JP6456226B2 - Toner and toner production method - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image used in an image forming method such as electrophotography and electrostatic printing.

  In recent years, image forming apparatuses such as copiers and printers have been required to have higher speed, higher image quality, and higher stability as the purpose of use and environment of use have diversified. At the same time, in copiers and printers, miniaturization and energy saving of the apparatus are progressing, and a magnetic one-component developing system using magnetic toner which is advantageous in these respects is preferably used.

  In electrophotography, a charging step of charging an electrostatic latent image carrier (hereinafter referred to as a photoconductor) by a charging means, and exposure for forming an electrostatic latent image by exposing the charged electrostatic latent image carrier. And a developing step of developing the electrostatic latent image with toner to form a toner image. Next, a transfer step for transferring the toner image to the recording material with or without the intermediate transfer member, and a nip portion formed by the pressure member and the rotatable image heating member for the recording material carrying the toner image. The image is output as an image through a fixing step of fixing by heating and pressurizing by passing. In particular, in the magnetic one-component development system, magnetic toner is held using a toner carrier (hereinafter referred to as a sleeve) provided with a magnetic field generating means such as a magnet roll, and conveyed to a development area for development.

  In order to cope with the recent improvement in image quality and energy saving, optimization of each process is important. Among them, for the image quality in particular, the electrostatic latent image is conventionally developed with toner to form a toner image. It is important to perform sufficient fixing at a low temperature for the developing process and energy saving.

  Here, focusing on the fixing process from the viewpoint of further improvement in image quality, as a problem that has become apparent with the diversification of the purpose of use and usage environment, the offset of the trailing edge of the high printing rate image in a high temperature and high humidity environment There is a problem.

  In general, in a fixing process, when a paper on which an unfixed image is formed with toner passes through a fixing device (especially, a portion through which the paper passes is hereinafter referred to as a fixing nip), heat and pressure are applied, The toner is fixed to the toner.

  The reason why the offset is more severe in the high printing rate image than in the low printing rate image is probably due to the amount of heat applied to the toner layer. The higher the printing rate image, the more the heat from the fixing device is dispersed in a larger amount of toner, and the more the toner that is insufficiently melted tends to increase. That is, a fixing failure is likely to occur. Furthermore, since the amount of heat applied from the fixing nip portion tends to be smaller as the rear end of the paper is reached, the rear end of the image tends to be disadvantageous in fixing.

  In particular, the above-described offset phenomenon tends to be prominent in paper left in a high temperature and high humidity environment. This is probably because when the paper containing a lot of moisture passes through the fixing device, it receives heat from the fixing device in the fixing nip portion, and water vapor is generated from the paper, so that the toner layer on the paper Is presumed to be pushed to the fixing film side. That is, when a paper left in a high temperature and high humidity environment is used in a state where fixing failure is likely to occur at the rear end of a high printing rate image, the above-described offset phenomenon is likely to occur.

  Conventionally, improvements such as a low softening temperature have been made in order to improve toner fixability. However, in such a design, although the heat melting property of the portion to which heat is sufficiently applied is improved, if the amount of heat to be applied is not sufficient, such as the rear edge of a high printing rate image, the melting speed of the toner is reduced. It was difficult to suppress the trailing edge offset of the high printing rate image without catching up.

  In order to suppress this offset phenomenon, the present inventors speculated that it is important to improve the toner fixing property and at the same time control the properties of the toner surface to improve the releasability from the fixing film.

  Patent Document 1 discloses a toner in which inorganic fine particles are strongly fixed to the surface as a toner excellent in high temperature storage stability and printing durability in a normal temperature and normal humidity environment during printing or in a high temperature and high humidity environment. However, even if the inorganic fine particles are strongly fixed to the toner particles, there is a tendency that the releasability from the film is hardly improved due to the gaps between the inorganic fine particles. Further, due to liberation of inorganic fine particles due to durability deterioration, further improvement is required for development durability in harsh environments.

  In Patent Document 2, a silane coupling is used in the reaction system in order to obtain a toner having a narrow charge amount distribution and a very small humidity dependency of the charge amount without exposing the colorant or polar substance to the toner surface. A method for producing a polymerized toner comprising adding an agent is disclosed. However, in such a method, the amount of silane compound deposited on the toner surface and the hydrolysis polycondensation of the silane compound are insufficient, and further improvement is required for environmental stability and development durability. Yes.

  Further, Patent Document 3 includes a silicon compound applied in the form of a continuous thin film on the surface as a means for controlling the charge amount of toner and forming a high-quality printed image regardless of the environment of temperature and humidity. A magnetically polymerized toner is disclosed.

  However, the polarity of the organic functional group is large, the amount of silane compound deposited on the toner surface and the hydrolysis polycondensation of the silane compound are inadequate, the degree of crosslinking is weak, durable developability at high temperature and high humidity, and end resistance Further improvement is necessary for the offset property.

  Furthermore, due to insufficient control of the surface properties of the magnetic material, it is very difficult to obtain a toner having the thermal conductivity range intended by the present invention, and the above-described offset phenomenon is suppressed in the second half of the durability. There wasn't.

  Furthermore, in Patent Document 4, as a toner for improving fluidity, release of fluidizing agent, low-temperature fixability, and blocking property, a polymerized toner having a coating layer formed by adhering granular lumps containing a silicon compound Is disclosed. However, as described above, it is difficult to improve the releasability from the film due to the gaps in the granular mass containing the silicon compound. Further, in such a configuration, the amount of silane compound deposited on the toner surface and hydrolysis polycondensation of the silane compound are insufficient. As a result, further improvement is required for image density changes and storage stability due to changes in chargeability under high temperature and high humidity.

  That is, there has been a demand for a toner capable of obtaining a high-quality image in which the occurrence of a trailing edge offset of a high printing rate image is suppressed even in a high temperature and high humidity environment.

JP 2006-146056 A Japanese Patent Laid-Open No. 03-089361 JP 09-179341 A JP 2001-75304 A

  The present invention provides a toner that solves the above problems. More specifically, the present invention provides a toner having excellent development durability and storage stability. Further, the present invention provides a toner capable of obtaining a high-quality image in which occurrence of a trailing edge offset of a high printing rate image is suppressed even under a high temperature and high humidity environment.

  As a result of intensive studies, the present inventors have found that the above-described problem can be solved by adopting the following configuration, and have reached the present invention.

That is, the present invention is a toner having toner particles containing a binder resin and a magnetic material,
The toner particles have an organosilicon polymer having a partial structure represented by the following formula (T3) on the surface,
R-Si (O _1/2 ) ₃ (T3)
(R in the formula (T3) represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

In the ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble part of the toner particles, the ratio [ST3] of the peak area of the partial structure represented by the formula (T3) to the total peak area of the organosilicon polymer is 40% or more. Yes,
The toner has a thermal conductivity of 0.190 W / (m · K) or more and 0.300 W / (m · K) or less.
The present invention also provides a toner manufacturing method for manufacturing the toner having the above-described configuration,
Particles of a polymerizable monomer composition containing a polymerizable monomer and the magnetic substance are formed in an aqueous medium, and the polymerizable monomer contained in the particles of the polymerizable monomer composition is The toner particles are obtained by polymerization.
The present invention relates to a toner manufacturing method.

  According to the present invention, a toner excellent in development durability and storage stability can be provided. Further, even in a high temperature and high humidity environment, it is possible to obtain a high quality image in which the occurrence of the trailing edge offset of the high printing rate image is suppressed.

It is an example of a method for measuring a surface layer from a cross section of toner particles. It is an example of curve fitting of a measurement chart of ²⁹ Si-NMR. 3 is an example of a reversing flow curve obtained by DSC measurement of toner. 1 is an example of an image forming apparatus.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to these descriptions.

The toner of the present invention is a toner having toner particles containing a binder resin and a magnetic material,
The toner particles have an organosilicon polymer having a partial structure represented by the following formula (T3) on the surface,
R-Si (O _1/2 ) ₃ (T3)
(R in the formula (T3) represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

In the ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble part of the toner particles, the ratio [ST3] of the peak area of the partial structure represented by the formula (T3) to the total peak area of the organosilicon polymer is 40% or more. Yes,
The toner has a thermal conductivity of 0.190 W / (m · K) or more and 0.300 W / (m · K) or less.

  Here, it is important that the toner particles in the present invention have an organosilicon polymer having a partial structure represented by the above formula (T3) on the surface. As a result, the hydrophobicity due to the organic structure can be improved, and a toner having excellent environmental stability such as development durability under a high temperature and high humidity environment can be obtained.

  Furthermore, the present inventors have found that the rear end offset described above is remarkably improved by having the organic structure. The mechanism for improving the rear end offset is not clear, but is estimated as follows.

  First, the rear end offset becomes apparent in a high printing rate image in a high temperature and high humidity environment. In particular, the trailing edge of the paper tends to deteriorate.

  The reason why the offset is more severe in the high printing rate image than in the low printing rate image is presumed to be due to the amount of heat applied to the toner layer as described above. The higher the printing rate image, the more the heat from the fixing device is dispersed in a larger amount of toner, and the more the toner that is insufficiently melted tends to increase. That is, a fixing failure is likely to occur.

  Furthermore, the closer to the rear edge of the paper, the smaller the amount of heat applied from the fixing nip portion. As a result, the trailing edge of the image tends to be less favorable for fixing, and the trailing edge offset is more likely to deteriorate.

  When paper containing a lot of moisture is passed through the fixing device, water vapor is generated by heat from the fixing device at the fixing nip portion. When the toner fixability is sufficient, the toners are bound to each other and fixed to the paper fiber, so that a good image can be obtained even if an image with a high printing rate is output. On the other hand, if the fixing property of the toner on the paper is insufficient, the water vapor will press the toner from the paper to the fixing film side. As a result, when a high-print-ratio image is output, it tends to be a spot-missed image with dots that are white.

  That is, if a paper containing a lot of moisture and left in a high-temperature and high-humidity environment is used in a state where fixing failure tends to occur at the rear edge of the high printing rate image, an image with the rear edge of the paper missing is formed.

  Here, by providing the surface of the toner particles with the organosilicon polymer having the partial structure represented by the above formula (T3), the hydrophobicity of the toner can be easily improved and the surface free energy can be easily reduced.

  In a high temperature and high humidity environment, the adhesive force acting between the toner and the fixing film is influenced by the liquid crosslinking force of the water. That is, as the toner surface becomes more hydrophilic, capillary condensation occurs between the particles, so that liquid cross-linking force is added and the adhesion force between the toners increases and the adhesion force between the fixing film and the toner tends to increase.

  On the other hand, in the toner having improved hydrophobicity such as the toner of the present invention, the capillary condensation between the toners is inhibited, and at the same time, the adhesion between the toner and the fixing film due to the liquid cross-linking force tends to decrease. In this state where the adhesive force tends to decrease, the toner is more easily fixed on the paper side due to the synergistic effect of improving the releasability with the fixing film due to the surface of the toner having a low surface free energy by the organosilicon polymer, resulting in an offset. It is thought that the phenomenon is suppressed.

In the toner of the present invention, the ratio of the peak area of the partial structure represented by the formula (T3) to the total peak area of the organosilicon polymer in the ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble matter of the toner particles [ It is important that ST3] is 40% or more. When [ST3] is 40% or more, the surface free energy on the surface of the toner particles is easily lowered.

The sample used for ²⁹ Si-NMR measurement may be a tetrahydrofuran-insoluble component or the toner itself. Although the same measurement results can be obtained for both samples, it is preferable to increase the concentration of the measurement object as the tetrahydrofuran insoluble matter because the measurement time is remarkably shortened.

  As a result, the surface free energy on the surface of the toner particles is likely to be sufficiently reduced, and in addition to the effect of suppressing the trailing edge offset described above, the environmental stability of the toner is easily improved. For example, it is presumed that the releasability between the toner and the sleeve is improved, but the developability in a high temperature and high humidity environment is likely to be improved.

  In addition, due to the durability of the organosilicon polymer due to the T3 structure and the hydrophobicity and chargeability of R in the above formula (T3), the low molecular weight (Mw1000 or less) that exists inside the toner particle surface more easily than the vicinity. When a release agent is added to a resin, a low Tg (40 ° C. or lower) resin, and toner particles, bleeding of the release agent (exudation to the toner surface) can be easily suppressed.

  As a result, good agitation of the toner in the developing device is required. In particular, even in a development durability test using a high printing rate image having a printing rate of 30% or more, a toner having excellent environmental stability and development durability and excellent storage stability can be obtained.

  [ST3] is important to be 40% or more, more preferably 50% to 90%, and still more preferably 50% to 80%.

  [ST3] is controlled by the type and amount of the organosilicon compound used for forming the organosilicon polymer, and the reaction temperature, reaction time, reaction solvent, and pH of the hydrolysis, addition polymerization and condensation polymerization during the formation of the organosilicon polymer. can do.

  Furthermore, it is important that the toner of the present invention has a thermal conductivity of 0.190 W / (m · K) or more and 0.300 W / (m · K) or less. More preferably, it is 0.230 W / (m · K) or more and 0.280 W / (m · K) or less.

  The thermal conductivity of the toner can be controlled by containing a magnetic material as described later and adjusting the content, particle size, and the like.

  As described above, the present inventors have the above-mentioned rear end only after having the organosilicon polymer on the surface of the toner particles, setting the above [ST3] to 40% or more, and further setting the thermal conductivity of the toner within the above range. It has been found that it is possible to obtain an image in which the occurrence of offset is highly suppressed.

  That is, by forming a specific organosilicon polymer on the surface of the toner particles, it is important to control the thermal conductivity of the toner while improving the releasability from the film even in a high temperature and high humidity environment. For the first time, it has been found that the occurrence of the trailing edge offset of the high printing rate image can be suppressed even when the amount of heat applied is insufficient, such as the trailing edge of the high printing rate image.

  The thermal conductivity of the toner can be adjusted to the above range by controlling the dispersion state of the magnetic material having high heat conductivity in the toner particles. Control of dispersion of the magnetic material in the toner particles can be achieved by a magnetic material as described later.

  If the thermal conductivity of the toner exceeds 0.300 W / (m · K), it is not preferable because fusing tends to occur at the end of the fixing unit that is severely heated. On the other hand, when it is less than 0.190 W / (m · K), no effect is obtained with respect to the rear end offset.

In the present invention, in the ²⁹ Si-NMR measurement of the tetrahydrofuran (THF) insoluble content of the toner particles, the structure in which the number of O _1/2 bonded to silicon is 2.0 with respect to the total peak area of the organosilicon polymer ( Hereinafter, it is preferable that the ratio [SX2] of the peak area and the above [ST3] satisfy the relationship [ST3] / [SX2] ≧ 1.00.

  When [ST3] is equal to or higher than [SX2], the balance between durability and chargeability due to the crosslinked structure of the siloxane structure is improved. Therefore, it is easy to improve environmental stability, storage stability and development durability.

  More preferably, the relationship of [ST3] / [SX2] ≧ 1.50 is satisfied, and further preferably, the relationship of [ST3] / [SX2] ≧ 2.00 is satisfied.

  The value of [ST3] / [SX2] is the kind and amount of the organosilicon compound used for forming the organosilicon polymer, and the reaction temperature, reaction time of hydrolysis, addition polymerization and condensation polymerization during the formation of the organosilicon polymer, It can be controlled by the reaction solvent and pH.

  In the partial structure represented by the above formula (T3), R represents an alkyl group having 1 to 6 carbon atoms and a phenyl group. When the hydrophobicity of R is large, there is a tendency that the charge amount fluctuation becomes large in a wide range of environments. Particularly preferred is an alkyl group having 1 to 5 carbon atoms, which is excellent in environmental stability.

  In the present invention, it is more preferable that R is an alkyl group having 1 to 3 carbon atoms from the viewpoint of easily improving the environmental stability of the toner and obtaining the effects of the present invention. Preferred examples of the hydrocarbon group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. More preferably, R is a methyl group from the viewpoints of environmental stability and storage stability.

  A typical production example of the organosilicon polymer used in the present invention is a method called a sol-gel method.

  In the sol-gel method, a metal alkoxide M (OR) n (M: metal, O: oxygen, R: hydrocarbon, n: oxidation number of metal) is used as a starting material, and hydrolysis and condensation polymerization are performed in a solvent. It is a method of gelling through a state, and is used for a method of synthesizing glass, ceramics, organic-inorganic hybrid, and nanocomposite. By using this production method, functional materials having various shapes such as surface layers, fibers, bulk bodies, and fine particles can be produced from a liquid phase at a low temperature.

  Specifically, the organosilicon polymer present in the surface layer of the toner particles is preferably produced by hydrolysis polycondensation of a silicon compound represented by alkoxysilane.

  By providing the surface layer containing the organosilicon polymer uniformly on the toner particles, the environmental stability is improved even if the inorganic fine particles are not fixed or adhered as in the conventional toner. In addition, it is possible to obtain a toner that is less likely to deteriorate in toner performance during long-term use and that has excellent storage stability.

  Furthermore, since the sol-gel method forms a material by starting from a solution and gelling the solution, various microstructures and shapes can be created. In particular, when the toner particles are produced in an aqueous medium, the toner particles are easily deposited on the surface of the toner particles due to the hydrophilicity of a hydrophilic group such as a silanol group of the organosilicon compound. However, when the hydrophobicity of the organosilicon compound is large (for example, when the hydrocarbon group of the organosilicon compound is a hydrocarbon group having more than 6 carbon atoms), the weight average particle size of the toner particles (on the surface of the toner particles ( There is a tendency that an aggregate which is 1/10 or less of μm) is easily formed. On the other hand, when the number of carbon atoms of the hydrocarbon group of the organosilicon compound is 0, the hydrophobicity is weakened, so that the charging stability of the toner is deteriorated. The fine structure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH, type and amount of the organometallic compound, and the like.

  In the present invention, the toner particles have a surface layer containing an organosilicon polymer having a partial structure represented by the above formula (T3). The organosilicon polymer is preferably an organosilicon polymer obtained by polymerizing an organosilicon compound having a structure represented by the following formula (Z).

（式（Ｚ）中、Ｒ¹は炭素数１乃至６のアルキル基又はフェニル基を表し、Ｒ²、Ｒ³及びＲ⁴は、それぞれ独立して、ハロゲン原子、ヒドロキシ基、アセトキシ基、又はアルコキシ基である。）

(In formula (Z), R ¹ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ² , R ³ and R ⁴ are each independently a halogen atom, a hydroxy group, an acetoxy group or an alkoxy group. Group.)

Hydrophobicity can be improved by the alkyl group and phenyl group of R ¹ , and toner particles excellent in environmental stability can be obtained. R ¹ is preferably an alkyl group having 1 to 6 carbon atoms and a phenyl group. When the hydrophobicity of R ¹ is large, the charge amount variation tends to increase in a wide range of environments. Therefore, in view of environmental stability, R ¹ is more preferably an alkyl group having 1 to 3 carbon atoms.

Preferred examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. A preferred example of R ¹ is a phenyl group. In this case, chargeability and fog prevention are good. More preferably, R ¹ is a methyl group from the viewpoints of environmental stability and storage stability.

R ^{2 to} R ⁴ are each independently a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups are hydrolyzed, addition-polymerized and condensation-polymerized to form a crosslinked structure, and a toner having excellent environmental stability and development durability can be obtained. The hydrolyzability is moderate at room temperature, and from the viewpoint of precipitation on the toner surface and coverage, an alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. The hydrolysis, addition polymerization and condensation polymerization of R ^{2 to} R ⁴ can be controlled by reaction temperature, reaction time, reaction solvent and pH.

In order to obtain the organosilicon polymer used in the present invention, an organosilicon compound having ^three reactive groups (R ² , R ³ and R ⁴ ) in one molecule excluding R ¹ in the formula (Z) shown above. (Hereinafter also referred to as trifunctional silane) may be used alone or in combination.

  In the present invention, the content of the organosilicon polymer is preferably 0.50 mass% or more and 50.00 mass% or less in the toner particles, and is 0.75 mass% or more and 40.00 mass% or less. More preferably.

  Examples of the formula (Z) include the following.

  Methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyl Triacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxy Hydroxysilane, methylethoxymethoxyhydroxysila , Methylsilane methyl diethoxy hydroxy silane, such as trifunctional.

  Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltri Trifunctional such as methoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane Silane.

  Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

  In the organosilicon polymer used in the present invention, the T unit structure represented by the formula (T3) is preferably 50 mol% or more, more preferably 60 mol% or more in the organosilicon polymer. By setting the content of the T unit structure represented by the formula (T3) to 50 mol% or more, the environmental stability of the toner can be further improved.

  In the present invention, an organosilicon compound having four reactive groups in one molecule (tetrafunctional) together with an organosilicon compound having a T unit structure represented by the formula (T3) to such an extent that the effects of the present invention are not impaired. Silane), an organosilicon polymer obtained by using together an organosilicon compound having two reactive groups in one molecule (bifunctional silane) or an organosilicon compound having one reactive group (monofunctional silane) It may be used. Examples of the organosilicon compound that may be used in combination include the following.

  Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane 3-anilinopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, hexamethyldisilane, tetraisocyanatesilane, methyltriisocyanatesilane, t-butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t- Butyldidiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chloro (decyl) dimethylsilane, methoxy (decyl) dimethyl Lan, ethoxy (decyl) dimethylsilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, triphenylchlorosilane, triphenylmethoxysilane, triphenylethoxysilane, Chloromethyl (dichloro) methylsilane, chloromethyl (dimethoxy) methylsilane, chloromethyl (diethoxy) methylsilane, di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, Dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxy Decylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, dichloro (methyl) -n-octylsilane, dimethoxy (methyl) -n-octylsilane, diethoxy (methyl) -n-octylsilane.

In general, it is known that in the sol-gel reaction, the bonding state of siloxane bonds generated varies depending on the acidity of the reaction medium. Specifically, when the reaction medium is acidic, hydrogen ions are electrophilically added to oxygen of one reactive group (for example, an alkoxy group (—OR group)). Next, the oxygen atom in the water molecule is coordinated to the silicon atom and becomes a hydrosilyl group by a substitution reaction. When water is sufficiently present, one H ⁺ attacks one oxygen of a reactive group (for example, an alkoxy group (-OR group)). Therefore, when the content of H ^{+ in} the reaction medium is small, The substitution reaction to the hydroxy group becomes slow. Therefore, a polycondensation reaction occurs before all of the reactive groups attached to the silane are hydrolyzed, and a one-dimensional linear polymer or a two-dimensional polymer is easily generated relatively easily.

  On the other hand, when the reaction medium is alkaline, hydroxide ions are added to silicon and go through a pentacoordinate intermediate. Therefore, all reactive groups (for example, alkoxy groups (—OR groups)) are easily removed and are easily substituted with silanol groups. In particular, when a silicon compound having three or more reactive groups on the same silane is used, hydrolysis and polycondensation occur three-dimensionally to form an organosilicon polymer having a large number of three-dimensional crosslinks. . The reaction is also completed in a short time.

  Therefore, in order to form the organosilicon polymer, it is preferable to proceed the sol-gel reaction with the reaction medium being in an alkaline state. Specifically, when producing in an aqueous medium, the pH should be 8.0 or more. preferable. As a result, an organosilicon polymer having higher strength and superior durability can be formed. The sol-gel reaction is preferably performed at a reaction temperature of 90 ° C. or more and a reaction time of 5 hours or more.

  By performing this sol-gel reaction at the above reaction temperature and reaction time, formation of coalesced particles in which silane compounds in a sol or gel state on the surface of the toner particles are bonded to each other can be suppressed.

  Furthermore, an organic titanium compound or an organic aluminum compound may be used together with the organosilicon compound to the extent that the effects of the present invention are not impaired.

  The following are mentioned as an organic titanium compound. Titanium methoxide, titanium ethoxide, titanium n-propoxide, tetra-i-propoxy titanium, tetra-n-butoxy titanium, titanium isobutoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, titanium diiso Propoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis (ethylacetoacetate), tetrakis (2 -Ethylhexyloxy) titanium, di-i-propoxy bis (acetylacetonato) titanium, titanium lactate, titanium methacrylate isopropoxide, triisopropoxy titanate, titanium methoxypropoxide, titanium steari Oxide.

  Examples of the organic aluminum compound include the following. Aluminum (III) n-butoxide, Aluminum (III) s-butoxide, Aluminum (III) s-butoxide bis (ethyl acetoacetate), Aluminum (III) t-butoxide, Aluminum (III) di-s-butoxide ethyl aceto Acetate, aluminum (III) diisopropoxide ethyl acetoacetate, aluminum (III) ethoxide, aluminum (III) ethoxyethoxy ethoxide, aluminum hexafluoropentandionate, aluminum (III) 3-hydroxy-2-methyl-4- Pyronate, aluminum (III) isopropoxide, aluminum-9-octadecenyl acetoacetate diisopropoxide, aluminum (III) 2,4-pe Tanjioneto, aluminum phenoxide, aluminum (III) 2,2,6,6-tetramethyl-3,5-heptanedionate.

  These compounds may be used alone or in combination. The charge amount can be adjusted by appropriately combining these or changing the addition amount.

  The toner of the present invention has a silicon atom concentration dSi (atomic%) and an oxygen atom concentration in the toner particle surface layer in the measurement using X-ray photoelectron spectroscopy (ESCA) of the toner particle surface layer. The ratio [dSi / (dSi + dO + dC)] of dSi (atomic%) to the sum of dO (atomic%) and the carbon atom concentration dC (atomic%) is preferably 0.025 or more, more preferably 0.050. It is above, More preferably, it is 0.100 or more.

  The ESCA performs elemental analysis of the surface layer existing at a thickness of several nanometers from the toner particle surface to the toner particle center (midpoint of the long axis). It is preferable to set the silicon atom concentration (dSi / [dSi + dO + dC]) in the toner particle surface layer to 0.025 or more because the surface free energy of the surface layer can be reduced. On the other hand, (dSi / [dSi + dO + dC]) is preferably 0.333 or less from the viewpoint of chargeability. More preferably, it is 0.286 or less.

  The concentration of silicon atoms in the surface layer of the toner particles can be controlled by the structure of R in the above formula (T3), the production method of the toner particles when forming the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH. it can. It can also be controlled by the content of the organosilicon polymer. In the present invention, the surface layer of the toner particles means a layer having a thickness of 0.0 to 10.0 nm from the toner particle surface toward the center of the toner particle (midpoint of the long axis).

  The toner of the present invention has a carbon atom concentration dC (atomic%) at a silicon atom concentration dSi (atomic%) in the measurement using X-ray photoelectron spectroscopy (ESCA) of the surface layer of the toner particles. The ratio [dSi / dC] to is preferably 0.15 or more and 5.00 or less. By setting [dSi / dC] within the above range, the surface free energy can be reduced, which is effective in storage stability and rear end offset resistance. [DSi / dC] is more preferably not less than 0.20 and not more than 4.00, and more preferably not less than 0.30 and not more than 3.00, in order to further improve storage stability and rear end offset resistance. Is more preferable.

  Further, when the ratio [dSi / dC] of the silicon atom concentration dSi (atomic%) to the carbon atom concentration dC (atomic%) is less than 0.15, the carbon amount of the toner particle surface layer is relatively large. Then, since surface free energy becomes large, the cohesion of particles and the adhesion force with the fixing film increase, and the rear end offset property tends to deteriorate. On the other hand, when [dSi / dC] exceeds 5.00, the hydrophobicity attributed to the carbon atom tends to be too small and the environmental stability tends to deteriorate. The [dSi / dC] can be controlled by the structure of R in the above formula (T3), the method for producing toner particles when forming the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH. .

  In the present invention, in cross-sectional observation of a toner particle using a transmission electron microscope (TEM), the toner is centered on the intersection of the major axis L of the toner particle cross-section and the axis L90 that passes through the center of the major axis L and is vertical. The particle cross section is divided into 16 equal parts. When the dividing axes from the center toward the surface of the toner particles are An (n = 1 to 32), the average thickness Dav. Is preferably 5.0 nm or more and 150.0 nm or less (see FIG. 1). In the present invention, the surface layer containing the organosilicon polymer and the portion other than the toner particle surface layer (so-called core portion) are preferably in contact with each other without a gap. In other words, it is preferably not a granular lump coating layer as disclosed in Patent Document 4. As a result, the occurrence of bleeding due to the resin component and the release agent inside the surface layer of the toner particles is suppressed, and a toner having excellent storage stability, environmental stability, and development durability can be obtained. From the viewpoint of storage stability, the average thickness Dav. Is more preferably 7.5 nm or more and 125.0 nm or less, and still more preferably 10.0 nm or more and 100.0 nm or less.

  Dav. Is within the above range, it is easy to balance bleeding suppression of resin components and release agents, development durability, and low-temperature fixability. In addition, it is easy to control the thermal conductivity of the toner within the scope of the present invention by appropriately providing the surface of the toner with an organosilicon polymer that tends to have a higher thermal conductivity than the binder resin constituting the toner particles. .

  The average thickness Dav. If it is less than 5.0 nm, bleeding of the resin component or the release agent in the toner particles may occur easily. As a result, the surface properties of the toner particles are likely to change, and environmental stability and development durability may deteriorate. In particular, even in a development durability test using a high printing rate image that requires agitation accompanying the fluidity of the toner in the developing device, it is easy to obtain a high-quality image until the latter half of the durability.

  On the other hand, the average thickness Dav. When the thickness exceeds 150.0 nm, the binding between the toners is easily inhibited, and as a result, the trailing edge offset resistance tends to deteriorate.

[Average thickness Dav. Of surface layer of toner particles containing organosilicon polymer] ]
The average thickness Dav. Of the surface layer of the toner particles containing the organosilicon polymer. Was determined by the following method.

First, the average thickness D ⁽ⁿ⁾ of the surface layer containing the organosilicon polymer of one toner particle was determined by the following method.
D ⁽ⁿ⁾ = (total of 32 locations of the thickness of the surface layer containing the organosilicon polymer on the shaft) / 32

This calculation was performed for 10 toner particles. The average value per toner particle is calculated from the thickness D ⁽ⁿ⁾ (n is an integer of 1 to 10 ⁾ of the surface layer of the obtained toner particles according to the following formula, and the surface layer containing the organosilicon polymer of the toner particles Average thickness Dav. Asked.
Dav. = {D ⁽¹⁾ + D ⁽²⁾ + D ⁽³⁾ + D ⁽⁴⁾ + D ⁽⁵⁾ + D ⁽⁶⁾ + D ⁽⁷⁾ + D ⁽⁸⁾ + D ⁽⁹⁾ + D ⁽¹⁰⁾ } / 10

  Average thickness Dav. Is a method for producing toner particles during the formation of the organosilicon polymer, the number of carbon atoms of the hydrocarbon group in the above formula (T3), the number of hydrophilic groups, the reaction temperature of the addition polymerization and condensation polymerization during the formation of the organosilicon polymer. , Reaction time, reaction solvent and pH. It can also be controlled by the content of the organosilicon polymer.

  In the present invention, in cross-sectional observation of a toner particle using a transmission electron microscope (TEM), the toner is centered on the intersection of the major axis L of the toner particle cross-section and the axis L90 that passes through the center of the major axis L and is vertical. The particle cross section is divided into 16 equal parts. When the dividing axis from the center toward the surface of the toner particle is An (n = 1 to 32), the thickness of the surface layer of the toner particle containing the organosilicon polymer on each of the 32 dividing axes is 5 The ratio of the number of split axes that is 0.0 nm or less (hereinafter also referred to as the ratio of the surface layer thickness of 5.0 nm or less) is preferably 20.0% or less, more preferably 10.0% or less, and even more preferably. Is 5.0% or less (see FIG. 1).

  When the ratio of the thickness of the surface layer of 5.0 nm or less is within the above range, it is possible to reduce the occurrence of bleeding such as resin components and release agents inside the surface layer of the toner particles. And development durability are easily improved.

[Ratio of the surface layer containing the organosilicon polymer in which the thickness FRAn of the surface layer containing the organosilicon polymer is 5.0 nm or less]
The ratio of the surface layer containing the organosilicon polymer in which the thickness FRAn of the surface layer containing the organosilicon polymer is 5.0 nm or less was determined by the following method.

First, the ratio of the surface layer containing an organosilicon polymer having a thickness FRAN of 5.0 nm or less with respect to one toner particle was determined based on the following formula.
(Ratio of the surface layer containing the organosilicon polymer in which the thickness FRAn of the surface layer containing the organosilicon polymer is 5.0 nm or less) = ((The thickness FRAn of the surface layer containing the organosilicon polymer is 5.0 nm or less) Number) / 32) × 100

  This calculation was performed for 10 toner particles. Thickness of the surface layer containing the organosilicon polymer of the toner particles The average value is obtained from the ratio of the surface layer containing the organosilicon polymer whose FRAN is 5.0 nm or less. It was set as the ratio of the surface layer containing the organosilicon polymer whose FRAn is 5.0 nm or less.

  The ratio of the thickness of the surface layer of 5.0 nm or less is the production method of the toner particles at the time of forming the organosilicon polymer, the number of hydrocarbon groups in the above formula (T3), the number of hydrophilic groups, the formation of the organosilicon polymer. It can be controlled by the reaction temperature, reaction time, reaction solvent and pH of the addition polymerization and condensation polymerization. It can also be controlled by the content of the organosilicon polymer.

  Next, a method for producing toner particles will be described.

  Hereinafter, specific embodiments in which the organosilicon polymer is contained in the toner particle surface layer will be described, but the present invention is not limited thereto.

  As the first production method, a polymerizable monomer composition containing an organosilicon compound for forming an organosilicon polymer and a polymerizable monomer for forming a binder resin is granulated in an aqueous medium. An embodiment (hereinafter also referred to as a suspension polymerization method) in which toner particles are obtained by polymerizing a polymerizable monomer is mentioned.

  Examples of the second production method include a mode in which after obtaining a toner particle matrix first, the toner particle matrix is put into an aqueous medium, and a surface layer of an organosilicon polymer is formed on the toner particle matrix in the aqueous medium. The toner particle matrix may be obtained by melt-kneading and pulverizing the binder resin, or may be obtained by aggregating and associating the binder resin particles in an aqueous medium. The organic phase dispersion prepared by dissolving the binder resin in an organic solvent may be obtained by suspending, granulating, and polymerizing the organic phase dispersion in an aqueous medium and then removing the organic solvent. .

  As a third production method, an organic phase dispersion prepared by dissolving a binder resin and an organosilicon compound for forming an organosilicon polymer in an organic solvent is suspended, granulated, and polymerized in an aqueous medium. Then, the organic solvent is removed to obtain toner particles.

  As a fourth production method, there is an aspect in which binder resin particles and organosilicon compound-containing particles for forming a sol or gel organosilicon polymer are aggregated in an aqueous medium and associated to form toner particles. Can be mentioned.

  As the fifth production method, a solvent containing an organosilicon compound for forming an organosilicon polymer is sprayed onto the surface of the toner particle matrix by spray drying, and the surface is polymerized by hot air and cooling. There is an embodiment in which the organic silicon polymer is formed on the surface layer of the toner particles by drying. The toner particle matrix may be obtained by melt-kneading and pulverizing the binder resin, or the binder resin particles may be obtained by agglomerating and associating in an aqueous medium, and the binder resin is dissolved in an organic solvent. The organic phase dispersion thus prepared may be obtained by suspending, granulating, and polymerizing in an aqueous medium and then removing the organic solvent.

  The toner particles produced by these production methods have good environmental stability (particularly chargeability under harsh environments) because the organosilicon polymer is formed near the surface of the toner particles. Further, even in a harsh environment, changes in the surface state of the toner particles due to bleeding of the resin present in the toner and the release agent added as necessary are suppressed.

  In the present invention, the obtained toner particles or toner may be surface-treated using hot air. By performing the surface treatment of the toner particles or toner using hot air, it is possible to promote the polycondensation of the organosilicon polymer in the vicinity of the surface of the toner particles and improve the environmental stability and the development durability.

  As the surface treatment using hot air, any means that can treat toner particles or toner surface with hot air and that can cool the toner particles or toner treated with hot air with cold air can be used. It may be something like this.

  As a device for performing surface treatment using hot air, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechano-fusion system (manufactured by Hosokawa Micron Co.), a faculty (manufactured by Hosokawa Micron Co., Ltd.), Meteor Inbo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) Is mentioned.

  In the above production method, examples of the aqueous medium include the following. Water; alcohols such as methanol, ethanol, and propanol, and mixed solvents thereof.

  As the method for producing the toner particles of the present invention, among the production methods described above, the suspension polymerization method which is the first production method is preferable. In the suspension polymerization method, the organosilicon polymer is likely to be uniformly deposited on the surface of the toner particles, has excellent adhesion between the surface layer and the inside, and has excellent storage stability, environmental stability, and development durability. Hereinafter, the suspension polymerization method will be further described.

  You may add a coloring agent, a mold release agent, polar resin, and low molecular weight resin to the said polymeric monomer composition as needed. Further, after the polymerization step is completed, the produced particles are washed and collected by filtration and dried to obtain toner particles. The temperature may be raised in the latter half of the polymerization step. Furthermore, in order to remove the unreacted polymerizable monomer or by-product, it is possible to partially distill off the dispersion medium from the reaction system in the latter half of the polymerization step or after the completion of the polymerization step.

  The materials described below are not only applicable to the suspension polymerization method but also applicable to the other production methods described above.

  Preferred examples of the polymerizable monomer in the suspension polymerization method include the following vinyl polymerizable monomers. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n -Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, Diethyl phosphate ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as til methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, Vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  In the polymerization of the polymerizable monomer, a polymerization initiator may be added. The following are mentioned as a polymerization initiator. 2,2′-azobis- (2,4-divaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxy carbonate, cumene hydroperoxide, 2,4-dichloro Peroxide polymerization initiators such as benzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 30.0% by mass relative to the polymerizable monomer, and may be used alone or in combination.

  In order to control the molecular weight of the binder resin constituting the toner particles, a chain transfer agent may be added during the polymerization of the polymerizable monomer. The addition amount of the chain transfer agent is preferably 0.001 to 15.000% by mass of the polymerizable monomer.

  On the other hand, in order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added during the polymerization of the polymerizable monomer. The following are mentioned as a crosslinking agent. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and the above acrylates were changed to methacrylate The.

  Moreover, the following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate. The addition amount of the crosslinking agent is preferably 0.001 to 15.000% by mass with respect to the polymerizable monomer.

  When the medium used in the polymerization of the polymerizable monomer is an aqueous medium, the following dispersion stabilizers in the aqueous medium of the particles of the polymerizable monomer composition can be used. .

  As an inorganic dispersion stabilizer, tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate , Bentonite, silica, and alumina.

  Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, and starch.

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

  In the present invention, when preparing an aqueous medium using a hardly water-soluble inorganic dispersion stabilizer, the amount of these dispersion stabilizers added is 0.2 to 2 with respect to 100.0 parts by mass of the polymerizable monomer. 0.0 part by mass is preferable. Moreover, it is preferable to prepare an aqueous medium using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.

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

  In the present invention, the binder resin used for the toner particles is not particularly limited, and conventionally known binder resins can be used. Preferred examples of the binder resin used for the toner particles include a vinyl resin and a polyester resin. The vinyl resin is preferably generated by polymerization of the above-described vinyl polymerizable monomer. For example, vinyl resin is excellent in environmental stability. In addition, the vinyl-based resin has an organic silicon polymer obtained by polymerizing the organosilicon compound having the structure represented by the above formula (Z), in terms of precipitation on the toner particle surface, surface uniformity, and long-term storage stability. It is preferable because it is excellent.

  On the other hand, as a polyester resin, what carried out condensation polymerization of the carboxylic acid component and alcohol component which are mentioned below can be used.

  Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol component include bisphenol A, hydrogenated bisphenol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin, trimethylolpropane, and pentaerythritol. Further, the polyester resin may be a polyester resin containing a urea group.

  On the other hand, the following resins or polymers can be exemplified as the vinyl resin, polyester resin and other binder resins.

  Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, 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-vinyl methyl ketone copolymer , Styrene-butadi Copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene copolymer such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, Polypropylene, polyvinyl butyral, silicone resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. These binder resins can be used alone or in combination.

  In the toner of the present invention, the resin may have a polymerizable functional group for the purpose of improving the viscosity change of the toner at a high temperature. Examples of the polymerizable functional group include a vinyl group, an isocyanate group, an epoxy group, an amino group, a carboxylic acid group, and a hydroxyl group.

  In the present invention, the toner particles may contain a polar resin. Preferred examples of the polar resin include saturated or unsaturated polyester resins. As said polyester resin, what carried out condensation polymerization of the carboxylic acid component and alcohol component which are mentioned below can be used.

  Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol component include bisphenol A, hydrogenated bisphenol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin, trimethylolpropane, and pentaerythritol. Further, the polyester resin may be a polyester resin containing a urea group.

  In the present invention, the polar resin preferably has a weight average molecular weight of 4,000 or more and less than 100,000. Further, the content of the polar resin is preferably 3.0 to 70.0% by mass, more preferably 3.0 to 50.0% by mass, based on the binder resin component contained in the toner particles. More preferably, it is 5.0 to 30.0% by mass.

  In the present invention, a release agent is preferably contained as one of the materials constituting the toner particles. The release agent usable for the toner particles includes paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof by Fischer-Tropsch method, polyethylene, polypropylene Polyolefin waxes and derivatives thereof, natural waxes and derivatives thereof such as carnauba wax and candelilla wax, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, curing Castor oil and derivatives thereof, plant waxes, animal waxes, and silicone resins. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products.

  In addition, it is preferable that content of a mold release agent is 5.0 thru | or 20.0 mass parts with respect to binder resin or 100.0 mass parts of polymerizable monomers.

  The toner particles in the present invention contain a magnetic substance in order to control the thermal conductivity within a desired range.

  Furthermore, the magnetic material used in the toner of the present invention is preferably a treated magnetic material obtained by surface-treating magnetic iron oxide with a silane compound. This is because it is preferable to hydrophobize the magnetic substance in the production by the suspension polymerization method preferably used for controlling the dispersibility of the magnetic substance. As a result of intensive studies on the dispersibility of the magnetic material, it has been found that it is preferable to treat with a silane compound.

  As a result of the study by the present inventors, as will be described later, by highly controlling the hydrophobization treatment with the silane compound on the surface of the magnetic material, the magnetic material can be unevenly distributed in the vicinity of the toner particle surface, and between the magnetic materials It has been found that can be uniformly dispersed without agglomeration. Furthermore, it has been found that the thermal conductivity can be controlled within a desired range only by achieving the presence state of the magnetic substance.

  Specifically, in the suspension polymerization method, a monomer composition containing a magnetic material is dispersed in an aqueous medium, granulated, and a polymerizable monomer contained in the granulated particles is polymerized. Therefore, the surface of the magnetic material to be used needs to be hydrophobized so as not to be exposed to the aqueous system. This is because normally untreated magnetic iron oxide has high hydrophilicity because functional groups such as hydroxyl groups exist on the surface.

  Here, silane compounds, titanate compounds, aluminate compounds, and the like are generally known as surface treatment agents, but these surface treatment agents all hydrolyze and undergo a condensation reaction with hydroxyl groups on the surface of magnetic iron oxide. It has a strong chemical bond and exhibits hydrophobicity. However, it is known that these hydrolyzed compounds undergo self-condensation and are liable to form polymers and oligomers. As a result of intensive studies by the present inventors, titanate compounds and aluminate compounds are susceptible to self-condensation after hydrolysis, and it is difficult to uniformly treat the magnetic iron oxide surface. This is considered to be because the activity of titanium and aluminum contained in the titanate compound and the aluminate compound is high. On the other hand, the silane compound can suppress the self-condensation while increasing the hydrolysis rate by controlling the hydrolysis conditions, and can uniformly treat the magnetic iron oxide surface. The present inventors consider that this is because the silicon activity of the silane compound is not as high as that of titanium or aluminum.

  For this reason, it is preferable to use a silane compound from the viewpoint of the uniformity of the surface treatment of the magnetic material. By improving the uniformity of the surface treatment of the magnetic material with the silane compound, the magnetic material is unevenly distributed in the vicinity of the surface of the toner particles, and the uniform dispersibility is easily improved. As a result, the thermal conductivity of the toner, which is an important physical property in the present invention, can be controlled, which is very preferable.

  Further, the magnetic iron oxide in the present invention has a silicon element on the surface, and the amount of silicon eluted when the magnetic iron oxide is dissolved until the dissolution rate of the iron element reaches 5.00% by mass, It is preferable that it is 0.05 mass% or more and 0.50 mass% or less on the basis of magnetic iron oxide. This is considered because the affinity between the magnetic iron oxide surface and the silane compound is improved, and the uniformity of the treatment with the silane compound is further improved. Further, the affinity between the magnetic iron oxide surface and the silane compound is improved, so that the amount of the silane compound bonded to the magnetic iron oxide surface is increased.

  For the above reasons, in the present invention, it is preferable that a specific amount of silicon element is present on the surface of magnetic iron oxide and in the vicinity thereof. Specifically, the magnetic iron oxide is dispersed in an aqueous hydrochloric acid solution, and the magnetic iron oxide is dissolved until the dissolution rate of the iron element is 5.00% by mass with respect to the total iron element amount contained in the magnetic iron oxide. The amount of silicon eluted up to that point is preferably 0.05% by mass or more and 0.50% by mass or less based on the magnetic iron oxide.

  Here, regarding the dissolution rate of the iron element of the magnetic iron oxide, the dissolution rate of the iron element is 100% by mass, which is a state in which the magnetic iron oxide is completely dissolved. It means that the whole iron oxide has melted. As a result of intensive studies by the present inventors, magnetic iron oxide is uniformly dissolved from the surface under acidic conditions.

  Therefore, it is considered that the amount of the element eluted before the iron element dissolution rate reaches 5.00% by mass indicates the amount of the element present on the magnetic iron oxide surface and its vicinity. When the amount of silicon present on and around the magnetic iron oxide surface is 0.05% by mass or more, as described above, the affinity between the silane compound and the magnetic iron oxide is improved, and the processing uniformity is improved. . For this reason, the dispersibility of the magnetic substance in the toner can be improved.

  On the other hand, when the amount of silicon present on the surface of the magnetic iron oxide and in the vicinity thereof is more than 0.50% by mass, the environmental stability of the toner tends to be lowered, which is not preferable. The reason for this is as follows.

  The area (covering area) that can be coated with one molecule is determined for the silane compound that surface-treats the magnetic iron oxide surface. For this reason, the maximum amount of the silane compound that can be condensed per unit area is determined by the covering area. For this reason, when the silicon content is more than 0.50% by mass, silicon and silanol groups derived from the silicon will remain on the surface of the magnetic iron oxide, resulting in a surface that easily adsorbs moisture, It becomes inferior to environmental stability.

  Further, in order to control the surface state of such a magnetic material, it is necessary to control it by assuming a magnetic toner manufacturing process manufactured by the present invention.

  That is, it is necessary to maintain the amount of the silane compound on the surface even in a polymerizable monomer such as styrene. As a result of intensive studies by the present inventors, the amount of residual carbon derived from the silane compound after styrene cleaning is preferably 0.40% by mass or more and 1.20% by mass or less based on magnetic iron oxide. . By washing with styrene, the adhesion amount of the silane compound on the surface of the magnetic material during the production of the magnetic toner produced according to the present invention can be estimated by the amount of residual carbon. In general, the present inventors consider that the hydrocarbon group is important for the silane compound to exhibit hydrophobicity, that is, the amount of carbon is effective in estimating the hydrophobic capacity.

  When the adhesion amount is less than 0.40% by mass, sufficient hydrophobic ability cannot be obtained, and the magnetic material is easily exposed to the aqueous system in the production method of the present invention. On the other hand, when the adhesion amount exceeds 1.20% by mass, unevenness is likely to occur in the coverage of the treatment agent, resulting in a decrease in processing uniformity, and unevenness in the presence of the magnetic substance between the toner particles. As a result, the uniformity of the toner particles tends to be poor and desired performance cannot be obtained.

  In addition, the silane compound obtained by treating the magnetic material used in the method for producing magnetic toner is preferably obtained by subjecting alkoxysilane to hydrolysis treatment, and the hydrolysis rate of alkoxysilane is preferably 50% or more. In general, silane compounds are used without being hydrolyzed and are often treated as they are. However, in this case, they cannot have a chemical bond with a hydroxyl group or the like on the surface of magnetic iron oxide and have only a physical adhesion strength. No. In this state, the silane compound is likely to be detached due to the share received during toner formation.

  For the reasons described above, in the present invention, the silane compound is preferably one obtained by subjecting alkoxysilane to hydrolysis treatment. By performing the hydrolysis treatment, the silane compound is adsorbed to the hydroxyl group on the surface of the magnetic iron oxide through a hydrogen bond, and a strong chemical bond is formed by heating and dehydrating it. Moreover, by forming a hydrogen bond, volatilization of the silane compound can be suppressed during heating, and it becomes easy to obtain a material that satisfies the regulations regarding the amount of moisture adsorption.

  For these reasons, in the present invention, the hydrolysis rate of the silane compound is preferably 50% or more, more preferably 80% or more, and still more preferably 90% or more. When the hydrolysis rate of the silane compound is 50% or more, the magnetic iron oxide surface can be treated with many treatment agents for the reasons described above. Furthermore, the uniformity of the surface treatment is improved, and the dispersibility of the magnetic material is further improved. For this reason, the uniformity between the toners is increased. For example, even when the toner is continuously used in a durability test or the like, the charging of the toner is stabilized, and as a result, a stable image can be obtained. The hydrolysis rate of the silane compound is a value obtained by subtracting the ratio of the remaining alkoxy groups with the hydrolysis rate of 100% when the alkoxysilane is completely hydrolyzed.

  Next, the magnetic material used in the method for producing a magnetic toner produced according to the present invention is preferably surface-treated in a gas phase with a silane compound.

  There are two types of methods for surface treatment of magnetic materials, dry and wet. When the surface treatment is performed by a dry method, a silane compound is added to the dried magnetic material, and the surface treatment is performed in a gas phase.

  In the case of wet surface treatment, the dried material is redispersed in an aqueous medium, or after the oxidation reaction, iron oxide is redispersed in another aqueous medium without drying, and the surface treatment with a silane compound is performed. I do. The magnetic material used in the present invention is a magnetic material that has been surface-treated in a gas phase with a silane compound (hereinafter also referred to as a dry method), which improves the dispersibility of the magnetic material between the magnetic toners produced by the present invention. It is preferable to achieve the above. The reason for this is as follows.

  In the dry method, since only a small amount of water is present in the reaction system, it is difficult to form a hydrogen bond between the hydrophilic group contained in the silane compound and water. Therefore, compared with the wet process in which water is present, the hydrogen bonding rate with the surface of the magnetic material is increased, and a more uniform and efficient hydrophobic treatment with a silane compound can be performed. Further, when the hydrophilic group of the treatment agent forms a hydrogen bond with water and adsorbs and reacts with the surface of the magnetic body while trapping water, the hydrophilic group remains on the surface of the treated magnetic body without being reacted. Since hydrophilic groups are easily compatible with water, when there are many magnetic hydrophilic groups, uneven distribution of magnetic substances during toner production tends to occur. Since the dry processing method can prevent such problems due to hydrogen bonding, the uniform coverage of the magnetic silane compound used in the magnetic toner produced by the present invention is improved. As a result, it is possible to further improve the dispersibility of the magnetic material and to easily improve the uniform chargeability of the toner.

  Hereinafter, details of a method for producing a magnetic material used for the magnetic toner produced by the production method of the present invention will be described.

  Hydrolysis of the alkoxysilane used in the magnetic material used in the present invention is preferably carried out as follows. Specifically, alkoxysilane is gradually added to an aqueous solution or a mixed solution of alcohol and water whose pH is adjusted to 4.0 or more and 6.5 or less, and uniformly dispersed using, for example, a disper blade. At this time, it is preferable that the liquid temperature of a dispersion liquid is 35 degreeC or more and 60 degrees C or less. Generally, the lower the pH and the higher the liquid temperature, the easier the alkoxysilane is hydrolyzed. As a result of diligent investigations by the present inventors, the use of a dispersing device capable of imparting high shear, such as a disperse blade, even under difficult hydrolysis conditions, increases the contact area of alkoxysilane and water, thereby efficiently adding water. Degradation could be promoted. This makes it possible to suppress self-condensation while increasing the hydrolysis rate. Specifically, alkoxysilane is gradually added to an aqueous solution or a mixed solution of alcohol and water whose pH is adjusted to 4.0 or more and 6.5 or less, and uniformly dispersed using, for example, a disper blade. At this time, it is preferable that the liquid temperature of a dispersion liquid is 35 degreeC or more and 60 degrees C or less. In the present invention, it is preferable to treat the surface of magnetic iron oxide with a silane compound in the gas phase. As described above, the magnetic substance of the present invention can have a strong chemical bond by adsorbing a silane compound on the surface of magnetic iron oxide by hydrogen bonding and dehydrating it. However, since the hydrogen bond between the silane compound and the surface of the magnetic iron oxide is a reversible reaction, it is possible to treat the surface of the magnetic iron oxide with more silane compounds when there is less water in the system. As a result, the hydrophobicity of the processed magnetic material is greatly increased, the toner charge is likely to rise quickly, and a good image density is easily obtained even in a high temperature and high humidity environment.

  A known stirring device can be used as a device for surface treatment of magnetic iron oxide. Specifically, a Henschel mixer (Mitsui Miike Chemical), a high speed mixer (Fukae Powtech), a hybridizer (Nara Machinery Co., Ltd.), etc. are preferable.

Magnetic iron oxide is composed mainly of triiron tetroxide or γ-iron oxide, and may contain elements such as phosphorus, cobalt, nickel, copper, magnesium, manganese, and aluminum. Magnetic material, it is preferable that a BET specific surface area is less than 2.0 m ² / g or more 20.0 m ² / g by a nitrogen adsorption method, not more than 3.0 m ² / g or more 10.0 m ² / g More preferred. The shape of the magnetic body includes a polyhedron, an octahedron, a hexahedron, a sphere, a needle, and a scale, but a polyhedron, an octahedron, a hexahedron, a sphere, and the like having a low anisotropy increase the image density. Preferred above.

  The magnetic material of the present invention preferably has a number average diameter of 0.12 μm or more and 0.40 μm or less, more preferably 0.18 μm or more and 0.35 μm or less, from the viewpoint of uniform dispersibility and color in the toner. More preferably, it is 0.20 μm or more and 0.28 μm or less.

  When the number average diameter of the magnetic material is in the above range, it is preferable to easily improve the processing uniformity of the surface of the magnetic material and to easily control the thermal conductivity to a desired range as described above. When the number average diameter of the magnetic material is less than 0.12 μm, the magnetic material is easily oxidized and easily reddish. On the other hand, if it exceeds 0.40 μm, the number of magnetic materials in the toner particles tends to decrease, and the thermal conductivity tends to decrease, such being undesirable.

  The number average diameter of the magnetic material can be measured using a transmission electron microscope. Specifically, after sufficiently dispersing the toner particles to be observed in the epoxy resin, a cured product obtained by curing in an atmosphere at a temperature of 40 ° C. for 2 days is obtained. The obtained cured product is used as a flaky sample by a microtome, and the particle diameters of 100 magnetic bodies in the field of view are measured with a transmission electron microscope (TEM) with a photograph with a magnification of 10,000 to 40,000 times. Then, the number average diameter is calculated based on the equivalent diameter of a circle equal to the projected area of the magnetic material. It is also possible to measure the particle size with an image analyzer.

  The magnetic material used in the magnetic toner produced according to the present invention can be produced, for example, by the following method. Specifically, an aqueous solution containing ferrous hydroxide is prepared by adding an alkali such as sodium hydroxide in an amount equivalent to or greater than the iron component to the ferrous salt aqueous solution. Air was blown in while maintaining the pH of the prepared aqueous solution at 7.0 or higher, and ferrous hydroxide was oxidized while heating the aqueous solution to 70 ° C. or higher, and seed crystals serving as the core of the magnetic iron oxide particles were formed. First generate. Next, an aqueous solution containing about 1 equivalent of ferrous sulfate is added to the slurry-like liquid containing seed crystals based on the amount of alkali added previously. The pH of the liquid is maintained at 5.0 or higher and 10.0 or lower, and the reaction of ferrous hydroxide proceeds while blowing air, and magnetic iron oxide particles are grown with the seed crystal as a core. At this time, it is possible to control the shape and magnetic properties of the magnetic iron oxide by selecting an arbitrary pH, reaction temperature, and stirring conditions. As the oxidation reaction proceeds, the pH of the liquid shifts to the acidic side, but the pH of the liquid is preferably not less than 5.0. After completion of the oxidation reaction, a silicon source such as sodium silicate is added to adjust the pH of the solution to 5.0 or more and 8.0 or less. In this way, a silicon coating layer is formed on the surface of the magnetic iron oxide particles. Magnetic iron oxide particles can be obtained by filtering, washing, and drying the magnetic iron oxide particles obtained as above.

  The amount of silicon element present on the surface of magnetic iron oxide can be controlled by adjusting the amount of silicon source such as sodium silicate added after the oxidation reaction is completed.

  Next, surface treatment with a silane compound, which is preferable in the present invention, is performed. Specifically, the liquid temperature is adjusted so that the aqueous solution whose pH is adjusted to 3.0 or more and 6.5 or less is 35 ° C. or more and 50 ° C. or less. Alkoxysilane is gradually added to this aqueous solution, and it is uniformly stirred and dispersed using, for example, a disper blade, etc., and hydrolysis is performed. The hydrolyzate thus obtained is added to magnetic iron oxide and mixed uniformly with a stirrer / mixer such as a high speed mixer or a Henschel mixer. Thereafter, drying and pulverization can be performed at a temperature of 80 ° C. or higher and 160 ° C. or lower to obtain a surface-treated magnetic body.

  When wet surface treatment is performed, after the oxidation reaction is completed, the dried product is redispersed, or after completion of the oxidation reaction, the iron oxide body obtained by washing and filtering is not dried but in another aqueous medium. And re-disperse to surface treatment. Specifically, the surface treatment is performed by adding alkoxysilane while sufficiently stirring the re-dispersed liquid to increase the temperature after hydrolysis, or adjusting the pH of the dispersion to an alkaline region after hydrolysis.

Examples of the silane compound that can be used for the surface treatment of magnetic iron oxide include those represented by the general formula (1).
RmSiYn (1)
(In the formula, R represents an alkoxy group or a hydroxyl group, m represents an integer of 1 to 3, Y represents an alkyl group or a vinyl group, and the alkyl group includes, as a substituent, an amino group, a hydroxyl group, It may have a functional group such as an epoxy group, an acrylic group, a methacryl group, etc. n represents an integer of 1 to 3, provided that m + n = 4.

  Examples of the silane compound represented by the general formula (1) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltri Acetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiet Sisilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, trimethylmethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, hydroxypropyltrimethoxy Examples thereof include silane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, and hydrolysates thereof.

  Among these, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, and n-octyltrimethoxysilane are preferable because the toner has good chargeability and magnetic dispersibility. Of these, isobutyltrimethoxysilane and n-hexyltrimethoxysilane are particularly preferable because the thermal conductivity of the toner can be easily controlled.

  When the silane compound is used, it can be treated alone or in combination of a plurality of types. When using several types together, you may process separately with each silane compound, and may process simultaneously.

  In the present invention, the content of the magnetic substance is preferably 20 parts by mass or more and 120 parts by mass or less, and 50 parts by mass or more and 100 parts by mass with respect to 100 parts by mass of the binder resin in controlling the thermal conductivity. Less than is more preferable. When the content of the magnetic material is increased, particularly when it exceeds 120 parts by mass, the thermal conductivity tends to be excessively high, and problems such as toner fusion are likely to occur. On the other hand, when the content of the magnetic material is small, especially when it is less than 50 parts by mass, the thermal conductivity tends to decrease, and in particular, the effect of suppressing the rear end offset cannot be expected.

  Note that the content of the magnetic substance in the toner can be measured using a thermal analyzer, TGA7, manufactured by PerkinElmer. The measuring method is as follows. The toner is heated from room temperature to 900 ° C. at a temperature rising rate of 25 ° C./min in a nitrogen atmosphere. The weight loss mass% between 100 ° C. and 750 ° C. is defined as the binder resin amount, and the remaining mass is approximately defined as the treated magnetic material amount.

In the present invention, the saturation magnetization (σs) of the toner at a magnetic field of 79.6 kA / m is 20.0 Am ² / kg or more and 30.0 Am ² / kg or less, and the residual magnetization (σr) is 1.5 Am ^2. / Kg or more and 2.0 Am ² / kg or less is preferred because the toner is prominent on the sleeve and the developability tends to be good.

  In the present invention, the toner particles may contain a charge control agent. A well-known thing can be used as a charge control agent. In particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is particularly preferable.

  Examples of the charge control agent that control toner particles to be negatively charged include the following. As an organic metal compound and a chelate compound, a monoazo metal compound, an acetylacetone metal compound, an aromatic oxycarboxylic acid, an aromatic dicarboxylic acid, an oxycarboxylic acid, and a dicarboxylic acid-based metal compound. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts, anhydrides or esters thereof, and phenol derivatives such as bisphenol. Furthermore, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, and calixarene can be mentioned.

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

  These charge control agents can be contained alone or in combination of two or more. Among these charge control agents, metal-containing salicylic acid compounds are preferable, and the metal is particularly preferably aluminum or zirconium. From the viewpoint of the chargeability of the toner, an aluminum 3,5-di-tert-butylsalicylate compound is preferably used.

  Further, as the resin charge control agent, a polymer having a sulfonic acid functional group is preferable. The polymer having a sulfonic acid functional group is a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group. Examples of the polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group include a polymer compound having a sulfonic acid group in the side chain. In particular, styrene and / or styrene (meta) containing a sulfonic acid group-containing (meth) acrylamide monomer in a copolymerization ratio of 2% by mass or more, preferably 5% by mass or more and having a glass transition temperature (Tg) of 40 to 90 ° C. ) A polymer compound which is an acrylic ester copolymer is preferred. Charge stability under high humidity is improved.

  As said sulfonic-acid-group-containing (meth) acrylamide type monomer, what can be represented by the following general formula (X) is preferable, and 2-acrylamido-2-methylpropanoic acid and 2-methacrylamido-2-methyl are specifically mentioned. And propanoic acid.

［上記一般式（Ｘ）中、Ｒ₁は水素原子、又はメチル基を示し、Ｒ₁とＲ₃は、それぞれ水素原子、Ｃ₁乃至Ｃ₁₀のアルキル基、アルケニル基、アリール基又はアルコキシ基を示し、ｎは１乃至１０の整数を示す。］

[In the general formula (X), R ₁ represents a hydrogen atom or a methyl group, and R ₁ and R ₃ represent a hydrogen atom, a C _{1 to} C ₁₀ alkyl group, an alkenyl group, an aryl group, or an alkoxy group, respectively. N represents an integer of 1 to 10. ]

  By adding 0.1 to 10.0 parts by mass of the polymer having a sulfonic acid group to 100 parts by mass of the binder resin in the toner particles, the charged state of the toner particles is further improved. Can do.

  The addition amount of these charge control agents is preferably 0.01 to 10.00 parts by mass with respect to 100.00 parts by mass of the binder resin or polymerizable monomer.

  The toner of the present invention may be used by treating the surface of toner particles with various organic fine powders or inorganic fine powders for the purpose of imparting various properties. The organic fine powder or inorganic fine powder preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles in view of durability when added to the toner particles.

As organic fine powder or inorganic fine powder, the following are used.
(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black, and carbon fluoride.
(2) Abrasive: metal oxide such as strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide, nitride such as silicon nitride, carbide such as silicon carbide, metal such as calcium sulfate, barium sulfate, calcium carbonate salt.
(3) Lubricant: Fluorine resin powders such as vinylidene fluoride and polytetrafluoroethylene, and fatty acid metal salts such as zinc stearate and calcium stearate.
(4) Charge controllable particles: metal oxides such as tin oxide, titanium oxide, zinc oxide, silica and alumina, carbon black.

  The organic fine powder or the inorganic fine powder treats the surface of the toner particles in order to improve the fluidity of the toner and to make the charge of the toner uniform. Hydrophobic treatment of organic fine powder or inorganic fine powder makes it possible to adjust the chargeability of the toner and improve the charging characteristics in a high-humidity environment. It is preferable to use a fine powder. As treatment agents for the hydrophobic treatment of organic fine powder or inorganic fine powder, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, and other organic silicon Examples of the compound include organic titanium compounds. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the inorganic fine powder is treated with silicone oil at the same time as or after the hydrophobic treatment with the coupling agent. Hydrophobized inorganic fine powder treated with silicone oil is preferable for maintaining a high toner charge amount even under a high humidity environment and reducing selective developability.

  The addition amount of these organic fine powders or inorganic fine powders is preferably 0.01 to 10.00 parts by weight, more preferably 0.02 to 5.00 parts by weight with respect to 100.00 parts by weight of the toner particles. Preferably, the amount is 0.03 to 1.00 parts by mass. By optimizing the amount of addition, contamination of the member due to embedding and release of organic fine powder or inorganic fine powder into toner particles is improved. These organic fine powders or inorganic fine powders may be used alone or in combination.

In the present invention, the BET specific surface area of the organic fine powder or inorganic fine powder is preferably 10 m ² / g or more and 450 m ² / g or less. The specific surface area BET of the organic fine powder or inorganic fine powder can be determined by a low temperature gas adsorption method by a dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, by using a specific surface area measuring device “Gemini 2375 Ver. 5.0” (manufactured by Shimadzu Corporation), nitrogen gas is adsorbed on the sample surface, and measurement is performed using the BET multipoint method. m ² / g) can be calculated.

  The organic fine powder or inorganic fine powder may be firmly fixed or adhered to the toner particle surface. Henschel mixers, mechano-fusions, cyclomixes, turbulizers, flexo-mixes, hybridizations, mechano-hybrids, and nobilta are available as externally added mixers for firmly adhering or adhering organic fine particles or inorganic fine particles to the toner particle surface. Can be mentioned. Further, the organic fine powder or the inorganic fine powder can be strongly fixed or adhered by increasing the rotational peripheral speed or extending the processing time.

  The weight average particle size (D4) of the toner of the present invention is preferably 4.0 to 10.0 μm, more preferably 5.0 to 10.0 μm, and still more preferably 6.0 to 9.0 μm. It is.

  The glass transition temperature (Tg) of the toner of the present invention is preferably 35 to 100 ° C., more preferably 40 to 80 ° C., and further preferably 45 to 70 ° C. When the glass transition temperature is in the above range, it is easy to achieve both storage stability and low-temperature fixability.

  The content of tetrahydrofuran (hereinafter referred to as THF) insolubles contained in the binder resin of the toner of the present invention may be less than 50.0% by mass with respect to toner components other than the colorant and inorganic substance of the toner. preferable. More preferably, it is 0.0 mass% or more and less than 45.0 mass%, More preferably, it is 5.0 mass% or more and less than 40.0 mass%. By setting the content of the THF-insoluble matter to less than 50.0% by mass, the low-temperature fixability can be improved.

  The content of THF-insoluble matter contained in the binder resin means the mass ratio of the ultra-high polymer component (substantially crosslinked polymer) that has become insoluble in the THF solvent. In the present invention, the content of insoluble THF in the binder resin is a value measured as follows.

1.0 g of toner is weighed (W1 g), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), subjected to a Soxhlet extractor, extracted for 20 hours using 200 ml of THF as a solvent, and soluble components extracted by the solvent are extracted. After concentration, vacuum drying is performed at 40 ° C. for several hours, and the amount of THF-soluble resin component is weighed (W2 g). The mass of a component other than the resin component such as a colorant in the toner is (W3 g). The THF-insoluble content is obtained from the following formula.
Content (mass%) of THF-insoluble matter = {(W1- (W3 + W2)) / (W1-W3)} × 100

  The content of the toner insoluble matter in the toner can be adjusted by the degree of polymerization and the degree of crosslinking of the binder resin.

  In the present invention, the weight average molecular weight (Mw) (hereinafter also referred to as toner weight average molecular weight) measured by gel permeation chromatography (GPC) of the THF soluble content is 5,000 to 50,000. Is preferred. When the weight average molecular weight (Mw) of the toner is within the above range, blocking resistance and development durability, low-temperature fixability, and high gloss of an image can be established. In the present invention, the weight average molecular weight (Mw) of the toner is the amount of low molecular resin added and the weight average molecular weight (Mw), the reaction temperature at the time of toner particle production, the reaction time, the amount of polymerization initiator, and the amount of chain transfer agent. And the amount of the crosslinking agent can be adjusted.

  In the present invention, in the molecular weight distribution measured by gel permeation chromatography (GPC) of the THF soluble matter of the toner, the ratio [Mw / Mn] of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 5 It is preferably 0.0 to 100.0, and more preferably 5.0 to 30.0. When [Mw / Mn] is within the above range, the fixable temperature range can be widened.

  The weight average molecular weight and number average molecular weight of other materials that can be used in the present invention can be measured by GPC as follows, for example.

The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min. As a column, in order to accurately measure a molecular weight region of 1 × 10 ³ to 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, combination or manufactured by Showa Denko KK of shodex GPC KF-801,802,803,804,805,806,807,800P, manufactured by Tosoh Corporation of _{TSKgel G1000H (H XL), G2000H} (H XL), G3000H (H XL ), G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), and TSKgourd column, particularly shodex KF-801, 802 manufactured by Showa Denko KK A combination of seven columns 803, 804, 805, 806, 807 is preferable.

  On the other hand, after the resin is dispersed and dissolved in THF and allowed to stand overnight, a sample processing filter (pore size 0.2 to 0.5 μm, for example, Myshor Disc H-25-2 (manufactured by Tosoh Corporation)) can be used. ) And use the filtrate as a sample. Measurement is performed by injecting 50 to 200 μl of a THF solution of the resin adjusted so that the resin concentration is 0.5 to 5 mg / ml as a sample concentration. An RI (refractive index) detector is used as the detector.

In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Or a molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 manufactured by Toyo Soda Kogyo Co., Ltd. It is appropriate to use a standard polystyrene sample of at least about 10 points, using .9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ .

(Measurement method of toner particle or toner physical properties)
[Preparation method of toner particles insoluble in tetrahydrofuran (THF)]
The tetrahydrofuran (THF) insoluble matter in the toner particles was prepared as follows.

  10.0 g of the toner particles are weighed, put into a cylindrical filter paper (No. 86R manufactured by Toyo Filter Paper) together with a magnetic stirrer, and put on a Soxhlet extractor. Extracted with 200 ml of THF as a solvent for 20 hours, the magnetic stirrer to which the magnetic substance contained in the toner particles was removed, and the residue in the cylindrical filter paper was vacuum dried at 40 ° C. for several hours. Was defined as the THF-insoluble content of the toner particles for NMR measurement.

  In the present invention, when the surface of toner particles is treated with the organic fine powder or inorganic fine powder, the organic fine powder or inorganic fine powder is removed by the following method to obtain toner particles.

  Charge 16.0 g of ion-exchanged water and 4.0 g of Contaminone N (neutral detergent manufactured by Wako Pure Chemicals, product No. 037-10361) into a glass 30 ml vial and mix thoroughly. 1.50 g of magnetic toner is added to the prepared solution, the magnet is brought closer to the bottom surface, and all the magnetic toner is submerged. Thereafter, the magnet is moved to remove air bubbles and to blend the magnetic toner into the solution.

  Set the tip of the ultrasonic vibrator UH-50 (manufactured by SMT Co., Ltd., using a titanium alloy tip with a tip diameter of φ6 mm) so that the tip is the center of the vial and 5 mm from the bottom of the vial. Inorganic fine particles are removed by sonic dispersion. After applying ultrasonic waves for 30 minutes, the entire amount of magnetic toner is taken out and dried in a dryer for 1 hour or more. The dried product is crushed with a spatula to obtain toner particles containing a magnetic substance.

(Confirmation method of partial structure represented by formula (T3))
The following method is used to confirm the partial structure represented by the formula (T3) in the organosilicon polymer contained in the toner particles.

The presence or absence of an alkyl group and a phenyl group represented by R in the formula (T3) was confirmed by ¹³ C-NMR. The detailed structure of the formula (T3) was confirmed by ¹ H-NMR, ¹³ C-NMR and ²⁹ Si-NMR. The equipment and measurement conditions used are shown below.

"Measurement condition"
Device: AVANCE III 500 manufactured by BRUKER
Probe: 4mm MAS BB / 1H
Measurement temperature: room temperature Sample rotation speed: 6 kHz
Sample: 150 mg of a measurement sample (THF insoluble portion of toner particles for NMR measurement) was put in a sample tube having a diameter of 4 mm.

  By this method, the presence or absence of an alkyl group and a phenyl group represented by R in the formula (T3) was confirmed. If the signal was confirmed, the structure of the formula (T3) was determined to be “Yes”.

"Measurement conditions for ¹³ C-NMR (solid)"
Measurement nuclear frequency: 125.77 MHz
Reference substance: Glycine (external standard: 176.03 ppm)
Observation width: 37.88 kHz
Measurement method: CP / MAS
Contact time: 1.75 ms
Repeat time: 4s
Integration count: 2048 times LB value: 50 Hz

"Measurement method of ²⁹ Si-NMR (solid)"
"Measurement condition"
Device: AVANCE III 500 manufactured by BRUKER
Probe: 4mm MAS BB / 1H
Measurement temperature: room temperature Sample rotation speed: 6 kHz
Sample: 150 mg of a measurement sample (THF insoluble portion of toner particles for NMR measurement) is placed in a sample tube having a diameter of 4 mm.
Measurement nuclear frequency: 99.36 MHz
Reference substance: DSS (external standard: 1.534 ppm)
Observation width: 29.76 kHz
Measuring method: DD / MAS, CP / MAS
²⁹ Si 90 ° Pulse width: 4.00 μs @ -1 dB
Contact time: 1.75 ms to 10 ms
Repeat time: 30 s (DD / MASS), 10 s (CP / MAS)
Integration count: 2048 times LB value: 50 Hz

(In the organosilicon polymer contained in the toner particles, the partial structure represented by the formula (T3) (T3 structure) and the structure in which the number of O _1/2 bonded to silicon is 2.0 (X2 structure) Ratio calculation method)
[Confirmation and quantification method of T3 structure, X1 structure, X2 structure, X3 structure, X4 structure]
The partial structures of T3, X1, X2, X3 and X4 can be confirmed by ¹ H-NMR, ¹³ C-NMR and ²⁹ Si-NMR.

After ²⁹ Si-NMR measurement of the THF-insoluble matter in the toner particles, O ₁ bonded to silicon represented by the following general formula (X4) by curve fitting a plurality of silane components having different substituents and bonding groups in the toner particles. X4 structure in which the number of _{/ 2} is 4.0, X3 structure in which the number of O _1/2 bonded to silicon represented by the following general formula (X3) is 3.0, represented by the following general formula (X2) X2 structure number of O _1/2 bonded to silicon is 2.0, X1 structure number is 1.0 O _1/2 bonded to silicon represented by the following general formula (X1), formula (T3 The peak is separated into a T unit structure represented by (), and the mol% of each component is calculated from the area ratio of each peak.

（式（Ｘ３）中のＲｆはケイ素に結合している有機基、ハロゲン原子、ヒドロキシ基またはアルコキシ基）

(Rf in formula (X3) is an organic group, halogen atom, hydroxy group or alkoxy group bonded to silicon)

（式（Ｘ２）中のＲｇ、Ｒｈはケイ素に結合している有機基、ハロゲン原子、ヒドロキシ基またはアルコキシ基）

(Rg and Rh in the formula (X2) are organic groups, halogen atoms, hydroxy groups or alkoxy groups bonded to silicon)

（式（Ｘ１）中のＲｉ、Ｒｊ、Ｒｋはケイ素に結合している有機基、ハロゲン原子、ヒドロキシ基またはアルコキシ基）

(Ri, Rj, and Rk in Formula (X1) are organic groups, halogen atoms, hydroxy groups, or alkoxy groups bonded to silicon)

  Curve fitting uses EXcalibur for Windows (registered trademark) version 4.2 (EX series), software for JNM-EX400 manufactured by JEOL. Click “1D Pro” from the menu icon to read the measurement data. Next, “Curve fitting function” is selected from “Command” on the menu bar, and curve fitting is performed. An example is shown in FIG. Peak splitting is performed so that the peak of the composite peak difference (a), which is the difference between the composite peak (b) and the measurement result (d), becomes the smallest.

  The area of the X1 structure, the area of the X2 structure, the area of the X3 structure, and the area of the X4 structure are obtained, and SX1, SX2, SX3, and SX4 are obtained by the following equations.

In the present invention, the silane monomer is specified by the chemical shift value, and the monomer component is removed from the total peak area in the ²⁹ Si-NMR measurement of the toner particles. The area of the X1 structure, the area of the X2 structure, the area of the X3 structure, and the X4 structure Was the total peak area of the organosilicon polymer.
SX1 + SX2 + SX3 + SX4 = 1.00
SX1 = {area of X1 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX2 = {area of X2 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX3 = {area of X3 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX4 = {area of X4 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
ST3 = {area of T3 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}

The chemical shift values of silicon in the X1, X2, X3, and X4 structures are shown below.
An example of X1 structure _{(Ri = Rj = -OC 2 H} 5, Rk = -CH 3): - 47ppm
Example of X2 structure (Rg = —OC ₂ H ₅ , Rh = —CH ₃ ): −56 ppm
Example of X3 structure (R = —CH ₃ ): −65 ppm

In addition, the chemical shift value of silicon in the case of the X4 structure is shown below.
X4 structure: -108 ppm

((Measurement of average thickness Dav. Of surface layer of toner particles and ratio of surface layer thickness of 5.0 nm or less, measured by cross-sectional observation of toner particles using transmission electron microscope (TEM)))
In the present invention, cross-sectional observation of toner particles is performed by the following method.

  As a specific method for observing the cross section of the toner particles, the toner particles are sufficiently dispersed in a room temperature curable epoxy resin and then cured in an atmosphere of 40 ° C. for 2 days. A flaky sample is cut out from the obtained cured product using a microtome equipped with diamond teeth. This sample is magnified by a magnification of 10,000 to 100,000 times with a transmission electron microscope (Electron microscope Tecnai TF20XT manufactured by FEI) (TEM), and the cross section of the toner particles is observed.

  In the present invention, the difference between the atomic weights of the resin used and the organosilicon compound is utilized, and the confirmation is performed utilizing the fact that the contrast becomes brighter when the atomic weight is large. Further, a ruthenium tetroxide staining method and an osmium tetroxide staining method are used in order to provide contrast between materials. The presence state of various elements in the toner particles can be confirmed by mapping various elements using a transmission electron microscope. For the particles used for the measurement, the equivalent circle diameter Dtem was determined from the cross-section of the toner particles obtained from the TEM micrograph, and the value was ± 10% of the weight average particle diameter of the toner particles determined by the method described later. It was included in the width.

  As described above, a bright field image of the cross section of the toner particles is obtained with an acceleration voltage of 200 kV using the FEI electron microscope Tecnai TF20XT. Next, using an EELS detector GIF Tridiem manufactured by Gatan, an EF mapping image of the Si-K end (99 eV) is obtained by the Three Window method, and it is confirmed that the organosilicon polymer is present on the surface layer. Next, for one toner particle in which the equivalent circle diameter Dtem is included in a width of ± 10% of the weight average particle diameter of the toner particle, the major axis L of the cross section of the toner particle and the axis L90 that passes through the center of the major axis L and is perpendicular to the major axis L90. The toner particle cross section is equally divided into 16 with the intersection of the two as the center (see FIG. 1). Next, the dividing axis from the center toward the surface layer of the toner particles is An (n = 1 to 32), the length of the dividing axis is RAn, and the thickness of the toner surface layer containing the organosilicon polymer is FRAn.

  Then, the average thickness Dav. Of the surface layer of the toner particles containing the organosilicon polymer at 32 locations on the split axis. Ask for. Further, the ratio of the number of split axes in which the thickness of the surface layer of the toner particles containing the organosilicon polymer on each of the 32 split axes is 5.0 nm or less is determined.

  In the present invention, in order to average, 10 toner particles were measured, and an average value per toner particle was calculated.

[Equivalent circle diameter (Dtem) obtained from cross section of toner particle obtained from transmission electron microscope (TEM) photograph]
The equivalent circle diameter (Dtem) obtained from the cross section of the toner particles obtained from the TEM photograph is obtained by the following method. First, for one toner particle, a circle equivalent diameter (Dtem) obtained from a cross section of the toner particle obtained from a TEM photograph is obtained according to the following formula.
[Equivalent circle diameter (Dtem) obtained from cross section of toner particles obtained from TEM photograph] = (RA1 + RA2 + RA3 + RA4 + RA5 + RA6 + RA7 + RA8 + RA9 + RA10 + RA11 + RA12 + RA13 + RA14 + RA15 + RA16 + RA17 + RA18 + RA21 + RA22 + RA23 + RA24 + RA22 + RA24 + RA24 + RA24 + RA24 + RA24 + RA24 + RA24 +

  The equivalent circle diameter of 10 toner particles is obtained, and the average value per one particle is calculated to obtain the equivalent circle diameter (Dtem) obtained from the cross section of the toner particles.

[Measurement of Average Thickness (Dav.) Of Surface Layer of Toner Particles]
The average thickness (Dav.) Of the surface layer of the toner particles is determined by the following method.

First, the average thickness D _(n) of the surface layer of one toner particle is determined by the following method. D _(n) = (total of 32 thicknesses of the surface layer on the dividing axis) / 32
In order to average, the average thickness D _(n) (n = 1 to 10) of the surface layer of 10 toner particles is calculated, the average value per toner particle is calculated, and the average thickness of the surface layer of toner particles ( Dav.).
Dav. = {D ₍₁₎ + D ₍₂₎ + D ₍₃₎ + D ₍₄₎ + D ₍₅₎ + D ₍₆₎ + D ₍₇₎ + D ₍₈₎ + D ₍₉₎ + D ₍₁₀₎ } / 10

[Measurement of ratio of surface layer thickness of 5.0 nm or less]
[Proportion in which surface layer thickness (FRAn) is 5.0 nm or less] = [{number of split axes in which surface layer thickness (FRAn) is 5.0 nm or less} / 32] × 100

  This calculation is performed for 10 toner particles, and the average value of the ratio of the obtained 10 surface layer thicknesses (FRAn) is 5.0 nm or less is obtained. The surface layer thickness (FRAn) of the toner particles is 5. The ratio was 0 nm or less.

(Concentration of each element present on the surface layer of toner particles)
The concentration of silicon atoms [dSi] (atomic%), the concentration of carbon atoms [dO] (atomic%), and the concentration of oxygen atoms [dO] (atomic%) present on the surface layer of the toner particles are determined by X-ray photoelectron spectroscopy. The surface composition analysis using (ESCA: Electron Spectroscopy for Chemical Analysis) was performed and calculated. In the present invention, the ESCA apparatus and measurement conditions are as follows.
Device used: Quantum2000 manufactured by ULVAC-PHI
X-ray photoelectron spectrometer measurement conditions: X-ray source Al Kα
X-ray: 100μm 25W 15kV
Raster: 300μm × 200μm
PassEnergy: 58.70 eV StepSize: 0.125 eV
Neutralizing electron gun: 20μA, 1V Ar ion gun: 7mA, 10V
Number of sweeps: Si 15 times, C 10 times, O 5 times

  In the present invention, from the measured peak intensity of each element, using the relative sensitivity factor provided by PHI, the concentration of silicon atoms [dSi], the concentration of carbon atoms [dC], The oxygen atom concentration [dO] (both atomic%) was calculated.

(Measurement of weight average particle diameter (D4) and number average particle diameter (D1) of toner (particle))
The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner (particles) are determined by a fine particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark) using a pore electrical resistance method equipped with an aperture tube of 100 μm. Using Beckman Coulter Multisizer 3 Version 3.51 (manufactured by Beckman Coulter, Inc.) and the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.). Measure with 55,000 channels, analyze the measured data, and calculate.

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

  Prior to measurement and analysis, the dedicated software is set 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, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter 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 or more and 60 μm or less.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, 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 is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. 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 is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, 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) About 10 mg of toner (particles) is added to the electrolytic aqueous solution little by little in a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 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 electrolytic solution (5) in which the toner (particles) is dispersed with a pipette is dropped into the round bottom beaker (1) installed in the sample stand so that the measured concentration becomes about 5%. Adjust to. 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. When the graph / volume% is set with the dedicated software, the “average diameter” on the analysis / volume statistics (arithmetic average) screen is the weight average particle size (D4), and the graph / number% is set with the dedicated software. The “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

(Method of thermal conductivity)
(1) Preparation of measurement sample About 5 g of toner (variable according to the specific gravity of the sample) is compression-molded at about 20 MPa for 60 seconds using a tablet molding compressor in an environment of 25 ° C. Two cylinders having a diameter of 25 mm and a height of 6 mm are prepared.

(2) Thermal conductivity measurement and measurement device: Hot disk method thermal property measurement device TPS2500S
Sample holder: Room temperature sample holder Sensor: Standard (RTK) Sensor software: Hot disk analysis 7

  Place the measurement sample on the mounting table of the sample holder for room temperature, and adjust the height of the table so that the surface of the measurement sample is the same height as the sensor.

  Place the second measurement sample and the attached metal piece on the sensor, and apply pressure using the screw on the sensor. The pressure is adjusted to 30 cN · m with a torque wrench. Make sure that the center of the measurement sample and sensor is directly under the screw.

  Start hot disk analysis and select the experiment type Bulk (Type I).

Enter the following in the input items.
Available Probing Depth: 6mm
Measurement time: 40s
Heating Power: 60mW
Sample Temperature: 23 ° C
TCR: 0.004679K ^-1
Sesor Type: Disk
Senor Material Type: Kapton
Sensor Design: 5465
Sensor Radius: 3.189mm

  After the input, measurement is started. After the measurement is completed, the Calculate button is selected, Start Point: 10 and End Point: 200 are input, the Standard Analysis button is selected, and Thermal Conductivity [W / mK] is calculated.

(Method for measuring hydrolysis rate of silane compound)
The hydrolysis rate of the silane compound will be described. When the alkoxysilane is subjected to a hydrolysis treatment, a mixture composed of a hydrolyzate, an unhydrolyzed product, and a condensate is obtained. Described below is the ratio of hydrolyzate in the resulting mixture. This mixture corresponds to the silane compound described above.

First, the alkoxysilane hydrolysis reaction will be described by taking methoxysilane as an example. When methoxysilane is hydrolyzed, the methoxy group becomes a hydroxyl group and methanol is produced. Therefore, the progress of hydrolysis can be known from the quantitative ratio of methoxy group and methanol. In the present invention, the quantitative ratio was measured by ¹ H-NMR (nuclear magnetic resonance) to determine the hydrolysis rate. Taking methoxysilane as an example, specific measurement and calculation methods are shown below.

First, ¹ H-NMR (nuclear magnetic resonance) of methoxysilane before being subjected to hydrolysis treatment was measured using deuterated chloroform, and the peak position derived from the methoxy group was confirmed. Thereafter, hydrolysis treatment was performed on methoxysilane to obtain a silane compound, and the hydrolysis reaction was stopped by setting the silane compound aqueous solution just before being added to the untreated magnetic substance to pH 7.0 and a temperature of 10 ° C. . Water in the obtained aqueous solution was removed to obtain a dried silane compound. A small amount of deuterated chloroform was added to the dried product, and ¹ H-NMR was measured. The peak derived from the methoxy group in the obtained spectrum was determined based on the peak position confirmed in advance. The peak area derived from the methoxy group was defined as A, and the peak area derived from the methyl group of methanol was defined as B, and the hydrolysis rate was determined by the following equation.
Hydrolysis rate (%) = {B / (A + B)} × 100

The measurement conditions for ¹ H-NMR were set as follows.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 1024 times Measurement temperature: 40 ° C

(Method for measuring the amount of silane compound contained in the treated magnetic substance eluted with styrene)
A glass vial having a capacity of 50 ml is charged with 20 g of styrene and 1.0 g of a treated magnetic substance, and the glass vial is set in “KM Shaker” (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd. The speed is set to 50 and shaken for 1 hour to elute the treatment agent in the treated magnetic material into styrene. Thereafter, the treated magnetic material and styrene are separated and sufficiently dried in a vacuum dryer.

  The carbon content per unit mass is measured with a HORIBA carbon / sulfur analyzer EMIA-320V for the dried processed magnetic material and the processed magnetic material before elution with styrene. Using the carbon amount value before and after elution of styrene, the elution rate of silane compound contained in the treated magnetic material into styrene is calculated. In addition, the sample preparation amount at the time of EMIA-320V measurement shall be 0.20g, and tungsten and tin are used as a combustion aid.

(Measurement method of iron element dissolution rate and silicon content)
In the present invention, the iron element dissolution rate of magnetic iron oxide and the content of metal elements other than iron with respect to the iron element dissolution rate can be determined by the following method. Specifically, 3 liters of deionized water is placed in a 5 liter beaker and heated with a water bath to 50 ° C. To this, 25 g of magnetic iron oxide is added and stirred. Then, special grade hydrochloric acid is added to make a 3 mol / L hydrochloric acid aqueous solution, and magnetic iron oxide is dissolved. Sampling is performed ten times or more from the start of dissolution until it is completely dissolved and transparent, filtered through a membrane filter having an opening of 0.1 μm, and the filtrate is collected. The filtrate is subjected to plasma emission spectroscopy (ICP) to quantify iron elements and metal elements other than iron elements, and the iron element dissolution rate of each sample is determined by the following equation.
Iron element dissolution rate = (iron element concentration in sample / iron element concentration when completely dissolved) × 100

  Further, the silicon content of each sample is obtained, and the silicon element dissolution rate is found up to 5% from the relationship between the iron element dissolution rate obtained by the above measurement and the element content detected at that time. The content of is determined.

(Measuring method of glass transition temperature (Tg) of toner and resin)
The glass transition temperature (Tg) of the toner and the resin is measured by the following procedure using a differential scanning calorimeter (DSC) M-DSC (trade name: Q2000, manufactured by TA Instruments). Weigh precisely 3 mg of the sample (toner, various resins) to be measured. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 1 ° C./min and normal temperature and humidity in a measurement temperature range of 20 to 200 ° C. Measurement is performed at a modulation amplitude of ± 0.5 ° C. and a frequency of 1 / min. The glass transition temperature (Tg: ° C.) is calculated from the obtained reversing heat flow curve. Tg is obtained as Tg (° C.) as the center value of the intersection of the baseline before and after endotherm and the tangent of the curve due to endotherm.

  In the endothermic chart at the time of temperature rise measured by DSC, the integrated value of heat per gram of toner (J / g) represented by the peak area of the endothermic main peak was measured. An example of a reversing flow curve obtained by DSC measurement of the toner is shown in FIG.

  The calorie integral value (J / g) is obtained using the reversing flow curve obtained from the above measurement. For the calculation, analysis software Universal Analysis 2000 for Windows (registered trademark) 2000 / XP Version 4.3A (manufactured by TA Instruments) was used, and a straight line connecting the measurement points at 35 ° C. and 135 ° C. using the function of Integral Peak Linear. And an integral value of heat (J / g) are determined from the region surrounded by the endothermic curve.

  Next, an example of an image forming apparatus that can suitably use the toner of the present invention will be described in detail with reference to FIG. In FIG. 4, reference numeral 100 denotes a photosensitive drum, which is provided with a primary charging roller 117, a developing device 140 having a developing sleeve 102, a transfer charging roller 114, a cleaner 116, a register roller 124, and the like. The photosensitive drum 100 is charged to, for example, −600 V by the primary 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 photoreceptor 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 photosensitive drum 100 is developed with a one-component toner by the developing device 140 to obtain a toner image, and the toner image is transferred onto the transfer material by the transfer roller 114 in contact with the photoreceptor via the transfer material. Is done. 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, toner remaining on a part of the photoconductor is cleaned by a cleaner 116.

  Although an image forming apparatus for magnetic one-component jumping development is shown here, it may be used for any method of jumping development or contact development.

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

<Production Example 1 of Magnetic Iron Oxide>
Ferrous salt aqueous solution containing ferrous hydroxide colloid by mixing and stirring 50 liters of 4.0 mol / L sodium hydroxide aqueous solution with 50 liters of ferrous sulfate first aqueous solution containing 2.0 mol / L of Fe ²⁺ Got. This aqueous solution was kept at 85 ° C., and an oxidation reaction was performed while blowing air at 20 L / min to obtain a slurry containing core particles.

  The obtained slurry was filtered and washed with a filter press, and then the core particles were dispersed again in water and reslurried. Magnetic iron oxide having a silicon-rich surface is obtained by adding sodium silicate that is 0.20 mass% in terms of silicon to the core particles to the reslurry liquid, adjusting the pH of the slurry liquid to 6.0, and stirring. Particles were obtained. The obtained slurry was filtered and washed with a filter press, and further reslurried with ion-exchanged water. To this reslurry liquid (solid content 50 g / L), 500 g (10% by mass with respect to magnetic iron oxide) of ion exchange resin SK110 (manufactured by Mitsubishi Chemical) was added, and ion exchange was performed by stirring for 2 hours. Thereafter, the ion exchange resin was removed by filtration through a mesh, filtered and washed with a filter press, dried and crushed to obtain magnetic iron oxide 1 having a number average diameter of 0.23 μm as shown in Table 1. .

<Production Example 2 of Magnetic Iron Oxide>
In the production of the magnetic iron oxide 1, a magnetic iron oxide 2 having a number average diameter of 0.23 μm as shown in Table 1 was obtained in the same manner except that the amount of sodium silicate added was changed to 0.05% by mass. It was.

<Production Example 3 of Magnetic Iron Oxide>
In the production of magnetic iron oxide 1, magnetic iron oxide 3 having a number average diameter of 0.23 μm as shown in Table 1 was obtained in the same manner except that the amount of sodium silicate added was changed to 0.5 mass%. It was.

<Production Example 4 of Magnetic Iron Oxide>
In the production of the magnetic iron oxide 1, a magnetic iron oxide 4 having a number average diameter of 0.23 μm as shown in Table 1 was obtained in the same manner except that the amount of sodium silicate added was changed to 0.01% by mass. It was.

<Production Example 5 of Magnetic Iron Oxide>
In the production of the magnetic iron oxide 1, a magnetic iron oxide 5 having a number average diameter of 0.23 μm as shown in Table 1 was obtained in the same manner except that the amount of sodium silicate added was changed to 0.55% by mass. It was.

<Manufacture example 6 of magnetic iron oxide>
Magnetic iron oxide 1 having a number average diameter of 0.28 μm as shown in Table 1 is the same as that of magnetic iron oxide 1 except that the amount of air blown and the oxidation reaction time are adjusted. 6 was obtained.

<Production Example 7 of Magnetic Iron Oxide>
Magnetic iron oxide 1 having a number average diameter of 0.20 μm as shown in Table 1 is the same as that of magnetic iron oxide 1 except that the amount of air blown and the oxidation reaction time are adjusted. 6 was obtained.

<Production Example of Silane Compound 1>
30 parts by mass of iso-butyltrimethoxysilane was added dropwise to 70 parts by mass of ion-exchanged water while stirring. Thereafter, this aqueous solution was kept at pH 5.5 and a temperature of 55 ° C., and hydrolyzed by dispersing for 120 minutes at a peripheral speed of 0.46 m / s using a disper blade. Thereafter, the pH of the aqueous solution was adjusted to 7.0 and cooled to 10 ° C. to stop the hydrolysis reaction. Thus, an aqueous solution containing the silane compound 1 having a hydrolysis rate of 99% was obtained.

<Production example of silane compounds 2 to 4>
About the silane compounds 2-4, the silane compounds 2-4 were obtained similarly except having changed the kind of silane compounds, pH, temperature, and time from the manufacture example of the silane compound 1 as shown in Table 2. Table 2 summarizes the physical properties of the obtained silane compounds.

<Production example of magnetic body 1>
100 parts by mass of magnetic iron oxide 1 is put into a high speed mixer (LFS-2 type, manufactured by Fukae Pautech Co., Ltd.), and 8.0 parts by mass of an aqueous solution containing the silane compound 1 is added over 2 minutes while stirring at a rotational speed of 2000 rpm. It was dripped. Thereafter, the mixture was mixed and stirred for 5 minutes. Next, in order to enhance the fixing property of the silane compound, after drying at 40 ° C. for 1 hour to reduce moisture, the mixture was dried at 110 ° C. for 3 hours to proceed the condensation reaction of the silane compound. Then, it pulverized and obtained the magnetic body 1 through the sieve with an opening of 100 micrometers. Table 3 shows the physical properties of the magnetic body 1.

<Manufacture of magnetic bodies 2-12>
In the production of the magnetic body 1, magnetic bodies 2 to 12 were obtained in the same manner except that the magnetic iron oxide, the silane compound and the amount added thereof were changed as shown in Table 3. Table 3 shows the physical properties of the obtained magnetic substance.

<Production example of charge control resin 1>
In a reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts by mass of methanol as a solvent, 150 parts by mass of 2-butanone and 100 parts by mass of 2-propanol, as a monomer 88 parts by mass of styrene, 6.0 parts by mass of 2-ethylhexyl acrylate, and 6.0 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and heated under reflux at normal pressure. A solution obtained by diluting 1.2 parts by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours. Further, a solution prepared by diluting 1.0 part by mass of 2,2′-azobisisobutyronitrile with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and further stirred for 5 hours under reflux at normal pressure to polymerize. Ended.

  Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less by a cutter mill equipped with a 150 mesh screen, and further finely pulverized by a jet mill. The fine powder was classified with a 250 mesh sieve to obtain particles of 60 μm or less. Next, methyl ethyl ketone was added to dissolve the particles so as to have a concentration of 10%, and the resulting solution was gradually poured into 20 times the amount of methyl ethyl ketone in methanol for reprecipitation. The resulting precipitate was washed with one-half the amount of methanol used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours.

  Furthermore, methyl ethyl ketone was added and redissolved so that the particles after the vacuum drying had a concentration of 10%, and the obtained solution was gradually poured into n-hexane 20 times the amount of methyl ethyl ketone and reprecipitated. The obtained precipitate was washed with half the amount of n-hexane used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours. The charge control resin thus obtained has a Tg of about 82 ° C., a main peak molecular weight (Mp) of 19,600, a number average molecular weight (Mn) of 11,700, and a weight average molecular weight (Mw) of 20,600. The acid value was 17.4 mgKOH / g. The obtained resin is designated as charge control resin 1.

<Synthesis of polyester resin 1>
・ Terephthalic acid: 11.1 mol
Bisphenol A-propylene oxide 2 mol adduct: 11.0 mol (PO-BPA)
The above monomer is charged into an autoclave together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirring device are attached to the autoclave, and the pressure is reduced to 210 ° C. according to a conventional method while decompressing in a nitrogen atmosphere The polyester resin 1 was obtained by carrying out the reaction until Tg reached 66 ° C. The weight average molecular weight (Mw) was 7,100, and the number average molecular weight (Mn) was 3,030.

<Synthesis of polyester resin 2>
(Synthesis of isocyanate group-containing prepolymer)
-Bisphenol A ethylene oxide 2 mol adduct 730 parts by mass-295 parts by mass of phthalic acid-3.0 parts by mass of dibutyltin oxide After stirring at 220 ° C for 7 hours and further reacting under reduced pressure for 5 hours, The mixture was cooled to 80 ° C. and reacted with 190 parts by mass of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate group-containing polyester resin. 25 parts by mass of an isocyanate group-containing polyester resin and 1 part by mass of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a polyester resin (2) mainly composed of a polyester containing a urea group. The resulting polyester resin (2) had a weight average molecular weight (Mw) of 23300, a number average molecular weight (Mn) of 3010, and a peak molecular weight of 7300.

<Production Example of Toner Particle 1>
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 720 parts by mass of ion-exchanged water and 450 parts by mass of a 0.1 M Na ₃ PO ₄ aqueous solution were added and heated to 60 ° C. After warming, 67.7 parts by mass of a 1.0 M CaCl ₂ aqueous solution was added to obtain an aqueous medium containing a dispersion stabilizer.

Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Methyltriethoxysilane 10.0 parts by mass Divinylbenzene 0.6 parts by mass Magnetic substance 10.0 parts by mass Polyester resin 1 0 parts by mass, charge control resin 1 1.0 parts by mass, mold release agent 10.0 parts by mass (behenyl behenate, melting point: 72.1 ° C.)
The polymerizable monomer composition 1 obtained by dispersing the above materials with an attritor (Mitsui Miike Chemical Co., Ltd.) for 3 hours was held at 60 ° C. for 20 minutes. Thereafter, the polymerizable monomer composition 1 obtained by adding 12.0 parts by mass of t-butyl peroxypivalate (toluene solution 50%), which is a polymerization initiator, to the polymerizable monomer composition 1 in an aqueous medium. The mixture was granulated for 12 minutes in a N ₂ atmosphere at 60 ° C. while maintaining the rotational speed of a high-speed stirring device TK homomixer (Special Machine Industries Co., Ltd.) at 12,500 rpm.

  Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring. At this time, the pH of the aqueous medium was 5.1. Next, 10.0 parts by mass of 1.0 N NaOH was added to adjust the pH to 8.0, and the temperature inside the container was raised to 90 ° C. and maintained for 7.5 hours. Thereafter, 4.0 parts by mass of 10% hydrochloric acid was added to 50 parts by mass of ion-exchanged water to adjust the pH to 5.1. Next, 300 parts by mass of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. Distillation at a temperature in the vessel of 100 ° C. was performed for 5 hours to obtain a polymer slurry 1. The distillation fraction was 300 parts by mass. Dilute hydrochloric acid was added to the container containing the polymer slurry 1 after cooling to 30 ° C. to remove the dispersion stabilizer. Furthermore, the toner particles having a weight average particle diameter of 7.5 μm were obtained by filtration, washing and drying. This toner particle was designated as toner particle 1.

  The formulation of toner particles 1 is shown in Table 4, and the physical properties are shown in Table 7. In TEM observation of the toner particles 1, silicon mapping was performed, and it was confirmed that uniform silicon atoms were present on the surface layer. In the following examples and comparative examples, the surface layer containing the organosilicon polymer was also confirmed by silicon mapping.

<Production Example of Toner Particle 2>
Toner particles 2 are obtained in the same manner as in the production example of toner particles 1 except that 10.0 parts by mass of phenyltrimethoxysilane is used instead of 10.0 parts by mass of methyltriethoxysilane used in the production example of toner particles 1. It was. The formulation of toner particles 2 is shown in Table 4, and the physical properties are shown in Table 7. Silicon mapping was performed in the TEM observation of the toner particles 2, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particle 3>
Toner particles 3 are obtained in the same manner as in the production example of toner particles 1 except that 10.0 parts by mass of ethyltrimethoxysilane is used instead of 10.0 parts by mass of methyltriethoxysilane used in the production example of toner particles 1. It was. The formulation of toner particles 3 is shown in Table 4, and the physical properties are shown in Table 7. Silicon mapping was performed in the TEM observation of the toner particles 3, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particle 4>
Toner particles 4 were produced in the same manner as in the production example of toner particles 1 except that 10.0 parts by mass of n-propyltriethoxysilane was used instead of 10.0 parts by mass of methyltriethoxysilane used in the production example of toner particles 1. Got. The formulation of toner particles 4 is shown in Table 4, and the physical properties are shown in Table 7. Silicon mapping was performed in the TEM observation of the toner particles 4, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particle 5>
Toner particles 5 were produced in the same manner as in the production example of toner particles 1 except that 10.0 parts by mass of n-butyltriethoxysilane was used instead of 10.0 parts by mass of methyltriethoxysilane used in the production example of toner particles 1. Got. The formulation of toner particles 5 is shown in Table 4, and the physical properties are shown in Table 7. Silicon mapping was performed in the TEM observation of the toner particles 5, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particle 6>
Instead of 10.0 parts by mass of methyltriethoxysilane used in the production example of toner particles 1, the amount was changed to 7.0 parts by mass of methyltriethoxysilane and 3.0 parts by mass of vinyltrichlorosilane. Immediately after the polymerizable monomer composition 1 to which 16.0 parts by mass of t-butyl peroxypivalate as a polymerization initiator (toluene solution 50%) was added was put into an aqueous medium, a 1.0 N NaOH aqueous solution was added. Toner particles were added in the same manner as in the production example of toner particles 1 except that 2.0 parts by mass was added and granulation was performed for 10 minutes while maintaining the rotation speed of the high-speed agitator at 12,000 rpm, and the pH was adjusted to 5.1. 6 was obtained. The formulation of toner particles 6 is shown in Table 4, and the physical properties are shown in Table 7. In TEM observation of the toner particles 6, silicon mapping was performed, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particle 7>
Toner particles 7 are obtained in the same manner as in the production example of toner particles 1 except that 10.0 parts by mass of methyltrimethoxysilane is used instead of 10.0 parts by mass of methyltriethoxysilane used in the production example of toner particles 1. It was. The formulation of toner particles 7 is shown in Table 4, and the physical properties are shown in Table 7. Silicon mapping was performed in the TEM observation of the toner particles 7, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particle 8>
Toner particles 8 were prepared in the same manner as in the production example of toner particles 1 except that 10.0 parts by mass of methyltriisopropoxysilane was used instead of 10.0 parts by mass of methyltriethoxysilane used in the production example of toner particles 1. Obtained. The formulation of toner particles 8 is shown in Table 4, and the physical properties are shown in Table 7. In the TEM observation of the toner particles 8, silicon mapping was performed, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particle 9>
Instead of 7.5 parts by weight of methyltriethoxysilane used in the production example of toner particles 1, 7.5 parts by weight of methyldiethoxychlorosilane was changed to 1.5 parts by weight of 1.0N NaOH aqueous solution and the pH was adjusted to 5 parts. The toner particles 9 were obtained in the same manner as in the production example of the toner particles 1 except that the toner particles were adjusted to 1. The formulation of toner particles 9 is shown in Table 4, and the physical properties are shown in Table 7. Silicon mapping was performed in the TEM observation of the toner particles 9, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particle 10>
Toner particles 10 were prepared in the same manner as in the toner particle 1 production example, except that 10.0 parts by mass of methyltriethoxysilane used in the production example of toner particles 1 was changed to 30.0 parts by mass of methyltriethoxysilane. Obtained. The formulation of toner particles 10 is shown in Table 4, and the physical properties are shown in Table 7. In TEM observation of the toner particles 10, silicon mapping was performed, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particle 11>
In the production example of the toner particles 1, 24.0 parts by mass of 24.0 parts by mass of a 1.0 mol / liter HCl aqueous solution added in the preparation of the aqueous dispersion medium is changed to 30.0 parts by mass to add an aqueous system. The pH of the medium was changed to 4.1, and 10.0 parts by mass of 1.0 N NaOH was added to adjust the pH to 10.0 parts by mass, 0.0 parts by mass, and 4.0 parts by mass of 10% hydrochloric acid. Is added to 50 parts by mass of ion-exchanged water, and the toner particles are prepared in the same manner as in the production example of toner particles 1 except that 4.0 parts by mass of 10% hydrochloric acid obtained by adjusting the pH to 5.1 is changed to 0.0 parts by mass. 11 was obtained. The formulation of toner particles 11 is shown in Table 4, and the physical properties are shown in Table 7. Silicon mapping was performed in the TEM observation of the toner particles 12, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particles 12 to 20>
In the production example of the toner particles 11, toner particles 12 to 20 were obtained in the same manner as in the production example of the toner particles 11 except that the magnetic materials 2 to 10 were used instead of the magnetic material 1. The formulations of toner particles 12 and 13 are shown in Table 4, and the physical properties are shown in Table 7. The formulations of toner particles 14 to 20 are shown in Table 5, and the physical properties are shown in Table 8. All toner particles were subjected to silicon mapping in TEM observation, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particles 21>
In the production example of toner particles 5, toner particles 21 were obtained in the same manner as in the production example of toner particles 5 except that 65 parts of the magnetic material 11 was used instead of the magnetic material 1. The formulation of toner particles 21 is shown in Table 5, and the physical properties are shown in Table 8. In the TEM observation of the toner particles 21, silicon mapping was performed, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particles 22>
In the production example of toner particles 6, toner particles 22 were obtained in the same manner as in the production example of toner particles 6 except that 100 parts of the magnetic material 12 was used instead of the magnetic material 1. The formulation of toner particles 22 is shown in Table 5, and the physical properties are shown in Table 8. In the TEM observation of the toner particles 22, silicon mapping was performed, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particles 23>
In the production example of the toner particles 5, toner particles 23 were obtained in the same manner as in the production example of the toner particles 5 except that 50 parts of the magnetic material 11 was used instead of the magnetic material 1. The formulation of toner particles 23 is shown in Table 5, and the physical properties are shown in Table 8. Silicon mapping was performed in the TEM observation of the toner particles 23, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particles 24>
In the production example of toner particles 6, toner particles 24 were obtained in the same manner as in the production example of toner particles 6 except that 110 parts of the magnetic material 12 was used instead of the magnetic material 1. The formulation of the toner particles 24 is shown in Table 5, and the physical properties are shown in Table 8. Silicon mapping was performed in the TEM observation of the toner particles 24, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particles 25>
[Production of Toner Base 25]
-Polyester resin 1 60.0 parts by mass-Polyester resin 2 40.0 parts by mass-Magnetic material 1 90.0 parts by mass-Charge control resin 1 1.0 parts by mass-Release agent 10.0 parts by mass (behenic acid Behenyl, melting point: 72.1 ° C.)
After mixing the above materials with a Henschel mixer, melt kneading at 135 ° C. with a twin-screw kneading extruder, cooling the kneaded material, coarsely crushing with a cutter mill, and crushing with a fine crusher using a jet stream Further, the toner base 25 having a weight average particle diameter of 7.3 μm was obtained by classification using an air classifier.

[Production of Toner Particles 25]
In a four-necked vessel equipped with a Liebig reflux tube, 700 parts by mass of ion-exchanged water, 1000 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 24.0 parts by mass of a 1.0 mol / liter aqueous HCl solution were added. The mixture was added and kept at 60 ° C. while stirring at 12,000 rpm using a high-speed stirring device TK-homomixer. To this, 85 parts by mass of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

  Next, 100.0 parts by mass of toner base 25 and 10.0 parts by mass of methyltriethoxysilane were mixed with a Henschel mixer, and then the toner material was added and stirred for 5 minutes while stirring at 5,000 rpm with a TK-homomixer. did.

  Subsequently, this mixed liquid was kept at 70 ° C. for 5 hours. The pH was 5.1. Next, 10.0 parts by mass of 1.0 N NaOH was added to adjust the pH to 8.0, and then the temperature was raised to 90 ° C. and maintained for 7.5 hours. Thereafter, 4.0 parts by mass of 10% hydrochloric acid and 50 parts by mass of ion-exchanged water were added to adjust the pH to 5.1. 300 parts by mass of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. Next, distillation at a temperature in the container of 100 ° C. was performed for 5 hours to obtain a polymer slurry 23. The distillation fraction was 320 parts by mass. Dilute hydrochloric acid was added to the container containing the polymer slurry 25 to remove the dispersion stabilizer. The toner particles having a weight average particle diameter of 6.3 μm were obtained by filtration, washing and drying. The toner particles were designated as toner particles 25. The formulation of the toner particles 25 is shown in Table 5, and the physical properties are shown in Table 8. Silicon mapping was performed in the TEM observation of the toner particles 25, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particles 26>
-Polyester resin 1 60.0 parts by mass-Polyester resin 2 40.0 parts by mass-Magnetic material 1 90.0 parts by mass-Charge control resin 1 1.0 parts by mass-Methyltriethoxysilane 10.0 parts by mass-Release 10.0 parts by mass of agent (behenyl behenate, melting point: 72.1 ° C.)
The said material was melt | dissolved in 400 mass parts of toluene, and the solution was obtained.

In a four-necked vessel equipped with a Liebig reflux tube, 700 parts by mass of ion-exchanged water, 1000 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 24.0 parts by mass of a 1.0 mol / liter aqueous HCl solution were added. The mixture was added and kept at 60 ° C. while stirring at 12,000 rpm using a high-speed stirring device TK-homomixer. To this, 85 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

  Next, 100 parts by mass of the lysis solution was added and stirred for 5 minutes while stirring at 12,000 rpm with a TK-homomixer. Subsequently, this mixed liquid was kept at 70 ° C. for 5 hours. The pH was 5.1. 10.0 parts by mass of 1.0N NaOH was added to adjust the pH to 8.0. Next, it heated up to 90 degreeC and hold | maintained for 7.5 hours. Thereafter, 4.0 parts by mass of 10% hydrochloric acid and 50 parts by mass of ion-exchanged water were added to adjust the pH to 5.1. 300 parts by mass of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. Next, distillation at a temperature in the container of 100 ° C. was performed for 5 hours to obtain a polymer slurry 26. The distillation fraction was 320 parts by mass. Dilute hydrochloric acid was added to the container containing the polymer slurry 26 to remove the dispersion stabilizer. Further, the toner particles having a weight average particle diameter of 6.2 μm were obtained by filtration, washing and drying. These toner particles were designated as toner particles 26. The formulation of the toner particles 26 is shown in Table 5, and the physical properties are shown in Table 8. Silicon mapping was performed in the TEM observation of the toner particles 26, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner Particles 27>
While stirring 100.0 parts by mass of the toner base 25 in a Henschel mixer, 10.0 parts by mass of toluene, 5.0 parts by mass of ethanol, 5.0 parts by mass of water, and 10.0 parts by mass of methyltriethoxysilane were mixed at 90 ° C. Then, 3.5 parts by mass of the organosilicon polymer solution reacted for 5 hours was sprayed and mixed uniformly.

The particles were circulated in the fluidized bed dryer for 30 minutes under conditions of an inlet temperature of 90 ° C. and an outlet temperature of 45 ° C. to perform drying and polymerization. Similarly, the obtained treated toner is sprayed in an Henschel mixer with 3.5 parts by mass of the organosilicon polymer solution with respect to 100 parts by mass of the treated toner, under conditions of an inlet temperature of 90 ° C. and an outlet temperature of 45 ° C. The fluidized bed dryer was circulated for 30 minutes. Similarly, spraying and drying of the organosilicon polymer solution was repeated a total of 10 times to obtain toner particles 27.
The formulation of the toner particles 27 is shown in Table 5, and the physical properties are shown in Table 8. Silicon mapping was performed in TEM observation of the toner particles 27, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Comparative Toner Particle 1>
Comparative toner particles 1 were prepared in the same manner as in the toner particle 1 production example, except that 10.0 parts by mass of methyltriethoxysilane used in the production example of toner particles 1 was changed to 1.0 part by mass of methyltriethoxysilane. Obtained. The formulation of Comparative Toner Particles 1 is shown in Table 6, and the physical properties are shown in Table 9. In TEM observation of comparative toner particles 1, silicon mapping was performed, and it was confirmed that a few silicon atoms were present on the surface layer.

<Production Example of Comparative Toner Particle 2>
Comparative toner particles 2 were prepared in the same manner as in the production example of comparative toner particles 1 except that 1.0 parts by mass of methyltriethoxysilane used in the production example of comparative toner particles 1 was changed to 10.0 parts by mass of tetraethoxysilane. Got. The formulation of comparative toner particles 2 is shown in Table 6, and the physical properties are shown in Table 9. In the TEM observation of the comparative toner particles 2, silicon mapping was performed, and it was confirmed that silicon atoms were present on the surface layer, although not uniform.

<Production Example of Comparative Toner Particle 3>
In the same manner as in the production example of the comparative toner particle 1, except that 1.0 part by mass of methyltriethoxysilane used in the production example of the comparative toner particle 1 was changed to 10.0 parts by mass of 3-methacryloxypropyltriethoxysilane. Thus, comparative toner particles 3 were obtained. The formulation of comparative toner particles 3 is shown in Table 6, and the physical properties are shown in Table 9. In the TEM observation of the comparative toner particles 3, silicon mapping was performed, and it was confirmed that some silicon atoms were present on the surface layer.

<Production Example of Comparative Toner Particle 4>
Comparative toner in the same manner as in Production Example of Comparative Toner Particle 1, except that 1.0 part by mass of methyltriethoxysilane used in Production Example of Comparative Toner Particle 1 was changed to 11.0 part by mass of aminopropyltrimethoxysilane. Particles 4 were obtained. The formulation of comparative toner particles 4 is shown in Table 6, and the physical properties are shown in Table 9. In the TEM observation of the comparative toner particles 4, silicon mapping was performed, and it was confirmed that some silicon atoms were present on the surface layer.

<Production Example of Comparative Toner Particle 5>
-Styrene 40.0 parts by mass-n-Butyl acrylate 20.0 parts by mass-Divinylbenzene 0.3 parts by mass-2,2'-azobis (2,4-dimethylvaleronitrile) 2.4 parts by mass-Magnetic substance ( BL-200, manufactured by Titanium Industry Co., Ltd.) 40.0 parts by mass The above materials were stirred and mixed with a homogenizer (manufactured by Masuda Kogyo Co., Ltd.) to prepare a polymerizable monomer mixture. An aqueous medium obtained by mixing the following polymerizable monomer-based mixture with the following components:
・ Ion-exchanged water 600 parts by mass ・ Tricalcium phosphate (TCP) 12 parts by mass did.

  Furthermore, in order to prevent sedimentation and coalescence of the obtained emulsion, the temperature was raised to 70 ° C. while slowly stirring at 200 rpm. After holding at 70 ° C. for 1 hour, a solution obtained by dissolving 0.5 parts by mass of γ-methacryloxypropyltrimethoxysilane (manufactured by Toray Silicone Co., Ltd.) in 0.2% acetic acid is added to the previously prepared emulsion. Further, the polymerization was carried out by maintaining at 70 ° C. for 7 hours. After completion of the polymerization, the weight average particle diameter is 8.0 μm by acid cleaning with dilute hydrochloric acid to remove TCP adhering to the surface of the obtained polymer particles, washing with water, and drying. Toner particles 5 were obtained. The formulation of comparative toner particles 5 is shown in Table 6, and the physical properties are shown in Table 9.

<Production Example of Comparative Toner Particle 6>
In the production example of toner particles 11, comparative toner particles 6 were obtained in the same manner as in the production example of toner particles 11 except that 30 parts by mass of the magnetic material 11 was used instead of the magnetic material 1. The formulation of the comparative toner particles 6 is shown in Table 6, and the physical properties are shown in Table 9. In the TEM observation of the comparative toner particles 6, silicon mapping was performed, and it was confirmed that uniform silicon atoms were present on the surface layer.

<Production Example of Toner 1>
To 100 parts by mass of toner particles 1, the surface is coated with 15.0 parts by mass of hexamethyldisilazane and 10 parts by mass of silicone oil of 100 cps with respect to 100 parts by mass of the silica base material having a specific surface area of 200 m ² / g according to the BET method. Toner 1 is a toner obtained by mixing 0.7 parts by mass of hydrophobic silica subjected to a hydrophobic treatment with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.).

  As a result of measuring the thermal conductivity of Toner 1, it was 0.260 W / (m · K).

[Example 1]
(Evaluation 1. Development durability)
A modified machine of LBP-6300 (manufactured by Canon) was used as the image forming apparatus. First, the process speed was modified by about 1.5 times to 300 mm / sec.

  As the developing sleeve, a modified cartridge in which a sleeve having a diameter of 14 mm to a diameter of 10 mm was mounted as the developing sleeve and the volume of the toner filling portion was 1.5 times was used.

  In an image forming apparatus equipped with a small-diameter developing sleeve, development durability can be strictly evaluated by promoting toner deterioration by increasing the process speed.

Using this remodeling machine, the durability of 3000 prints with a high printing rate image with a printing rate of 30% in a high temperature and high humidity environment (32.5 ° C / 80% RH) using toner particles 1 A test was conducted.
In particular, by evaluating in a high-temperature and high-humidity environment (32.5 ° C./80% RH), it becomes possible to more strictly evaluate image defects and environmental stability due to toner deterioration.

  In addition, the durability test using a high printing rate image results in faster toner consumption in the developing device. This makes it possible to perform tests that require toner agitation in addition to environmental stability and development durability. .

  In the evaluation results of the toner particles 1, a good image with a high image density was obtained before and after the durability use test. Table 10 shows the evaluation results. In Table 10, the numerical values in parentheses indicate the initial image density and the difference between the initial image density and the image density after endurance.

  The criteria for determining image density are described below.

<Image density>
The image density formed a solid black image portion, and the density of the solid black image was measured with a Macbeth reflection densitometer (manufactured by Macbeth).

The criteria for determining the reflection density of the solid black image at the first end of durable use are as follows.
A: Very good (above 1.48)
B: Good (from 1.44 to less than 1.48)
C: Normal (from 1.40 to less than 1.44)
D: Bad (less than 1.40)

  The criteria for determining the image density in the second half of the endurance use are as follows.

The smaller the difference between the reflection density of the solid black image at the end of durable use and the solid black image after the durable use of 3000 sheets, the better.
A: Very good (difference is less than 0.06)
B: Good (difference is 0.06 or more and less than 0.12)
C: Normal (difference is 0.12 or more and less than 0.18)
D: Bad (difference is 0.18 or more)

(Evaluation 2. Storage stability)
(Evaluation of storage stability)
10 g of toner 1 was put in a 100 ml glass bottle, and left for 15 days at a temperature of 50 ° C. and a humidity of 20%, and then judged visually.
A: No change B: There are aggregates, but they are loosened immediately C: Aggregates that are difficult to loosen D: Obvious caking occurs

(Evaluation of long-term storage)
10 g of toner 1 was placed in a 100 ml glass bottle and left to stand for 3 months at a temperature of 45 ° C. and a humidity of 95%.
A: No change B: There are aggregates, but they are loosened immediately C: Aggregates that are difficult to loosen D: Obvious caking occurs

(Evaluation 3. Rear end offset)
As the image forming apparatus, the modified machine used in Evaluation 1 was used, and the setting of the fixing device was changed so as to lower the temperature control of the fixing device by 10 ° C. Similarly, the modified cartridge used in Evaluation 1 was used as the cartridge.

  In a high-temperature and high-humidity environment (32.5 ° C./80% RH), the following evaluation was performed with the fixing device removed during the evaluation and the fixing device sufficiently cooled using a fan or the like. By sufficiently cooling the fixing device after the evaluation, the temperature of the fixing nip portion that has risen after image output is cooled, so that it is possible to evaluate the toner fixability more strictly and with better reproducibility.

When evaluating the trailing edge offset, a standing paper of 90 g / m ² (paper left in the above high temperature and high humidity environment for 48 hours or more) was used. By using a relatively heavy paper, it becomes possible to more strictly evaluate the fixability, and by using a paper that is left unattended, it is possible to strictly evaluate the rear end offset.

Using the toner particles 1, a solid black image was output on the above-mentioned left sheet in a state where the fixing device was sufficiently cooled. At this time, the toner loading amount on the paper was adjusted to 9 g / m ² .

  As a result of evaluation of toner particles 1, a good solid black image having no missing image was obtained.

  The criteria for determining the rear end offset will be described below.

<Rear end offset>
The trailing edge offset was evaluated by visual observation of the level of missing of the solid black image output by the above procedure. The criteria for determining the trailing edge offset are as follows.
A: Very good (no missing holes)
B: Good (If you look closely, you will see some missing spots)
C: Normal (Pots are missing but not noticeable)
D: Poor (potential missing)

[Examples 2 to 28, Comparative Examples 1 to 6]
In Example 1, evaluation was performed in the same manner as in Example 1 except that instead of toner particles 1, toner particles 2 to 27, toner 1 and comparative toner particles 1 to 6 were used. Table 10 shows the evaluation results.

  100: electrostatic latent image carrier (photoconductor), 102: developing sleeve, 114: transfer member (transfer roller), 116: cleaner, 117: charging member (charging 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 a binder resin and a magnetic material,
The toner particles have an organosilicon polymer having a partial structure represented by the following formula (T3) on the surface,
R-Si (O _1/2 ) ₃ (T3)
(R in the formula (T3) represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.)
In the ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble part of the toner particles, the ratio [ST3] of the peak area of the partial structure represented by the formula (T3) to the total peak area of the organosilicon polymer is 40% or more. Yes,
A toner having a thermal conductivity of 0.190 W / (m · K) or more and 0.300 W / (m · K) or less. Magnetic body toner according to 請 Motomeko 1 Ru surface-treated magnetic material der with a silane compound. A silane compound wherein the silane compound is subjected to hydrolysis treatment in the alkoxysilane, the toner of the hydrolysis rate of the silane compound described 請 Motomeko 2 Ru der 50% or more. The magnetic substance is magnetic iron oxide, and the magnetic iron oxide has a silicon element on the surface, and is eluted when the magnetic iron oxide is dissolved until the dissolution rate of the iron element reaches 5.00% by mass. the amount of silicon that is, toner according to magnetic iron oxide in any one of 0.05 wt% to 0.50 wt% or less der Ru請 Motomeko 1 to 3 as a reference. In the ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble matter of the toner particles, the ratio of the peak area of the structure in which the number of O _1/2 bonded to silicon is 2.0 with respect to the total peak area of the organosilicon polymer [ The toner according to claim 1, wherein SX2] and [ST3] satisfy a relationship of [ST3] / [SX2] ≧ 1.00. The toner according to any one of claims 1 to 5, wherein the organosilicon polymer is an organosilicon polymer obtained by polymerizing an organosilicon compound having a structure represented by the following formula (Z).

(In formula (Z), R ¹ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ² , R ³ and R ⁴ are each independently a halogen atom, a hydroxyl group, an acetoxy group or an alkoxy group. .) The toner according to claim 6, wherein R ¹ in the formula (Z) is a methyl group, an ethyl group, a propyl group, or a phenyl group. R ² in the formula (Z), R ³ and R ^4, the toner according to 請 Motomeko 6 or 7 Ru alkoxy der independently. The toner particles form particles of a polymerizable monomer composition containing a polymerizable monomer and the magnetic substance in an aqueous medium, and the polymerization contained in the particles of the polymerizable monomer composition the toner according to any one of Ah Ru請 Motomeko 1 to 8 in the toner particles obtained by polymerizing sexual monomer. A toner production method for producing the toner according to claim 1,
Particles of a polymerizable monomer composition containing a polymerizable monomer and the magnetic substance are formed in an aqueous medium, and the polymerizable monomer contained in the particles of the polymerizable monomer composition is The toner particles are obtained by polymerization.
And a method for producing the toner.

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