by adding 100 g of toner particles left in a 60 ° C., 60% environment for 3 days or more.

(1) Conditioning operation (a) The rotational speed of the blade in the clockwise direction with respect to the powder layer surface (the direction in which the powder layer is loosened by the rotation of the blade) is set to the peripheral speed 60 at the outermost edge of the blade. (Mm / sec), and the angle between the trajectory drawn by the outermost edge of the moving blade and the surface of the powder layer is a speed of 5 (deg) (hereinafter referred to as the vertical approach speed to the powder layer). In some cases, the angle formed may be abbreviated as an angle formed from the bottom surface of the toner powder layer to the position of 10 mm from the surface of the powder layer. Thereafter, in the clockwise rotation direction with respect to the powder layer surface, the rotation speed of the blade is 60 (mm / sec), and the angle forming the vertical entry speed to the powder layer is 2 (deg). After performing an operation to enter the position 1 mm from the bottom of the magnetic toner powder layer at a speed, the blade rotation speed is 60 (mm / sec) in the clockwise rotation direction with respect to the powder layer surface, and the powder The angle forming the extraction speed from the body layer is moved at a speed of 5 (deg) from the bottom surface of the toner powder layer to a position of 100 mm to perform extraction. When the extraction is completed, the toner attached to the blade is wiped off by rotating the blade alternately in small clockwise and counterclockwise directions.
(B) By performing the series of operations (1) to (a) five times, the air entrained in the toner powder layer is removed and a stable magnetic toner powder layer is formed.

(2) Split operation A toner powder layer having the same volume is formed by scraping the toner powder layer at the split portion of the above-described cell dedicated to FT-4 measurement and removing the toner on the powder layer.

(3) Measurement operation (a) Conditioning operation similar to (1)-(a) above is performed once. Next, the rotation speed of the blade is 100 (mm / sec) in the counterclockwise rotation direction (the direction in which the powder layer is pushed in by the rotation of the blade), and the direction perpendicular to the powder layer Is entered at a speed at which the angle formed becomes 5 (deg) from the bottom surface of the toner powder layer to a position of 10 mm. Thereafter, the rotation speed of the blade is set to 60 (mm / sec) in the clockwise rotation direction with respect to the powder layer surface, and the angle forming the vertical entry speed to the powder layer is 2 (deg). After performing an operation to enter the position 1 mm from the bottom of the powder layer at a speed, the blade rotation speed was set to 60 (mm / sec) in the clockwise rotation direction with respect to the powder layer surface, and the powder Extraction is performed from the bottom surface of the powder layer to a position of 100 mm at a speed at which the angle forming the vertical extraction speed from the layer is 5 (deg). When the extraction is completed, the toner attached to the blade is wiped off by rotating the blade alternately in small clockwise and counterclockwise directions.
(B) The above series of operations is repeated seven times, and the measurement is started from the position of 100 mm from the bottom surface of the toner powder layer at the seventh rotation speed of the blade of 100 (mm / sec). TEA100 is the sum of the rotational torque and the vertical load obtained when approaching 10 mm from the bottom.

<Toner compression rate>
In the present invention, the toner compression rate is a value obtained by the following equation.
Compression rate = {1- (apparent density / tap density)} × 100%

  The apparent density and tap density of the present invention are measured by the following method using a powder tester (manufactured by Hosokawa Micron).

A cylindrical container having a diameter of 5.03 cm, a height of 5.03 cm, and a volume of 100 cm ³ is uniformly fed from above through a sieve having a mesh opening of 608 μm (24 mesh) for 30 seconds, and the apparent density ( g / cm ³ ).

After measuring the apparent density, a cylindrical cap is put on, powder is added to this upper edge, and tapping with a tap height of 1.8 cm is performed 180 times. After completion, the cap is removed, the powder is ground on the upper surface of the container and weighed, and the density in this state is defined as the tap density (g / cm ³ ).

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. “Part” is based on mass unless otherwise specified.

<Production example of magnetic material>
In an aqueous ferrous sulfate solution, 1.0 equivalent of a caustic soda solution (containing 1 mass% sodium hexametaphosphate in terms of P with respect to Fe) is mixed with an iron ion to prepare an aqueous solution containing ferrous hydroxide. Prepared. While maintaining the aqueous solution at pH 9, air was blown in, and an oxidation reaction was performed at 80 ° C. to prepare a slurry liquid for generating seed crystals.

Subsequently, the ferrous sulfate aqueous solution was added to this slurry liquid so that it might become 1.0 equivalent with respect to the original alkali amount (sodium component of caustic soda). The slurry was maintained at pH 8 and the oxidation reaction was advanced while blowing air, and the pH was adjusted to about 6 at the end of the oxidation reaction. As a silane coupling agent, 0.6 part of n-C ₆ H ₁₃ Si (OCH ₃ ) ₃ was added to 100 parts of the magnetic substance and sufficiently stirred. The produced hydrophobic iron oxide particles were washed, filtered and dried by a conventional method. After the aggregated particles were crushed, heat treatment was performed at a temperature of 70 ° C. for 5 hours to obtain a magnetic material.

The average particle diameter of the magnetic body 0.26 .mu.m, saturation magnetization and the residual magnetization in a magnetic field 79.6 kA / m (1000 oersteds) is ^{67.3Am 2 /kg(emu/g),4.0Am 2 / kg (emu} / g )Met.

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

Next, the fatty acid metal salt slurry thus obtained was washed by filtration. The obtained washed fatty acid metal salt cake was roughly crushed and then dried at 105 ° C. using a continuous instantaneous air dryer. Then, after pulverizing with a nano grinding mill [NJ-300] (manufactured by Sanrex) under conditions of an air volume of 6.0 m ³ / min and a processing speed of 80 kg / h, reslurry and fine particles using a wet centrifugal classifier The coarse particles were removed. Then, it dried at 80 degreeC using the continuous instantaneous airflow dryer, and obtained the fatty-acid metal salt fine particle 1. The resulting fatty acid metal salt fine particles 1 had a volume-based median diameter (D50) of 0.45 μm and a span value of 0.92. The physical properties of the fatty acid metal salt 1 are shown in Table 1.

<Production of fatty acid metal salt 2>
Fatty acid metal salt fine particles 2 were obtained in the same manner except that the 0.2 mass% zinc sulfate aqueous solution was changed to a 0.30 mass% calcium chloride aqueous solution in the production of fatty acid metal salt 1. The obtained fatty acid metal salt fine particles 2 had a volume-based median diameter (D50) of 0.50 μm and a span value of 1.22. The physical properties of the fatty acid metal salt 2 are shown in Table 1.

<Production of fatty acid metal salt 3>
In the production of fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 0.25% by mass sodium stearate aqueous solution, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.15% by mass zinc sulfate aqueous solution. did. Other steps were carried out in the same manner as in the production of fatty acid metal salt 1 to obtain fatty acid metal salt 3. The obtained fatty acid metal salt 3 had a volume-based median diameter (D50) of 0.30 μm and a span value of 0.83. The physical properties of the fatty acid metal salt 3 are shown in Table 1.

<Production of fatty acid metal salt 4>
In the production of fatty acid metal salt 1, 0.5% by weight sodium stearate aqueous solution was changed to 0.70% by weight sodium stearate aqueous solution, 0.2% by weight zinc sulfate aqueous solution was changed to 0.40% by weight zinc sulfate aqueous solution, The pulverization conditions were an air volume of 4.0 m ³ / min and a treatment speed of 40 kg / h. In other processes, the median diameter (D50) of fatty acid metal salt 4 on the volume basis was 0.60 μm, and the span value was 1.12. The physical properties of the fatty acid metal salt 4 are shown in Table 1.

<Production of fatty acid metal salt 5>
In the production of fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 0.7% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.3% by mass zinc sulfate aqueous solution. . The pulverization conditions were an air volume of 4.0 m ³ / min and a processing speed of 50 kg / h. Other steps were carried out in the same manner as in the production of fatty acid metal salt 1 to obtain fatty acid metal salt fine particles 5. The obtained fatty acid metal salt fine particles 5 had a volume-based median diameter (D50) of 0.64 μm and a span value of 0.98. The physical properties of the fatty acid metal salt 5 are shown in Table 1.

<Production of fatty acid metal salt 6>
In the production of the fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was converted to 0.30% by mass sodium stearate aqueous solution, 0.2% by mass zinc sulfate aqueous solution to 0.15% by mass zinc sulfate aqueous solution, The pulverization conditions were changed to an air volume of 10.0 m ³ / min, and the pulverization process was further changed to 3 times. Other processes were the same as the production of fatty acid metal salt 1 to obtain fatty acid metal salt 6. The obtained fatty acid metal salt 6 had a volume-based median diameter (D50) of 0.15 μm and a span value of 1.22. The physical properties of the fatty acid metal salt 6 are shown in Table 1.

<Production of fatty acid metal salt 7>
In the production of fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was converted to 0.80% by mass sodium stearate aqueous solution, 0.2% by mass zinc sulfate aqueous solution to 0.40% by mass zinc sulfate aqueous solution, The pulverization condition was changed to an air volume of 3.5 m ³ / min, and the treatment speed was 40 kg / h. Other processes were the same as the production of fatty acid metal salt 1 to obtain fatty acid metal salt 7. The obtained fatty acid metal salt 7 had a volume-based median diameter (D50) of 0.65 μm and a span value of 1.35. The physical properties of the fatty acid metal salt 7 are shown in Table 1.

<Production of fatty acid metal salt 8>
In the production of fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was converted to 0.80% by mass sodium stearate aqueous solution, 0.2% by mass zinc sulfate aqueous solution to 0.40% by mass zinc sulfate aqueous solution, The pulverization conditions were changed to an air volume of 3.5 m ³ / min, the processing speed was changed to 40 kg / h, and fine pulverized powder was removed with a wind classifier after pulverization. Other steps were carried out in the same manner as the production of fatty acid metal salt 1 to obtain fatty acid metal salt 8. The fatty acid metal salt 8 obtained had a volume-based median diameter (D50) of 0.65 μm and a span value of 1.75. The physical properties of the fatty acid metal salt 8 are shown in Table 1.

<Production of fatty acid metal salt 9>
In the production of the fatty acid metal salt 8, the wind-type classification conditions were changed, and fine coarse powder was removed. Other steps were carried out in the same manner as in the production of the fatty acid metal salt 8 to obtain a fatty acid metal salt 9. The resulting fatty acid metal salt 8 had a volume-based median diameter (D50) of 0.65 μm and a span value of 1.92. The physical properties of the fatty acid metal salt 9 are shown in Table 1.

<Production of fatty acid metal salt 10>
In the production of fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 0.05% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.02% by mass zinc sulfate aqueous solution. did. Further, the pulverization condition was changed to an air volume of 10.0 m ³ / min, and the pulverization process was changed three times. Other processes were the same as the production of the fatty acid metal salt 1 to obtain the fatty acid metal salt 10. The obtained fatty acid metal salt 10 had a median diameter (D50) based on volume of 0.12 μm and a span value of 1.25. The physical properties of the fatty acid metal salt 10 are shown in Table 1.

<Fatty acid metal salt 11>
Commercially available zinc stearate (MZ2 manufactured by NOF Corporation) is used as fatty acid metal salt 11. The median diameter (D50) on a volume basis was 1.29 μm, and the span value was 1.61. The physical properties of the fatty acid metal salt 11 are shown in Table 1.

<Fatty acid metal salt 12>
Commercially available zinc stearate (SZ2000, manufactured by Sakai Chemical Industry Co., Ltd.) is designated as fatty acid metal salt 12. The median diameter (D50) on a volume basis was 5.30 μm, and the span value was 1.84. The physical properties of the fatty acid metal salt 12 are shown in Table 1.

<Production of fatty acid metal salt 13>
In the production of fatty acid metal salt 3, fatty acid metal salt 13 was obtained in the same manner except that the step of removing fine particles and coarse particles was not performed. The obtained fatty acid metal salt 13 had a volume-based median diameter (D50) of 0.30 μm and a span value of 1.77. Table 1 shows the physical properties of the fatty acid metal salt 13.

The production example of silica fine particles is shown below. A silica base having a BET specific surface area of 300 m ² / g was used.

<Silica fine particles 1>
After spraying 5.0 parts of dimethyl silicone oil (viscosity = 100 mm ² / s) to 100 parts of silica, and stirring for 30 minutes, the temperature is raised to 300 ° C. while stirring and stirring is continued for 2 hours. The reaction was terminated. After completion of the reaction, crushing treatment was performed.

  Subsequently, 30 parts of hexamethyldisilazane was sprayed to 100 parts of the obtained silica fine particles, and the silane compound treatment was performed in a fluidized state of silica. After continuing this reaction for 60 minutes, reaction was complete | finished and the silica particle 1 was obtained. Table 2 shows the physical properties of the silica fine particles 1 obtained.

<Silica fine particles 2, 3, 4>
In the production of the silica fine particles 1, silica fine particles 2, 3, and 4 were obtained in the same manner except that the amount of dimethyl silicone oil was changed as shown in Table 2. Table 2 shows the physical properties of the obtained silica fine particles 2, 3, and 4.

<Silica fine particle 5>
In the production of the silica fine particles 1, the same procedure as in the silica fine particles 1 except that the addition amount of dimethyl silicone oil (viscosity = 100 mm ² / s) was 11.5 parts and hexamethyldisilazane was changed to isobutyltrimethoxysilane. Thus, silica fine particles 5 were obtained. Table 2 shows the physical properties of the silica fine particles 5 thus obtained.

<Silica fine particle 6>
Spray 11.5 parts of dimethyl silicone oil (viscosity = 100 mm ² / s) to 100 parts of silica base and 30 parts of hexamethyldisilazane to 100 parts of silica base and stir for 30 minutes. After continuing, the temperature was raised to 150 ° C. while stirring and stirring was continued for 3 hours to complete the reaction, whereby silica fine particles 6 were obtained. Table 2 shows the physical properties of the silica fine particles 6 thus obtained.

<Silica fine particle 7>
After spraying 4.0 parts of dimethyl silicone oil (viscosity = 100 mm ² / s) to 100 parts of silica, and stirring for 30 minutes, the temperature is raised to 300 ° C. while stirring and stirring is continued for 2 hours. The reaction was terminated. After completion of the reaction, crushing treatment was performed.

Subsequently, 30 parts of hexamethyldisilazane was sprayed to 100 parts of the obtained silica fine particles, and the silane compound treatment was performed in a fluidized state of silica. The reaction was continued for 60 minutes and then dried. Thereafter, 1.0 part of dimethyl silicone oil (viscosity = 100 mm ² / s) is sprayed on 100 parts of the obtained silica fine particles, and after stirring for 30 minutes, the temperature is raised to 300 ° C. while stirring. The mixture was further stirred for 2 hours to complete the reaction. After completion of the reaction, pulverization was performed to obtain silica fine particles 7. Table 2 shows the physical properties of the silica fine particles 7 obtained.

<Silica fine particle 8>
30 parts of hexamethyldisilazane were sprayed on the inside of 100 parts of the silica base, and the silane compound was treated in a fluidized state of silica. This reaction was continued for 60 minutes, and then the reaction was terminated.

Subsequently, 5.0 parts of dimethyl silicone oil (viscosity = 100 mm ² / s) was sprayed onto the silica fine particles obtained, and after stirring for 30 minutes, the temperature was raised to 300 ° C. while stirring. After stirring for 2 hours to complete the reaction, crushing treatment was performed. Thereafter, the obtained silica fine particles were washed with benzene to obtain silica fine particles 8. Table 2 shows the physical properties of the silica fine particles 8 thus obtained.

<Silica fine particle 9>
After 100 parts of the silica raw material was dispersed in 400 parts of toluene, 5.0 parts of dimethyl silicone oil having a viscosity of 300 cs was added and stirring was continued for 30 minutes, and then toluene was distilled off by heating. Next, drying and crushing were performed to obtain silica fine particles 9.

<Silica fine particle 10>
After spraying 30.0 parts of hexamethyldisilazane to 100 parts of silica raw material and continuing stirring for 30 minutes, the temperature was raised to 150 ° C. with stirring and stirring was continued for 3 hours to complete the reaction. Silica fine particles 10 were obtained. Table 2 shows the physical properties of the silica fine particles 10 thus obtained.

<Manufacture of toner particles (1)>
450 parts of 0.1M Na ₃ PO ₄ aqueous solution is added to 720 parts of ion-exchanged water and heated to 60 ° C., and then 67.7 parts of 1.0M CaCl ₂ aqueous solution is added to contain a dispersion stabilizer. An aqueous medium was obtained.

・ Styrene 76.00 parts ・ n-butyl acrylate 24.00 parts ・ Divinylbenzene 0.52 parts ・ Iron complex of monoazo dye (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 1.00 parts ・ Magnetic substance 90.00 parts ・10.00 parts of amorphous polyester (saturated polyester resin obtained by condensation reaction of EO adduct of bisphenol A and terephthalic acid: Mn = 5,000, acid value = 12 mgKOH / g, Tg = 68 ° C.)
The above components were uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.) to obtain a monomer composition. The monomer composition was heated to 60 ° C., 15.0 parts of paraffin wax (endothermic peak top temperature: 77.2 ° C.) was mixed and dissolved therein, and then the polymerization initiator 2,2′-azobis (2 , 4-dimethylvaleronitrile) was dissolved.

The monomer composition was put into the aqueous medium and stirred at 18.8 m / s for 10 minutes in a TK homomixer (Special Machine Industries Co., Ltd.) at 60 ° C. and N ₂ atmosphere. Grained. Thereafter, the temperature was raised to 70 ° C. at a rate of 0.5 ° C./min while stirring with a paddle stirring blade, and the reaction was allowed to proceed for 5 hours while maintaining the temperature at 70 ° C. Thereafter, the temperature was raised to 90 ° C., held for 2 hours, and then gradually cooled to 30 ° C. at a rate of 0.5 ° C./min. After cooling, hydrochloric acid was added for washing, followed by filtration and drying to obtain magnetic toner particles 1.

  100 parts of this magnetic toner particle 1 and 1.0 part of hydrophobic silica fine powder having a number average primary particle size of 12 nm were mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), and the weight average particle size (D4) was 7.0 μm toner particles (1) were obtained.

<Production of toner particles (2)>
In the production of toner particles (1), toner particles (2) having a weight average particle diameter (D4) of 7.5 μm were obtained in the same manner except that the amount of amorphous polyester added was changed to 35.0 parts. It was.

<Manufacture of toner particles (3)>
Toner particles (2) having a weight average particle diameter (D4) of 6.8 μm were obtained in the same manner except that the amount of amorphous polyester added was changed to 7.0 parts in the production of toner particles (1). It was.

<Production of toner particles (4)>
Toner particles (2) having a weight average particle diameter (D4) of 7.7 μm were obtained in the same manner except that the amount of amorphous polyester added was changed to 40.0 parts in the production of toner particles (1). It was.

<Manufacture of toner particles (5)>
In toner particles (1), the amount of amorphous polyester added was changed to 3.0 parts to produce toner particles, and then the weight average particle diameter (D4) was adjusted to 5.2 μm by air classification. Similarly, toner particles (5) were obtained.

<Manufacture of toner particles 6>
-Synthesis of organic fine particle emulsion-
In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 83 parts of styrene, methacrylic acid When 83 parts of acid, 110 parts of butyl acrylate, and 1 part of ammonium persulfate were charged and stirred at 3800 rpm for 30 minutes, a white emulsion was obtained. This was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours to obtain an aqueous vinyl resin (a copolymer of methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion was obtained. This is designated as [fine particle dispersion 1].

  The volume average particle diameter of the fine particles contained in the obtained [fine particle dispersion 1] was measured by a particle size distribution measuring apparatus (“LA-920”, manufactured by Horiba, Ltd.) using a laser light scattering method. there were. Further, a part of [Fine Particle Dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 58 ° C., and the weight average molecular weight (Mw) was 130,000.

-Preparation of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

-Synthesis of low molecular weight polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid, And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 7 hours under normal pressure. Subsequently, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 3 hours to obtain [Low molecular weight polyester 1].

-Synthesis of prepolymer-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 7 hours under normal pressure. Further, the reaction was carried out under reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1].

  The obtained [Intermediate polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, a glass transition temperature (Tg) of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.

  Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. [Prepolymer 1] was obtained.

-Synthesis of ketimine-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophorone diamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1].

-Preparation of masterbatch (MB)-
1200 parts of water, 540 parts of carbon black (Printtex 35, manufactured by Degussa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1200 parts of a polyester resin (manufactured by Sanyo Chemical Industries, Ltd., RS801) are added, and a Henschel mixer is added. (Mitsui Mining Co., Ltd.) The obtained mixture was kneaded at 110 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain a carbon black masterbatch. This is designated as [Masterbatch 1].

-Preparation of oil phase-
In a reaction vessel equipped with a stirrer and a thermometer, 378 parts of [Low molecular weight polyester 1], 100 parts of carnauba wax, and 947 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining the time, it was cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a reaction vessel and mixed for 1 hour to obtain a dissolved product. This is referred to as [Raw material solution 1].

  Next, 1324 parts of [Raw Material Solution 1] is transferred to a reaction vessel, and using a bead mill (Ultra Visco Mill, manufactured by IMEX), liquid feeding speed: 1 kg / hr, disk peripheral speed: 6 m / second, 0.5 mm Carbon black and wax were dispersed under the conditions of zirconia bead filling amount: 80% by volume and pass number: 3 times.

  Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and a dispersion was obtained using a bead mill under the same conditions as described above, with a pass number of 2 times. This is designated as [Pigment and Wax Dispersion 1].

  The obtained [Pigment and Wax Dispersion 1] had a solid content concentration (130 ° C., 30 minutes) of 50%.

-Emulsification-
[Pigment and wax dispersion 1] 749 parts, [Prepolymer 1] 115 parts, and [Ketimine compound 1] 2.9 parts are placed in a reaction vessel, and 5 using a TK homomixer (manufactured by Koki Co., Ltd.). 2,000 rpm for 2 minutes. Thereafter, 1200 parts of [Aqueous Phase 1] was added to the reaction vessel, and mixed with a TK homomixer at a rotational speed of 13,000 rpm for 25 minutes to obtain an aqueous medium dispersion. This is designated as [Emulsified slurry 1].

-Deorganic solvent-
[Emulsion slurry 1] is put into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging is performed at 45 ° C. for 4 hours, and the organic solvent is distilled off. A dispersion was obtained. This is designated as [Dispersion Slurry 1].

-Cleaning and drying-
[Dispersion Slurry 1] After 100 parts were filtered under reduced pressure, washing and drying were performed as follows.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2) 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(4) Add 100 parts of ion-exchanged water to the filter cake of (3), add an aqueous solution in which a fluorine-based surfactant equivalent to 0.1% of the solid content of the cake is dissolved, and mix with a TK homomixer (at a rotational speed of 12000 rpm). 10 minutes) and then filtered.
(5) 300 parts of ion-exchanged water was added to the filter cake of (4), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice to obtain a filter cake.

  Next, the obtained filter cake was dried at 45 ° C. for 48 hours with a circulating dryer, and sieved with a mesh having a mesh size of 75 μm, whereby toner particles 6 having a weight average particle diameter (D4) of 5.8 μm were obtained.

<Manufacture of toner 1>
To 100 parts of toner particles (1), 1.0 part of silica fine particles 1 and 0.2 part of fatty acid metal salt 1 are added, and a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) is used to The speed was adjusted to 40.0 m / s and mixing was performed for 240 seconds. Thereafter, the operation was paused for 60 seconds, and a mixing process for 240 seconds was further performed to obtain toner 1. Table 3 shows the formulation and physical properties of Toner 1.

<Manufacture of toners 2, 3, 4, 5>
Toners 2, 3, 4, and 5 were obtained in the same manner except that silica fine particles 1 were changed to silica fine particles 2, 3, 4, and 5 in the production of toner 1. Table 3 shows the formulations and physical properties of the toners 2, 3, 4, and 5.

<Manufacture of Toner 6, 7, 8>
In the production of the toner 1, the toner particles 6, 7, 8 was obtained. Table 3 shows the formulations and physical properties of the toners 6, 7, and 8.

<Manufacture of toner 9>
In the production of the toner 1, the toner particles (1) were changed to the toner particles (5), and the silica fine particles 1 were changed to the silica fine particles 5. Furthermore, using a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), the peripheral speed of the stirring blade was adjusted to 40.0 m / s and mixing was performed for 300 seconds, and then the operation was stopped for 60 seconds. Then, after performing the mixing process for 300 seconds again, the rest for 60 seconds was performed, and the mixing process for 360 seconds was further performed, and the toner 9 was obtained. Table 3 shows the formulation and physical properties of Toner 9.

<Manufacture of Toner 10>
In the production of the toner 1, the toner particles (1) are changed to the toner particles (5), and the time of the first mixing step is changed to 180 seconds, and the time of the second mixing step is changed to 120 seconds. Toner 10 was obtained. Table 3 shows the formulation and physical properties of Toner 10.

<Manufacture of toner 11>
In the production of the toner 9, a toner 11 was obtained in the same manner except that the time of the first and second mixing steps was changed to 360 seconds. Table 3 shows the formulation and physical properties of Toner 11.

<Manufacture of toner 12>
In the production of the toner 10, the toner 12 was obtained in the same manner except that the time of the first and second mixing steps was changed to 120 seconds. Table 3 shows the formulation and physical properties of Toner 12.

<Manufacture of toner 13>
A toner 13 was obtained in the same manner as in the production of the toner 12 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 2 and the mixing process time was changed to 360 seconds. Table 3 shows the formulation and physical properties of Toner 13.

<Manufacture of toner 14>
A toner 13 was obtained in the same manner as in the production of the toner 12 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 3 and the mixing process time was changed to 300 seconds. Table 3 shows the formulation and physical properties of Toner 14.

<Manufacture of toners 15 and 16>
Toners 15 and 16 were obtained in the same manner except that the fatty acid metal salt 1 was changed to the fatty acid metal salts 4 and 5 in the production of the toner 12. Table 3 shows the formulations and physical properties of the toners 15 and 16.

<Manufacture of toner 17>
A toner 17 was obtained in the same manner as in the production of the toner 12 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 6 and the mixing process time was changed to 240 seconds. Table 3 shows the formulation and physical properties of Toner 17.

<Manufacture of toners 18, 19, and 20>
Toners 18, 19, and 20 were obtained in the same manner except that the fatty acid metal salt 1 was changed to the fatty acid metal salts 7, 8, and 9 in the production of the toner 12. Table 3 shows the formulations and physical properties of the toners 18, 19, and 20.

<Manufacture of toner 21>
A toner 21 was obtained in the same manner except that the silica fine particles 5 were changed to the silica fine particles 6 in the production of the toner 20. Table 3 shows the formulation and physical properties of Toner 21.

<Production of Comparative Toners 1, 2, 3>
Comparative toners 1, 2, and 3 were obtained in the same manner except that the fatty acid metal salt 1 was changed to the fatty acid metal salts 10, 11, and 12 in the production of the toner 1. Table 3 shows the formulations and physical properties of Comparative Toners 1, 2, and 3.

<Production of Comparative Toners 4, 5, and 6>
Comparative toners 4, 5, and 6 were obtained in the same manner except that silica fine particles 1 were changed to silica fine particles 7, 8, and 9 in the production of toner 1. Table 3 shows the formulations and physical properties of the comparative toners 4, 5, and 6.

<Production of Comparative Toner 7>
0.2 parts of fatty acid metal salt 13 is added to 100 parts of toner particles (6), and a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) is used. Mixed for minutes. To this, 1.0 part of silica fine particles 10 was added, and mixed for 5 minutes under the condition of a peripheral speed of 33.0 m / s with a Henschel mixer. The mixed powder was passed through a mesh having an opening of 100 μm to obtain a comparative toner 7. Table 3 shows the formulation and physical properties of the comparative toner 7.

<Example 1>
1. Development characteristic test LBP3410 (manufactured by Canon Inc.) was used as an image forming apparatus for the durability development test. For the evaluation, a cartridge for which the LBP3410 cartridge was modified and the linear pressure of the cleaning blade was changed from about 4.0 kgf / m to 8.0 kgf / m was used. When the linear pressure is high, transfer residual toner and external additives staying between the photosensitive drum and the cleaning blade are more strongly pressed against the photosensitive drum, and fusion is promoted. The cartridge 1 was filled with toner 1 and evaluated. In a room temperature and normal humidity environment (23 ° C./60% RH), a horizontal line having a printing rate of 4% was subjected to a 5000-sheet printing test in a 7-second intermittent mode. As a recording medium, A4 75 g / m ² paper was used, and an endurance test was conducted for 2 days, in which 2500 sheets per day were passed in 7 seconds intermittently. Before and after passing the paper, a chart with a solid image formed on the entire surface of the printing paper is output one by one, and this solid image is measured with a Macbeth densitometer (manufactured by Macbeth) using an SPI filter with a reflection densitometer. Went. The original used a chart with an image ratio of 5%. The evaluation was performed for the image density after durability for each environment, and the reflection density at the initial stage of durability was also evaluated in a high temperature and high humidity environment. The density before and after durability was evaluated according to the following evaluation criteria.
○ Evaluation standard for durability initial density Rank A: Reflection density at the start of durability is 1.55 or more Rank B: Reflection density at the start of durability is 1.50 or more and less than 1.55 Rank C: Reflection density at the start of durability is 1 40 or more and less than 1.50 Rank D: Reflection density at the start of durability is less than 1.40 ○ Evaluation standard for density after durability Rank A: Reflection density after durability is 1.40 or more Rank B: Reflection density after durability 1.35 or more and less than 1.40 Rank C: Reflection density after endurance is 1.30 or more and less than 1.35 Rank D: Reflection density after endurance is 1.20 or more and less than 1.30 Rank E: Reflection density after endurance Is less than 1.20

In addition, three white images were output before paper passing durability, and the reflectance was measured using a REFECTMETER MODEL TC-6DS manufactured by Tokyo Denshoku. On the other hand, the reflectance of the transfer paper (standard paper) before white image formation was measured in the same manner. The filter used was a green filter, and fog was calculated according to the following formula.
Fog (reflectance) (%) = reflectance of standard paper (%)-reflectance of white image sample (%)

The fog was evaluated according to the following criteria using the maximum fog value obtained.
○ Evaluation standard rank A of initial durability fog A: Less than 0.2% Rank B: 0.2% or more and less than 0.5% Rank C: 0.5% or more and less than 1.5% Rank D: 1.5% or more

2. Starting streak evaluation test The starting streak was evaluated in the endurance test on the morning of the second day after the end of endurance of 1000 sheets and on the morning of the third day after the end of endurance of 2000 sheets. At that time, five solid white images were continuously output to evaluate the degree of streaks.
Rank A: Image level with no problem on the image Rank B: A state in which streaks can be confirmed slightly.
Rank C: State in which streaks can be confirmed slightly in the charging member cycle.
Rank D: A clear streak occurs, but disappears after two solid white images are output.
Rank E: A clear streak occurs in the image and does not disappear even after two solid white images are output.

In addition, after the end of the endurance of 2000 sheets, after the evaluation on the first day of the 2000th day, the sheet was left for another 7 days, and then 5 solid white images were output continuously to evaluate the degree of streaking. If it is left after the endurance, the agglomerates continue to receive pressure on the photosensitive drum, so that fusion to the photosensitive drum is promoted, which makes it difficult to start lines.
Rank A: Image level with no problem on the image Rank B: A state in which streaks can be confirmed slightly.
Rank C: A state in which streaks can be confirmed slightly for three charging members.
Rank D: A clear streak occurs, but disappears after two solid white images are output.
Rank E: A clear streak occurs in the image, and it does not disappear after two solid white images are output.

<Examples 2 to 21>
An image output test was performed in the same manner as in Example 1 except that toners 2 to 21 were used. As a result, all the toners were at a level where there was no practical problem in the above two tests. The evaluation results are shown in Table 5.

<Comparative Examples 1 to 7>
An image output test was performed in the same manner as in Example 1 except that the comparative toners 1 to 7 were used. The evaluation results are shown in Table 4.

  DESCRIPTION OF SYMBOLS 100 Electrostatic latent image carrier (photoreceptor), 102 Toner carrier, 114 Transfer member (transfer roller), 116 Cleaner, 117 Contact charging member (charge roller), 121 Laser generator (latent image forming means, exposure device) , 123 laser, 124 register roller, 125 transport belt, 126 fixing device, 140 developing device, 141 stirring member

Claims (10)

A toner having toner particles containing at least a binder resin, a colorant, and a wax, a fatty acid metal salt, and an inorganic fine powder,
The inorganic fine powder contains silica fine particles,
The silica fine particles are treated with at least one of alkoxysilane or alkoxysilazane, and are treated with silicone oil,
The silica fine particles have a release rate of silicone oil from the silica fine particles of 50% by mass or less based on the amount of carbon.
The toner, wherein the fatty acid metal salt has a volume-based median diameter (D50) of 0.15 μm or more and 0.65 μm or less.   The toner according to claim 1, wherein the silica fine particles are treated with silicone oil and then treated with at least one of alkoxysilane or alkoxysilazane. 3. The toner according to claim 1, wherein a span value obtained by the following formula (1) of the fatty acid metal salt is 1.75 or less.
Span value = (D95−D5) / D50 (1)   4. The toner according to claim 1, wherein a median diameter (D50) of the fatty acid metal salt on a volume basis is 0.30 μm or more and 0.60 μm or less. 5.   The toner according to any one of claims 1 to 4, wherein a liberation rate of the fatty acid metal salt from the toner is 10.0% by mass or more and 40.0% by mass or less. The toner according to claim 1, wherein the toner has a compression ratio of 30 or less obtained from the following formula (2).
Compression rate = {1- (apparent density / tap density)} × 100 (2)   The total energy when the stirring speed measured by the powder fluidity measuring device of the toner particles is 100 revolutions is 500 mJ or more and 1000 mJ or less. toner.   The silica fine particles have a treatment amount of silicone oil of 0.5 parts by mass or more and 11.0 parts by mass or less with respect to 100 parts by mass of the silica fine particle base material. The toner described in 1.   The toner according to claim 1, wherein the toner is produced in an aqueous medium.   The toner according to claim 1, wherein the toner particles are produced by a suspension polymerization method.

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