JP2017203889A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that is excellent in low-temperature fixability and environmental stability and is excellent in transferability during durable use.SOLUTION: The present invention is a toner including a toner particle that includes a surface layer containing an organic silicon polymer and a silicone oil on its surface. The organic silicon polymer is a polymer including a vinyl polymer part and a siloxane polymer part and having a specific structure, and when a particle obtained by washing the toner by a water washing method is a toner A, in measurement ofSi-NMR with the toner A as a sample, the ratio [SAT3] of a peak area of a partial structure and the ratio [SAMe2D2] of a peak area of a partial structure represented by the following formula (Me2D2) satisfy the relationship 0.001≤([SAMe2D2]/[SAT3])×100≤10.000. MeSi(O)(Me2D2).SELECTED DRAWING: None

Description

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

In recent years, with the development of computers and multimedia, there is a demand for means for outputting high-definition full-color images in a wide range of fields from offices to homes.
In office use where many copies or prints are made, there is a demand for high durability that does not deteriorate image quality even when a large number of copies or prints are made. On the other hand, for use in small offices and homes, there is a demand for downsizing the image forming apparatus from the viewpoints of obtaining high-quality images and saving space, energy, and weight. In order to meet the above requirements, it is necessary to further improve toner performance such as environmental stability, member contamination, low-temperature fixability, development durability and storage stability.
In particular, in the case of a full-color image, color toners are superimposed to form an image. However, if the color toners of the respective colors are not developed in the same manner, color reproducibility is deteriorated and color unevenness occurs. When pigments or dyes used as toner colorants are deposited on the surface of toner particles, the developability is affected and color unevenness may occur.
Further, in the formation of a full-color image, the fixing property and the color mixing property at the time of fixing are important. For example, in order to achieve the desired high speed, a binder resin suitable for low-temperature fixability is selected, but this binder resin has a great influence on the developability and durability of the color toner.
Furthermore, there is a demand for a means for outputting a high-definition full-color image that can be used for a long period of time in various environments where the temperature and humidity are different. In order to meet such a demand, it is necessary to solve problems such as a change in toner charge amount and a change in toner surface property caused by differences in use environment of temperature and humidity. In addition, it is necessary to solve problems such as contamination of members such as a developing roller, a charging roller, a regulating blade, and a photosensitive drum. Therefore, development of a toner having stable development durability that does not cause stable chargeability and member contamination even after long-term storage in various environments is demanded.
Further, as a development durability condition, there is a method of giving stronger damage to the toner as follows. For example, every time an image is output, the printer is stopped for a certain period of time, and the stop and drive are repeated (hereinafter referred to as intermittent durability). It is necessary to solve the problem that the chargeability and surface property of the toner change due to such damage, transferability deteriorates, and an image cannot be output accurately. One of the causes of fluctuations in transferability is a phenomenon in which a toner release agent or resin component oozes out from the inside of toner particles (hereinafter also referred to as “bleed”), and the surface chargeability of the toner. Can be mentioned. Another example is that the surface shape changes due to stress due to durability, and the adhesion between the toner and the member changes. These are likely to occur in harsh environments such as low temperature and low humidity and high temperature and high humidity.
As one means for solving such a problem, there is a method of covering the surface of toner particles with a resin.
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 image output or in a high temperature and high humidity environment.
However, even if the inorganic fine particles are strongly fixed to the toner particles, the occurrence of bleeding due to the release agent or the resin component from the gaps between the inorganic fine particles and the liberation of the inorganic fine particles due to the deterioration of durability may cause durability and member contamination in harsh environments. However, further improvements are needed.
Further, in Patent Document 2, in order to obtain a toner having a narrow charge amount distribution and a charge amount having little humidity dependency without exposing a colorant or a polar substance to the surface of the toner particles, a silane cup is used in the reaction system. A method for producing a polymerized toner comprising adding a ring agent is disclosed.
However, in such a method, the precipitation amount of the silane compound on the surface of the toner particles and the hydrolysis and condensation polymerization of the silane compound are insufficient, and further improvement is required for environmental stability and development durability. It has become.
Further, Patent Document 3 includes a silicon compound applied in the form of a continuous thin film on the surface as a method of controlling the charge amount of toner and forming a high-quality output image regardless of the environment of temperature and humidity. A method using a polymerized toner is disclosed.
However, the polarity of the organic functional group is large, the amount of silane compound deposited on the surface of the toner particles, the hydrolysis and condensation polymerization of the silane compound are insufficient, the degree of crosslinking is weak, and the chargeability changes under high temperature and high humidity. Further improvements are necessary for the image density change due to the contamination and the member contamination due to durability deterioration.
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, there is insufficient generation of bleed from the release agent or resin component from the gaps of the granular mass containing the silicon compound, the amount of silane compound deposited on the surface of the toner particles, and the hydrolysis and condensation polymerization of the silane compound. As a result, environmental stability deteriorates. Therefore, further improvement is required for image density change, occurrence of member contamination due to toner fusion, and storage stability. Further, Patent Documents 5 and 6 disclose a toner containing a polyhedral oligosilces siloxane compound as a toner for improving environmental stability.
However, polyhedral oligosilces siloxane compounds and derivatives thereof are easy to crystallize and are difficult to form a uniform film. Polyhedral oligosilces siloxane compounds and derivatives thereof are particles of a few nanometers, and tend to be granular lumps or aggregates. Therefore, the occurrence of bleeding that the release agent and resin components ooze out from the gaps of the polyhedral oligosilces siloxane, the change in image density caused by insufficient amount of silicon surface deposition, the occurrence of member contamination due to toner fusion, Further improvements are needed for storage stability.

JP 2006-146056 A Japanese Patent Laid-Open No. 03-089361 JP 09-179341 A JP 2001-75304 A JP 2010-145994 A JP 2010-145995 A

  An object of the present invention is to provide a toner that is excellent in low-temperature fixing and environmental stability and excellent in transferability under low temperature and low humidity during durability.

The present invention is a toner having toner particles having a surface layer containing an organosilicon polymer and having silicone oil on the surface,
The organosilicon polymer is a polymer having a vinyl polymer part and a siloxane polymer part, and having a partial structure represented by the following formulas (T3a), (T3b) and (T3c),
In the measurement of ²⁹ Si-NMR using the toner A as a sample when the particles obtained by washing the toner with a water washing method are used as toner A,
The ratio [SAT3] of the peak area of the partial structure represented by the following formulas (T3a), (T3b) and (T3c) and the ratio [SAMe2D2] of the peak area of the partial structure represented by the following formula (Me2D2) are:
0.001 ≦ ([SAMe2D2] / [SAT3]) × 100 ≦ 10.000
The present invention relates to a toner that satisfies the following relationship. Here, the partial structure represented by the formula (Me2D2) is a structure of (CH ₃ ) ₂ Si (O _1/2 ) ₂ within a dotted frame represented by the following formula.

（式（Ｔ３ｂ）中のＬ¹は炭化水素基を表わし、式（Ｔ３ｃ）中のＬ²はＣＯＯＣ_nＨ_2nを表わし（ｎは１から１０までの整数）、Ｌ³は水素かメチル基を表わす。）

(L ¹ in the formula (T3b) represents a hydrocarbon group, L ² in the formula (T3c) represents COOC _n H _2n (n is an integer from 1 to 10), and L ³ represents hydrogen or a methyl group. Represents.)

  According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixing and environmental stability and excellent in transferability under low temperature and low humidity during durability.

It is explanatory drawing of the toner particle cross section obtained by TEM observation. 3 is a ²⁹ Si-NMR measurement chart of toner particles of the present invention. It is a figure which shows the reversing heat flow curve obtained by DSC measurement of the toner of this invention. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus used in the present invention.

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

The present invention is a toner having toner particles having a surface layer containing an organosilicon polymer and having silicone oil on the surface,
The organosilicon polymer is a polymer having a vinyl polymer part and a siloxane polymer part, and having a partial structure represented by the following formulas (T3a), (T3b) and (T3c),
In the measurement of ²⁹ Si-NMR using the toner A as a sample when the particles obtained by washing the toner with a water washing method are used as toner A,
The ratio [SAT3] of the peak area of the partial structure represented by the following formulas (T3a), (T3b) and (T3c) and the ratio [SAMe2D2] of the peak area of the partial structure represented by the following formula (Me2D2) are:
0.001 ≦ ([SAMe2D2] / [SAT3]) × 100 ≦ 10.000
It is characterized by satisfying the relationship.

（式（Ｔ３ｂ）中のＬ¹は炭化水素基を表わし、式（Ｔ３ｃ）中のＬ²はＣＯＯＣ_nＨ_2nを表わす（ｎは１から１０までの整数）、Ｌ³は水素またはメチル基を表わす。）

(L ¹ in formula (T3b) represents a hydrocarbon group, L ² in formula (T3c) represents COOC _n H _2n (n is an integer from 1 to 10), L ³ represents hydrogen or a methyl group. Represents.)

  In the present invention, a toner having toner particles having a surface layer containing an organosilicon polymer and having silicone oil on the surface, the organosilicon polymer comprising a vinyl polymer part and a siloxane polymer part A toner having The organosilicon polymer has a partial structure represented by the formulas (T3a), (T3b), and (T3c), so that the chargeability due to the vinyl polymer structure and the durability and storage stability due to the siloxane polymer are improved. Can be improved. In addition, by having a compound having a partial structure represented by the formula (Me2D2) on the toner surface, a change in toner surface property is suppressed during durability, and a toner having excellent environmental stability and transferability can be obtained.

In the present invention, when particles obtained by washing the toner with a water washing method are used as toner A, in the ²⁹ Si-NMR measurement using toner A as a sample, the formulas (T3a), (T3b) and The ratio [SAT3] of the peak area of the partial structure represented by (T3c) and the ratio [SAMe2D2] of the peak area of the partial structure represented by the formula (Me2D2) are:
0.001 ≦ ([SAMe2D2] / [SAT3]) × 100 ≦ 10.000
Satisfy the relationship.

  The process of washing the toner by the water washing method is a process of removing external additives (organic fine particles or inorganic fine particles) present on the toner surface. Therefore, by performing this treatment, it becomes possible to confirm the properties of the particles before external addition (or particles not externally added).

  When the formulas (T3a), (T3b) and (T3c) and the formula (Me2D2) satisfy 0.001 ≦ ([SAMe2D2] / [SAT3]) × 100 ≦ 10.000, environmental stability is improved. Especially, the transfer latitude under a low temperature and low humidity becomes wide. It is considered that the siloxane of the silicone oil is present on the surface layer containing the siloxane polymer, so that charging by contact with the charging member is performed well. The transfer latitude tends to be narrow on high-speed machines and thick transfer paper.

In the partial structures represented by the formulas (T3a), (T3b) and (T3c), L ¹ is a hydrocarbon group. A hydrocarbon group having 1 to 8 carbon atoms is preferred. When the carbon number of L ¹ is large, the vinyl polymer and the siloxane polymer become far away, so the balance between the chargeability of the vinyl polymer and the discharge property of the siloxane polymer is deteriorated, and the charge amount in a low temperature and low humidity environment. Tend to be larger. The change in charge amount can be reduced by the partial structure represented by the formula (Me2D2) and the partial structure ratio represented by the formulas (T3a), (T3b), and (T3c). L ¹ is preferably a methylene group (—CH ₂ —) and a phenylene group (—C ₆ H ₄ —). Durability is improved.

In the partial structures represented by the formulas (T3a), (T3b), and (T3c), L ² is COOC _n H _2n (n is an integer from 1 to 10)). L ² has an ester bond and is easily bonded. Furthermore, if n of L ² is large, the vinyl polymer and the siloxane polymer become far away, so that the balance between the chargeability of the vinyl polymer and the discharge property of the siloxane polymer is deteriorated, and charging is performed in a low temperature and low humidity environment. The amount tends to increase. The change in charge amount can be reduced by the partial structure represented by the formula (Me2D2) and the partial structure ratio represented by the formulas (T3a), (T3b), and (T3c). n is preferably 1 or more and 3 or less. Particularly preferably, n is 3. L ³ is a hydrogen group or a methyl group. Particularly preferred is a hydrogen group. Durability is improved under low temperature and low humidity.

  When the value of ([SAMe2D2] / [SAT3]) × 100 is less than 0.001, the discharge due to the siloxane structure of the surface layer containing the siloxane polymer is increased, and the transfer latitude is deteriorated. In addition, the toner surface properties are likely to deteriorate due to durability, and durability is reduced.

  When the value of ([SAMe2D2] / [SAT3]) × 100 is more than 10.000, the charging of the partial structure represented by the formula (Me2D2) increases, and the transfer latitude is deteriorated. Further, the silicone oil is easily transferred to the member, and the member is contaminated.

  ([SAMe2D2] / [SAT3]) × 100 is preferably 0.005 ≦ ([SAMe2D2] / [SAT3]) × 100 ≦ 5.000 because the environmental stability and transferability during durability are improved. It is more preferable that 0.010 ≦ ([SAMe2D2] / [SAT3]) × 100 ≦ 3.000.

In ²⁹ Si-NMR measurement using toner A as a sample, partial structures represented by the formulas (T3a), (T3b), and (T3c) with respect to the total peak area of the organosilicon polymer (hereinafter also referred to as T3 structure). ) Of the peak area [SAT3] × 100 preferably satisfies the relationship [SAT3] × 100 ≧ 20.000. Since the surface free energy of the toner particles can be lowered, there is an effect of excellent durability. Moreover, since uneven | corrugated shape is easy to form, it is preferable.

  In addition, the low surface energy of the T3 structure of the organosilicon polymer improves the agitation of the toner and makes it possible to obtain a toner with excellent development durability.

  Regarding [SAT3] × 100, it is preferable to satisfy the relationship of 100.000 ≧ [SAT3] × 100 ≧ 20.000, and it is more preferable to satisfy the relationship of 95.000 ≧ [SAT3] × 100 ≧ 30.000. From the viewpoints of storage stability and durability, [SAT3] × 100 is preferably 100.000 or less, more preferably 95.000 or less, and further preferably 90.000 or less.

  SAT3 should be controlled by the type and amount of the organosilicon compound used to form 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.

In ²⁹ Si-NMR measurement using toner A as a sample, the ratio of the peak area of the partial structure represented by the above formula (Me2D2) (hereinafter also referred to as Me2D2 structure) to the total peak area of the organosilicon polymer [ SAMe2D2] × 100 preferably satisfies the relationship of 10.000 ≧ [SAMe2D2] × 100 ≧ 0.001.

  Since the surface free energy of the toner particles can be uniformly reduced, there are excellent effects in environmental stability and anti-member contamination. Regarding [SAMe2D2] × 100, it is preferable to satisfy the relationship of 10.000 ≧ [SAMe2D2] × 100 ≧ 0.001, and it is more preferable to satisfy the relationship of 5.000 ≧ [SAMe2D2] × 100 ≧ 0.010.

  [SAMe2D2] can be controlled by the amount of silicone oil. It can be controlled by the type and amount of the organosilicon compound used for forming the silicone oil, and the reaction temperature, reaction time, reaction solvent, and pH of hydrolysis, addition polymerization and condensation polymerization during the formation of the organosilicon polymer.

In the present invention, in ²⁹ Si-NMR measurement using toner A as a sample, 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 of toner A (hereinafter referred to as , Also referred to as X2 structure), the ratio of the peak area [SAX2] × 100 preferably satisfies the relationship of 50.000> [SAX2] × 100 ≧ 0.100. When [SAX2] × 100 is 50.000> [SAX2] × 100 ≧ 0.100, the balance between durability and chargeability due to the crosslinked structure of the siloxane structure is improved. Moreover, there is little crystallization and it can be made into a thin film form.

  Therefore, it is excellent in environmental stability, storage stability and development durability. More preferably, it is 50.000> [SAX2] × 100 ≧ 1.000, and further preferably satisfies the relationship of 50.000> [SAX2] × 100 ≧ 10.000.

  [SAX2] is controlled by the type and amount of the organosilicon compound used to form 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.

  In the present invention, the compound having a partial structure represented by the formula (Me2D2) is a compound containing 50 mol% or more of the structure of the formula (Me2D2).

When the toner Ah is a particle obtained by washing the toner A with hexane, the SiO ₂ amount MA (mass%) of the toner A and the SiO ₂ amount MAh (mass%) of the toner Ah are measured by fluorescent X-ray analysis. Is preferably 0.00010 ≦ (MA−MAh) /MA≦5.000. By containing the SiO ₂ component extracted with hexane, the balance between charging and discharging in a low-temperature and low-humidity environment is improved, and transferability is improved. More preferably, it is 0.00100 <= (MA-MAh) / MA <= 2.0000, More preferably, it is 0.01000 <= (MA-MAh) / MA <1.000.

  (MA-MAh) / MA can be controlled by the amount of silicone oil, for example. It can be controlled by the type and amount of the organosilicon compound used for forming the silicone oil, and the reaction temperature, reaction time, reaction solvent, and pH of hydrolysis, addition polymerization and condensation polymerization during the formation of the organosilicon polymer.

In the present invention, the toner Ah is a particle obtained by washing the toner A with hexane. In measurement of ²⁹ Si-NMR of insoluble content of tetrahydrofuran using toner Ah as a sample, the peak area of the partial structure represented by the formulas (T3a), (T3b) and (T3c) with respect to the total peak area of the organosilicon polymer The ratio [SAhtT3] preferably satisfies the relationship [SAhtT3] ≧ 0.20. Since the surface free energy of the toner particles can be further reduced, there is an effect of excellent environmental stability.

  Regarding [SAhtT3], it is preferable to satisfy a relationship of 1.00 ≧ [SAhtT3] ≧ 0.20, and it is more preferable to satisfy a relationship of 0.95 ≧ [SAhtT3] ≧ 0.30. From the viewpoints of storage stability and durability, [SAhtT3] is preferably 1.00 or less, more preferably 0.95 or less, and even more preferably 0.90 or less.

  [SAhtT3] is controlled by the type and amount of the organosilicon compound used to form the organosilicon polymer, and the reaction temperature, reaction time, reaction solvent, and pH of the hydrolysis, addition polymerization, and condensation polymerization during the organosilicon polymer formation. can do.

In the present invention, in ²⁹ Si-NMR measurement of tetrahydrofuran (THF) insoluble matter using toner Ah as a sample, O _1/2 bonded to silicon with respect to the entire peak area of the organosilicon polymer of THF insoluble matter of toner Ah. It is preferable that the ratio [SAhtX2] of the peak area of the structure having a number of 2.0 (hereinafter also referred to as X2 structure) satisfies the relationship of 0.50> [SAhtX2] ≧ 0.00. When [SAhtX2] is 0.50> [SAhtX2] ≧ 0.00, the balance between durability and chargeability due to the crosslinked structure of the siloxane structure is improved. More preferably, 0.50> [SAhtX2] ≧ 0.01, and further preferably 0.50> [SAhtX2] ≧ 0.05. [SAhtX2] of 0.01 or more is preferable because crystallization is small and a thin film can be formed. Excellent environmental stability, storage stability and development durability.

  [SAhtX2] is controlled by the type and amount of the organosilicon compound used to form 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.

  Further, since the softening point (Tg) of the vinyl polymer is lower than that of the siloxane polymer, the vinyl polymer has an excellent effect for continuous fixing of a solid image having a printing rate of 100%. Since the surface free energy on the toner surface is low, it has an excellent effect on member contamination. Also, the vinyl polymer and the partial structure represented by the formulas (T3a), (T3b), and (T3c) allow the low molecular weight (Mw 1000 or less) resin, low Tg (40 ° C. or less) to be easily oozed out from the surface layer. ) Resin and release agent bleed, toner stirrability is improved, and a toner having excellent solid continuous fixability and durability during development can be obtained.

In the present invention, in ²⁹ Si-NMR measurement of tetrahydrofuran (THF) insoluble matter using toner Ah as a sample, the number of O _1/2 bonded to silicon is 1 with respect to the total peak area of the organosilicon polymer of toner Ah. The ratio [SAhtX1] of the peak area of the structure of 0.0 (hereinafter also referred to as X1 structure) preferably satisfies the relationship of 0.25> [SAhtX1] ≧ 0.00. When [SAhtX1] is 0.25> [SAhtX1] ≧ 0.00, the balance between durability and chargeability due to the crosslinked structure of the siloxane structure is improved. Moreover, there is little crystallization and it can be made into a thin film form. Therefore, it is excellent in environmental stability, storage stability and development durability, and is excellent in fog and image density stability even in various environments. More preferably, 0.10> [SAhtX1] ≧ 0.00, and more preferably 0.05> [SAhtX1] ≧ 0.00.

  [SAhtX1] is controlled by the type and amount of the organosilicon compound used to form the organosilicon polymer, and the reaction temperature, reaction time, reaction solvent, and pH of the hydrolysis, addition polymerization, and condensation polymerization during the organosilicon polymer formation. can do.

（式（Ｘ１）中のＲⁱ、Ｒ^j、Ｒ^k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）

(R ⁱ , R ^j and R ^k in the formula (X1) are an organic group, a halogen atom, a hydroxy group or an alkoxy group bonded to silicon)

  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 and condensation polymerization of a silicon compound represented by alkoxysilane.

  By uniformly providing the toner particles with a surface layer containing this organosilicon polymer, environmental stability is improved and the inorganic particles are not fixed or adhered as in the case of conventional toners, and the toner particles are used for a long time. Therefore, it is possible to obtain a toner that is less likely to deteriorate in toner performance and 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 ( It tends to form an aggregate that is 1/10 or less of μm). 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 formulas (T3a), (T3b), and (T3c).

  In the organosilicon polymer, the THF-insoluble content of the organosilicon polymer is preferably 50.0% by mass or more. Storage stability and component contamination are improved. More preferably, it is 75.0 mass% or more, More preferably, 90.0 mass% or more is preferable.

  In the present invention, the silicon intensity G measured by fluorescent X-ray measurement (wavelength dispersive X-ray fluorescence analyzer) of the toner and the Si intensity GA of the toner A are 80.00 ≦ (GA / G) × 100.00 ≦ 100. Preferably it is 0.00.

  When (GA / G) × 100.00 is 80.00 or more, it does not deviate from the particle surface, so that there is little change in the surface state and durability stability is improved. Preferably, 90.00 ≦ (GA / G) × 100 ≦ 100.00.

  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以上１０以下の炭化水素基及び炭素数３以上１０以下のメタクリロキシアルキル基を表し、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、アルコキシ基を表す。）

(In Formula (Z), R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms and a methacryloxyalkyl group having 3 to 10 carbon atoms, and R ² , R ^3, and R ⁴ are each independently Represents a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group.)

  In the present invention, a vinyl group and an allyl group are particularly preferable as the hydrocarbon group having 1 to 10 carbon atoms in the formula (Z). As the methacryloalkyl group having 3 to 10 carbon atoms, a methacryloxypropyl group is particularly preferable. Good environmental stability and component contamination.

R ¹ is preferably exemplified by an allyl group. In this case, chargeability and fog prevention are good. More preferably, R ¹ is a vinyl group from the viewpoints of environmental stability and durability stability.

R ² , R ^3, and 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 resistance to member contamination and development durability can be obtained. From the viewpoints of moderate hydrolyzability at room temperature, precipitation on the surface of the toner particles 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 , R ³ and R ⁴ can be controlled by the 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.

  Vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltriisocyanatesilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane, vinylmethoxyethoxychlorosilane, vinyl Diethoxychlorosilane, vinyltriacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, vinylmethoxydihydroxysilane, vinylethoxy Dihydroxysilane, vinyldimethoxyhydroxysilane, vinyl Ethoxymethoxy hydroxy silane, vinyl diethoxy hydroxy silane, trifunctional vinyl silane such as.

  Trifunctional allylsilanes such as allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allyltrihydroxysilane.

  Trifunctional methacryloalkylsilanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane.

  Trifunctional acryloalkylsilanes such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane.

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

  Moreover, in this invention, the organosilicon compound (tetrafunctional silane) which has four reactive groups in one molecule with the organosilicon compound which has a structure represented by Formula (Z) to such an extent that the effect of this invention is not impaired. ), 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) May be. Examples of the organosilicon compound that may be used in combination 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 , Methyl diethoxy hydroxy silane, trifunctional methylsilane like.

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

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

  3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triemethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, Trifunctional silanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriisocyanate silane.

  Disilazane and disiloxane such as hexamethyldisilazane, hexamethyldisiloxane.

Tetrafunctional silanes such as tetraethoxysilane, tetramethoxysilane, tetrachlorosilane, tetraisocyanate silane, tetraaminosilane.
Bifunctional silanes such as dimethyldiethoxysilane, dimethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane.

  Chlorodimethylvinylsilane, dimethylethoxyvinylsilane, allylchlorodimethylsilane, allylmethoxydimethylsilane, allylethoxydimethylsilane, 3- (methoxydimethylsilyl) -propyl acrylate, 3- (ethoxydimethylsilyl) -propyl acrylate, chlorotrimethylsilane, trimethyl Methoxysilane, trimethylethoxysilane, dimethylethylchlorosilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, chlorotriethylsilane, triethylmethoxysilane, triethylethoxysilane, chlorodimethylpropylsilane, dimethylmethoxypropylsilane, dimethylethoxypropylsilane, dimethylisopropyl Chlorosilane, dimethylisopropylmethoxysilane, dimethyl Sopropylethoxysilane, chlorodiethylisopropylsilane, diethylmethoxyisopropylsilane, diethylethoxyisopropylsilane, triisopropylsilyl chloride, butylchlorodimethylsilane, butyldimethylmethoxysilane, butyldimethylethoxysilane, tert-butyldimethylchlorosilane, tert-butyldimethyl Methoxysilane, tert-butyldimethylethoxysilane, chloro (dimethyl) texylsilane, (dimethyl) texylmethoxysilane, (dimethyl) texylethoxysilane, dimethyl-n-octylchlorosilane, dimethyl-n-octylmethoxysilane, dimethyl-n -Octylethoxysilane, chloro (decyl) dimethylsilane, (decyl) dimethylmethoxysilane, (decyl) Dimethylethoxysilane, dimethyloctadecylchlorosilane, dimethyloctadecylmethoxysilane, dimethyloctadecylethoxysilane, chlorodimethylphenylsilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, benzylchlorodimethylsilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, chlorodimethyl (3-phenyl-propyl) silane, dimethyl (3-phenyl-propyl) methoxysilane, dimethyl (3-phenyl-propyl) ethoxysilane, allylchlorodimethylsilane, allyldimethylmethoxysilane, allyldimethylethoxysilane, 3- (methoxy Dimethylsilyl) -propyl acrylate, 3- (ethoxydimethylsilyl) -propyl acrylate A monofunctional silane.

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. If water is present in sufficient, H ⁺ 1 one by reactive group (e.g., alkoxy group (-OR group)) to oxygen one attack, less H ⁺ content of the reaction medium Sometimes the substitution reaction to the hydroxy group is slow. Therefore, a condensation polymerization 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. This is because when substituted with a silanol group, the electron density of silicon becomes sparse and attracts hydroxide ions. 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 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, you may use an organic titanium compound and an organic aluminum compound with the said organosilicon compound to such an extent that the effect of this invention is 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.

  In addition, these compounds may be used independently or may be used in multiple types. The charge amount can be adjusted by appropriately combining these or changing the addition amount.

  Examples of silicone oils that can be preferably used in the present invention include reactive silicone oils such as amino modification, epoxy modification, carboxyl modification, carbinol modification, methacryl modification, mercapto modification, and phenol modification; polyether modification, methylstyryl modification, and alkyl modification. And non-reactive silicone oils such as fatty acid modified, alkoxy modified and fluorine modified; straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil and methyl hydrogen silicone oil.

  Among these silicone oils, alkyl groups, aryl groups, alkyl groups in which some or all of the hydrogen atoms are substituted with fluorine atoms, and silicone oils having hydrogen as a substituent are preferable. Specific examples include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, and fluorine-modified silicone oil. This is preferable for maintaining a high toner charge amount even in a high humidity environment and reducing selective developability.

These silicone oils preferably have a viscosity at 25 ° C. of 1 mm ² / s to 10,000 mm ² / s, more preferably 3 mm ² / s to 5,000 mm ² / s, and even more preferably 5 mm ^2. / S or more and 1,000 mm ² / s or less. If it is less than 1 mm ² / s, sufficient hydrophobicity may not be obtained, and if it exceeds 10,000 mm ² / s, aggregates are likely to be formed and sufficient fluidity may not be obtained.

  The toner of the present invention is obtained by measuring the surface layer (surface layer, outermost layer) of toner Ah using X-ray photoelectron spectroscopy (ESCA: Electron Spectroscopy for Chemical Analysis). The silicon atom concentration dSi (dSi / [dSi + dO + dC]) with respect to the sum of the oxygen atom concentration dO and the carbon atom concentration dC (dSi + dO + dC) is preferably 1.0 atom% or more, more preferably 2.5 atoms. % Or more, and more preferably 5.0 atomic% or more and 10.0 atomic% or more.

  The ESCA performs elemental analysis of the surface layer existing at a thickness of several nanometers from the surface of the toner particle to the center of the toner particle (midpoint of the long axis). When the concentration of silicon atoms (dSi / [dSi + dO + dC]) in the surface layer of the toner particles is 1.0 atomic% or more, the surface free energy of the surface layer can be reduced. By adjusting the silicon atom concentration to 1.0 atomic% or more, the fluidity can be further improved, and the occurrence of member contamination and fogging can be further suppressed.

  On the other hand, the concentration of silicon atoms (dSi / [dSi + dO + dC]) in the surface layer of the toner Ah is preferably 33.3 atomic% or less from the viewpoint of chargeability. More preferably, it is 28.6 atomic% or less.

The concentration of silicon atoms in the surface layer of the toner Ah, the above formula (T3a), the structure of R ^a in (T3b) and (T3c), a method of manufacturing the toner particles at the time of organosilicon polymer formation, reaction temperature, reaction time , And can be controlled by reaction solvent and pH. It can also be controlled by the content of the organosilicon polymer. In the present invention, the surface layer of toner particles means a layer existing at a thickness of 0.0 nm or more and 10.0 nm or less from the surface of the toner particles toward the center of the toner particles (midpoint of the long axis). The dSi / [dSi + dO + dC] is controlled by the structure of the above formulas (T3a), (T3b) and (T3c), the method for producing the toner particles when forming the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH. can do.

  In the present invention, in cross-sectional observation of toner particles 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 passing through the center of the major axis L and perpendicular When the particle cross section is equally divided into 16 and the dividing axis from the center toward the surface of the toner particle is An (n = 1 to 32), 32 organosilicon polymers on the dividing axis are contained. Average thickness Dav. Is preferably 2.5 nm or more and 150.0 nm or less. 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 above. In addition, polyhedral oligosilces siloxane compounds and derivatives thereof tend to be a granular mass or aggregate of several nanometers. Bleeding that the mold release agent and the resin component ooze out from the gaps between the granular lump and the aggregate tends to occur.

  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. The average thickness Dav. If it is less than 2.5 nm, bleeding due to a resin component or a release agent in the toner particles tends to occur. For this reason, the surface properties of the toner particles change and the environmental stability and the development durability tend to deteriorate. The average thickness Dav. When the thickness exceeds 150.0 nm, the low-temperature fixability tends to deteriorate. From the viewpoint of storage stability, the average thickness Dav. Is more preferably 5.0 nm or more and 125.0 nm or less, and still more preferably 7.5 nm or more and 100.0 nm or less.

  The average thickness Dav. Is a method for producing toner particles when forming an organosilicon polymer, the number of carbon atoms of the hydrocarbon group, the number of hydrophilic groups in the above (T3a), (T3b) and (T3c), addition during formation of the organosilicon polymer. It can be controlled by the reaction temperature, reaction time, reaction solvent and pH of polymerization and condensation polymerization. It can also be controlled by the content of the organosilicon polymer.

  In the present invention, in cross-sectional observation of toner particles 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 passing through the center of the major axis L and perpendicular Contains the organosilicon polymer on each of the 32 divided axes when the particle cross section is equally divided into 16 and the divided axis from the center to the surface of the toner particle is An (n = 1 to 32). The ratio of the number of split axes whose surface layer thickness is 2.5 nm or less (hereinafter also referred to as the ratio of surface layer thickness 2.5 nm or less) is preferably 20.0% or less. Is 10.0% or less, more preferably 5.0% or less (see FIG. 1).

  When the ratio of the thickness of the surface layer of 2.5 nm or less is within the above range, the occurrence of bleeding due to the resin component, release agent, or the like inside the surface layer of the toner particles can be reduced. Therefore, environmental stability, storage stability and development durability are improved. Further, when the ratio of the thickness of the surface layer of 2.5 nm or less is 20.0% or less, a toner having excellent fog and image density stability can be obtained even in various environments.

  The ratio of the thickness of the surface layer of 2.5 nm or less is the production method of the toner particles when forming the organosilicon polymer, the carbon number of the hydrocarbon group in the above formulas (T3a), (T3b) and (T3c), the hydrophilic group , The reaction temperature of addition polymerization and condensation polymerization at the time of forming the organosilicon polymer, reaction time, reaction solvent and pH. It can also be controlled by the content of the organosilicon polymer.

The organosilicon polymer is preferably an organosilicon polymer insoluble in THF. Due to the durability of the organic silicon polymer insoluble in THF due to the structure of the formulas (T3a), (T3b) and (T3c), and the hydrophobicity and chargeability of ^{Ra in} the formula (R ^a T3), it is more inside than the surface layer. The existing low molecular weight (Mw 1000 or less) resin and low Tg (40 ° C. or less) resin, and in some cases, bleeding of the release agent can be suppressed. As a result, the toner can be further improved in stirring properties, and a toner excellent in storage stability, environmental stability and development durability can be obtained.

  The organosilicon polymer insoluble in THF preferably has a silicon concentration of 50.0 mol% or more in the organosilicon polymer. This is because the organosilicon compound is easily formed into a layer. When the organosilicon polymer insoluble in THF has a silicon concentration of 50.0 mol% or less in the organosilicon polymer, the organosilicon polymer is easily crystallized and easily granulated, so that the storage stability is deteriorated. More preferably, it is 25.0 mol% or less.

In the present invention, the ratio (%) of the amount of SiO ₂ soluble in THF to the amount of SiO ₂ in the toner Ah is preferably 50.0% or less. Storage stability and component contamination are improved. More preferably, it is 25.0% or less, More preferably, it is 10.0% or less.

The ratio (%) of the amount of SiO ₂ soluble in THF to the amount of SiO _{2 in} toner Ah can be adjusted by the degree of polymerization of the binder resin and the organosilicon polymer, the degree of crosslinking, and the amount of the organosilicon polymer. It is.

  Examples of the mixer for treating the particle surface include Henschel mixer, mechanofusion, cyclomix, turbulizer, flexomix, hybridization, mechanohybrid, and nobilta. Moreover, the particle | grain surface can be uniformly processed with the compound which has the partial structure represented by Formula (Me2D2) by making a rotational peripheral speed faster or extending processing time. Next, a method for producing toner particles will be described.

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

  In the first production method, particles of a polymerizable monomer composition containing an organosilicon compound for forming an organosilicon polymer and a polymerizable monomer for forming a binder resin are contained in an aqueous medium. The toner particles are obtained by polymerizing a polymerizable monomer (hereinafter also referred to as suspension polymerization method).

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. Well, it may be particles of a polymerizable monomer composition containing a polymerizable monomer for forming a binder resin, and the particles of the polymerizable monomer composition are being polymerized. It may be toner particles,
In addition, an organic phase dispersion prepared by dissolving a binder resin in an organic solvent is suspended in an aqueous medium, particles are formed (granulated), polymerized, and then the organic solvent is removed. It may be a thing.

  In the third production method, a binder resin and an organic silicon compound for forming an organosilicon polymer are dissolved in an organic solvent, and the organic phase dispersion is suspended in an aqueous medium to form particles. (Granulation) and after polymerization, the organic solvent is removed to obtain toner particles.

  As the fourth production method, there is an aspect in which the binder resin particles and the organosilicon compound-containing particles for forming the 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 aggregating and associating in an aqueous medium, and the binder resin is dissolved in an organic solvent. The organic phase dispersion thus produced may be suspended in an aqueous medium to form particles (granulation), polymerized, and then removed to remove 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 condensation polymerization of the organosilicon polymer in the vicinity of the surface of the toner particles, thereby improving the environmental stability and the development durability.

  As the surface treatment using the hot air, any means can be used as long as it can treat the toner particles or the surface of the toner with hot air and can cool the toner particles or toner treated with the hot air with cold air. 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., Ltd.), a faculty (manufactured by Hosokawa Micron Co., Ltd.), Meteor Inbo MR Type (New Japan) (Matic Industries Co., Ltd.).

  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 completion of the polymerization step, the produced particles are washed, 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, Acrylic polymerizable monomers such as n-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 toethyl methacrylate; methylene aliphatic monocarboxylic esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl Vinyl ethers such as methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, 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-based or diazo-based polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxycarbonate, cumene hydroperoxide, 2,4- Peroxide-based polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5% by mass or more and 30.0% by mass or less with respect 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% by mass or more and 15.000% by mass or less 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% by mass or more and 15.000% by mass or less 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 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer. The amount is preferably 2.0 parts by mass or less. 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 generated 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 resin is obtained by polymerizing an organosilicon compound having a structure represented by the above formula (Z) to deposit the organosilicon polymer on the surface of toner particles, surface uniformity, and long-term storage stability. It is preferable because of its superiority.

  On the other hand, as the polyester resin, those obtained by condensation polymerization of the following carboxylic acid component and alcohol component 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.

  Styrene such as polystyrene and polyvinyltoluene, and homopolymers of substituted styrene; 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-methacrylic acid Ethyl copolymer, styrene-butyl methacrylate copolymer, styrene-dimethyl methacrylate ethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Coalescence, styrene-pig Styrene copolymers such as ene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; 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 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 hydroxy 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 the polyester resin, those obtained by condensation polymerization of the following carboxylic acid component and alcohol component 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.

  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% by mass or more and 70.0% by mass or less, more preferably 3.0% by mass or more based on the binder resin component contained in the toner particles. It is 50.0 mass% or less, More preferably, it is 5.0 mass% or more and 30.0 mass% or less.

  In the present invention, a crystalline polyester may be contained in addition to the polyester resin. Crystalline polyester is a polyester having a melting point.

  As an alcohol component which comprises the crystalline polyester resin used for this invention, the following C2-C16 aliphatic diol and aromatic diol are mentioned. You may use the alcohol component shown below in combination of 2 or more types.

  Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octane Diol, 1,9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, 1,12-undecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecane Diol, 1,16-hexadecanediol and the like.

  An aromatic diol such as bisphenol A or an alkylene oxide adduct of bisphenol A.

  Here, in order to obtain a polyester resin having a melting point, α, ω-linear alkanediol is preferred, 1,4-butanediol or 1,6-hexanediol is more preferred, and 1,4-butanediol is further preferred. preferable.

  The content of the aliphatic diol or aromatic diol having 2 to 16 carbon atoms is 50 mol% or more in the alcohol component. In order to further improve the low-temperature fixability by an abrupt change in viscosity, it is preferably 80 mol% or more and 100 mol%, more preferably 90 mol% or more and 100 mol% or less.

  Moreover, in this invention, you may use a polyhydric alcohol together as said alcohol component other than the said C2-C16 aliphatic alcohol or aromatic diol. Examples of the polyhydric alcohol component include trivalent or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane. You may use these alcohol components in combination of 2 or more types.

  Examples of the carboxylic acid component constituting the crystalline polyester resin used in the present invention include the following aromatic dicarboxylic acids and aliphatic dicarboxylic acids. You may use the carboxylic acid component shown below in combination of 2 or more types.

  Examples of the aromatic dicarboxylic acid having 2 to 16 carbon atoms include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, anhydrides of these acids, and alkyl esters thereof (1 to 3 carbon atoms). Can be mentioned. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Terephthalic acid or an alkyl ester of terephthalic acid (having 1 to 3 carbon atoms) is preferable because the charging stability of the toner is improved.

  Examples of the aliphatic dicarboxylic acid having 2 to 16 carbon atoms include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10- Examples include decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, and 1,14-tetradecanedicarboxylic acid. In addition, anhydrides of those acids and alkyl (1 to 3 carbon atoms) esters of those acids are included.

  The aliphatic dicarboxylic acid having 2 to 16 carbon atoms may be an unsaturated aliphatic dicarboxylic acid having 2 to 16 carbon atoms, and examples thereof include fumaric acid and maleic acid.

  The content of the aromatic dicarboxylic acid having 2 to 16 carbon atoms is 50 mol% or more, preferably 50 mol% or more and 70 mol% or less, more preferably 50 mol% or more and 60 mol% in the carboxylic acid component. It is less than mol%.

  The content of the aliphatic dicarboxylic acid having 2 to 16 carbon atoms is 50 mol% or more in the carboxylic acid component, preferably 70 mol% or more and 100 mol% or less, more preferably 90 mol% or more and 100 mol%. It is less than mol%.

  When the aliphatic dicarboxylic acid having 2 to 16 carbon atoms is an unsaturated aliphatic dicarboxylic acid having 2 to 16 carbon atoms, the unsaturated aliphatic dicarboxylic acid having 2 to 16 carbon atoms is included in the carboxylic acid component. The content of dicarboxylic acid is preferably less than 50 mol%, more preferably 0.01 mol% or more and 25.0 mol% or less, and further preferably 0.10 mol% or more and 10.0 mol% or less. It is. When the content of the unsaturated aliphatic dicarboxylic acid having 2 to 16 carbon atoms is less than 50 mol% in the carboxylic acid component, the low-temperature fixability is improved.

  Moreover, in this invention, even if it uses a trivalent or more carboxylic acid component other than C2-C16 aromatic dicarboxylic acid or C2-C16 aliphatic dicarboxylic acid as a carboxylic acid component. Good.

  Examples of the trivalent or higher polyvalent carboxylic acid compound include trimellitic acid, tri-n-ethyl 1,2,4-tricarboxylate, tri-n-butyl 1,2,4-tricarboxylate, 1,2,4- Tri-n-hexyl tricarboxylate, triisobutyl 1,2,4-benzenetricarboxylate, tri-n-octyl 1,2,4-benzenetricarboxylate, tri-2-ethylhexyl 1,2,4-benzenetricarboxylate and And lower alkyl esters of tricarboxylic acid. Among trivalent or higher polyvalent carboxylic acid compounds, trimellitic acid and trimellitic anhydride are preferred because they are inexpensive and easy to control the reaction.

  Moreover, you may use monovalent carboxylic acid and monohydric alcohol as needed. Specifically, benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, stearin Monovalent carboxylic acids such as acids; such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, dodecyl alcohol Monohydric alcohol. These carboxylic acid components can be used in combination of two or more.

  In the polyester resin used in the present invention, the total of all aliphatic dicarboxylic acid components and all aliphatic diol components may be 25 mol% or more with respect to the total (100 mol%) of all carboxylic acid components and all alcohol components. preferable. In order to improve the low-temperature fixability, 50 mol% or more is more preferable.

  The polyester resin can be produced by a normal polyester synthesis method. Specifically, after a polycarboxylic acid and a polyhydric alcohol are esterified or transesterified, the low-boiling polyhydric alcohol is subjected to polycondensation according to a conventional method under reduced pressure or by introducing nitrogen gas. Reaction is performed to obtain a polyester resin. In the esterification or transesterification reaction, a usual esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, and magnesium acetate can be used as necessary. For polymerization, known polymerization catalysts such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide can be used. Further, the polymerization temperature and the amount of catalyst are not particularly limited, and may be arbitrarily selected as necessary.

  In the present invention, it is preferable that a release agent is contained as one of the materials constituting the toner particles. As the release agent usable for the toner particles, 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, Polyolefin wax such as polypropylene and derivatives thereof, natural wax such as carnauba wax and candelilla wax and derivatives thereof, fatty acids such as higher aliphatic alcohol, stearic acid and palmitic acid, or compounds thereof, acid amide wax, ester wax , Ketones, hydrogenated 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 to 20.0 mass parts with respect to binder resin or 100.0 mass parts of polymerizable monomers.

  In the present invention, the toner particles may contain a colorant. It does not specifically limit as said coloring agent, The well-known thing shown below can be used.

  As the yellow pigment, yellow iron oxide, condensed azo compound, isoindolinone compound, anthraquinone compound, azo metal complex, methine compound, and allylamide compound are used. Specific examples include the following.

  C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 47, 155, 168, 180.

  Examples of the orange pigment include the following.

  Permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK.

  Examples of red pigments include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following.

  C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177184, 185, 202, 206, 220, 221, 254.

  Examples of blue pigments include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specific examples include the following.

  C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 66.

  Examples of purple pigments include fast violet B and methyl violet lake.

  Examples of the green pigment include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

  Examples of the black pigment include carbon black, aniline black, non-magnetic ferrite, magnetite, the above-described yellow colorant, red colorant, and blue colorant, and those that are toned in black. These colorants can be used alone or in combination and further in the form of a solid solution.

  Further, depending on the toner production method, it is necessary to pay attention to the polymerization inhibiting property and the dispersion medium transferability of the colorant. If necessary, the surface of the colorant may be subjected to surface modification with a substance that does not inhibit polymerization. In particular, since dyes and carbon black often have polymerization inhibiting properties, care must be taken when using them.

  Moreover, as a preferable method for treating the dye, there is a method in which a polymerizable monomer is polymerized in the presence of the dye in advance and the obtained colored polymer is added to the polymerizable monomer composition. On the other hand, carbon black may be treated with a substance (for example, organosiloxane) that reacts with the surface functional group of carbon black in addition to the same treatment as the above dye.

  In addition, it is preferable that content of a coloring agent is 3.0 to 15.0 mass parts with respect to 100.0 mass parts of binder resins or polymerizable monomers.

  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 their metal salts, anhydrides or esters, 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 these Onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (including phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; resin charge control agents.

  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. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.

  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 sulfo group (sulfonic acid group), a sulfonic acid group, or a sulfonic acid ester group.

  Examples of the polymer or copolymer having a sulfo group, a sulfonate group, or a sulfonate group include a polymer compound having a sulfo group in the side chain. In particular, styrene and / or styrene having a sulfo 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 ° C. or more and 90 ° C. or less. A polymer compound which is a (meth) acrylic acid ester copolymer is preferred. Charge stability under high humidity is improved.

  As said sulfo group containing (meth) acrylamide type monomer, what can be represented by following formula (X) is preferable, and, specifically, 2-acrylamido-2-methylpropanoic acid and 2-methacrylamide-2-methylpropanoic acid are preferable. Etc.

（式（Ｘ）中、Ｒ₁は、水素原子、又は、メチル基を表し、Ｒ₂およびＲ₃は、それぞれ独立して、水素原子、炭素数１以上１０以下のアルキル基、アルケニル基、アリール基、又は、アルコキシ基を表し、ｎは、１以上１０以下の整数を表す。）

(In formula (X), R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group. A group or an alkoxy group, and n represents an integer of 1 or more and 10 or less.)

  By adding the polymer having a sulfo group to the toner particles in an amount of 0.1 parts by weight or more and 10.0 parts by weight or less with respect to 100 parts by weight of the binder resin, the charged state of the toner particles is further improved. can do.

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

  The toner of the present invention can be obtained by treating the surface of toner particles with various organic fine particles or inorganic fine particles for the purpose of imparting various properties. The organic fine particles or inorganic fine particles preferably have a particle size of 1/10 or less of the weight average particle size of the toner particles from the viewpoint of durability when added to the toner particles.

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

  The organic fine particles or inorganic fine particles treat the surface of the toner particles in order to improve the fluidity of the toner and to make the charge of the toner uniform. By subjecting the organic fine particles or inorganic fine particles to a hydrophobic treatment, it is possible to adjust the chargeability of the toner and to improve the charging characteristics under a high humidity environment. Therefore, the organic fine particles or the inorganic fine particles subjected to the hydrophobic treatment are used. It is preferable. As the treatment agent for hydrophobic treatment of organic fine particles or inorganic fine particles, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, An organic titanium compound is mentioned. These treatment agents may be used alone or in combination.

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

  The addition amount of these organic fine particles or inorganic fine particles is preferably 0.01 parts by mass or more and 10.00 parts by mass or less, more preferably 0.02 parts by mass or more and 50.00 parts by mass or less with respect to 100.00 parts by mass of toner particles. It is preferably 00 parts by mass or less, and more preferably 0.03 parts by mass or more and 1.00 parts by mass or less. By optimizing the addition amount, the contamination of the member due to embedding or releasing organic fine particles or inorganic fine particles in the toner particles is improved. These organic fine particles or inorganic fine particles may be used alone or in combination.

In the present invention, the BET specific surface area of the organic fine particles or inorganic fine particles is preferably 10 m ² / g or more and 450 m ² / g or less.

The specific surface area BET of the organic fine particles or inorganic fine particles can be determined by a low temperature gas adsorption method by a dynamic constant pressure method according to a BET method (preferably a BET multipoint method). For example, by using a specific surface area measuring apparatus (trade name: 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. The BET specific surface area (m ² / g) can be calculated.

  Organic fine particles or inorganic fine particles may be firmly fixed or adhered to the surface of the toner particles. Examples of externally added mixers for firmly adhering or adhering organic fine particles or inorganic fine particles to the toner particle surface include Henschel mixer, mechano-fusion, cyclomix, turbulizer, flexo-mix, hybridization, mechano-hybrid, and nobilta. It is done. Further, the organic fine particles or the inorganic fine particles can be strongly fixed or adhered by increasing the rotational peripheral speed or increasing the treatment time.

  Hereinafter, the physical properties of the toner will be described.

  In the toner of the present invention, the viscosity at 80 ° C. measured by a constant load extrusion type capillary rheometer is preferably 1,000 Pa · s or more and 40,000 Pa · s or less. When the 80 ° C. viscosity is 1,000 Pa · s or more and 40,000 Pa · s or less, the toner has excellent low-temperature fixability. The viscosity at 80 ° C. is more preferably 2,000 Pa · s or more and 20,000 Pa · s or less. In the present invention, the 80 ° C. viscosity can be adjusted by the addition amount of the low molecular weight resin, the monomer species at the time of producing the binder resin, the initiator amount, the reaction temperature, and the reaction time.

  The viscosity value at 80 ° C. measured by a constant load extrusion type capillary rheometer of toner can be determined by the following method.

As an apparatus, a flow tester CFT-500D (manufactured by Shimadzu Corporation) is used for measurement under the following conditions.
Sample: About 1.0 g of toner is weighed, and molded with a load of 100 kg / cm ² for 1 minute using a pressure molding machine to obtain a sample.
-Die hole diameter: 1.0mm
-Die length: 1.0mm
・ Cylinder pressure: 9.807 × 10 ⁵ (Pa)
Measurement mode: Temperature rise method Temperature rise rate: 4.0 ° C./min By the above method, the viscosity (Pa · s) of the toner at 30 ° C. to 200 ° C. is measured, and the viscosity at 80 ° C. (Pa · s). ) This value is the 80 ° C. viscosity measured by a capillary rheometer of the toner constant load extrusion method.

  The toner of the present invention preferably has a weight average particle diameter (D4) of 4.0 μm or more and 9.0 μm or less, more preferably 5.0 μm or more and 8.0 μm or less, and further preferably 5.0 μm or more and 7 or less. 0.0 μm or less.

  The glass transition temperature (Tg) of the toner of the present invention is preferably 35 ° C. or higher and 100 ° C. or lower, more preferably 40 ° C. or higher and 80 ° C. or lower, and further preferably 45 ° C. or higher and 70 ° C. or lower. When the glass transition temperature is in the above range, the blocking resistance, the low temperature offset resistance, and the transparency of the transmission image of the overhead projector film can be further improved.

  In the present invention, the weight average molecular weight (Mw) (hereinafter also referred to as the weight average molecular weight of the toner) measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble content of the toner is 5,000 to 50. 1,000 or less. 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, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) [Mw / Mn] in the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble content of the toner. Is preferably 5.0 or more and 100.0 or less, more preferably 5.0 or more and 30.0 or less. When [Mw / Mn] is within the above range, the fixable temperature range can be widened.

  The content of the tetrahydrofuran insolubles in the toner of the present invention is preferably less than 50.0% by mass, more preferably 0.0% by mass or more and 45.45% by mass with respect to the toner components other than the toner colorant and inorganic fine particles. It is less than 0% by mass, more preferably 5.0% by mass or more and less than 40.0% by mass. By setting the content of the THF-insoluble matter to less than 50.0% by mass, the low-temperature fixability can be improved.

(Measurement method of toner particle or toner physical properties)
(Method for adjusting toner particles or toner insoluble content of tetrahydrofuran (THF))
The content of toner particles or toner insoluble in tetrahydrofuran (THF) was adjusted as follows.

  Toner particles to be measured or 1.0 g of toner to be measured are weighed, put into a cylindrical filter paper (Toyo Filter Paper No. 86R), passed through a Soxhlet extractor, extracted with 200 mL of THF as a solvent for 20 hours, and the filtrate in the cylindrical filter paper is removed. What was obtained by vacuum drying at 40 ° C. for several hours was defined as the THF-insoluble content of the toner particles for NMR measurement. When the insoluble content is small, the toner particles to be measured or the tetrahydrofuran (THF) insoluble content of the toner to be measured are prepared using a plurality of Soxhlet extraction apparatuses, and the resulting insoluble content is combined into toner particles or the tetrahydrofuran of the toner. (THF) was insoluble.

(Content of toner insoluble matter in THF)
The content of the THF insoluble matter in the toner means the mass ratio of the ultra-high molecular weight polymer component (substantially crosslinked polymer) that has become insoluble in the THF solvent. In the present invention, the content of THF insolubles in the toner to be measured is a value measured as follows.

1.0 g of toner to be measured is weighed (W1 g), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi), passed through a Soxhlet extractor, extracted with 200 mL of THF as a solvent for 20 hours, and extracted with a solvent. After concentrating the soluble component, vacuum drying is performed at 40 ° C. for several hours, and the amount of the THF soluble resin component is weighed (W2 g). The mass of components other than the resin component such as the 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 of the binder resin and the organosilicon polymer, the degree of crosslinking, and the amount of the organosilicon polymer.

(Method for preparing toner A)
In the present invention, toner A is obtained by the following method.

  160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water, and dissolved with a hot water bath to prepare a sucrose concentrate. Neutral detergent for pH7 precision measuring instrument washing with 31.0g of the above sucrose concentrate in a centrifuge tube and Contaminone N (trade name) (nonionic surfactant, anionic surfactant, organic builder) 6 mL of an aqueous solution of 10% by weight of Wako Pure Chemical Industries, Ltd.) to prepare a dispersion. To this dispersion, 1.0 g of toner is added, and the mass of toner is loosened with a spatula or the like.

  The centrifuge tube is shaken with a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube for swing rotor (50 mL) and separated by a centrifuge at 3500 rpm for 30 minutes. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the toner separated in the uppermost layer is collected with a spatula or the like. The collected toner is filtered with a vacuum filter and then dried with a dryer for 1 hour or more. The dried product is crushed with a spatula to obtain toner A.

(Preparation method of toner Ah)
In the present invention, toner Ah obtained by washing toner A with hexane is obtained by the following method. Add 1.0 g of toner to 100 mL of hexane, and loosen the mass of toner with a spatula or the like. Shake the centrifuge tube on a shaker at 350 spm (strokes per min) for 5 minutes. After shaking, the solution is filtered with a vacuum filter and then dried with a dryer for 1 hour or longer. The dried product is crushed with a spatula to obtain toner Ah.

(Partial structure represented by (T3a), (T3b) and (T3c) and confirmation method of partial structure represented by formula (Me2D2))
To confirm the partial structure represented by (T3a), (T3b) and (T3c) and the partial structure represented by formula (Me2D2) in the toner particles or the organosilicon polymer contained in the toner, the following method is used. Use.

The presence or absence of a hydrocarbon group represented by R ^a in the formula (R ^a T3) was confirmed by ¹³ C-NMR. The detailed structures of the formula (R ^a T3) and the formula (Me2D2) were 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 matter of toner A and toner Ah for NMR measurement) was put in a sample tube having a diameter of 4 mm.

  With this method, the presence or absence of hydrocarbon groups represented by (T3a), (T3b) and (T3c) was confirmed. If the signal was confirmed, the partial structures represented by (T3a), (T3b) and (T3c) were determined to be “present”.

(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)
Apparatus: JNM-ECX500II manufactured by JEOL RESONANCE
Probe: 3.2mmφ
Measurement temperature: room temperature Sample rotation speed: 6 kHz
Sample: 150 mg of measurement sample (THF insoluble matter of toner A and toner Ah for NMR measurement) is put in a sample tube having a diameter of 4 mm.
Measurement nuclear frequency: 97.38 MHz
Reference substance: DSS (external standard: 1.534 ppm)
Measuring method: DD / MAS
²⁹ Si 90 °
Flip angle 45 °
Delay time 180sec
Pulse sequence Single pulse dec solid
Integration count: 20480 times

(Confirmation and quantification method of T3 structure, Me2D2 structure, X1 structure, X2 structure, X3 structure, X4 structure)
The partial structures of T3, Me2D2, 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 toner, the peak is separated into the following structure, and the mol% of each component is calculated from the area ratio of each peak. The structure of the following formula is a structure within a dotted frame. In curve fitting, an X4 structure in which the number of O _1/2 bonded to silicon represented by the following general formula (X4) is 4.0, an O _{1 /} bonded to silicon represented by the following general formula (X3) X3 structure in which the number of ₂ is 3.0, X2 structure in which the number of O _1/2 bonded to silicon represented by the following formula (X2) is 2.0, and bonding to silicon represented by the following formula (X1) Peak separation into an X1 structure in which the number of O _1/2 to be 1.0 is 1.0, a structure represented by the formula (T3), and a structure represented by the formula (Me2D2). The structure represented by the formula (T3) is a part of the X3 structure, and the structure represented by the formula (Me2D2) is a part of the X2 structure. Note that each structure is a structure within a dotted frame represented by the following formula.

（式（Ｘ３）中のＲ^f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）

(R ^f in Formula (X3) is an organic group, halogen atom, hydroxy group or alkoxy group bonded to silicon)

（式（Ｘ２）中のＲ^g、Ｒ^h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）

(R ^g and R ^{h in} formula (X2) are organic groups, halogen atoms, hydroxy groups or alkoxy groups bonded to silicon)

（式（Ｘ１）中のＲⁱ、Ｒ^j、Ｒ^k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）

(R ⁱ , R ^j and R ^k in the formula (X1) are an organic group, a halogen atom, a hydroxy group or an alkoxy group bonded to silicon)

  For curve fitting, JOEL Delta version 5.0.4 (trade name), software for JNM-ECX500II manufactured by JEOL RESONANCE is used. Each peak was peaked up. Waveform separation was performed using a Gaussian peak. An example is shown in FIG. Peak division is performed so that the peak of the synthetic peak difference (a), which is the difference between the synthetic 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. 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 The total area was defined as the total peak area SX of the organosilicon polymer of the toner.
[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)}
[SR ^a T3] = {R ^a T3 structure area / (X1 structure area + X2 structure area + X3 structure area + X4 structure area)}
[SMe2D2] = {Area of Me2D2 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.
Example of X1 structure (R ⁱ = R ^j = -OC ₂ H ₅ , R ^k = -CH ₃ ): -47 ppm
An example of X2 structure _{^{(R g = -OC 2 H 5}} , Rh = -CH 3): - 56ppm
An example of the X3 structure (T3 structure) (R ^a = —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
Example of Me2D2 structure: −22 ppm

  In the present invention, when the toner A is an NMR sample, the above [SX], [SX1], [SX2], [SX3], [SX4], [ST3], and [SMe2D2] are changed as follows.

[SX] the [SAX], [SX1] the [SAX1], [SX2] the [SAX2], [SX3] the [SAX3], [SX4] the [SAX4], the ^{[SR a T3] [SAT3]} , [SMe2D2] was changed to [SAMe2D2].

In the present invention, when toner Ah obtained by washing toner A with hexane is used as an NMR sample, the above [SX], [SX1], [SX2], [SX3], [SX4], [SR ^a T3 ] And [SMe2D2] were changed as follows.

[SX] the [SAhX], [SX1] the [SAhX1], [SX2] the [SAhX2], [SX3] the [SAhX3], [SX4] the [SAhX4], the ^{[SR a T3] [SAhT3]} , [SMe2D2] was changed to [SAhMe2D2].

In the present invention, when the THF-insoluble matter of toner A is used as an NMR sample, the above [SX], [SX1], [SX2], [SX3], [SX4], [SR ^a T3], and [SMe2D2] are as follows. It changed as follows.

[SX] is [SAtX], [SX1] is [SAtX1], [SX2] is [SAtX2], [SX3] is [SAtX3], [SX4] is [SAtX4], and [SR ^a T3] is [SAtT3], [SMe2D2] was changed to [SAtMe2D2].

In the present invention, when the THF-insoluble matter of toner Ah obtained by washing toner A with hexane is used as an NMR sample, the above [SX], [SX1], [SX2], [SX3], [SX4], [SR ^a T3] and [SMe2D2] were changed as follows.

[SX] is [SAhtX], [SX1] is [SAhtX1], [SX2] is [SAhtX2], [SX3] is [SAhtX3], [SX4] is [SAhtX4], [ST3] is [SAhtR ^a T3], [SMe2D2] was changed to [SAhtMe2D2].

(Measurement method of G / GA of SiO ₂ amount (% by mass) and silicon intensity G and Si intensity GA of toner A by fluorescent X-ray measurement (wavelength dispersive X-ray fluorescence analyzer))
The measurement of fluorescent X-rays conforms to JIS K 0119-1969, and is specifically as follows.

  As a measuring device, a wavelength dispersion type fluorescent X-ray analyzer “Axios” (manufactured by PANalytical) and attached dedicated software “SuperQ ver. 4.0F” (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data ) Is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).

  As a measurement sample, about 4 g of toner was put in a dedicated aluminum ring for press and leveled, and a tablet-forming compressor “BRE-32” (manufactured by Maekawa Test Instruments Co., Ltd.) was used. Pellets that are pressed for 2 seconds and molded to a thickness of about 2 mm and a diameter of about 39 mm are used.

  The measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and the count rate (unit: cps) which is the number of X-ray photons per unit time is measured.

The amount of SiO ₂ (% by mass) in the particles was determined as follows.

Silica (SiO ₂ ) fine powder is added to 100 parts by mass of polystyrene resin particles (Mw 20000, Tg = 80 ° C.) so as to be 0.10 parts by mass, and sufficiently mixed using a coffee mill. Similarly, the silica fine powder is mixed with polystyrene resin particles (Mw 20000, Tg = 80 ° C.) so as to be 0.20 parts by mass and 0.50 parts by mass, respectively, and these are used as samples for the calibration curve.

For each sample, a pellet for a calibration curve was prepared as described above using a tablet molding compressor, and the diffraction angle (2θ) was observed at 109.08 ° when PET was used as a spectroscopic crystal. The counting rate (unit: cps) of Si-Kα rays is measured. At this time, the acceleration voltage and current value of the X-ray generator are 24 kV and 100 mA, respectively. A calibration curve of a linear function is obtained with the X-ray count rate obtained on the vertical axis and the added amount of SiO ₂ in each calibration curve sample on the horizontal axis.

Next, the toner to be analyzed is pelletized as described above with a tablet compression machine. Next, the counting rate of Si-Kα rays is measured. Then, the SiO ₂ content (% by mass) in the toner to be analyzed is obtained from the calibration curve.

  In the present invention, the silicon count rate may be referred to as silicon strength.

  In the present invention, G / GA was determined by setting the silicon intensity of the toner measured by fluorescent X-ray to G (unit: cps) and the silicon intensity of toner A as GA.

(Ratio of the amount of SiO ₂ soluble in THF to the amount of SiO _{2 in} toner Ah (%))
The ratio (%) of the amount of SiO ₂ soluble in THF to the silicon compound in toner Ah is a value measured as follows.

1.0 g of toner Ah is weighed, placed in AhW1 (g), cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi), passed through a Soxhlet extractor, extracted for 20 hours using 200 mL of THF as a solvent, and soluble components extracted by the solvent The concentrate insoluble in THF and the THF-insoluble matter in the cylindrical filter paper are vacuum-dried at 40 ° C. for several hours, and the THF-soluble component amount AhW2 (g) and the THF-insoluble component amount AhW3 (g) are weighed. By a fluorescent X-ray measurement, by using the calibration curve, the SiO ₂ content in the toner Ah AhSi1 (wt%), SiO ₂ content of soluble in component in THF in the toner Ah (mass%) AhSi2 (mass%), the SiO ₂ content of insoluble in component in THF and AhSi3 (mass%).

The ratio (%) of the amount of SiO ₂ soluble in THF to the amount of SiO _{2 in} toner Ah is (AhW2) × (AhSi2) / (AhW1) × (AhSi1) × 100.

(Measurement of the average thickness Dav. Of the surface layer of the toner particles and the ratio of the thickness of the surface layer of 2.5 nm or less as measured by cross-sectional observation of the toner particles using a 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. The sample is magnified to a magnification of 10,000 to 100,000 times with a transmission electron microscope (trade name: 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 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, using a transmission electron microscope (trade name: electron microscope Tecnai TF20XT, manufactured by FEI), a bright field image of a toner particle cross section is obtained at an acceleration voltage of 200 kV. Next, using an EELS detector (trade name: 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. To do.

  The organosilicon polymer of the present invention forms a uniform film on the surface layer, and the organosilicon polymer is in contact with the surface of the resin in a flat surface, which suppresses peeling and embedding of the organosilicon polymer during durability. Therefore, it is preferable.

  Moreover, the shape of the organosilicon polymer of the present invention is preferably a layered shape, a hemispherical convex or network shape having a radius of 50 nm or more.

  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 long axis L of the cross section of the toner particle and an axis L90 that passes through the center of the long axis L and is perpendicular to the long axis. 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 surface layer of the toner particles 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 divided axes in which the thickness of the surface layer of the toner particles containing the organosilicon polymer on each of the 32 existing divided axes is 2.5 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) determined 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 + RA21 + RA22 + RA23 + RA24 + 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.

[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

[Ratio of the surface layer containing the organosilicon polymer in which the thickness FRAn of the surface layer containing the organosilicon polymer is 2.5 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 2.5 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 2.5 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 2.5 nm or less) = ((the thickness FRAN of the surface layer containing the organosilicon polymer is 2.5 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 having a thickness FRAN of 2.5 nm or less containing the organosilicon polymer. It was set as the ratio of the surface layer containing the organosilicon polymer whose FRAn is 2.5 nm or less.

(Concentration of silicon element in the surface layer of toner particles (atomic%))
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. Surface composition analysis using analysis (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 ULVAC-PHI, the concentration of silicon atoms [dSi] and the concentration of carbon atoms [dC] existing in the surface layer of the toner particles. , And oxygen atom concentration [dO] (both are atomic% (same as atomic%)).

(Measurement of weight average molecular weight (Mw), number average molecular weight (Mn) and main peak molecular weight (Mp) of toner (particle) and various resins)
The weight average molecular weight (Mw), number average molecular weight (Mn), and main peak molecular weight (Mp) of the toner (particles) and various resins are measured using gel permeation chromatography (GPC) under the following conditions.

(Measurement condition)
Column (made by Showa Denko KK): Shodex GPC KF-801, KF-802, KF-803, KF-804, KF-805, KF-806, KF-807 (diameter 8.0 mm, length 30 cm) 7 series, eluent: tetrahydrofuran (THF)
・ Temperature: 40 ℃
・ Flow rate: 0.6 mL / min ・ Detector: RI
Sample concentration and amount: 10 μL of 0.1% by mass sample

(Sample preparation)
Measurement target (toner (particles), various resins)
0.04 g was dispersed and dissolved in 20 mL of tetrahydrofuran, allowed to stand for 24 hours, filtered through a 0.2 μm filter (trade name: MYSHORIDISK H-25-2, manufactured by Tosoh Corporation), and the filtrate was used as a sample. Use.

  The calibration curve uses a molecular weight calibration curve created with a monodisperse polystyrene standard sample. As standard polystyrene samples for preparing calibration curves, TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-40, F-20, F-10, manufactured by Tosoh Corporation F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 are used. At this time, a standard polystyrene sample of at least about 10 points is used.

  In creating the molecular weight distribution of GPC, the chromatogram rises from the baseline on the high molecular weight side and starts measurement from the starting point, and the molecular weight is measured up to about 400 on the low molecular weight side.

(Measurement of toner (particles), glass transition temperature (Tg) of various resins and integral value of heat)
The glass transition temperature (Tg) and calorific value of the toner (particles) and various resins were determined by the following procedure using a differential scanning calorimeter (DSC) M-DSC (trade name: Q2000, manufactured by TA Instruments). To measure. 3 mg of a sample to be measured (toner (particles), various resins) is precisely weighed. 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 ° C. 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 calorie integral value (J / g) per 1 g of toner (particles) represented by the peak area of the endothermic main peak is measured. An example of a reversing flow curve obtained by DSC measurement of 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 (trade name) 2000 / XP Version 4.3A (manufactured by TA Instruments Co., Ltd.) was used, and a line connecting measurement points at 35 ° C. and 135 ° C. was used, using the function of Integral Peak Linear. The calorie integral value (J / g) is obtained from the region surrounded by the endothermic curve.

(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 measured with a fine particle size distribution measuring apparatus (trade name: Coulter Counter Multisizer 3, equipped with a 100 μm aperture tube. The number of effective measurement channels using Beckman Coulter Co., Ltd.) and dedicated software (product name: Beckman Coulter Multisizer 3 Version 3.51, manufactured by Beckman Coulter Co.) for setting measurement conditions and analyzing measurement data Measure with 25,000 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 (trade name) 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 measurement count is 1 time, and the Kd value is (standard particle 10.0 μm, Beckman Coulter, Inc. Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II (trade name), 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 dedicated to 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 in this, as a dispersant, Contaminon N (trade name) (nonionic surfactant, anionic surfactant, pH 7 consisting of an organic builder About 0.3 mL of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for precision measuring instrument washing (manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass 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 an ultrasonic disperser having an electric output of 120 W (trade name: Ultrasonic Dispersion System Tetora 150, manufactured by Nikka Bios Co., Ltd.) A predetermined amount of ion-exchanged water is placed in the water tank, and about 2 mL of Contaminone N (trade name) is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) 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 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).

(Measurement method of average circularity of toner (particles))
The average circularity of the toner (particles) is measured using “FPIA-3000 type” (manufactured by Sysmex Corporation), which is a flow type particle image analyzer, under the measurement / analysis conditions during calibration.

  A suitable amount of surfactant and alkylbenzene sulfonate as a dispersant is added to 20 mL of ion-exchanged water, 0.02 g of a measurement sample is added, and a tabletop ultrasonic cleaner disperser with an oscillation frequency of 50 kHz and an electric output of 150 watts is added. (Product name: VS-150, manufactured by Vervo Crea Co., Ltd.) is used for dispersion treatment for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC.

  The flow type particle image analyzer equipped with a standard objective lens (10 ×) is used for measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, 3000 toners (particles) are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is determined. The analysis particle diameter is limited to 1.98 μm or more and 19.92 μm or less, and the average circularity of the toner (particles) is obtained.

  In measurement, automatic focus adjustment is performed using standard latex particles (for example, 5100A (trade name) manufactured by Duke Scientific is diluted with ion-exchanged water) before the measurement is started. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  Further, when the mode circularity is 0.98 or more and 1.00 or less in the circularity distribution of the toner (particles), it means that most of the toner (particles) have a shape close to a true sphere. The decrease in the adhesion force of the toner (particles) to the photoreceptor due to the mirror image force, van der Waals force, etc. becomes more remarkable, and the transfer efficiency becomes high, which is preferable.

  Here, the mode circularity is a circularity from 0.40 to 1.00, 0.40 or more and less than 0.41, 0.41 or more and less than 0.42,... Or more and less than 1.00 and It is 61 divisions every 0.01 as in 1.00, and the circularity of each measured particle is assigned to each division range, and the circularity of the division range where the frequency value is maximum in the circularity frequency distribution is said.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

  A production example of the charge control resin used in the present invention will be described.

(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 90 parts by mass of styrene, 6.1 parts by mass of 2-ethylhexyl acrylate, and 6.1 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and heated under reflux at normal pressure. A solution prepared by diluting 1.0 part 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. The polymerization was terminated.

  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 particles were classified by a 250-mesh sieve to obtain particles having a size 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 obtained precipitate was washed with one half of 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 81 ° C., a main peak molecular weight (Mp) of 19,200, a number average molecular weight (Mn) of 11,300, a weight average molecular weight (Mw) of 20,200, and an acid value of 18. It was 2 mgKOH / g. Let the obtained resin be charge control resin (1).

(Example of production of polyester resin (1))
・ Terephthalic acid: 12.2 mol part ・ Bisphenol A-propylene oxide 2 mol adduct: 11.2 mol part ・ Dibutyltin oxide: 0.07 mol part The above monomers are charged into an autoclave, a pressure reducing device, a water separation device A nitrogen gas introducing device, a temperature measuring device, and a stirring device were attached to the autoclave. Under reduced pressure under a nitrogen atmosphere, the reaction was carried out at 205 ° C. until Tg reached 64 ° C. according to a conventional method to obtain a polyester resin (1). The weight average molecular weight (Mw) was 6800, the number average molecular weight (Mn) was 3010, the acid value was 0.1 mgKOH / g, the hydroxyl value was 18.4 mgKOH / g, and Tg was 58.6 ° C.

(Example of production of polyester resin (2))
(Synthesis of isocyanate group-containing prepolymer)
-Bisphenol A ethylene oxide 2 mol adduct: 11.5 mol parts-Phthalic acid: 10.0 mol parts-Dibutyltin oxide: 0.065 mol parts The above monomers are charged into an autoclave, and a decompressor, water separator, A nitrogen gas introducing device, a temperature measuring device and a stirring device were attached to the autoclave. The reaction was stirred for 8 hours at 215 ° C. in a nitrogen atmosphere, further reacted for 4 hours under reduced pressure, then cooled to 80 ° C., and reacted with 4.8 mol parts of isophorone diisocyanate in ethyl acetate for 2 hours. Thus, an isocyanate group-containing polyester resin was obtained. 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 obtained polyester resin (2) has a weight average molecular weight (Mw) of 21,800, a number average molecular weight (Mn) of 2,900, a peak molecular weight of 6,800, an acid value of 10.3 mgKOH / g, a hydroxyl value of 15.2 mgKOH / g, Tg 59 8 ° C.

(Example of production of polyester resin (3))
-1,6-hexanediol: 400.0 parts by mass-1,4-butanedicarboxylic acid: 485.0 parts by mass The above monomers are charged into an autoclave, and a pressure reducing device, a water separator, a nitrogen gas introducing device, and temperature measurement. The apparatus and stirrer were attached to an autoclave. Under a nitrogen atmosphere, the reaction was performed at 185 ° C. for 4 hours, the reaction was performed at 200 ° C. for 4 hours, and the reaction was performed at 160 ° C. and 9 kpa for 4 hours to obtain a polyester resin (3). The weight average molecular weight (Mw) was 13700, the number average molecular weight (Mn) was 2900, the acid value was 0.3 mgKOH / g, the hydroxyl value was 18.2 mgKOH / g, and the melting point was 57.7 ° C. The polyester resin (3) is also called crystalline polyester.

(Production example of polyester resin (4))
-Bisphenol A ethylene oxide 2 mol adduct: 11.0 mol parts-Bisphenol A propylene oxide 2 mol adduct: 10.4 mol parts-Terephthalic acid: 13.5 mol parts-Dodecenyl succinic acid: 6 mol parts Was put in an autoclave, and a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device, and a stirring device were attached to the autoclave. In a nitrogen atmosphere, the temperature was raised to 200 ° C. over 1 hour, and it was confirmed that the reaction system was uniformly stirred. 0.14 mol part of tin distearate was added with respect to the total mass of these monomers. Further, while distilling off the generated water, the temperature was raised from 200 ° C. to 240 ° C. over 5 hours, and a dehydration condensation reaction was carried out at 240 ° C. for another 2 hours. Next, the temperature was lowered to 190 ° C., 1 mol part of trimellitic anhydride was gradually added, and the reaction was continued at 190 ° C. for 1 hour. As a result, a polyester resin having a glass transition temperature of 54.6 ° C., an acid value of 12.2 mg KOH / g, a hydroxyl value of 19.6 mg KOH / g, a weight average molecular weight of 49200, a number average molecular weight of 5400, and a softening point of 101 ° C. 4) was obtained.

(Production example of styrene resin (1))
30 parts by mass of xylene was placed in a pressure-resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer, and the temperature was raised to 205 ° C. The pressure at this time was 0.3 MPa. A mixture of 99.0 parts by mass of styrene monomer, 1.0 part of n-butyl acrylate, and 3.4 parts of di-tert-butyl peroxide was charged into a dropping funnel, and the mixture was pressurized with xylene at 205 ° C. over 2 hours ( 0.3 MPa). After the dropwise addition, the reaction was further carried out at 205 ° C. for 2 hours to complete the solution polymerization, and xylene was removed. The weight average molecular weight of the obtained styrene resin was 3220, and Tg was 53.2 ° C. This is designated as styrene resin (1).

(Production example of toner particles (1))
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 700 parts by mass of ion-exchanged water, 1000 parts by mass of a 0.1 mol / L Na ₃ PO ₄ aqueous solution, and 1.0 mol / L HCl. 24.0 parts by mass of an aqueous solution was added, and a high-speed stirring apparatus K. The mixture was maintained at 60 ° C. while stirring at 13,000 rpm using a homomixer (Special Machine Industries Co., Ltd.). To this, 85 parts by mass of a 1.0 mol / L 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 .
Styrene 69.0 parts by mass n-butyl acrylate 31.0 parts by mass 1,6-hexanediol diacrylate 0.1 parts by mass vinyltriethoxysilane 8.5 parts by mass copper phthalocyanine pigment 6.5 parts by mass (Pigment Blue 15: 3)
-Polyester resin (1) 5.0 parts by mass-Charge control resin (1) 0.5 parts by mass-Release agent 10.0 parts by mass (behenyl behenate, melting point: 72.1 ° C)
The polymerizable monomer composition (1) obtained by dispersing the above material with an attritor (manufactured by Mitsui Miike Chemical Industries Co., Ltd.) for 3 hours was held at 60 ° C. for 20 minutes. Thereafter, a polymerizable monomer composition (1) obtained by adding 16.0 parts by mass of a polymerization initiator t-butyl peroxypivalate (toluene solution 50%) to the polymerizable monomer composition (1). The mixture was put into the aqueous medium and granulated for 10 minutes while maintaining the rotation speed of the high-speed stirrer at 13,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was carried out for 4 hours while slowly stirring. At this time, the pH of the aqueous medium was 5.1. Next, 10.0 parts by mass of 1.0 mol / L sodium hydroxide aqueous solution 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 of 100 ° C. in the vessel 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. Further, filtration, washing and drying were performed to obtain particles (1) having a weight average particle diameter of 5.8 μm.

  With respect to 100 parts by mass of the particles (1), 0.10000 parts by mass of dimethyl silicone oil having a viscosity of 100 cps (manufactured by Shin-Etsu Silicone Co., Ltd., KF-96-100cs) has a peripheral speed of 20.0 m / sec. Toner particles (1) are toner particles obtained by mixing for 3 minutes with a Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.).

  The formulation and conditions of toner particles (1) are shown in Table 1, and the physical properties are shown in Table 5. Silicon mapping was performed in the TEM observation of the toner particles (1), and it was confirmed that silicon atoms were uniformly present on the surface layer. It was confirmed that the surface layer was not a coating layer formed by fixing granular lumps containing a silicon compound. In the following examples and comparative examples, the surface layer containing the organosilicon polymer was also confirmed by silicon mapping.

<Production of Toner Particles (2) to (14), Toner Particles (18) to (22) and Toner Particles (27) to (30)>
The toner particles (2) to (14), the toner particles (18) to (22), and the toner particles are manufactured in the same manner as the toner 1 except that the manufacturing conditions and formulations shown in Tables 1, 2, 3, and 4 are used. (27) to (30) were obtained. Tables 5, 6, 7, and 8 show the physical properties of the obtained toner particles.
These toners were subjected to silicon mapping in TEM observation. In the toner particles (2) to (14), the toner particles (18) to (22) and the toner particles (27) to (30), it is confirmed that uniform silicon atoms are present on the surface layer, and a silicon compound is contained. It confirmed that it was not the coating layer formed by adhering the granular lump.

(Production example of toner particles (15))
In the production example of the toner particles (1), in the preparation of the aqueous dispersion medium, 24.0 parts by mass of a 1.0 mol / L aqueous HCl solution was changed to 30.0 parts by mass, and the pH of reaction 1 of the aqueous medium was set to 4.0. The pH of reaction 2 and reaction 3 was changed so that 10.0 parts by mass of 1.0 mol / L sodium hydroxide aqueous solution was 0.0 parts by mass and 4.0 parts by mass of 10% hydrochloric acid was 0.0 parts by mass. A toner particle (15) was obtained in the same manner as in the production example of the toner particle (1) except that the value was changed to 4.0. The formulation and conditions of the toner particles (15) are shown in Table 2, and the physical properties are shown in Table 6. Silicon mapping was performed in the TEM observation of the toner particles (15), and it was confirmed that uniform silicon atoms were present on the surface layer. It was confirmed that the surface layer was not a coating layer formed by fixing granular lumps containing a silicon compound.

(Production example of toner particles (16))
In the production example of the toner particles (1), in the preparation of the aqueous dispersion medium, 24.0 parts by mass of a 1.0 mol / L aqueous HCl solution was changed to 27.0 parts by mass, and the pH of the aqueous medium in Reaction 1 was changed to 4. The reaction mixture was changed to 5 by changing 10.0 parts by mass of 1.0 mol / L sodium hydroxide aqueous solution to 0.0 parts by mass, and 4.0 parts by mass of 10% hydrochloric acid to 0.0 parts by mass. A toner particle (16) was obtained in the same manner as in the production example of the toner particle (1) except that the pH of the toner was changed to 4.5. The formulation and conditions of the toner particles (16) are shown in Table 2, and the physical properties are shown in Table 6. Silicon mapping was performed in TEM observation of the toner particles (16), and it was confirmed that uniform silicon atoms were present on the surface layer. It was confirmed that the surface layer was not a coating layer formed by fixing granular lumps containing a silicon compound.

(Production example of toner particles (17))
In the production example of toner particles (1), 10.0 parts by mass of a 1.0 mol / L sodium hydroxide aqueous solution was changed to 30.0 parts by mass, the pH of reaction 1 was changed to 11.8, and reaction 2 was completed. Toner particles (17) were obtained in the same manner as in the production example of toner particles (1) except that hydrochloric acid was added later to adjust the pH to 5.1. The formulation and conditions of the toner particles (17) are shown in Table 2, and the physical properties are shown in Table 6. Silicon mapping was performed in TEM observation of the toner particles (17), and it was confirmed that uniform silicon atoms were present on the surface layer. It was confirmed that the surface layer was not a coating layer formed by fixing granular lumps containing a silicon compound.

(Production example of toner particles (23))
(Manufacture of toner base (23))
Polyester resin (1) 60.0 parts by mass Polyester resin (2) 40.0 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 parts by mass Charge control resin (1) 0.5 parts by mass Release agent 10.0 parts by mass (behenyl behenate, melting point: 72.1 ° C.)
The above materials were mixed with a Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.), then melt kneaded with a twin-screw kneading extruder at 140 ° C., the kneaded product was cooled, coarsely pulverized with a cutter mill, and a jet stream was used. The toner base (23) having a weight average particle diameter of 6.2 μm was obtained by pulverizing with a fine pulverizer and further classifying with an air classifier.

(Production of toner particles (23))
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 / L Na ₃ PO ₄ aqueous solution and 24.0 parts by mass of a 1.0 mol / L aqueous HCl solution were added. , High-speed stirring device T. K. The mixture was maintained at 60 ° C. while stirring at 13,000 rpm using a homomixer (Special Machine Industries Co., Ltd.). To this, 85 parts by mass of a 1.0 mol / L 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, the aqueous dispersion medium is changed to T.P. K. While stirring at 5,000 rpm with a homomixer (Special Machine Industries Co., Ltd.), 121.6 parts by mass of the toner base (23) and 10.0 parts by mass of vinyltriethoxysilane were added and stirred for 5 minutes.

  The mixture was then held at 65 ° C. for 4 hours. The pH was 5.1. Next, 10.0 parts by mass of a 1.0 mol / L aqueous sodium hydroxide solution 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 of 100 ° C. in the vessel 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 (23) to remove the dispersion stabilizer. After filtering, washing and drying, toner particles having a weight average particle diameter of 6.2 μm were obtained. This toner particle was designated as toner particle (23). Table 7 shows the physical properties of Toner Particles (23). Silicon mapping was performed in TEM observation of the toner particles (23), and it was confirmed that uniform silicon atoms were present on the surface layer. It was confirmed that the surface layer was not a coating layer formed by fixing granular lumps containing a silicon compound.

(Production example of toner particles (24))
Polyester resin (1) 60.0 parts by mass Polyester resin (2) 40.0 parts by mass Styrenic resin (1) 5.0 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 parts by mass Charge control resin (1) 0.5 parts by mass Vinyltriethoxysilane 10.0 parts by weight Release agent 10.0 parts by weight (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 / L Na ₃ PO ₄ aqueous solution and 24.0 parts by mass of a 1.0 mol / L aqueous HCl solution were added. , High-speed stirring device T. K. The mixture was maintained at 60 ° C. while stirring at 13,000 rpm using a homomixer (Special Machine Industries Co., Ltd.). To this, 85 parts by mass of a 1.0 mol / L 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, the aqueous dispersion medium is changed to T.W. K. While stirring at 13,000 rpm with a homomixer (Special Machine Industries Co., Ltd.), 100 parts by mass of the solution was added and stirred for 5 minutes. The mixture was then held at 65 ° C. for 4 hours. The pH was 5.1. 10.0 parts by mass of a 1.0 mol / L aqueous sodium hydroxide solution 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 (24). The distillation fraction was 320 parts by mass. Dilute hydrochloric acid was added to the container containing the polymer slurry (24) to remove the dispersion stabilizer. Further, the toner particles having a weight average particle diameter of 6.1 μm were obtained by filtration, washing and drying. These toner particles were designated as toner particles 24. Table 7 shows the physical properties of Toner Particles (24). 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 and a styrenic resin layer was present on the inner side. It was confirmed that the surface layer was not a coating layer formed by fixing granular lumps containing a silicon compound.

(Production example of toner particles (25))
(Preparation of resin particle dispersion (1))
-Polyester resin (3): 100 parts by mass-Methyl ethyl ketone: 50 parts by mass-Isopropyl alcohol: 20 parts by mass Methyl ethyl ketone and isopropyl alcohol were charged into a container. Thereafter, the resin was gradually added, stirred, and completely dissolved to obtain an amorphous polyester resin (1) solution. The container containing the amorphous polyester resin (1) solution is set at 65 ° C., and a 10% aqueous ammonia solution is gradually added dropwise to a total of 5 parts by mass with stirring, and 250 parts by mass of ion-exchanged water. The portion was gradually added dropwise at a rate of 10 mL / min to effect phase inversion emulsification. Further, the solvent was removed by reducing the pressure with an evaporator to obtain a resin particle dispersion (1) of a polyester resin (3). The resin particles had a volume average particle size of 120 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water.

(Preparation of resin particle dispersion (2))
-Polyester resin (4): 100 parts by mass-Methyl ethyl ketone: 50 parts by mass-Isopropyl alcohol: 20 parts by mass Methyl ethyl ketone and isopropyl alcohol were charged into a container. Thereafter, the above resin was gradually added, stirred, and completely dissolved to obtain a polyester resin (4) solution. The container containing the polyester resin (4) solution is set at 40 ° C., and a 10% aqueous ammonia solution is gradually added dropwise to a total of 3.5 parts by mass with stirring, and further 230 parts by mass of ion-exchanged water. Was gradually added dropwise at a rate of 10 mL / min to effect phase inversion emulsification. Further, the solvent was removed under reduced pressure to obtain a resin particle dispersion (2) of polyester resin (4). The volume average particle diameter of the resin particles was 140 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water.

(Preparation of sol-gel dispersion (1))
-Vinyl triethoxysilane 100 mass parts-Styrene 7.0 mass parts-Methyl ethyl ketone: 70 mass parts Methyl ethyl ketone and styrene were put into the container. Thereafter, vinyltriethoxysilane was gradually added and held at 80 ° C. for 1 hour with stirring. While stirring, a 10% aqueous ammonia solution was gradually added dropwise to a total of 3.5 parts by mass, the temperature was raised at a rate of temperature increase of 20 ° C./1 h, and held at 95 ° C. for 3 hours. Further, 230 parts by mass of ion-exchanged water was gradually dropped and emulsified at a rate of 10 parts by mass / min. Further, the solvent was removed under reduced pressure to obtain a sol-gel dispersion (1). The volume average particle diameter of the sol-gel particles was 180 nm. The sol-gel particle solid content was adjusted to 20% with ion-exchanged water. The sol-gel solution of the sol-gel dispersion (1) was stored at 10 ° C. or lower with stirring, and used within 24 hours after preparation. The surface of the particles is preferably in a highly viscous sol or gel state because the adhesion between the particles becomes better.

(Preparation of colorant particle dispersion (1))
-Copper phthalocyanine (Pigment Blue 15: 3): 50 parts by mass-Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts by mass-Ion-exchanged water: 190 parts by mass After being dispersed for 10 minutes by a homogenizer (Ultra Turrax manufactured by IKA), dispersion treatment was performed for 20 minutes at a pressure of 250 MPa using an ultimateizer (counter-impact type wet pulverizer: manufactured by Sugino Machine Co., Ltd.), and the volume average of the colorant particles A colorant particle dispersion (1) having a particle size of 118 nm and a solid content of 20% was obtained.

(Preparation of release agent particle dispersion)
-Olefin wax (melting point: 84 ° C): 60 parts by mass-Ionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 2.0 parts by mass-Ion exchange water: 240 parts by mass Heat and fully disperse with IKA Ultra Turrax T50, then heat to 115 ° C. with a pressure discharge type gorin homogenizer and disperse for 1 hour, release with volume average particle size 170 nm, solid content 20% An agent particle dispersion was obtained.

(Preparation of toner particles 25)
-Resin particle dispersion (1): 100 parts by mass-Resin particle dispersion (2): 300 parts by mass-Sol-gel solution of resin particle dispersion (1): 300 parts by mass-Colorant particle dispersion (1): 50 Part by mass / Partner release agent particle dispersion: 50 parts by mass After adding 2.5 parts by mass of the ionic surfactant Neogen RK to the flask, the above materials were stirred. Subsequently, 1 mol / L nitric acid aqueous solution was dropped to adjust the pH to 3.8, 0.35 parts by mass of aluminum polysulfate was added thereto, and the mixture was dispersed with IKA Ultra Turrax. The flask was heated to 50 ° C. with stirring in an oil bath for heating. After holding at 50 ° C. for 40 minutes, a mixed solution of 300 parts by mass of the sol-gel solution of the resin particle dispersion (1) was slowly added thereto. Thereafter, a 1 mol / L sodium hydroxide aqueous solution was added to bring the pH in the system to 7.0, and then the stainless steel flask was sealed, and gradually heated to 90 ° C. while stirring was continued. Held for hours. Furthermore, it hold | maintained at 95 degreeC for 7.5 hours. Thereafter, 2.0 parts by mass of the ionic surfactant Neogen RK was added and reacted at 100 ° C. for 5 hours. After completion of the reaction, 320 parts by mass of a fraction was collected at 85 ° C. by distillation under reduced pressure. Then, cooling, filtration, and drying were performed. The resultant was redispersed in 5 L of ion-exchanged water at 40 ° C., stirred with a stirring blade (300 rpm) for 15 minutes, and filtered.

  This redispersion and filtration washing were repeated, and when the electric conductivity reached 6.0 μS / cm or less, the washing was terminated to obtain toner particles (25). Table 7 shows the physical properties of Toner Particles (25). 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. It was confirmed that the surface layer was not a coating layer formed by fixing granular lumps containing a silicon compound.

(Production example of toner particles (26))
Toner base (23) While stirring 121.6 parts by mass in Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.), 10.0 parts by mass of toluene, 5.0 parts by mass of ethanol, 5.0 parts by mass of water, and vinyl. An organosilicon polymer solution obtained by reacting 10.0 parts by mass of triethoxysilane at 90 ° C. 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 Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.) with 3.5 parts by mass of the organosilicon polymer solution with respect to 100 parts by mass of the treated toner to obtain an inlet temperature of 90. The fluidized bed dryer was circulated for 30 minutes under the conditions of ℃ and outlet temperature of 45 ℃.

  Similarly, spraying and drying of the organosilicon polymer solution was repeated a total of 10 times to obtain toner particles (26). Table 7 shows the physical properties of Toner Particles (26). 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. It was confirmed that the surface layer was not a coating layer formed by fixing granular lumps containing a silicon compound.

(Production example of comparative toner particle (1))
Comparative toner particles (in the same manner as in the production example of the toner particles (13) except that 0.10000 parts by mass of the dimethyl silicone oil having a viscosity of 100 cps used in the production example of the toner particles (13) was changed to 0.00000 parts by mass. 1) was obtained. The formulation and conditions of the comparative toner particles (1) are shown in Table 4, and the physical properties are shown in Table 8. Silicon mapping was performed in the TEM observation of the comparative toner particles (1), and it was confirmed that some silicon atoms were present on the surface layer. It was confirmed that the surface layer was not a coating layer formed by fixing granular lumps containing a silicon compound.

(Production example of comparative toner particles (2) to (4))
Comparative toner particles (2) to (4) were obtained in the same manner as in the toner 1 except that the production conditions and formulations shown in Table 4 were used. Table 8 shows the physical properties of the toner particles obtained. Silicon mapping was performed in TEM observation, and it was confirmed that silicon atoms were present on the surface layer, although not uniform.

(Production example of comparative toner particles (5))
High-speed stirrer K. In a four-necked flask equipped with a homomixer (Special Kika Kogyo Co., Ltd.), 900 parts by mass of ion-exchanged water and 95 parts by mass of polyvinyl alcohol are added and heated to 55 ° C. while stirring at 1300 rpm. An aqueous dispersion medium was used.

(Composition of monomer dispersion)
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Carbon black 10.0 parts by mass Release agent (behenyl behenate, melting point: 72.1 ° C) 10.0 parts by mass After being dispersed for 3 hours by Mitsui Miike Chemical Industries, Ltd., 14.0 parts by mass of t-butyl peroxypivalate as a polymerization initiator was added to prepare a monomer dispersion.

  Next, the obtained monomer dispersion was put into the dispersion medium in the above four-necked flask and granulated for 10 minutes while maintaining the above rotation speed. Subsequently, under stirring at 50 rpm, polymerization was carried out at 55 ° C. for 1 hour, then at 65 ° C. for 4 hours, and further at 80 ° C. for 5 hours. After completion of the above polymerization, the slurry was cooled, and the dispersant was removed by repeating washing with purified water. Further, comparative black toner particles (1) serving as a base were obtained by washing and drying. The weight average particle size was 5.7 μm.

  3 parts by mass of 0.3 part by mass sodium dodecylbenzenesulfonate solution was added to a solution obtained by mixing 2 parts by mass of isoamyl acetate, 4.0 parts by mass of tetraethoxysilane as a silicon compound and 0.5 parts by mass of methyltriethoxysilane. A silane mixed solution A of isoamyl acetate, tetraethoxysilane, and methyltriethoxysilane was prepared by stirring using an ultrasonic homogenizer.

Black toner particle dispersion A was prepared by adding 1.0 part by weight of the base comparative black toner particles (1) to 30 parts by weight of a 0.3% by weight aqueous sodium dodecylbenzenesulfonate solution. Next, the silane mixed solution A was added to the black toner particle dispersion A, and then 5 parts by mass of a 30% by mass NH ₄ OH aqueous solution was added, followed by reaction at room temperature (25 ° C.) for 15 hours. The obtained reaction product was washed with ethanol and then washed with purified water, and the particles were filtered and dried to obtain comparative toner particles (5). The weight average particle diameter of the obtained toner particles was 5.9 μm. The formulation and conditions of the comparative toner particles (5) are shown in Table 4, and the physical properties are shown in Table 8. Silicon mapping was performed in the TEM observation of the comparative toner particles (5), and it was confirmed that some silicon atoms were present on the surface layer. The surface layer confirmed the coating layer formed when the granular lump containing a silicon compound adheres.

(Production example of comparative toner particle (6))
Instead of 10.0 parts by weight of vinyltriethoxysilane used in the production example of toner particles (1), 3.0 parts by weight of vinyltriethoxysilane was used, and in reaction 1, a 1.0 mol / L sodium hydroxide aqueous solution was added. In addition to 8.0 parts by mass, pH 5.1 of reaction 1 was changed to pH 7.0, 10.0 parts by mass of 1.0 mol / L sodium hydroxide aqueous solution was changed to 0.0 parts by mass, and pH 8.0 was changed to 7.0, 90 ° C of reaction 2 was changed to 70 ° C, 100 ° C of reaction 3 was changed to 70 ° C, and 4.0 parts by mass of 10% hydrochloric acid added before reaction 3 Comparative toner particles (6) were obtained in the same manner as in the production example of the toner particles (1) except that was changed to 2.0 parts by mass. The formulation and conditions of the comparative toner particles (6) are shown in Table 4, and the physical properties are shown in Table 8.

(Production example of comparative toner particles (7))
(Production example of comparative intermediate polyester (1))
-Bisphenol A ethylene oxide 2 mol adduct 680 parts by mass-Bisphenol A propylene oxide 2 mol adduct 80 parts by mass-Terephthalic acid 280 parts by mass-Trimellitic anhydride 20 parts by mass-Dibutyltin oxide 2.5 parts by mass A reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe was reacted at normal pressure and 230 ° C. for 8 hours, and further reacted under reduced pressure of 10 to 15 mmHg for 5 hours to produce a comparative intermediate polyester ( 1) was obtained.

  The comparative intermediate polyester (1) had a number average molecular weight of 2150, a weight average molecular weight of 9550, Tg of 54 ° C., an acid value of 0.4 mgKOH / g, and a hydroxyl value of 45 mgKOH / g.

(Production example of comparative prepolymer (1))
-Comparative intermediate polyester (1) 410 parts by mass-Isophorone diisocyanate 90 parts by mass-Ethyl acetate 500 parts by mass The above materials are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C for 5 hours. As a result, a comparative prepolymer (1) was obtained. The weight percent free isocyanate of the comparative prepolymer (1) was 1.20%.

(Production example of comparative polyester (1))
-220 parts by mass of bisphenol A ethylene oxide 2-mole adduct-560 parts by mass of bisphenol A propylene oxide 3-mole adduct-220 parts by mass of terephthalic acid-50 parts by mass of adipic acid-2.5 parts by mass of dibutyltin oxide The mixture was placed in a reaction vessel equipped with a stirrer and a nitrogen introduction tube, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at 5 hours under reduced pressure of 10 to 15 mmHg. Thereafter, 45 parts by mass of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain a comparative polyester (1). Comparative polyester (1) had a weight average molecular weight of 3700, Tg of 42 ° C., and an acid value of 24 mgKOH / g.

(Production example of comparative masterbatch (1))
・ C. I. Pigment Blue 15: 3 40 parts by mass, polyester resin (1) 60 parts by mass, water 30 parts by mass The above materials are mixed with a Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.), and the pigment aggregate is soaked with water. Got. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., and pulverized to a mean particle size of 1 mm with a pulverizer, to obtain a comparative master batch 1.

(Production example 1 of comparative vinyl copolymer resin particles (1))
-Sodium dodecyl sulfate 2.0 mass part-Ion exchange water 500 mass part The said material was put into the reaction container with a cooling tube, a stirrer, and a nitrogen introduction tube, and it heated at 80 degreeC. Thereafter, 2.5 parts by mass of potassium persulfate dissolved in 100 parts by mass of ion-exchanged water was added, and 15 minutes later, 60 parts by mass of styrene, 20 parts by mass of butyl acrylate, 20 parts by mass of methacrylic acid, p-styryl. A mixed solution of 100 parts by mass of trimethoxysilane and 3.5 parts by mass of n-octyl mercaptan was added dropwise over 90 minutes, and the mixture was kept at 80 ° C. for 60 minutes. Then, it was cooled to 30 ° C. to obtain a dispersion of comparative vinyl copolymer resin particles 1. The average particle size of the comparative vinyl copolymer resin particles 1 was 55 nm. The solid had a number average molecular weight of 10,300, a weight average molecular weight of 16,200, and a Tg of 59 ° C.

(Production example of comparative toner particle (7))
-Comparative polyester (1) 540 parts by mass-Paraffin wax (1) (melting point: 75.0 ° C) 80 parts by mass-Ethyl acetate 1 450 parts by mass The above materials are placed in a container equipped with a stir bar and a thermometer and stirred. The temperature was raised to 80 ° C., held at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of comparative masterbatch (1) and 100 parts by mass of ethyl acetate were charged in a container and mixed for 1 hour to obtain a comparative raw material solution (1).

  1500 parts by mass of the comparative raw material solution (1) was transferred to a container, and using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feed speed was 1 kg / hour, the disk peripheral speed was 7 m / second, and the particle diameter was 0.5 mm. 80% by volume of zirconia beads were filled and circulated three times under the above conditions. Next, 650 parts by mass of a 65% by mass ethyl acetate solution of comparative polyester (1) was added and circulated once in the bead mill under the above conditions to obtain a comparative pigment / wax dispersion (1). The comparative pigment / wax dispersion (1) was prepared by adding ethyl acetate so that the solid content concentration (measurement conditions: 130 ° C., 30 minutes) was 50% by mass.

  970 parts by weight of ion-exchanged water, 40 parts by weight of a 25% by weight aqueous dispersion of resin fine particles for dispersion stabilization (styrene copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate), dodecyl 150 mass parts of 50.0 mass% aqueous solution of diphenyl ether disulfonate sodium MON-7 (manufactured by Sanyo Chemical Industries) and 100 mass parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This is referred to as a comparative aqueous phase (1).

  Comparative pigment / wax dispersion (1) 980 parts by mass, as amines, 2.5 parts by mass of isophorone diamine K. After mixing for 3 minutes at 7000 rpm using a homomixer (Special Machine Industries Co., Ltd.), 90 parts by mass of the comparative prepolymer (1) was added. K. The mixture was mixed at 7000 rpm for 3 minutes using a homomixer (Special Machine Industries Co., Ltd.). Further, 1200 parts of comparative aqueous phase (1) was added. K. Using a homomixer (Special Machine Industries Co., Ltd.), mixing was performed at 12000 rpm for 15 minutes to obtain a comparative emulsified slurry (1).

  The comparative emulsified slurry (1) was put into a container in which a stirrer and a thermometer were set, and the solvent was removed at 30 ° C. for 8 hours to obtain a comparative dispersed slurry (1).

  A dispersion of comparative vinyl copolymer resin particles (1) was added to the comparative dispersion slurry (1) so that the solid content ratio was 1: 0.12, and the mixture was heated to 75 ° C. over 30 minutes. A solution prepared by dissolving 100 parts of magnesium chloride hexahydrate in 100 parts by mass of ion-exchanged water was kept at 70 ° C. while adding little by little. After 4 hours, an aqueous hydrochloric acid solution was added to adjust the pH to 5, followed by heating to 80 ° C. After 2 hours, it was cooled to obtain a comparative dispersion slurry (1). After filtering, washing and drying, toner particles having a weight average particle diameter of 5.9 μm were obtained. This toner particle was used as comparative toner particle (7).

  The formulation and conditions of the comparative toner particles (7) are shown in Table 4, and the physical properties are shown in Table 8. Silicon mapping was performed in the TEM observation of the comparative toner particles (7), and it was confirmed that some silicon atoms were present on the surface layer. A coating layer formed of granular lumps containing a silicon compound was confirmed on the surface layer.

(Production example of comparative toner particles (8))
Instead of 100.0 parts by mass of vinyltriethoxysilane used in the preparation example of toner particles (25) (preparation of sol-gel solution of resin particle dispersion (1)), 3.0 parts by mass of octamethylsilsesquioxane ( Comparative toner particles (8) were obtained in the same manner as in the production example of toner particles (25) except that the product was changed to PPS-octamethyl substituted product (manufactured by Sigma-Aldrich). The formulation and conditions of the comparative toner particles (8) are shown in Table 4, and the physical properties are shown in Table 8. Silicon mapping was performed in TEM observation of the comparative toner particles (8), and it was confirmed that a few silicon atoms were present on the surface layer.

(Production example of comparative toner particle (9))
Instead of 100.0 parts by mass of vinyltriethoxysilane used in the preparation of toner particles (25) (preparation of sol-gel solution of resin particle dispersion (1)), 3.0 parts by mass of octavinylsilsesquioxane ( A comparative toner particle (9) was obtained in the same manner as in the production example of the toner particle (25) except that the product was changed to PPS-octavinyl substituted product manufactured by Sigma-Aldrich. The formulation and conditions of the comparative toner particles (9) are shown in Table 4, and the physical properties are shown in Table 8. Silicon mapping was performed by TEM observation of the comparative toner particles (9), and it was confirmed that a few silicon atoms were present on the surface layer. A coating layer formed of granular lumps containing a silicon compound was confirmed on the surface layer.

(Production example of comparative toner particles (10))
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 700 parts by mass of ion-exchanged water, 1000 parts by mass of a 0.1 mol / L Na ₃ PO ₄ aqueous solution, and 1.0 mol / L HCl. 24.0 parts by mass of an aqueous solution was added, and a high-speed stirring device T.I. K. The mixture was maintained at 60 ° C. while stirring at 13,000 rpm using a homomixer (Special Machine Industries Co., Ltd.). To this, 85 parts by mass of a 1.0 mol / L 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 .

Styrene 69.0 parts by mass n-butyl acrylate 31.0 parts by mass 1,6-hexanediol diacrylate 0.1 parts by mass Copper phthalocyanine pigment 6.5 parts by mass (Pigment Blue 15: 3) B.15: 3)
-Polyester resin (1) 5.0 parts by mass-Charge control resin (1) 0.5 parts by mass-Release agent 10.0 parts by mass (behenyl behenate, melting point: 72.1 ° C)
The polymerizable monomer composition (C10) obtained by dispersing the above material with an attritor (manufactured by Mitsui Miike Chemical Industries, Ltd.) for 3 hours was held at 60 ° C. for 20 minutes. Thereafter, the polymerizable monomer composition C10 obtained by adding 16.0 parts by mass of t-butylperoxypivalate as a polymerization initiator (toluene solution 50%) to the polymerizable monomer composition (C10) was added to the aqueous system. The mixture was put into the medium and granulated for 10 minutes while maintaining the rotation speed of the high-speed stirring device at 13,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was carried out for 4 hours while slowly stirring. At this time, the pH of the aqueous medium was 5.1. Next, 10.0 parts by mass of 1.0 mol / L sodium hydroxide aqueous solution 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 container of 100 ° C. was performed for 5 hours to obtain a polymer slurry C10. The distillation fraction was 300 parts by mass. Dilute hydrochloric acid was added to the container containing the polymer slurry (C10) after cooling to 30 ° C. to remove the dispersion stabilizer. Further, filtration, washing and drying were performed to obtain particles (C10) having a weight average particle diameter of 5.8 μm. The particles (C10) are referred to as comparative toner particles (10). Table 4 shows the formulation and conditions of the comparative toner particles (10). Silicon mapping was performed in TEM observation of the comparative toner particles (10), and it was confirmed that a few silicon atoms were present on the surface layer.

(Production example of toner (1))
Toner particles (1) Hydrophobic surface having a specific surface area of 180 m ² / g by BET method with respect to 100 parts by mass of the toner particles, and having the surface hydrophobized with 3.0% by mass of hexamethyldisilazane and 3% by mass of 100 cps silicone oil Mitsui Henschel Mixer (Mitsui Miike Chemical Co., Ltd.) with 0.2 mass parts of silica and 0.25 mass parts of aluminum oxide with a specific surface area of 50 m ² / g by BET method Toner (1) is obtained by mixing for 3 minutes. The physical properties are shown in Tables 5 and 9.

(Production example of toners (2) to (31))
Toners (2) to (31) were obtained in the same manner as in the production example of toner (1) except that toner particles (1) were changed to toner particles (2) to (31) in the toner (1) production example. . The physical properties are shown in Tables 5-7 and Tables 9-11.

(Production example of comparative toners (1) to (9))
Comparative toners (1) to (9) were prepared in the same manner as in the toner (1) production example except that the toner particles (1) were changed to comparative toner particles (1) to (9) in the toner (1) production example. Obtained. The physical properties are shown in Table 8.

(Production example of comparative toner (10))
Comparative toner particles (10) have a specific surface area of 180 m ² / g based on BET method with respect to 100 parts by mass of the toner, and the surface was hydrophobized with 3.0% by mass of hexamethyldisilazane and 3% by mass of 100 cps silicone oil. Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.) with 2.2 parts by weight of hydrophobic silica and 0.25 parts by weight of aluminum oxide having a specific surface area of 50 m ² / g by BET method A toner obtained by mixing for 10 minutes using a machine manufactured by Kikai Co., Ltd. is referred to as a comparative toner (10). The physical properties are shown in Tables 8 and 12. Silicon mapping was performed in TEM observation of the comparative toner particles (10), and it was confirmed that granular inorganic fine particles containing a silicon compound were embedded in the toner surface.

<Example 1>
The following evaluation was performed using the toner (1). The evaluation results are shown in Table 13.

(Evaluation of environmental stability and development durability)
A toner cartridge of a tandem Canon laser beam printer LBP9660Ci having the configuration as shown in FIG. 4 was charged with 245 g of toner (1). Then, the toner cartridge was left for 24 hours in each environment of low temperature and low humidity L / L (temperature 5.0 ° C./humidity 10% RH) and high temperature high humidity H / H (30.0 ° C./85% RH). A toner cartridge left for 24 hours under each environment is attached to the LBP9660Ci, and an image with a printing ratio of 1.0% is printed out to 20,000 sheets in the A4 paper lateral direction. The solid image density (toner applied amount 0.40 mg / cm ² ), fogging, and member contamination (filming, development streaks, drum fusion) at the time of output of 20,000 sheets were evaluated. Endurance was performed with intermittent endurance for 1 second each time two sheets were output.

(Measurement of toner particles and toner triboelectric charge)
The toner particles and the triboelectric charge amount of the toner were determined by the following method.

  First, toner particles or toner and a standard carrier for negatively charged polarity toner (trade name: N-01, manufactured by Japan Imaging Society) were each left for a predetermined time in the following environment.

  It was allowed to stand for 24 hours at low humidity (5.0 ° C./10% RH) and for 24 hours at high temperature and high humidity (30.0 ° C./85% RH). After the standing, the toner particles or the toner and the standard carrier were mixed for 60 seconds using a turbula mixer in each environment so that the mass of the toner particles or toner was 5% by mass to obtain a two-component developer.

  Next, the mixed two-component developer is mixed in a metal container having a conductive screen having an opening of 20 μm at the bottom in an environment of normal temperature and normal humidity (25 ° C./50% RH) within 1 minute after mixing. The sample was sucked with a suction machine, and the mass difference before and after suction and the potential accumulated in the capacitor connected to the container were measured. At this time, the suction pressure was 4.0 kPa. From the mass difference before and after the suction, the stored potential, and the capacity of the capacitor, the triboelectric charge amount of the toner particles or toner was calculated using the following formula.

The standard carrier for negatively charged polarity toner (trade name: N-01, manufactured by the Japan Imaging Society) used for the measurement was one that passed through 250 mesh.
Q = (A × B) / (W1-W2)
Q (mC / kg): Toner particle or toner triboelectric charge amount A (μF): Capacitor capacity B (V): Potential difference accumulated in the capacitor W1-W2 (kg): Mass difference before and after suction

(Evaluation of image density)
For image density, using a Macbeth densitometer (trade name: RD-914, manufactured by Macbeth) equipped with an SPI auxiliary filter, the low temperature and low humidity (L / L) (5.0 ° C./10% RH), The image density of the fixed image portion of the solid image that was output in an environment of high temperature and high humidity (H / H) (30.0 ° C./85% RH) at the initial stage and after the endurance output of 20,000 sheets was measured.

The image density evaluation criteria are as follows. The transfer paper was A4 size of 70 g / m ² and printed in the A4 horizontal direction.
A: 1.45 or more B: 1.40 or more and less than 1.45 C: 1.30 or more and less than 1.40 D: 1.25 or more and less than 1.30 E: 1.20 or more and less than 1.25 F: 1. Less than 20

(Evaluation of fogging)
In the initial 0% print ratio image and 0% print ratio image after 20,000 sheets endurance output, the white color of the white portion of the output image measured by “Reflectometer” (manufactured by Tokyo Denshoku) The fog density (%) was calculated from the difference between the brightness and the whiteness of the transfer paper. The fog density was evaluated as image fog according to the following criteria. The transfer paper was A4 size of 110 g / m ² and printed in the A4 horizontal direction.
A: Less than 1.0% B: 1.0% or more and less than 1.5% C: 1.5% or more and less than 2.0% D: 2.0% or more and less than 2.5% E: 2.5% or more Less than 3.0% F: 3.0% or more

(Parts contamination assessment)
After the endurance output of 20,000 sheets, the first half portion is output as a halftone image (toner applied amount 0.25 mg / cm ² ) and the second half portion is a solid image (toner applied amount 0.40 mg / cm ² ). A mixed image was output and evaluated according to the following criteria. The transfer paper was A4 size of 70 g / m ² and printed in the A4 horizontal direction.
A: Neither vertical stripes in the paper discharge direction nor small points with different densities are seen on the developing roller or on the halftone and solid images.
B: Although there are 1 to 2 circumferential thin stripes on both ends of the developing roller or 1 to 3 fusions on the photosensitive drum, the discharge direction is on the halftone and solid images. There are no vertical streaks or spots with different diameters of 5 mm or less.
C: There are 3 or more and 5 or less narrow streaks in the circumferential direction at both ends of the developing roller, or 3 or more and 5 or less fused material on the photosensitive drum, but in the discharge direction on the image of the halftone portion or the solid portion. There are only a few vertical streaks and points with a diameter of 5 mm or less with different concentrations. However, it can be erased by image processing.
D: There are 6 to 20 circumferential thin stripes on both ends of the developing roller or 6 to 20 fusions on the photosensitive drum, and fine stripes on the halftone and solid images. Several dots and points with a diameter of 5 mm or less with different concentrations can be seen. It cannot be erased even with image processing.
E: There are 21 or more streaks and spots with different densities of 5 mm or less on the image on the developing roller and the halftone portion, which cannot be erased even by image processing.

(Evaluation of low temperature fixability (low temperature offset end temperature))
The fixing unit of the Canon laser beam printer LBP9660Ci was modified so that the process speed could be adjusted. Using this modified LBP9660Ci, an unfixed toner image having a toner loading of 0.40 mg / cm ² is heated and pressed oillessly on the image receiving paper at a process speed of 300 mm / sec, and the fixed image is applied to the image receiving paper. Formed.

Fixability is determined by using Kimwipe (trade name: S-200, Crecia Co., Ltd.), rubbing the fixed image 10 times with a load of 75 g / cm ² , and a temperature at which the density reduction rate before and after rubbing is less than 5%. It was set as the low temperature offset end temperature. Evaluation was carried out at room temperature and normal humidity (25 ° C./50% RH).

(Evaluation of storage stability)
(Evaluation of storage stability)
10 g of toner was put in a 100 mL glass bottle, and left for 3 days at a temperature of 50 ° C. and a humidity of 25%, and then judged visually.
A: No change B: There are aggregates, but they are loosened immediately C: Aggregates that are difficult to loosen are generated D: No fluidity E: Obvious caking occurs

(Evaluation of long-term storage)
10 g of toner was put into a 100 mL glass bottle, and left for 1 week at a temperature of 45 ° C. and a humidity of 97%, and then judged visually.
A: No change B: There are aggregates, but they are loosened immediately C: Aggregates that are difficult to loosen are generated D: No fluidity E: Obvious caking occurs

(Evaluation of transcription latitude)
The laser beam printer LBP9660Ci manufactured by Canon was modified so that the voltage difference (hereinafter also referred to as transfer bias) between the photoconductor and the transfer roller could be adjusted.

The initial or end-of-life toner cartridge was left for 24 hours in the environment of the measurement object. As the transfer paper, 90 g / m ² paper was used. A voltage was applied between the photoreceptor and the transfer roller (hereinafter also referred to as transfer bias). A voltage was applied every 100 V so that the transfer roller was changed from +100 V to +1000 V with respect to the photosensitive member, and the transfer efficiency with respect to the transfer bias was measured. Transferability and solid image DrrM the weight per unit area of the transfer residual toner on the photosensitive member (the toner amount ^{0.40mg / cm 2) (mg /} cm 2), the unit area of the toner transferred onto the transfer material The hit weight is TrM (mg / cm ² ). The sum of DrrM and TrM represents the amount of toner on the solid black photoconductor. The transfer efficiency Tr (%) was determined as follows.
Tr = DrrM / (DrrM + TrM) × 100

A voltage range in which a transfer efficiency of 95% or more was obtained was defined as a transfer latitude. The width TrV of the transfer voltage value at that time was evaluated as follows.
A: 700V or more B: 600V or more and less than 700V C: 500V or more and less than 600V D: 400V or more and less than 500V E: Less than 400V

<Examples 2 to 30>
The same evaluation as in Example 1 was performed except that the toner (1) in Example 1 was changed to toners (2) to (30). The results are shown in Tables 13-15.

<Comparative Examples 1-10>
The same evaluation as in Example 1 was performed except that the toner (1) of Example 1 was changed to comparative toners (1) to (10). The results are shown in Table 16.

<Example 31>
The same evaluation as in Example 1 was performed except that the toner (1) of Example 1 was changed to toner particles (1). The results are shown in Table 15. The evaluation results of toner (1) and toner particles (1) were inferior.

<Example 32>
The same evaluation as in Example 1 was performed except that the toner (1) in Example 1 was changed to the toner (31). The results are shown in Table 15.

<Example 33>
A toner cartridge of a tandem Canon laser beam printer LBP9660Ci having a configuration as shown in FIG. 4 was used, and 245 g of toner (1) (cyan) was loaded. Similarly, 245 g of toner (27) (black), toner (29) (magenta), and toner (30) (yellow) were filled in each LBP9660Ci toner cartridge. The cartridge sets of the four colors were left for 24 hours in respective environments of low temperature and low humidity L / L (5.0 ° C./10% RH) and high temperature and high humidity H / H (30.0 ° C./85% RH). Cyan, black, magenta, and yellow cartridges are set in LBP9660Ci after being left for 24 hours in each environment, and an image with a printing ratio of 1.0% is printed out to 20,000 sheets in the A4 paper lateral direction, The solid image density and fog at the time of outputting 20,000 sheets, and the contamination of the member at the time of outputting 20,000 sheets (filming, development streaks, fusion of toner to the photosensitive drum) were evaluated. Endurance was performed with intermittent endurance for 1 second each time two sheets were output. As a result, there were no practical problems and good results were obtained.

  DESCRIPTION OF SYMBOLS 1 Photoconductor, 2 Developing roller, 3 Toner supply roller, 4 Toner, 5 Regulating blade, 6 Developing device, 7 Laser beam, 8 Charging device, 9 Cleaning device, 10 Cleaning charging device, 11 Stirring blade, 12 Driving roller, 13 Transfer Roller, 14 Bias Power Supply, 15 Tension Roller, 16 Transfer Conveyor Belt, 17 Driven Roller, 18 Paper, 19 Paper Feed Roller, 20 Adsorption Roller, 21 Fixing Device

Claims (7)

A toner having toner particles having a surface layer containing an organosilicon polymer and having silicone oil on the surface;
The organosilicon polymer is a polymer having a vinyl polymer part and a siloxane polymer part, and having a partial structure represented by the following formulas (T3a), (T3b) and (T3c),
In the measurement of ²⁹ Si-NMR using the toner A as a sample when the particles obtained by washing the toner with a water washing method are used as toner A,
The ratio [SAT3] of the peak area of the partial structure represented by the following formulas (T3a), (T3b) and (T3c) and the ratio [SAMe2D2] of the peak area of the partial structure represented by the following formula (Me2D2) are:
0.001 ≦ ([SAMe2D2] / [SAT3]) × 100 ≦ 10.000
A toner characterized by satisfying the following relationship:

(L ¹ in formula (T3b) represents a hydrocarbon group, L ² in formula (T3c) represents COOC _n H _2n (n is an integer from 1 to 10), L ³ represents hydrogen or a methyl group. Represents.)

When the toner Ah is a particle obtained by washing the toner A with hexane, the SiO ₂ amount MA (mass%) of the toner A and the SiO ₂ amount MAh (mass%) of the toner Ah are measured by fluorescent X-ray analysis. The toner according to claim 1, wherein the relationship of 0.00010 ≦ (MA−MAh) /MA≦5.000. In the ²⁹ Si-NMR measurement using the tetrahydrofuran (THF) insoluble matter of the toner Ah as a sample,
The ratio [SAhtT3] of the partial area represented by the formulas (T3a), (T3b), and (T3c) to the total peak area [SAhtX] of the organosilicon polymer of the THF-insoluble portion of the toner Ah is [ The toner according to claim 2, satisfying a relationship of SAhtT3] ≧ 0.20. A 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 of THF-insoluble matter in ²⁹ Si-NMR measurement using the THF-insoluble matter of toner Ah as a sample 4. The toner according to claim 2, wherein a ratio [SAhtX2] of a peak area (hereinafter also referred to as an X2 structure) satisfies a relationship of 0.50> [SAhtX2] ≧ 0.00.

(R ^g and R ^{h in} formula (X2) are each independently an organic group, a halogen atom, a hydroxy group, or an alkoxy group.) The toner according to claim 1, wherein the silicone oil has a viscosity at 25 ° C. of 1 mm ² / s to 10,000 mm ² / s.   Average thickness Dav. Of the surface layer of toner particles containing an organosilicon polymer. The toner according to claim 1, wherein the toner is 2.5 nm or more and 150.0 nm or less.   The toner according to claim 1, wherein the relationship between the Si strength G of the toner and the Si strength GA of the toner A is 80.00 ≦ (GA / G) × 100 ≦ 100.00.

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