JP6366381B2 - Toner production method - Google Patents

Description

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

  In recent years, 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.

  Further, when used in offices where many copies or prints are made, high durability without deterioration in image quality is required even with a large number of copies or prints. On the other hand, for use in small offices and homes, there is a demand for downsizing of the 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, long-term storage and transferability.

  In the case of full color in particular, 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 reproduction is inferior and color unevenness occurs. A pigment or dye used as a toner colorant is deposited on the surface of the toner, so that the influence on development is increased. Further, in a full-color image, fixability and color mixing at the time of fixing are important. In order to achieve the required high speed, a binder resin suitable for low-temperature fixability is selected, but the influence on the developability and durability of the binder resin is also great. Furthermore, there is a demand for means for outputting a high-definition full-color image that can be used for a long period of time in various environments having different temperatures and humidity. One of the effects is a change in toner charge amount and a change in toner surface property due to the effects of temperature and humidity. Therefore, development of a toner having stable chargeability even when stored for a long time in a wide range of environments is demanded.

  One of the causes of fluctuations in storage stability and charge amount of toner due to temperature and humidity is a phenomenon in which the toner release agent and resin component ooze out from the inside of the toner (hereinafter this phenomenon is called bleed). And the surface property of the toner is changed.

  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 printing or in a high temperature and high humidity environment. However, even if the inorganic fine particles are strongly fixed to the toner particles, the generation of bleeding due to the release agent or the resin component from the gaps between the inorganic fine particles, or the durability and member contamination in the harsh environment due to the release of the inorganic fine particles due to durability deterioration On the other hand, further improvements are needed.

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

  Furthermore, Patent Document 3 discloses a polymerized toner that covers the toner surface with silane as a means for controlling the charge amount of the toner and forming a high-quality printed image regardless of the temperature and humidity environment. Yes. However, the polarity of the organic functional group is large, the amount of silane compound deposited on the toner surface and hydrolysis polycondensation are insufficient, and image density changes due to changes in chargeability under high temperature and high humidity, and contamination of parts due to toner fusion Further improvement is necessary for the occurrence of odor and storage stability.

  Furthermore, in Patent Document 4, as a toner for improving fluidity, release of fluidizing agent, low-temperature fixability, and anti-blocking property, polymerization having a coating layer formed by adhering granular lumps containing a silicon compound. Toner is disclosed. However, there is a need for further improvement against the occurrence of bleeding in which the release agent and the resin component ooze out from the gaps between the particle blocks containing the silicon compound. In addition, the amount of silane compound deposited on the toner surface and the change in image density due to the change in chargeability under high temperature and high humidity caused by insufficient hydrolysis polycondensation, toner fusing and granular lump containing silicon compound There is a need for further improvements in the occurrence of component contamination and storage stability due to separation.

  Further, in Patent Document 5, an outer shell layer made of a silicon compound is formed on the surface of the toner base particles in order to suppress image quality deterioration due to changes in the toner surface characteristics due to detachment or embedding of the particles attached due to external stress. A directly formed toner is disclosed. However, the amount of silane compound deposited on the toner surface and hydrolytic polycondensation are insufficient, and this prevents changes in image density due to changes in chargeability under high temperature and high humidity, as well as the occurrence of component contamination due to toner fusing and storage stability. Further improvements are needed.

JP 2006-146056 A Japanese Patent Laid-Open No. 03-089361 Japanese Patent Laid-Open No. 08-095284 JP 2001-75304 A JP2013-120251A

  The present invention provides a toner and a method for producing the toner that solve the above problems. More specifically, the object is to provide a toner excellent in environmental stability, storage stability, low-temperature fixability, and transferability.

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

That is, the present invention comprises a surface layer containing an organosilicon polymer that is a polymer of an organosilicon compound ,
A binder resin, a pigment and a pigment dispersant ;
What manufacturing method der toner having toner particles having,
The manufacturing method comprises:
A polymerizable monomer constituting the binder resin,
The pigment,
The pigment dispersant, and
The organosilicon compound
A step of producing the toner particles by granulating a polymerizable monomer composition containing an aqueous medium and polymerizing the polymerizable monomer;
Organosilicon polymer has a unit represented by the following formula (1),

（式（１）中、Ｒは、炭素数６以下の炭化水素基、又はアリール基である。）

(In the formula (1), R is more than 6 hydrocarbon group having a carbon also is an aryl group.)

The pigment dispersant is
An adsorbing component adsorbing to the pigment;
A polymer component having affinity for the binder resin and the polymerizable monomer, and
Connecting portion for binding the polymer component and the adsorbing component
Consists of
In the measurement using X-ray photoelectron spectroscopy (ESCA) on the surface of the toner particles, the silicon element concentration dSi is 0 with respect to the total concentration (dC + dO + dSi) of the carbon element concentration dC, oxygen element concentration dO and silicon element concentration dSi on the toner surface. .5 atomic% or more,
The pigment dispersant SP value difference between the binder resin is not more ± 2.0 following a method for producing a toner, wherein the adsorption rate to the pigment is 30% or more.

  According to the present invention, a toner having excellent environmental stability, storage stability, low-temperature fixability, and transferability can be provided.

It is a figure which shows an example of the cross-sectional image of the toner of this invention observed by TEM. 3 is a chart measured by ²⁹ Si-NMR of the toner particles of the present invention. a. D. From the measurement result b. It is a synthetic peak difference obtained by subtracting a synthetic peak. b. Is a synthetic peak obtained by synthesizing split peaks. c. Is a divided peak obtained by dividing the synthetic peak. d. Is the peak of the measurement result. It is a figure which shows the reversing heat flow curve measured by the differential scanning calorimeter (DSC) 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.

  The present invention is a toner having a surface layer containing an organosilicon polymer and toner particles having a binder resin, a pigment, and a pigment dispersant, and the organosilicon polymer has a unit represented by the following formula (1). And

（式（１）中、Ｒは、炭素数６以下の炭化水素基、又はアリール基である。）

(In the formula (1), R is more than 6 hydrocarbon group having a carbon also is an aryl group.)

  In the measurement using the X-ray photoelectron spectroscopic analysis (ESCA) of the toner particle surface, the silicon element concentration dSi with respect to the total concentration (dC + dO + dSi) of the carbon element concentration dC, oxygen element concentration dO, and silicon element concentration dSi on the toner surface is It is 0.5 atomic% or more.

  ESCA performs elemental analysis of the outermost surface of several nm, and the surface energy of the outermost layer can be reduced when the concentration of silicon element is 0.5 atomic% or more in the outermost layer of the toner particles. By adjusting the concentration of the silicon element to 0.5 atomic% or more, the fluidity is further improved, and the generation of fog can be further suppressed. The concentration of silicon element in the outermost layer of the toner particles can be controlled by the reaction temperature, reaction time, reaction solvent and pH. Moreover, it can control by the quantity of an organosilicon polymer. In the present invention, the outermost layer portion is 0.0 nm or more and 10.0 nm or less from the toner surface toward the center of the toner.

  An SP value difference between the pigment dispersant and the binder resin is ± 2.0 or less, and an adsorption rate to the pigment is 30% or more. In addition, the pigment dispersant is an azo compound, which binds the adsorbing component having an adsorptive property to the pigment, the polymer component having an affinity to the binder resin and the dispersion medium, and the polymer component and the adsorbing component. It is characterized by comprising a connecting part.

  By setting the adsorption rate of the pigment dispersant in the above range, the pigment can be covered with the pigment dispersant, and the influence on the toner charging property due to the polarity of the pigment itself can be reduced. Further, by setting the SP value in the above range, the polymer chain of the pigment dispersant adsorbed on the pigment exists in an extended state in the binder resin. This prevents the pigment from aggregating due to steric hindrance and allows the pigment to be uniformly dispersed in the binder resin, and the effect of the extended polymer chain increases the toner leakage effect, resulting in good chargeability and transferability. Turn into. Furthermore, by covering the surface of the pigment with a pigment dispersant and dispersing it in the binder resin, precipitation of the pigment near the surface layer can be suppressed, and the surface layer containing the organosilicon polymer can be made stronger. Surface layer can be formed, and harsh environmental stability, long-term storage and development durability are improved. In the present invention, the binder resin is a resin existing within 300 nm from the surface layer of the toner particles. The above effect can be obtained by uniformly dispersing the pigment in the resin present in this region. In the present invention, a plurality of resins can be used as the binder resin. In that case, the effect of the present invention can be obtained by setting the difference between the SP value of each resin used as the binder resin and the SP value of the pigment dispersant to ± 2.0 or less.

  The adsorption rate of the pigment dispersant to the pigment can be controlled within the above range by appropriately selecting the structure of the azo skeleton portion of the pigment dispersant.

Furthermore, in the measurement of ²⁹ Si-NMR of the THF-insoluble matter of the toner particles, the ratio ST3 of the peak area attributed to the structure of the formula (1) to the total peak area of the organosilicon polymer is expressed by the following formula (a ), The hydrophobicity can be improved, and a toner having excellent environmental stability can be obtained.
ST3 ≧ 0.40 (a)

In the ²⁹ Si-NMR measurement of the THF-insoluble matter in the toner particles, the ratio ST3 of the peak area attributed to the structure of the formula (1) to the total peak area of the organosilicon polymer satisfies the formula (a). Thus, the surface free energy on the toner surface can be lowered, and therefore, there are excellent effects on environmental stability and member contamination. Further, due to the durability of the structure of the polymer of the formula (1) and the hydrophobicity and chargeability of R in the formula (1), a low molecular weight (Mw 1000 or less) resin, low Tg (40 ° C or lower) Resin and release agent bleed is suppressed, toner agitation is improved, and toner with excellent environmental stability and development durability at the time of high printing rate durability with a printing rate of 30% or more in particular. Can be obtained. Furthermore, in order to improve the low-temperature fixability, the storage stability can be ensured even with a toner having a lowered glass transition point, and a toner having both low-temperature fixability and storage stability can be obtained.

  The peak area of ST3 can be controlled by the monomer species, reaction temperature, reaction time, reaction solvent and pH.

In the present invention, the structure of (SX3) in which the number of O _1/2 bonded to silicon with respect to the total peak area of the organosilicon polymer is 3.0 in the ²⁹ Si-NMR measurement of the THF-insoluble matter of the toner particles The relationship between the ratio S (SX3) / S (SX2) of the peak area S (SX3) and the ratio of the peak area S (SX2) of the (SX2) structure in which the number of O _1/2 bonded to silicon is 2.0. ) ≧ 1.00 (b)
It is preferable to satisfy.

（式（ＳＸ３）中のＲｆはケイ素に結合している有機基、ハロゲン原子、ヒドロキシ基またはアルコキシ基）

(Rf in Formula (SX3) is an organic group, halogen atom, hydroxy group or alkoxy group bonded to silicon)

（式（ＳＸ２）中のＲｇ、Ｒｈはケイ素に結合している有機基、ハロゲン原子、ヒドロキシ基またはアルコキシ基）

(Rg and Rh in the formula (SX2) are organic groups, halogen atoms, hydroxy groups or alkoxy groups bonded to silicon)

  By satisfying the formula (b), the mechanical strength is higher when the formula (1) is contained and the three cross-linking components are two or more cross-linking components, and the bleed component of the inner components is suppressed from the surface layer, and the harsh environment stability Excellent long-term storage and development durability. Moreover, since the chargeability of the organosilicon compound itself is improved, it is excellent in fog in a wide range of environments.

  Further, in the cross-sectional observation of the toner particles using a transmission electron microscope (TEM) in the cross-sectional observation of the toner particles, the average thickness Dav. Is 2.5 nm or more, the bleeding of the internal release agent and resin component can be suppressed more than the surface layer. Thereby, preservation stability, environment. A toner having excellent stability and development durability can be obtained. The average thickness Dav. Of the surface layer of the toner particles containing the organosilicon polymer. Is less than 2.5 nm, the resin component and the release agent in the toner tend to bleed. For this reason, the surface property of the toner changes, and the harsh environmental stability and development durability tend to be deteriorated. Average thickness of surface layer containing organosilicon polymer of toner particles Dav. However, if it is 150.0 nm or more, the low-temperature fixability tends to deteriorate.

  The average thickness Dav. Of the surface layer of the toner particles containing the organosilicon polymer. Can be controlled by the reaction temperature, reaction time, reaction solvent and pH of hydrolysis, addition polymerization and condensation polymerization. Moreover, it can control by the quantity of an organosilicon polymer.

  The organosilicon polymer is preferably a polymer obtained by polymerizing a compound having a structure represented by the following formula (2).

R ₁ in the formula (2) is preferably a hydrocarbon group having 6 or less carbon atoms. The hydrophobicity due to the hydrocarbon group of R ₁ can be improved, and a toner excellent in environmental stability can be obtained. When the hydrophobicity of R ₁ is large, the charge amount variation tends to increase in a wide range of environments. In particular, a carbon number of 3 or less, which is excellent in environmental stability, is preferable.

In the present invention, a methyl group, an ethyl group, and a propyl group are particularly preferable as the organosilicon compound having 3 or less carbon atoms in the hydrocarbon group R ₁ of the formula (2). Chargeability is good and fog is good. R ₂ , R ₃ and R ₄ are each independently a halogen atom, a hydroxyl group or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups undergo hydrolysis, addition polymerization and condensation polymerization to form a crosslinked structure, A toner excellent in member contamination and development durability can be obtained. A methoxy group or an ethoxy group is most preferable from the viewpoints of moderate hydrolyzability and toner surface precipitation and coverage. The hydrolysis, addition polymerization and condensation polymerization of R _{2 to} R ₄ can be controlled by the reaction temperature, reaction time, reaction solvent and pH.

  In the present invention, the adsorbing component of the pigment dispersant is preferably represented by the following formula (3).

［前記一般式（３）中、Ｒ₅、Ｒ₆及びＡｒのいずれかは、単結合又は連結基を介してポリマー成分が結合する構造を有し、Ｒ₅は、アルキル基、フェニル基、ＯＲ₉基又はＮＲ₁₀Ｒ₁₁基を表し、Ｒ₉〜Ｒ₁₁は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ｒ₅がポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ｒ₅に結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ₇−及び−ＮＨＣＨ（ＣＨ₂ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ₇は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ｒ₆は、アルキル基、フェニル基、ＯＲ₁₃基又はＮＲ₁₄Ｒ₁₅基を表し、Ｒ₁₄〜Ｒ₁₅は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ｒ₆がポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ｒ₆に結合する連結基は、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ₁₂−、−ＮＨＣＯＣ（ＣＨ₃）₂−及び−ＮＨＣＨ（ＣＨ₂ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ１２は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ａｒは、アリール基を表し、Ａｒがポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ａｒに結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ₇−及び−ＮＨＣＨ（ＣＨ₂ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ₇は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。前記単結合又は連結基が、Ｒ₅、Ｒ₆、又はＡｒに結合する場合は、Ｒ₅、Ｒ₆、又はＡｒの水素原子と置換して結合する。］

[In the general formula (3), any one of R ₅ , R ₆ and Ar has a structure in which a polymer component is bonded via a single bond or a linking group, and R ₅ is an alkyl group, a phenyl group, OR represents ₉ group or NR ₁₀ R ₁₁ group, R ₉ to R ₁₁ are each independently a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₅ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₅ is an amide group, ester group, urethane group, urea group, alkylene group, phenylene group, —O A divalent linking group selected from the group consisting of —, —NR ₇ — and —NHCH (CH ₂ OH) —, and R ₇ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group; R ₆ represents an alkyl group, a phenyl group, an OR ₁₃ group or an NR ₁₄ R ₁₅ group, and R _{14 to} R ₁₅ each independently represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₆ is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to R ₆ is an alkylene group, a phenylene group, —O—, —NR ₁₂ —, —NHCOC (CH _{3 2} ) A divalent linking group selected from the group consisting of —NH— (CH ₂ OH) —, and R 12 represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Ar represents an aryl group, and when Ar is bonded to the polymer component, it is bonded through a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, —O—, —NR ₇ — and —NHCH (CH ₂ OH) —, a divalent linking group selected from the group consisting of R ₇ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Represents. When the single bond or linking group is bonded to R ₅ , R ₆ , or Ar, it is bonded to a hydrogen atom of R ₅ , R ₆ , or Ar. ]

  When the adsorbing component has the above-described structure, the adsorption rate to the pigment is improved from the viewpoints of steric hindrance of the adsorbing component, π-π interaction with the pigment, and hydrogen bondability.

  The polymer component preferably has a skeleton having an affinity for the toner binder resin from the viewpoint of the affinity for the toner binder resin. Further, when a toner is produced by a suspension polymerization method, it preferably has a skeleton having an affinity for the polymerizable monomer constituting the binder resin. That is, when the binder resin of the toner is a vinyl resin, the polymer component of the pigment dispersant is preferably composed mainly of a vinyl resin. On the other hand, when the toner binder resin is a polyester resin, the polymer component of the pigment dispersant is preferably composed mainly of a polyester resin.

  When the toner is produced by the dissolution suspension method, it is preferable to select a polymer component of the pigment dispersant having a structure having an affinity for the organic solvent used at the time of toner production. Note that the binder resin, the polymerizable monomer constituting the binder resin, and the organic solvent in the case of the dissolution suspension method are sometimes abbreviated as a dispersion medium.

  As described above, when the toner component of the polymer component in the present invention is a vinyl resin, the polymer component of the pigment dispersant is preferably composed mainly of a vinyl resin. The polymer component mainly composed of the vinyl resin is preferably a polymer or copolymer containing a monomer unit represented by the following general formula (4) as a constituent component.

（式（４）中、Ｒ₁₆は、水素原子又は炭素数が１若しくは２のアルキル基である。Ｒ₁₇は、フェニル基、カルボキシル基、カルボン酸エステル基又はカルボン酸アミド基である。）

(In the formula (4), R ₁₆ is .R ₁₇ hydrogen atom or a carbon number is 1 or 2 alkyl groups, a phenyl group, a carboxyl group, a carboxylic acid ester group or a carboxylic acid amide group.)

  A typical production example of the organosilicon polymer of the present invention includes 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 synthesizing glass, ceramics, organic-inorganic hybrid, and nanocomposite through gelation through the state. According to this method, functional materials having various shapes such as fibers, bulk bodies, and fine particles can be produced from a liquid phase at a low temperature.

  Specifically, the surface layer of the toner particles is generated by hydrolysis polycondensation of a silicon compound typified by alkoxysilane. By providing this surface layer uniformly on the surface of the toner particles, the environmental stability is improved without the adhesion and adhesion of inorganic fine particles as is done with conventional toners, and during long-term use. It is possible to obtain a toner that hardly deteriorates in toner performance and has excellent storage stability. 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 preferable that the coating layer is not agglomerated as disclosed in Patent Document 4.

  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 likely to be 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 has 6 or more carbon atoms), there is a tendency that particle aggregates are easily formed on the surface of the toner particles. 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 tends to be deteriorated. The microstructure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH, type and amount of organometallic compound, and the like.

In order to obtain the organosilicon polymer, an organosilicon compound having _three reactive groups (R ₂ , R ₃ and R ₄ ) in one molecule excluding the hydrocarbon group R 1 in the formula (2) (hereinafter referred to as trifunctional) It is preferable to use at least one kind of silane.

  Examples of the formula (2) include the following.

For example, methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane , Methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, Methyldimethoxyhydroxysilane, methylethoxymethoxyhydro Shishiran, methylsilane of such trifunctional methyl diethoxy hydroxy silane;
Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltri Trifunctional such as methoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane Hexylsilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyl Triacetoxy silane, such as trifunctional phenylsilane phenyl trihydroxy silane;
Vinyl triisocyanate silane, p-styryltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane , Vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyltriacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, Vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyl Trifunctional vinyl silanes such as methoxyhydroxysilane, vinylethoxymethoxyhydroxysilane, vinyldiethoxyhydroxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allyltrihydroxysilane Such trifunctional allylsilanes can be mentioned.

  The organosilicon compounds may be used alone or in combination of two or more.

  The content of the organosilicon compound satisfying the formula (2) is preferably 50 mol% or more, more preferably 60 mol% or more in the organosilicon polymer. By setting the content of the organosilicon compound satisfying the formula (2) to 50 mol% or more, the environmental stability of the toner can be further improved.

  In addition to the organosilicon compound having the structure of the formula (2), an organosilicon compound having three reactive groups in one molecule (trifunctional silane), and an organosilicon compound having two reactive groups in one molecule ( An organosilicon polymer obtained by using a bifunctional silane) or an organosilicon compound having one reactive group (monofunctional silane) may be used. Examples of the organosilicon compound that may be used in combination include the following.

  Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane 3-anilinopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Examples include methyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, hexamethyldisilane, tetraisocyanate silane, and methyltriisocyanate 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. When water is present sufficiently, one H ⁺ attacks one oxygen of a reactive group (for example, an alkoxy group-OR group), so when the content of H ^{+ in} the reaction medium is low, the reaction proceeds to a hydroxy group. The substitution reaction becomes slow. Therefore, a polycondensation reaction occurs before all of the reactive groups attached to the silane are hydrolyzed, and a one-dimensional linear polymer or a two-dimensional polymer is easily generated relatively easily.

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

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

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

  Further, examples of the titanium coupling agent include the following. 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.

  The following are mentioned as an aluminum type coupling agent. Aluminum (III) n-butoxide, Aluminum (III) s-butoxide, Aluminum (III) s-butoxide bis (ethyl acetoacetate), Aluminum (III) t-butoxide, Aluminum (III) di-s-butoxide ethyl aceto Acetate, aluminum (III) diisopropoxide ethyl acetoacetate, aluminum (III) ethoxide, aluminum (III) ethoxyethoxy ethoxide, aluminum hexafluoropentandionate, aluminum (III) 3-hydroxy-2-methyl-4- Pyronate, aluminum (III) isopropoxide, aluminum-9-octadecenyl acetoacetate diisopropoxide, aluminum (III) 2,4-pe Tanjioneto, aluminum phenoxide, aluminum (III) 2,2,6,6-tetramethyl-3,5-heptanedionate.

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

  Next, a method for producing toner particles in the present invention will be described.

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

  As the first production method, toner particles are obtained by granulating a polymerizable monomer composition containing a polymerizable monomer, a colorant and an organosilicon compound in an aqueous medium, and polymerizing the polymerizable monomer. (Hereinafter also referred to as suspension polymerization method).

  The second production method is an embodiment in which after obtaining a toner base first, the toner base is put into an aqueous medium and a surface layer of an organosilicon polymer is formed on the toner base in the aqueous medium. The toner base may be obtained by melt-kneading the binder resin and the colorant and pulverizing them, and the binder resin particles and the colorant particles are aggregated and associated in an aqueous medium. In addition, an organic phase dispersion prepared by dissolving a binder resin and a colorant in an organic solvent is suspended, granulated, and polymerized in an aqueous medium. It may be obtained by removing the organic solvent.

  As a third production method, an organic phase dispersion prepared by dissolving a binder resin, a silane compound and a colorant in an organic solvent is suspended, granulated and polymerized in an aqueous medium, and then the organic solvent is removed. In this embodiment, toner particles are obtained.

  The fourth production method is an embodiment in which binder resin particles, colorant particles, and organic silicon compound-containing particles in a sol or gel state are aggregated in an aqueous medium and associated to form toner particles.

  As the fifth production method, an organosilicon compound-containing compound is sprayed onto the surface of the toner base by a spray-drying method, and the surface is polymerized or dried by hot air and cooling to form an organosilicon compound-containing surface layer It is. The toner base may be obtained by melt-kneading and pulverizing the binder resin and the colorant, and may be obtained by aggregating and associating the binder resin particles and the colorant particles in an aqueous medium. An organic phase dispersion prepared by dissolving a binder resin, a silane compound, and a colorant in an organic solvent may be obtained by suspending, granulating, and polymerizing in an aqueous medium and then removing the organic solvent.

  The toner particles produced by these production methods are formed in a state where the organosilicon compound is deposited on the toner particle surface in the vicinity of the toner particle surface, so that the environmental stability (chargeability in a harsh environment) is good. . Further, even in a harsh environment, changes in the surface state of the toner particles due to the release agent inside the toner and the bleeding of the resin are suppressed.

  Further, the surface treatment of toner particles or toner may be performed 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 performance.

  As the surface treatment using hot air, any means that can treat toner particles or toner surface with hot air and that can cool the toner particles or toner treated with hot air with cold air can be used. It may be something like this. As a device for performing surface treatment using hot air, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechano-fusion system (manufactured by Hosokawa Micron Corporation), a faculty (manufactured by Hosokawa Micron Corporation), Meteor Inbo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) Is mentioned.

  In the present invention, examples of the aqueous medium include the following. Water, alcohols such as methanol, ethanol, propanol, and mixed solvents thereof.

  As the method for producing the toner of the present invention, among the above-described production methods, 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, the adhesion between the surface layer and the inside is excellent, and the storage stability, environmental stability and development durability are improved. Hereinafter, the suspension polymerization method will be further described.

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

  As the other additives, the following resins can be used as long as the effects of the present invention are not affected. Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer , Styrene-butadi Copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene copolymer such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. It can be used alone or in combination.

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

  The polar resin is intended to improve toner particle shape, material dispersibility, fixability, or image characteristics. Monomers containing hydrophilic functional groups such as amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups cannot be used because they are soluble in water and dissolve in aqueous suspension to cause emulsion polymerization. In order to introduce the monomer components in the toner particles, random copolymers of these with vinyl compounds such as styrene or ethylene, block copolymers, copolymers such as graft copolymers, polyesters and polyamides. Such polycondensates or addition polymers such as polyethers and polyimines can be used.

  The toner particles may have a core-shell structure having a core part and a shell part. In the core-shell structure, the toner particle has a resin shell portion so as to cover the core portion. By adopting such a structure, it is possible to reduce the precipitation of the core portion on the surface of the toner particles, and therefore it becomes easy to reduce charging defects and to suppress the occurrence of blocking in each environment. The shell portion is a portion having a different contrast in an image of a toner cross section of a transmission electron microscope (TEM).

The resin constituting the shell portion preferably has a molecular chain polar structure. In the present invention, the molecular chain polar structure refers to a molecular structure having many δ ⁺ or δ ⁻ electron density states in atoms in the molecule. Adhesiveness with the organosilicon polymer is improved, and storage stability and development durability are improved. This is probably because the organosilicon polymer has a polar structure.

  Resin molecules are composed of a plurality of types of atoms, and the constituent atoms have inherent electronegativity, and the values differ greatly depending on the atoms. Due to this difference in electronegativity, electrons are localized in the molecule. In this localization, the state changes depending on the type, number, and bonding mode of the atoms to be configured, and the polarity of the molecular chain changes.

  The molecular chain polar structure is preferably a bond structure formed by condensation polymerization or addition polymerization. Specifically, ester bond (—COO—), ether bond (—O—), amide bond (—CONH—), imine bond (—NH—), urethane bond (—NHCOO—), urea bond (—NHCONH) -).

For example, in an ether bond such as (—CH ₂ —O—CH ₂ —), the electron on the carbon atom is slightly deficient (δ ⁺ ), and the electron on the oxygen atom is slightly excessive (δ ⁻ ). Further, a bond angle with an oxygen atom as a vertex is generated. Thus, if there are many polarized molecular chains, the polarity of the molecule, that is, the resin will increase, and if there are few polarized molecular chains, it will decrease. In general, molecules composed of hydrocarbons have low polarity.

  When the shell part of the resin has a molecular chain polar structure, charging stability is improved. In addition, when toner particles are produced in a polar solvent such as an aqueous medium or a hydrophilic medium, the resin shell portion having a molecular chain polar structure is more uniformly formed in the vicinity of the toner particle surface. Improves charging stability under high-temperature and low-humidity environments and durability during high-speed printing.

  A suitable material for the shell portion of the resin is a polyester resin or a derivative thereof.

  The polyester resin can be produced from a polyvalent alcohol and a polyvalent carboxylic acid by a known production method. Among the monomers constituting the polyester resin, polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, and dipropylene glycol. , Triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2,2,4-trimethylpentane-1,3-diol, hydrogenated bisphenol A, represented by the following general formula (A) And diols represented by the following general formula (B). These polyhydric alcohols may be used alone or in a mixed state. However, it is not limited to these, and other trivalent or higher alcohols can be used as the crosslinking component.

［一般式（Ａ）中、Ｒはエチレン基又はプロピレン基であり、ｘ及びｙはそれぞれ１以上の整数であり、且つｘ＋ｙの平均値は２〜１０である。］

[In general formula (A), R is an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2-10. ]

［一般式（Ｂ）中、Ｒ’は、以下に示すいずれかの基を示す。Ｒ’は同一であっても異なっていても良い。

[In General Formula (B), R ′ represents any of the following groups. R ′ may be the same or different.

  Among the monomers constituting the polyester resin, polyvalent carboxylic acids include naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, succinic acid, adipic acid, And dicarboxylic acids such as sebacic acid and azelaic acid; dicarboxylic anhydrides such as phthalic anhydride and maleic anhydride; and lower alkyl esters of dicarboxylic acids such as dimethyl terephthalate, dimethyl maleate and dimethyl adipate.

  The polyester resin may be cross-linked by using the following trivalent or higher carboxylic acid.

  Trimellitic acid, tri-n-ethyl 1,2,4-tricarboxylate, tri-n-butyl 1,2,4-tricarboxylate, tri-n-hexyl 1,2,4-tricarboxylate, 1,2,4 4-benzenetricarboxylic acid triisobutyl, 1,2,4-benzenetricarboxylic acid tri-n-octyl, 1,2,4-benzenetricarboxylic acid tri-2-ethylhexyl and lower alkyl ester of tricarboxylic acid. However, it is not limited to these, and other trivalent or higher carboxylic acids or trivalent or higher carboxylic acid lower alkyl esters can be used as the crosslinking component.

  Moreover, you may use monovalent carboxylic acid and monovalent alcohol. 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 Monocarboxylic acids such as acids; monofunctional such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, dodecyl alcohol Monomer.

  The polyester resin can be produced by a normal polyester synthesis method. Specifically, after the esterification reaction or transesterification reaction between the polyvalent carboxylic acid and the polyhydric alcohol, the polycondensation reaction is performed according to a conventional method by introducing a low boiling polyhydric alcohol under reduced pressure or introducing nitrogen gas. A polyester resin is obtained. In the esterification or transesterification reaction, an ordinary 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.

  It is also a preferred embodiment that the polyester resin is a vinyl-modified polyester resin modified with a vinyl monomer.

  The vinyl-modified polyester resin has a structure in which a polyester and a vinyl polymer are bonded to each other, the internal protection performance is given by a polyester skeleton, and the charging stability can be improved by a vinyl polymer unit.

  This vinyl-modified polyester resin is obtained by chemically bonding a vinyl polymer obtained by addition polymerization of an aromatic vinyl monomer and an acrylate monomer and a polyester, or an aromatic vinyl monomer and a methacrylic monomer. A vinyl polymer to which an acid ester monomer is added and a polyester are preferably chemically bonded.

  The vinyl-modified polyester resin contains a transesterification reaction between a hydroxyl group contained in the polyester and an acrylic ester or methacrylic ester contained in the vinyl polymer, and a hydroxyl group contained in the polyester and the vinyl polymer. It can produce | generate by ester reaction with the carboxy group. The vinyl-modified polyester resin preferably contains 1 to 60% by mass of a vinyl monomer as a monomer constituting the resin, more preferably 10 to 50% by mass, and further 15 to 40%. % By mass. By setting the content of the vinyl monomer within the above range, the chargeability and the low-temperature fixability can be further improved.

  As a particularly preferable polyester resin or vinyl-modified polyester resin, it is preferable to contain bisphenol A and / or linear alkyl diol as an alcohol constituting the resin in an amount of less than 50 mol% with respect to 100 mol% of the total alcohol. Moreover, it is preferable to contain 50 mol% or more of linear aryl dicarboxylic acid and / or linear alkyl dicarboxylic acid as carboxylic acid in 100 mol% of all carboxylic acids.

  Examples of vinyl monomers that can be used to produce the vinyl-modified polyester resin include vinyl polymerizable monomers copolymerizable with styrene. Examples of such vinyl polymerizable monomers include the vinyl polymerizable monomers described below.

  In the case of producing a vinyl-modified polyester resin, a polymerizable group for bonding the vinyl polymer and the polyester is a polyester resin, a vinyl polymer, a monomer constituting the polyester, and a vinyl polymerizable monomer. It is preferable to include in at least any one of. Among the monomers constituting the polyester resin, those that can react with the vinyl polymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer include those having a carboxy group or a hydroxy group, and acrylic acid or methacrylic acid esters.

As a manufacturing method of the said vinyl modified polyester resin, the manufacturing method shown to the following (i)-(iv) can be mentioned, for example.
(I) A method of forming a vinyl-modified polyester resin while polymerizing a polyester in the presence of a vinyl-based polymer. An organic solvent can be appropriately used.
(Ii) A method for producing a vinyl-modified polyester resin by polymerizing a vinyl polymerizable monomer in the presence of the polyester after forming the polyester.
(Iii) By forming a vinyl polymer and polyester and then adding a vinyl polymerizable monomer and / or a monomer constituting the polyester (alcohol, carboxylic acid, etc.) in the presence of these polymers. This is a method for producing a vinyl-modified polyester resin. Also in this case, an organic solvent can be appropriately used.
(Iv) A method of producing a vinyl-modified polyester resin by forming a vinyl polymer and a polyester and then bonding them together by an ester bond or an amide bond. Also in this case, an organic solvent can be appropriately used.

  In the production methods (i) to (iv) above, the reaction may be performed in the presence of a low softening point compound. Among the above production methods (i) to (iv), the production method (ii) is particularly preferable because the molecular weight control of the vinyl polymer unit is easy.

  Furthermore, a vinyl-modified polyester resin having a block type in which a vinyl polymer is bonded to a polyester terminal by introducing a vinyl group only at the terminal of the polyester unit and polymerizing a vinyl monomer by the production method of (ii) above. Is particularly preferable from the viewpoint of low-temperature fixability and charging stability.

  As one of the materials constituting the core of the toner of the present invention, a release agent is preferably contained. Examples of the release agent component usable in the toner according to the present invention include 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, Polyolefin wax such as polyethylene and polypropylene and derivatives thereof, natural wax such as carnauba wax and candelilla wax and derivatives thereof Fatty acids such as higher fatty alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones , Hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, and silicones. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products.

  In particular, in the case of ester wax, one having at least one long-chain ester moiety having 10 or more carbon atoms represented by the following formulas (a) to (f) inhibits transparency of an overhead projector transparency film (OHP film). Without preferred.

（式中、ａ及びｂは独立して０乃至４の整数を示し、ａ＋ｂは４であり、Ｒ¹及びＲ²は独立して炭素数が１〜４０の有機基を示し、ｎ及びｍは独立して０〜１５の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b independently represent an integer of 0 to 4, a + b is 4, R ¹ and R ² independently represent an organic group having 1 to 40 carbon atoms, and n and m are Independently represents an integer of 0 to 15, and n and m are not 0 at the same time.)

（式中、ａ及びｂは独立して１〜３の整数を示し、ａ＋ｂは４であり、Ｒ¹は炭素数が１〜４０の有機基を示しｎ及びｍは独立して０〜１５の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b independently represent an integer of 1 to 3, a + b is 4, R ¹ represents an organic group having 1 to 40 carbon atoms, and n and m independently represent 0 to 15) Indicates an integer, and n and m are not 0 at the same time.)

（式中、ａ及びｂは独立して０〜３の整数を示し、ａ＋ｂは２または３であり、Ｒ¹及びＲ²は独立して炭素数が１〜４０の有機基を示し、且つＲ¹とＲ²との炭素数差が１０以上である基を示し、Ｒ³は炭素数が１以上の有機基を示し、ｃは２または１であり、ａ＋ｂ＋ｃ＝４であり、ｎ及びｍは独立して０〜１５の整数を示し、ｎとｍが同時に０になることはない。）
Ｒ¹−ＣＯＯ−Ｒ² （ｄ）
（式中、Ｒ¹及びＲ²は炭素数が１〜４０の炭化水素基を示し、且つＲ¹及びＲ²は、お互いに同じでも異なる炭素数でもよい。）

(Wherein, a and b independently represent an integer of 0 to 3, a + b is 2 or 3, R ¹ and R ² independently represent an organic group having 1 to 40 carbon atoms, and R ¹ and the number of carbon atoms difference between R ² represents a group of 10 or more, R ³ represents one or more organic groups having a carbon number, c is 2 or 1, a + b + c = a 4, n and m are Independently represents an integer of 0 to 15, and n and m are not 0 at the same time.)
R ¹ —COO—R ² (d)
(Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, and R ¹ and R ² may be the same or different from each other.)

（式中、Ｒ¹及びＲ²は炭素数が１〜４０の炭化水素基を示し、ｎは２乃至２０の整数であり、且つＲ¹及びＲ²は、お互いに同じでも異なる炭素数でもよい。）

Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, n is an integer of 2 to 20, and R ¹ and R ² may be the same or different from each other. .)

（式中、Ｒ¹及びＲ²は炭素数が１〜４０の炭化水素基を示し、ｎは２〜２０の整数であり、且つＲ¹及びＲ²は、お互いに同じでも異なる炭素数でもよい。）

(In the formula, R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, n is an integer of 2 to 20, and R ¹ and R ² may be the same or different from each other. .)

  As a molecular weight of a mold release agent, it is preferable that a weight average molecular weight (Mw) is 3001,500, More preferably, it is 400-1250. By adjusting the weight average molecular weight within the above range, the low-temperature fixability can be further improved. Further, when the weight average molecular weight / number average molecular weight ratio (Mw / Mn) is 1.5 or less, the peak of the DSC endothermic curve of the release agent becomes sharper, and the mechanical strength of the toner particles at room temperature is improved. In particular, excellent toner characteristics exhibiting sharp melting characteristics upon fixing can be obtained.

Specific examples of the ester wax include compounds represented by the following formula.
1) CH ₃ (CH ₂ ) ₂₀ COO (CH ₂ ) ₂₁ CH ₃
2) CH ₃ (CH ₂ ) ₁₇ COO (CH ₂ ) ₉ OOC (CH ₂ ) ₁₇ CH ₃
3) CH ₃ (CH ₂ ) ₁₇ OOC (CH ₂ ) ₁₈ COO (CH ₂ ) ₁₇ CH ₃

  There is a need for full-color double-sided images. When a double-sided image is formed, the toner image on the transfer material first formed on the front surface can be used again. There is a possibility of passing. At that time, it is necessary to sufficiently consider the high-temperature offset resistance of the fixed image of the toner. Specifically, it is preferable to add 2 to 30% by mass of a release agent in the toner particles.

  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, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, ethyl Acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl Acrylic polymerizable monomers such as 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, diethylphos Fate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as acrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  The shell part is preferably composed of a vinyl polymer formed from these vinyl polymerizable monomers and an added resin. Among these vinyl polymers, a styrene polymer, a styrene-acrylic copolymer, or a styrene-methacrylic copolymer is used from the viewpoint of efficiently covering a release agent that mainly forms the inside or the center. preferable. In addition, the adhesion between the organosilicon polymer and the core or shell part is improved, and the storage stability and development durability are improved.

  Further, a polymerization initiator may be added during the polymerization of the polymerizable monomer. The following are mentioned as a polymerization initiator.

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

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

  On the other hand, in order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added during the polymerization of the polymerizable monomer. The following are mentioned as a crosslinking agent.

  Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and the above acrylates were changed to methacrylate The.

  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. As an addition amount of a crosslinking agent, it is preferable that it is 0.001-15,000 mass% with respect to a polymerizable monomer.

  The binder resin constituting the toner particles is preferably a vinyl resin. The vinyl resin is produced by polymerization of the vinyl polymerizable monomer described above. Vinyl resin is excellent in environmental stability. A vinyl resin is preferable because an organosilicon polymer obtained by polymerizing a compound having the structure represented by the formula (1) is excellent in precipitation on the toner particle surface and surface uniformity.

  When the medium used in the polymerization of the polymerizable monomer is an aqueous medium, the following can be used as a dispersion stabilizer for the particles of the polymerizable monomer composition. 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, alumina . Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch.

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

  In the present invention, when an aqueous medium is prepared using a hardly water-soluble inorganic dispersion stabilizer, the amount of these dispersion stabilizers added is 0.2 with respect to 100.0 parts by mass of the polymerizable monomer. It is preferable that it is -2.0 mass parts. Moreover, it is preferable to prepare an aqueous medium using 300.0 to 3,000. 0 parts by mass of water with respect to 100.0 parts by mass of the polymerizable monomer composition.

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

  The colorant used in the toner of the present invention is not particularly limited, and known ones shown below can be used.

  Examples of yellow pigments include yellow iron oxide, navel yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake. Isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment Yellow 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.

  Red pigments include Bengala, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamine Lake B, Alizarin Lake, etc. Examples include 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, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  Blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, indanthrene blue BG and other copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dyes Examples include lake compounds. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 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 a solid solution state.

  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 may be modified by subjecting the colorant to a surface treatment 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.

  A preferable method for treating the dye includes a method in which a polymerizable monomer is previously polymerized in the presence of the dye and the obtained colored polymer is added to the polymerizable monomer composition. Moreover, about carbon black, you may process with the substance (for example, organosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

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

  Examples of the charge control agent that control the toner to be negatively charged include the following. As organometallic compounds and chelate compounds, monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol. Furthermore, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, and calixarene can be mentioned. Examples of the charge control agent that controls the toner to be positively charged include the following. Nigrosine-modified products such as nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (phosphorungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, Gallic acid, ferricyanide, ferrocyanide, etc.); metal salt of higher fatty acid; resin charge control agent. These charge control agents can be contained alone or in combination of two or more. Among these charge control agents, metal-containing salicylic acid compounds are preferable, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.

  The charge control resin that can be used in the present invention is preferably a polymer having a sulfonic acid functional group. The polymer having a sulfonic acid functional group is a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group.

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

  The sulfonic acid group-containing (meth) acrylamide monomer is preferably a monomer represented by the following general formula (5), specifically 2-acrylamide-2-methylpropanoic acid or 2-methacrylamide-2-methyl. And propanoic acid.

［上記一般式（５）中、Ｒ₁は水素原子、又はメチル基を示し、Ｒ₁とＲ₃は、それぞれ水素原子、Ｃ１〜Ｃ１０のアルキル基、アルケニル基、アリール基、又はアルコキシ基を示し、ｎは１〜１０の整数を示す。］

[In the general formula (5), R ₁ represents a hydrogen atom or a methyl group, and R ₁ and R ₃ represent a hydrogen atom, a C1-C10 alkyl group, an alkenyl group, an aryl group, or an alkoxy group, respectively. , N represents an integer of 1-10. ]

  When the polymer having a sulfonic acid group according to the present invention is contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin in the toner particles, the toner is charged in combination with the water-soluble initiator. The state can be made even better. The addition amount of these charge control agents is preferably 0.01 to 10.00 parts by mass with respect to 100.0 parts by mass of the binder resin or polymerizable monomer.

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

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

  The organic fine powder or the inorganic fine powder treats the surface of the toner particles in order to improve the fluidity of the toner and to make the charge of the toner particles uniform. By adjusting the hydrophobicity of the organic or inorganic fine powder, it is possible to adjust the chargeability of the toner and improve the charging characteristics in a high humidity environment. Therefore, the organic or inorganic fine powder subjected to the hydrophobic treatment is used. It is preferable. When the organic or inorganic fine powder added to the toner absorbs moisture, the chargeability as the toner is lowered, and the developability and transferability are easily lowered.

  As treatment agents for the hydrophobic treatment of organic fine powder or inorganic fine powder, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, and other organic silicon Examples of the compound include organic titanium compounds. These treatment agents may be used alone or in combination.

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

  The addition amount of the organic fine powder or inorganic fine powder is preferably 0.01 to 10.00 parts by mass, more preferably 0.02 to 1.00 parts by mass with respect to 100.0 parts by mass of the toner particles. More preferably, it is 0.03-1.00 mass part. Component contamination due to embedding and release of organic fine powder or inorganic fine powder in toner particles is improved. These organic fine powders or inorganic fine powders may be used alone or in combination.

Here, the BET specific surface area of the organic fine powder or the inorganic fine powder is preferably 10 m ² / g or more and 450 m ² / g or less.

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

  The organic fine powder or inorganic fine powder may be firmly fixed or adhered to the toner particle surface. For firmly fixing or adhering to the surface of the toner particles of the present invention, a Henschel mixer, mechanofusion, cyclomix, turbulizer, flexomix, hybridization, mechanohybrid, and nobilta can be used.

  Further, the organic fine powder or the inorganic fine powder can be strongly fixed or adhered by increasing the rotational peripheral speed or extending the processing time.

  The 80 ° C. viscosity of the toner of the present invention 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 1000 to 40000 Pa · s, the toner has excellent low-temperature fixability. The viscosity at 80 ° C. is more preferably 2,000 Pa · s to 20,000 Pa · s. 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 value of 80 ° C. viscosity measured by a constant-load extrusion type capillary rheometer of toner can be obtained by the following method.

As an apparatus, for example, a flow tester CFT-500D (manufactured by Shimadzu Corporation) is used, and measurement is performed under the following conditions.
Sample: About 1.0 g of toner is weighed and molded using a pressure molding machine at a load of 100 kg / cm ² for 1 minute to obtain a sample.
-Die hole diameter: 1.0 mm
-Die length: 1.0 mm
・ Cylinder pressure: 9.807 × 10 ⁵ (Pa)
・ Measurement mode: Temperature rising method ・ Temperature rising speed: 4.0 ° C./min

  By measuring the viscosity (Pa · s) of the toner at 30 to 200 ° C. by the above method, the viscosity (Pa · s) at 80 ° C. is obtained. This value is the 80 ° C. viscosity measured by a capillary rheometer of the toner constant load extrusion method.

  The weight average particle diameter (D4) of the toner of the present invention is preferably 4.0 to 9.0 μm, more preferably 5.0 to 8.0 μm, and still more preferably 5.0 to 7.0 μm. It is.

  The glass transition temperature (Tg) of the toner of the present invention is preferably 35 to 100 ° C, more preferably 35 to 80 ° C, and further preferably 45 to 70 ° C. By being in the above-mentioned range, it is possible to further improve the blocking resistance, the low-temperature offset resistance, and the transparency of the transmitted image of the overhead projector film.

  The content of insoluble content of tetrahydrofuran (THF) in the toner of the present invention is preferably less than 50.0% by mass, more preferably 0.0% by mass with respect to toner components other than the toner colorant and inorganic fine powder. % Or more and less than 45.0% by mass, and 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.

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

1.0 g of toner is weighed (W1 g), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), passed through a Soxhlet extractor, and extracted for 20 hours using 200 ml of THF as a solvent. After concentrating the soluble component extracted with the solvent, it is vacuum-dried 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 a pigment in the toner is (W3 g). The THF-insoluble content is obtained from the following formula.
Content (mass%) of THF insoluble matter = (W1− (W3 + W2)) / (W1−W3) × 100

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

  In the present invention, the weight average molecular weight (Mw) (hereinafter also referred to as the weight average molecular weight of the toner) measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the toner is 5,000 to 50. , 000 is preferable. When the weight average molecular weight (Mw) of the toner is within the above range, both blocking resistance and development durability, low-temperature fixability and image gloss can be achieved. In the present invention, the weight average molecular weight (Mw) of the toner includes the addition amount and the weight average molecular weight (Mw) of the low molecular resin, the reaction temperature, the reaction time, the initiator amount, the chain transfer agent amount, and the crosslinking amount at the time of toner production. It can be adjusted by the amount of the agent.

  In the present invention, the ratio [Mw / Mn] of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the toner is: It is preferably 5.0 to 100.0, and more preferably 5 to 30. When [Mw / Mn] is within the above range, the fixable region can be widened.

  A method for measuring and evaluating physical properties relating to the toner of the present invention will be described below.

<Concentration of silicon element present on toner particle surface (atomic%)>
In the present invention, the concentration (atomic%) of silicon element with respect to the total concentration (dC + dO + dSi) of carbon element concentration dC, oxygen element concentration dO, and silicon element concentration dSi present on the toner particle surface is determined by ESCA (X-ray photoelectron spectroscopy). The composition was analyzed 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, the surface atomic concentration (atomic%) was calculated from the measured peak intensity of each element using a relative sensitivity factor provided by PHI.

<Method for Confirming Partial Structure of Formula (1), SX1, SX2, SX3, and SX4>
The partial structure confirmation method of T3R, SX1, SX2, SX3 and SX4 can be confirmed by ¹ H-NMR, ¹³ C-NMR and ²⁹ Si-NMR.

The presence or absence of the hydrocarbon group of the formula (1) was confirmed by ¹³ C-NMR. A structure in which the number of O _1/2 bonded to silicon is 1.0 was defined as a structure (SX1). Further, the peak area of the (SX1) structure was defined as S (SX1). A structure in which the number of O _1/2 bonded to silicon is 4.0 was defined as a structure of (SX4). Further, the peak area of the (SX4) structure was defined as S (SX4).

（式（ＳＸ１）中のＲｉ、Ｒｊ、Ｒｋはケイ素に結合している有機基、ハロゲン原子、ヒドロキシ基またはアルコキシ基）

(In the formula (SX1), Ri, Rj and Rk are organic groups, halogen atoms, hydroxy groups or alkoxy groups bonded to silicon)

装置：ＢＲＵＫＥＲ製 ＡＶＡＮＣＥＩＩＩ ５００
プローブ：４ｍｍ ＭＡＳ ＢＢ／１Ｈ
測定温度：室温
試料回転数：６ｋＨｚ
試料：測定試料（ＮＭＲ測定用のトナー粒子のＴＨＦ不溶分）１５０ｍｇを直径４ｍｍのサンプルチューブに入れる。

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

  The presence or absence of the R hydrocarbon group of the formula (1) was confirmed. If the signal was confirmed, the structure of the formula (1) was determined to be “Yes”.

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

<Confirmation and quantification method of SX1, SX2, SX3 and SX4 structure>
The SX1, SX2, SX3 and SX4 structures were confirmed by ²⁹ Si-NMR.

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

  After the measurement, a plurality of silane components having different substituents and bonding groups of the toner particles are peak-separated into SX1 structure, SX2 structure, SX3 structure, and SX4 structure by curve fitting. Calculate mol% of ingredients. Curve fitting was performed using EXcalibur for Windows (registered trademark) version 4.2 (EX series), software for JNM-EX400 manufactured by JEOL. Click “1D Pro” from the menu icon to read the measurement data. Next, “Curve fitting functonon” was selected from “Command” on the menu bar, and curve fitting was performed. An example is shown in FIG. Peak splitting was 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), was the smallest.

  SX1, SX2, SX3, and SX4 were determined by the following equations by determining the area of the SX1 structure, the area of the SX2 structure, the area of the SX3 structure, and the area of the SX4 structure.

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 of the organosilicon polymer having the partial structure represented by formula (1) in the ²⁹ Si-NMR measurement of the toner particles. The area was S (SX).
S (SX1) + S (SX2) + S (SX3) + S (SX4) = S (SX)
S (SX1) = area of SX1 structure / S (SX)
S (SX2) = area of SX2 structure / S (SX)
S (SX3) = area of SX3 structure / S (SX)
S (SX4) = area of SX4 structure / S (SX)

For example, chemical shift values of silicon in the partial structures represented by formula (SX1), formula (SX2), formula (SX3), and formula (SX4) are shown below.
Example of SX1 structure (Y = —OC ₂ H ₅ , —OC ₂ H ₅ , —CH ₃ ): −47 ppm
Example of SX2 structure (Y = —OC ₂ H ₅ , —CH ₃ ): −56 ppm
Example of structure of formula (1) (R = —CH ₃ ): −65 ppm

Further, the chemical shift value of silicon in the case of having the SX4 structure is shown below.
SX4 structure: -108 ppm

<Measurement method of adsorption rate of pigment dispersant to pigment>
The adsorption rate of the pigment dispersant to the colorant was measured as follows.

[Create calibration curve]
(A) The mass ratio of the liquid medium and the pigment dispersant in the colorant composition, polymerizable monomer composition or toner composition having the same formulation as the toner actually produced (however, 10% by mass with respect to the colorant 300 ml of the “liquid medium and pigment dispersant solution” prepared in (1) is added. This solution was added to a mayonnaise bottle (mayonnaise 450: manufactured by Nippon Yamamura Glass Co., Ltd.), and shaken for 10 hours with a paint shaker (manufactured by TOYOSEIKI) (solution 1). Further, a liquid medium is added to the solution 1 to prepare solutions in which the content ratio of the pigment dispersant is diluted to 1/5 and 1/10 (hereinafter referred to as the solution 2 and the solution 3, respectively).
(B) Solutions 1, 2, and 3, which were allowed to stand at 25 ° C. for 24 hours, were filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm as a sample solution, and pigmented using GPC under the following conditions: The dispersant was measured, and a calibration curve for the azo compound concentration (g / ml) in the liquid medium was prepared.
・ High-speed GPC device: “HLC-8220GPC” [manufactured by Tosoh Corporation]
-Column: Duplex of LF-804-Eluent: THF
・ Flow rate: 1.0 ml / min
・ Oven temperature: 40 ℃
・ Sample injection amount: 0.025 ml

[Measurement of adsorption rate]
(A) The mass ratio of the liquid medium, the colorant and the pigment dispersant in the colorant composition, polymerizable monomer composition or toner composition having the same formulation as the toner actually produced (however, with respect to the colorant, 300 ml of a “liquid medium, a coloring agent and an azo compound solution” prepared by adding a pigment dispersant corresponding to 10% by mass) was prepared. This solution was added to a mayonnaise bottle (mayonnaise 450: manufactured by Nippon Yamamura Glass Co., Ltd.) and shaken with a paint shaker (manufactured by TOYOSEIKI) for 10 hours (solution 4). After preparing Solution 4, it was allowed to stand at 25 ° C. for 24 hours, and centrifuged under the following conditions.
・ Kokusan Co., Ltd .: High-speed centrifuge H-9R
・ Centrifuge tube: PPT-010
・ Sample: A composition equivalent to about 80% of the volume of the centrifuge tube is added. ・ Centrifuge condition: 3 minutes at 10000 rpm (25 ° C.)
(B) The supernatant of the centrifuged composition is collected, filtered through a filter (Nippon Millipore, Mirex LH, pore diameter 0.45 μm, diameter 13 mm), and the supernatant is obtained using the GPC under the same conditions as the calibration curve. The concentration of the pigment dispersant in the liquid was measured.
(C) From the above measurement results, the adsorption rate (%) was calculated by the following equation.
Adsorption rate (%) = {pigment dispersant concentration in solution 1 (g / liquid medium 1 ml) −supernatant pigment dispersant concentration in solution 4 (g / liquid medium 1 ml)} / {pigment dispersant concentration in solution 1 ( g / liquid medium 1 ml)} × 100

<Measurement of SP value of binder resin and pigment dispersant>
The SP values of the binder resin and the pigment dispersant were measured by the cloud point titration measurement method as follows.

  In a 50 ml sample tube, about 1.48 g of a precisely weighed binder resin, crystalline polyester, or pigment dispersant is dissolved in about 10.00 g of precisely weighed chloroform. Next, one drop (about 200 mg) of methanol is added with a Pasteur pipette, the lid is closed, the mass is measured, and the mixture is stirred for 1 minute with a microrotor for magnetic stirrer (total length 3 mm × diameter Φ3). After stirring, visually stir the solution to see if it is cloudy. If not cloudy, repeat the above procedure until cloudy.

  Similarly, heptane is used instead of methanol.

From the respective masses of chloroform and methanol or heptane at the time of cloudiness, SP values of the binder resin and the pigment dispersant were calculated from the following formulas.
SP value of binder resin and pigment dispersant = (SP _α + SP _β ) / 2
^{_{SP α = (Vm 1/2 × SPm}} + Vc · ml 1/2 × SPc) / (Vm 1/2 + Vc 1/2)
SP _β (Vc ^1/2 × SPc + Vh ^1/2 × SPh) / (Vc ^1/2 + Vh ^1/2 )
Vm (cm ³ ): volume of methanol at the time of cloudiness (specific gravity of methanol: 0.792)
Vc (cm ³ ): volume of chloroform at the time of cloudiness (specific gravity of chloroform: 1.490)
Vh (cm ³ ): volume of heptane at the time of cloudiness (specific gravity of heptane: 0.684)
SPm: SP value of methanol (14.5 cal / cm ³ )
SPc: SP value of chloroform (9.3 cal / cm ³ )
SPh: SP value of heptane (7.4 cal / cm ³ )

SPm, SPc, and SPh are cited from the following literature.
Cited References: Solubility Parameters: ALLAN F. M.M. BARTON Chemistry Department, Victoria University of Wellington, Private Bag, Wellington, New Zealand
Received June 7, 1974 (Revised Manuscript Received October 29, 1974)

  In the toner obtained by polymerizing a vinyl polymerizable monomer to obtain a binder resin, only the vinyl polymerizable monomer and the initiator in each formulation are used in the toner particles of Examples and Comparative Examples described later. The SP value of the resin prepared by performing bulk polymerization under the same reaction conditions (temperature and time) as the toner particles was defined as the SP value of the binder resin.

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

  A suitable amount of a surfactant, preferably an alkylbenzene sulfonate, is added to 20 ml of ion-exchanged water, and then 0.02 g of a measurement sample is added. A desktop ultrasonic cleaner with an oscillation frequency of 50 kHz and an electric output of 150 watts. Dispersion treatment is performed for 2 minutes using a disperser (for example, “VS-150” (manufactured by Vervo Creer, etc.) to obtain a dispersion for measurement, and the temperature of the dispersion is 10 ° C. or more and 40 ° C. or less. Cool as appropriate.

  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 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is 85%. The analysis particle diameter is limited to the equivalent circle diameter of 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, Duke Scientific 5100A diluted with ion-exchanged water) before the start of measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  Further, in the circularity distribution of the toner, when the mode circularity is 0.98 to 1.00, 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 to the photoreceptor due to the mirror image force, van der Waals force, etc. becomes more remarkable, and the transfer efficiency becomes very 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 divided into 61 every 0.01 as 1.00, and the measured circularity of each particle is assigned to each divided range, and the circularity of the divided range where the frequency value is maximum in the circularity frequency distribution is said.

<How to find the equivalent circle diameter Dtem of a toner measured by cross-sectional observation of toner particles using a transmission electron microscope (TEM)>
The cross section of the toner particles of the present invention can be observed by the following method.

  As a specific method for observing the cross section, 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. Using a transmission electron microscope (TEM), the cross section of the toner is observed at a magnification of 10,000 to 100,000. In the present invention, the difference between the atomic weights of the binder resin and the organosilicon compound to be used is utilized, and the confirmation is made by 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 may be used in order to provide contrast between materials.

  Furthermore, a TEM bright field image was acquired at an acceleration voltage of 200 kV using an FEI electron microscope Tecnai TF20XT. Next, using an EELS detector GIF Tridiem manufactured by Gatan, an EF mapping image of the Si-K end (99 eV) was obtained by the Three Window method, and it was confirmed that the organosilicon polymer was present on the surface layer.

  The average thickness Dav. Of the surface layer containing the organosilicon polymer of the toner particles by TEM. As for the particles for obtaining the diameter, the equivalent circle diameter Dtem is obtained from the cross-sectional area of the toner obtained from a TEM micrograph, and the value is within a range of ± 10% of the weight average particle diameter obtained by the method described later using a Coulter counter. Contained particles are regarded as applicable particles.

  One toner particle corresponding to the above is divided into 16 equal parts around the intersection of the long axis L90 and the vertical axis L90 passing through the center of the long axis L (see FIG. 1). Next, assuming that the axis from the center is RAn (n = 1 to 32) and the length of the axis is Arn, the average of the lengths of the axes from the 32 centers is Arav. And

[Equivalent circle diameter Dtem obtained from cross-sectional area of toner obtained from TEM micrograph]
The equivalent circle diameter Dtem obtained from the cross-sectional area of the toner obtained from a TEM micrograph was obtained by the method described later.
Equivalent circle diameter determined from the cross-sectional area of the toner obtained from photomicrographs of TEM Dtem = (Ar1 + Ar2 + Ar3 + Ar4 + Ar5 + Ar6 + Ar7 + Ar8 + Ar9 + Ar10 + Ar11 + Ar12 + Ar13 + Ar14 + Ar15 + Ar16 + Ar17 + Ar18 + Ar19 + Ar20 + Ar21 + Ar22 + Ar23 + Ar24 + Ar25 + Ar26 + Ar27 + Ar28 + Ar29 + Ar30 + Ar31 + Ar32) / 16

  In the present invention, a circle equivalent diameter of 10 particles is obtained for averaging, an average value per particle is calculated, and a circle equivalent diameter Dtemav. And

[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

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

[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 stations, eluent: tetrahydrofuran (THF)
・ Temperature: 40 ℃
・ Flow rate: 0.6ml / min
・ Detector: RI
Sample concentration and amount: 10 μl of 0.1% by mass sample

[Sample preparation]
0.04 g of a measurement target (toner, various resins) was dispersed and dissolved in 20 ml of tetrahydrofuran, allowed to stand for 24 hours, and filtered with a 0.2 μm filter [Mysholy disk H-25-2 (manufactured by Tosoh Corporation)]. The filtrate is used as a sample.

  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 polystyrenes F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F- manufactured by Tosoh Corporation 4, F-2, F-1, A-5000, A-2500, A-1000, and A-500 are used. At this time, at least about 10 standard polystyrene samples are 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.

<Method for Measuring Glass Transition Temperature (Tg) of Toner and Various Resins>
The glass transition temperature (Tg) of the toner and various resins is measured according to the following procedure using a differential scanning calorimeter (DSC) M-DSC (trade name: Q1000, manufactured by TA Instruments). Weigh precisely 6 mg of the sample (toner, various resins) to be measured. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 1 ° C./min and normal temperature and humidity in a measurement temperature range of 20 to 200 ° C. Measurement is performed at a modulation amplitude of ± 0.5 ° C. and a frequency of 1 / min. The glass transition temperature (Tg: ° C.) is calculated from the obtained reversing heat flow curve. Tg is obtained as Tg (° C.) as the center value of the intersection of the baseline before and after endotherm and the tangent of the curve due to endotherm.

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

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

<Method for Measuring Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are measured with a fine particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, Beckman 2) Effective measurement channel number 25,000 using “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) and attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” for measurement condition setting and measurement data analysis Measure in the channel, analyze the measurement data, and calculate.

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

  Prior to measurement and analysis, the dedicated software is set as follows.

  In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

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

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10.0 mass% aqueous solution of a neutral detergent for washing a vessel with a product of Wako Pure Chemical Industries, Ltd. by 3.0 mass times with ion exchange water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . 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).

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In addition, the part in the following mixing | blending shows a mass part unless there is particular description. Examples 22 to 25 relating to toner particles 22 to 25 are Reference Examples 22 to 25.

  A production example of the pigment dispersant used in the present invention will be described.

<Production Example of Polymer Component (P-1) of Pigment Dispersant>
100 parts of propylene glycol monomethyl ether was heated while being purged with nitrogen, and refluxed at a liquid temperature of 120 ° C. or higher, and tert-butyl peroxybenzoate [organic peroxide polymerization initiator, manufactured by NOF Corporation, Product name: Perbutyl Z] A mixture of 1.25 parts was added dropwise over 3 hours. After completion of the dropwise addition, the solution was stirred for 3 hours and then distilled at atmospheric pressure while raising the liquid temperature to 170 ° C. After reaching the liquid temperature of 170 ° C., it was distilled for 1 hour under reduced pressure at 1 hPa to remove the solvent. Obtained. The solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was separated by filtration to obtain a polymer component (P-1).

<Production Example of Polymer Component (P-2) of Pigment Dispersant>
In the production method of the polymer component (P-1), (styrene / acrylic acid / butyl acrylate / stearyl acrylate = 60/4/30/6 [mol ratio]) is changed to (styrene / stearyl acrylate / acrylic acid = The polymer component (P-2) was obtained in the same manner as the polymer component (P-1) except that the ratio was changed to 90/4/6 [mol ratio].

<Production Example of Polymer Component (P-3) of Pigment Dispersant>
In the production method of the polymer component (P-1), (styrene / acrylic acid / butyl acrylate / stearyl acrylate = 60/4/30/6 [mol ratio]) is changed to (styrene / acrylic acid / methyl acrylate = The polymer component (P-3) was obtained in the same manner as the polymer component (P-1) except that the ratio was changed to 84/4/8 [mol ratio]).

<Production Example of Pigment Dispersant 1>
A partial structure of a pigment dispersant represented by the following formula (1A) was produced according to the following scheme.

  First, 3.11 parts of 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 30 parts of chloroform, and ice-cooled to 10 ° C. or less, and 1.89 parts of diketene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. Then, it stirred at 65 degreeC for 2 hours. After completion of the reaction, the mixture was extracted with chloroform and concentrated to obtain compound (1A).

  Next, 40.00 parts of methanol and 5.29 parts of concentrated hydrochloric acid were added to 4.25 parts of dimethyl 2-aminoterephthalate (manufactured by Merck & Co., Inc.), and the mixture was ice-cooled to 10 ° C or lower. To this solution, 2.10 parts of sodium nitrite dissolved in 6.00 parts of water was added and reacted at the same temperature for 1 hour. Next, 0.990 parts of sulfamic acid was added and the mixture was further stirred for 20 minutes (diazonium salt solution). To 70.00 parts of methanol, 4.51 parts of compound (1A-1) was added, and the mixture was cooled to 10 ° C. or lower with ice, and the diazonium salt solution was added. Thereafter, a solution obtained by dissolving 5.83 parts of sodium acetate in 7.00 parts of water was added and reacted at 10 ° C. or lower for 2 hours. After completion of the reaction, 300.00 parts of water was added and stirred for 30 minutes, and then the solid was filtered off and purified by recrystallization from N, N-dimethylformamide to obtain compound (1A-2). Next, 8.58 parts of compound (1A-2) and 0.40 part of palladium-activated carbon (palladium 5%) were added to 150.00 parts of N, N-dimethylformamide, and the reaction was performed under a hydrogen gas atmosphere (reaction pressure 0). 0.1 to 0.4 MPa) and stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was filtered off and concentrated to obtain compound (1A).

  Next, pigment dispersant 1 was produced according to the following scheme by combining the amino group of compound (1A) and the carboxyl group of polymer component (P-1) by amidation.

［上記構造式中で、「ｃｏ」とは、共重合体を構成する各単量体単位の配列が無秩序であることを示す記号である。］

[In the above structural formula, “co” is a symbol indicating that the arrangement of the monomer units constituting the copolymer is disordered. ]

  First, 1.98 parts of compound (1A) was added to 500.00 parts of tetrahydrofuran, and heated to 80 ° C. to dissolve. After dissolution, the temperature was lowered to 50 ° C., 37.50 parts of polymer component (P-1) was added and dissolved, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC · HCl). After adding 96 parts and stirring at 50 degreeC for 5 hours, liquid temperature was gradually returned to room temperature, and reaction was completed by stirring overnight. After completion of the reaction, the solution was filtered and concentrated, and purified by reprecipitation with methanol to obtain Pigment Dispersant 1.

<Production Example of Pigment Dispersant 2>
In the production of pigment dispersant 1, pigment dispersant 2 was obtained in the same manner as pigment dispersant 1 except that (1A) was changed to (2A) below.

<Production Example of Pigment Dispersant 3>
Pigment dispersant 3 represented by the following structure was produced according to the following scheme.

［スキーム中、「ｃｏ」とは、共重合体を構成する各単量体単位の配列が無秩序であることを表す記号である。］

[In the scheme, “co” is a symbol indicating that the arrangement of the monomer units constituting the copolymer is disordered. ]

  First, 30.0 parts of water and 11.0 parts of concentrated hydrochloric acid were added to 5.00 parts of 4-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was ice-cooled to 10 ° C or lower. To this solution, 3.46 parts of sodium nitrite dissolved in 8.10 parts of water was added and reacted at the same temperature for 1 hour. Next, 0.657 part of sulfamic acid was added and the mixture was further stirred for 20 minutes (diazonium salt solution). To 48.0 parts of water, 8.13 parts of acetoacetanilide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was ice-cooled to 10 ° C. or less, and the diazonium salt solution was added. Then, what dissolved 14.30 parts of sodium carbonate in 80.00 parts of water was added, and it was made to react at 10 degrees C or less for 2 hours. After completion of the reaction, 50.00 parts of water was added and stirred for 30 minutes, and then the solid was filtered off and purified by recrystallization from N, N-dimethylformamide to obtain compound (3A-1).

  Next, 3.00 parts of the compound (3A-1) and 1.20 parts of triethylamine were added to 30.00 parts of chloroform, and the mixture was ice-cooled to 10 ° C or lower. To this solution, 1.03 part of acryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and reacted at the same temperature for 20 minutes. This was extracted with chloroform, concentrated and purified to obtain compound (3A-2).

  Next, 4.7 parts of styrene, 2.89 parts of butyl acrylate, 1.47 parts of stearyl acrylate, 9.44 parts of N, N-dimethylformamide, 1.06 parts of compound (3A-2), azobisiso 0.327 parts of butyronitrile was added, and the mixture was stirred at 80 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, the pigment dispersant 3 was obtained by purification by recrystallization from N, N-dimethylformamide.

<Production Example of Pigment Dispersant 4>
Manufacture of pigment dispersant 1 was performed in the same manner as pigment dispersant 1 except that (1A) was changed to (4A) and (P-1) was changed to (P-3), and pigment dispersant 4 was obtained. .

<Production Example of Pigment Dispersant 5>
Manufacture of pigment dispersant A1 was carried out in the same manner as pigment dispersant 1 except that (1A) was changed to (5A), and pigment dispersant 5 was obtained.

  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, 255.0 parts of methanol, 145.0 parts of 2-butanone and 100.0 parts of 2-propanol, As a monomer, 88.0 parts of styrene, 6.2 parts of 2-ethylhexyl acrylate, and 6.6 parts of 2-acrylamido-2-methylpropanesulfonic acid were added and heated under reflux with normal pressure. A solution obtained by diluting 0.8 part of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20.0 parts of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours. Further, a solution obtained by diluting 1.2 parts of 2,2′-azobisisobutyronitrile with 20.0 parts of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours under reflux at normal pressure to polymerize. Ended.

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

  Furthermore, methyl ethyl ketone was added and redissolved so that the particles after the vacuum drying had a concentration of 10%, and the obtained solution was gradually poured into n-hexane 20 times the amount of methyl ethyl ketone and reprecipitated. The obtained precipitate was washed with half the amount of n-hexane used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours. The charge control resin thus obtained has a Tg of about 82 ° C., a main peak molecular weight (Mp) of 19,300, a number average molecular weight (Mn) of 12,700, and a weight average molecular weight (Mw) of 21,100. The acid value was 20.4 mgKOH / g. The obtained resin is designated as charge control resin 1.

<Examples of polyester resin production>
・ Terephthalic acid: 11.1 mol
-Bisphenol A-propylene oxide 2-mol adduct (PO-BPA): 10.8 mol
The above monomer is charged into an autoclave together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirring device are attached to the autoclave, and the pressure is reduced to 220 ° C. in a conventional manner while reducing the pressure in a nitrogen atmosphere The reaction was carried out until Tg reached 70 ° C. to obtain a polyester resin. The weight average molecular weight (Mw) was 8,200, and the number average molecular weight (Mn) was 3,220.

<Example of production of amorphous polyester resin for toner binder resin>
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device,
Terephthalate: 42 parts Bisphenol A-propylene oxide 2-mole adduct: 59 parts Bisphenol A-propylene oxide 3-mole adduct: 37 parts Dibutyltin oxide: 0.03 part, charged in nitrogen atmosphere at 220 ° C. under normal pressure for 22 hours Reaction was performed, and the reaction was further performed under reduced pressure of 10 to 20 mmHg for 1.5 hours to obtain an amorphous polyester resin. The physical properties of the obtained amorphous polyester resin are shown below.
Mw = 9750, Mw / Mn = 2.55, Tg = 71.2 (° C.), acid value = 6.1 (mgKOH / g), SP value = 10.37 (cal / cm ³ )

<Production example of crystalline polyester resin>
A reactor equipped with a stirrer, a thermometer, and an outlet cooler was charged with 175.0 parts of sebacic acid, 166.5 parts of 1,9-nonanediol, and 0.3 parts of tetrabutyl titanate, and the mixture was heated at 180 ° C. for 6 hours. Reaction was performed. Thereafter, the temperature was raised to 200 ° C., the pressure inside the system was gradually reduced, and the reaction was carried out for 5 hours under reduced pressure to obtain a crystalline polyester. The physical properties of the obtained crystalline polyester resin are shown below.
Melting point Tm = 78.4 (° C.), Mw = 20100, acid value = 4.1 (mgKOH / g), SP value = 9.60 (cal / cm ³ )

<Production Example of Toner Particle 1>
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 700.0 parts of ion-exchanged water and 1000.0 parts of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution and 1.0 mol 24.0 parts of a 1 liter HCl aqueous solution was added, and the mixture was kept at 60 ° C. while stirring at 12,000 rpm using a high-speed stirring device TK-homomixer. To this, 85 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene 70.0 parts n-Butyl acrylate 30.0 parts Divinylbenzene 0.1 part Methyltriethoxysilane 1.0 part Pigment dispersant 2 1.0 part Carbon black 10.0 parts Polyester resin 5.0 parts Charge control Agent 1 (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.5 part charge control resin 1 0.5 part mold release agent [behenyl behenate, endothermic main peak temperature 72.1 ° C.] 10.0 parts Polymerization obtained by dispersing the above materials with an attritor for 3 hours Monomer composition 1 was held at 60 ° C. for 20 minutes. Thereafter, the polymerizable monomer composition 1 in which 14.0 parts of tert-butyl peroxypiparate as a polymerization initiator (toluene solution 50%) was added to the polymerizable monomer composition 1 was added to the aqueous dispersion medium. And granulated for 10 minutes while maintaining the rotation speed of the high-speed agitator at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 73 ° C., and the reaction was allowed to proceed for 4 hours with slow stirring. At this time, the pH in the aqueous medium was 5.2. Next, 10.0 parts of 1.0 N NaOH was added to adjust the pH to 8.1, and the temperature inside the container was raised to 88 ° C. and maintained for 8 hours. Thereafter, 4.0 parts of 10% hydrochloric acid was added to 50 parts of ion-exchanged water to adjust the pH to 5.1. Next, 300.0 parts of ion exchange water was added, the reflux tube was removed, and a distillation apparatus was attached. Next, distillation at a temperature in the vessel of 98 ° C. was performed for 5 hours to obtain a polymer slurry 1. The distillation fraction was 310.0 parts.

  Dilute hydrochloric acid was added to the container containing the polymer slurry 1 after cooling to 30 ° C. to remove the dispersion stabilizer. Further, the toner particles having a weight average particle size of 5.5 μm were obtained by filtration, washing and drying. This toner particle was designated as toner particle 1. The formulation and conditions of the toner particles 1 are shown in Table 1, and the physical properties are shown in Table 4.

<Production example of toner particles 2 to 13>
In the production example of toner particles 1, toner particles 2 to 13 were obtained in the same manner as in the production example of toner particles 1 except that the formulation shown in Table 1 was used. The formulation and conditions of toner particles 2 to 13 are shown in Table 1, and the physical properties are shown in Table 4.

<Production Example of Toner Particle 14>
In the production example of toner particles 1, toner particles 14 were prepared in the same manner as in the production example of toner particles 1 except that the pH and pH were adjusted to 4.2 using 10% hydrochloric acid to obtain the formulation and conditions described in Table 1. Obtained. The formulation and conditions of the toner particles 14 are shown in Table 1, and the physical properties are shown in Table 4.

<Production Example of Toner Particles 15 and 16>
In the production example of toner particles 1, toner particles 15 and 16 are prepared in the same manner as in the production example of toner particles 1 except that the pH and pH are adjusted using 1.0 N NaOH to obtain the formulation and conditions described in Table 1. Obtained. The formulation and conditions of toner particles 15 and 16 are shown in Table 1, and the physical properties are shown in Table 4.

<Production Example of Toner Particles 17 to 21>
In the production example of toner particles 1, toner particles 17 to 21 were obtained in the same manner as in the production example of toner particles 1 except that the formulation shown in Table 2 was used. The formulation and conditions of toner particles 17 to 21 are shown in Table 2, and the physical properties are shown in Table 5.

<Production Example of Toner Particles 22>
[Production of Toner Base 22]
Amorphous polyester resin 100.0 parts Pigment dispersant 2 1.0 parts Carbon black 10.0 parts Charge control agent 1 (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.5 parts Charge control resin 1 0.5 parts Mold release agent (behenyl behenate, endothermic main peak temperature 72.1 ° C.) 10.0 parts The above materials are mixed with a Henschel mixer and then biaxially kneaded at 135 ° C. After melt-kneading with an extruder, cooling the kneaded product, coarsely pulverizing with a cutter mill, pulverizing with a fine pulverizer using a jet stream, and further classifying with an air classifier, weight average particles A toner base 22 having a diameter of 5.6 μm was obtained.

[Production of Toner Particles 22]
In a four-necked vessel equipped with a Liebig reflux tube, 700.0 parts of ion-exchanged water, 1000.0 parts of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution and 24.0 parts of a 1.0 mol aqueous HCl solution were added. The mixture was added and kept at 60 ° C. while stirring at 12,000 rpm using a high-speed stirring device TK-homomixer. To this, 85.0 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium 22 containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

  Next, 100.0 parts of toner base 22 and 1.0 part of methyltriethoxysilane were mixed with a Henschel mixer. Next, while stirring the aqueous dispersion medium 22 at 5,000 rpm with a TK-homomixer, the toner material was added and stirred for 5 minutes. Subsequently, this mixed liquid was kept at 70 ° C. for 5 hours. The pH was 5.0. Next, it heated up to 85 degreeC and hold | maintained for 5 hours. Thereafter, 300.0 parts of ion exchange 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 22. The distillation fraction was 315.0 parts. Dilute hydrochloric acid was added to the container containing the polymer slurry 22 to remove the dispersion stabilizer. Further, the toner particles having a weight average particle size of 5.5 μm were obtained by filtration, washing and drying. These toner particles were designated as toner particles 22. The formulation and conditions of the toner particles 22 are shown in Table 2, and the physical properties are shown in Table 5.

<Production Example of Toner Particles 23>
Amorphous polyester resin 100.0 parts Carbon black 10.0 parts Pigment dispersant 2 1.0 parts Charge control agent 1 (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.5 part Charge control resin 1 0.5 part Methyltriethoxysilane 1.0 part Release agent [behenyl behenate, endothermic main peak temperature 72.1 ° C.] 10.0 parts It melt | dissolved in the part and the solution 23 was obtained.

In a four-necked vessel equipped with a Liebig reflux tube, 700.0 parts of ion-exchanged water, 1000.0 parts of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution and 24.0 parts of a 1.0 mol aqueous HCl solution were added. The mixture was added and kept at 60 ° C. while stirring at 12,000 rpm using a high-speed stirring device TK-homomixer. To this, 85.0 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium 23 containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

  Next, while stirring the aqueous dispersion medium 23 at 12,000 rpm with a TK-homomixer, 100.0 parts of the solution 23 was added while stirring at 12,000 rpm with a TK-homomixer, and stirred for 5 minutes. Subsequently, this mixed liquid was kept at 70 ° C. for 5 hours. The pH was 5.0. Next, it heated up to 85 degreeC and hold | maintained for 5 hours. Thereafter, 300.0 parts of ion exchange 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 18. The distillation fraction was 310.0 parts. Dilute hydrochloric acid was added to the container containing the polymer slurry 18 to remove the dispersion stabilizer. Furthermore, the toner particles having a weight average particle diameter of 5.6 μm were obtained by filtration, washing and drying. The formulation and conditions of the toner particles 23 are shown in Table 2, and the physical properties are shown in Table 5.

<Production Example of Toner Particles 24>
"Preparation of resin particle dispersion (1)"
Amorphous polyester resin 100.0 parts Methyl ethyl ketone 50.0 parts Isopropyl alcohol 25.0 parts 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 solution was set at 65 ° C., and while stirring, 10% aqueous ammonia solution was gradually added dropwise to a total of 5.0 parts, and further 230.0 parts of ion-exchanged water was added. The solution was gradually added dropwise at a rate of 10 ml / min for phase inversion emulsification. Further, the solvent was removed by reducing the pressure with an evaporator to obtain a resin particle dispersion (1) of an amorphous polyester resin (1). The resin particles had a volume average particle size of 140 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water.

"Preparation of sol-gel solution of resin particle dispersion"
After adding 1.0 part of methyltriethoxysilane to 100.0 parts (solid content 20.0 parts) of the resin particle dispersion and keeping it at 70 ° C. for 1 hour with stirring, the temperature is increased at 20 ° C./1 h at 80 ° C. Hold for 3 hours. Thereafter, the mixture was cooled to obtain a sol-gel solution of a resin particle dispersion in which resin fine particles were coated with sol-gel. The volume average particle diameter of the resin particles was 225 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water. The sol-gel solution of the resin particle dispersion was stored at 10 ° C. or lower with stirring and used within 48 hours after preparation.

"Preparation of colorant particle dispersion"
Carbon black 50.0 parts Pigment dispersant 2 1.0 parts Ion exchange water 190.0 parts The above components are mixed and dispersed for 10 minutes with a homogenizer (IKA Ultra Tarrax), and then an optimizer (anti-collision type wet pulverizer). : Manufactured by Sugino Machine Co., Ltd.) for 15 minutes at a pressure of 250 MPa to obtain a colorant particle dispersion 1 having a volume average particle diameter of 135 nm and a solid content of 20%.

"Preparation of release agent particle dispersion"
Olefin wax (melting point: 84 ° C.) 60.0 parts Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 2.0 parts Ion-exchanged water 240.0 parts After sufficiently dispersing with UltraTurrax T50 manufactured by the manufacturer, the dispersion is heated to 110 ° C. with a pressure discharge type gorin homogenizer and dispersed for 1 hour to obtain a release agent particle dispersion liquid having a volume average particle size of 170 nm and a solid content of 20%. Obtained.

“Preparation of Toner Particles 24”
Resin particle dispersion 300.0 parts Sol particle solution of resin particle dispersion 300.0 parts Colorant particle dispersion 50.0 parts Release agent particle dispersion 50.0 parts Ionic surfactant Neogen RK 2 in flask After addition of 4 parts, the above materials were stirred. Next, 1N aqueous nitric acid solution was added dropwise to adjust the pH to 3.8, 0.4 parts of aluminum polysulfate was added thereto, and the mixture was dispersed with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After holding at 48 ° C. for 40 minutes, a mixed solution of 300.0 parts of a sol-gel solution of resin particle dispersion was slowly added thereto.

  Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed, gradually heated to 85 ° C. while continuing stirring, and maintained at 85 ° C. for 4 hours. did. Thereafter, 2.0 parts of the ionic surfactant Neogen RK was added and reacted at 95 ° C. for 5 hours. After completion of the reaction, cooling and filtration were performed. It re-dispersed 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 became 7.0 μS / cm or less, the washing was terminated and toner particles 24 were obtained. The formulation and conditions of toner particles 24 are shown in Table 2, and the physical properties are shown in Table 5.

<Production Example of Toner Particles 25>
While stirring 100.0 parts of toner base 22 with a Henschel mixer in a high-speed stirrer, 10.0 parts of toluene, 5.0 parts of ethanol, 5.0 parts of water, and 15.0 parts of vinyltriethoxysilane were added at 85 ° C. 3.5 parts of the organosilicon polymer solution reacted for 5 hours is sprayed.

  Then, the particles were circulated in the fluidized bed dryer for 30 minutes under conditions of an inlet temperature of 80 ° C. and an outlet temperature of 45 ° C. to perform drying and polymerization. Similarly, the obtained treated toner was sprayed in an Henschel mixer with 3.5 parts of the organosilicon polymer solution on 100.0 parts of the treated toner, under conditions of an inlet temperature of 80 ° C. and an outlet temperature of 45 ° C. The fluidized bed dryer was circulated for 30 minutes.

  Similarly, spraying and drying of the organosilicon polymer solution was repeated a total of 10 times to obtain toner particles 25.

<Production Example of Toner Particles 26 to 33>
In the toner particle production example, toner particles 26 to 33 were obtained in the same manner as in the toner particle production example except that the formulation shown in Table 2 was used. The formulation and conditions of toner particles 26 to 33 are shown in Table 2, and the physical properties are shown in Table 5.

<Production example of comparative toner particles 1 to 9>
Comparative toner particles 1 to 9 were obtained in the same manner as in the toner particle 1 manufacturing example except that the formulation shown in Table 3 was used in the toner particle 1 manufacturing example. The formulations and conditions of comparative toner particles 1 to 9 are shown in Table 3, and the physical properties are shown in Table 6.

<Production Example of Comparative Toner Particle 10>
In a four-necked flask equipped with a high-speed stirrer TK-homomixer, 900.0 parts by mass of ion-exchanged water and 95.0 parts by mass of polyvinyl alcohol are added and heated to 55 ° C. while stirring at a rotational speed of 1300 rpm. Thus, an aqueous dispersion medium was obtained.

(Composition of monomer dispersion)
Styrene 70.0 parts n-Butyl acrylate 30.0 parts Pigment dispersant 5 1.0 part Carbon black 10.0 parts Salicylic acid silane compound 1.0 part Release agent (behenyl behenate, endothermic main peak temperature 72.1 (C) 10.0 parts The above materials were dispersed with an attritor for 3 hours, and then 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, washing and drying were performed to obtain black toner particles as a base material. The weight average particle size was 5.70 μm.
To a mixed solution of 2 parts of isoamyl acetate, 3.5 parts of tetraethoxysilane as a silicon compound and 0.5 part of methyltriethoxysilane, 3.0 parts of 0.3 part by weight sodium dodecylbenzenesulfonate solution was added. A mixed solution A of isoamyl acetate, tetraethoxysilane, and methyltriethoxysilane was prepared by stirring using a sonic homogenizer.

The mixed solution A is added to 1.0 part of a base black toner particle in 30.0 parts of a 0.3% by mass sodium dodecylbenzenesulfonate aqueous solution, and then mixed with 5.0 parts of a 29.0% by mass NH ₄ OH aqueous solution. And stirred at room temperature (25 ° C.) for 12 hours. After washing with ethanol, it was washed with purified water, and the particles were filtered and dried to obtain comparative toner particles 10. The weight average particle size of the obtained toner was 5.8 μm. The formulation and conditions of the comparative toner particles 10 are shown in Table 3, and the physical properties are shown in Table 6.

  Comparative toner particle 10 had a coating layer formed by adhering the granular masses together.

“Observation of surface layer of toner particle 1”
With respect to the toner particles 1, a TEM bright field image was obtained at an acceleration voltage of 200 kV using an electron microscope TecnaiTF20XT manufactured by FEI. From the obtained TEM image, an EF mapping image at the Si-K end (99 eV) was obtained by the Three Window method using an EELS detector GIFTridiem manufactured by Gatan. From the acquired mapping image, it was confirmed that the toner particles 1 were covered with a surface layer having silicon. Moreover, it was confirmed that the thickness of the surface layer containing silicon is the same as the thickness obtained using the above transmission electron microscope (TEM).

<Production Example of Toner 1>
Hydrophobic silica 0.5% having a surface area of 210 m ² / g by BET method, 4% by weight of hexamethyldisilazane, and 3% by weight of 100 cps silicone oil with respect to 100.0 parts of toner particles 1 Toner 1 is a toner obtained by mixing 0.2 part of aluminum oxide and 0.2 part of aluminum oxide having a specific surface area of 70 m ² / g by BET method using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.).

<Production example of toners 2 to 33>
Toners 2 to 33 were obtained in the same manner as in the manufacturing example of toner 1 except that toner particle 1 was changed from toner particles 2 to 33 in the manufacturing example of toner 1.

<Production Example of Comparative Toners 1 to 10>
Comparative toners 1 to 10 were obtained in the same manner as in the production example of comparative toner particles 1 except that the toner particles 1 were changed from comparative toner particles 1 to 10 in the production example of toner 1.

"Evaluation of properties after cleaning toner 1"
A mixture of 1.0 part of toner 1, 100.0 parts of ion-exchanged water, and 0.01 part of sodium dodecylbenzenesulfonate was ultrasonically dispersed for 5 minutes and centrifuged. The upper 20% of the filtrate was collected. The obtained filtrate was dried and the physical properties thereof were measured. As a result, the toner 1 after washing had the same toner physical property results as the toner particles 1 (Tables 1, 4 and 7).

“Evaluation of physical properties of toners 2 to 33 and comparative toners 1 to 10 after cleaning”
In the physical property evaluation after cleaning of the toner 1, when the toner 1 is changed to the toner N (N = 2 to 33) and the comparative toner M (M = 1 to 10), the toner N, the toner particle N, the comparative toner M, and the comparison The toner particles M were the same as the toner physical property results (Tables 1 to 9).

<Example 1>
The following evaluation was performed using toner 1.

  A toner cartridge of a tandem laser beam printer HP Color Laser Jet Enterprise CP4525dn (manufactured by Hewlett Packard) having the configuration as shown in FIG. 4 was used, and 240 g of toner 1 was loaded. And under each environment of low temperature and low humidity L / L (10 ° C./15% RH), normal temperature and normal humidity N / N (25 ° C./50% RH), super high temperature high humidity SHH (32.5 ° C./90% RH) Left for 24 hours. After leaving for 24 hours in each environment, print out up to 1,000 images with a printing ratio of 35%, and evaluate initial and fogging when outputting 1,000 sheets, and transferability when outputting 1,000 sheets. It was. As image output paper, A4 size high white paper GF-C081 (manufactured by Canon Marketing Japan Inc.) was used.

<Evaluation of fog>
The fog density (%) is calculated from the difference between the whiteness of the white portion of the printed image and the whiteness of the transfer paper measured by “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.), and the image fog is evaluated according to the following criteria. did. A, B, and C are practical levels.
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

<Evaluation of transferability>
In the evaluation of transferability, after printing 1,000 sheets, a solid image was developed on a drum under the condition of a printing rate of 5% under each environment, and then transferred to the image output paper to obtain an unfixed image. The transfer efficiency was determined from the change in weight between the toner amount on the drum and the toner amount on the transfer paper. (The transfer efficiency is 100% when the entire amount of toner on the drum is transferred onto the image output paper.) The evaluation rank is as follows. A, B, and C are practical levels.
A: Transfer efficiency is 95% or more B: Transfer efficiency is 90% or more and less than 95% C: Transfer efficiency is 85% or more and less than 90% D: Transfer efficiency is 80% or more and less than 85% E: Transfer efficiency is less than 80

<Preservation test>
About 10 g of toner was placed in a 100 ml glass bottle and allowed to stand at 55 ° C. for 5 days. A, B, and C are practical levels.
A: No change B: There is an aggregate, but loosens immediately C: Hard to loosen D: No fluidity E: Obvious caking

<Long-term storage stability test>
About 10 g of toner was placed in a 100 ml glass bottle and left to stand at 45 ° C./95% for 1 month. A, B, and C are practical levels.
A: No change B: There is an aggregate, but loosens immediately C: Hard to loosen D: No fluidity E: Obvious caking

<Evaluation of low temperature fixability (low temperature offset end temperature)>
Canon fixing unit of laser beam printer CP4525dn manufactured by Canon has been modified so that the fixing temperature can be adjusted, and an unfixed toner image with a toner loading of 0.4 mg / cm ^{2 at} a process speed of 230 mm / sec is received by a modified fixing device. Then, heat and pressure were applied without oil to form a fixed image on the image receiving paper.

The fixing property is Kimwipe [S-200 (Crecia)], and the fixed image is rubbed 10 times with a load of 75 g / cm ² , and the temperature at which the density reduction rate before and after the rub is less than 5% is finished at the low temperature offset. It was temperature. Evaluation was carried out at room temperature and normal humidity (25 ° C./50% RH).

<Examples 2 to 30>
The same evaluation as in Example 1 was performed except that the toner 1 of Example 1 was changed from toner 2 to 30. The results are shown in Table 10, Table 11, and Table 12.

<Comparative Examples 1 to 10>
The same evaluation as in Example 1 was performed except that the toner 1 of Example 1 was changed from the comparative toner 1 to 10. The results are shown in Table 10, Table 11, and Table 12.

<Examples 31 to 33>
A toner cartridge of a tandem laser beam printer HP Color Laser Jet Enterprise CP4525dn (manufactured by Hewlett Packard) having the configuration shown in FIG. 4 was used, and 240 g of toner 1 (black) was loaded. Similarly, 240 g of toner 31 (yellow), toner 32 (magenta), and toner 33 (cyan) were filled in a CP4525dn toner cartridge. The four color cartridges are respectively low temperature and low humidity L / L (10 ° C / 15% RH), normal temperature and normal humidity N / N (25 ° C / 50% RH), super high temperature and high humidity SHH (32.5 ° C / 90% RH). ) In each environment for 24 hours. After leaving for 24 hours in each environment, set black, yellow, magenta, and cyan cartridges to CP4525dn, and print up to 1,000 images with a print ratio of 35%. The transferability at the time of fog and 1,000 sheets output was evaluated. As a result, good results were obtained without any practical problems.

  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: Charging for cleaning Device: 11: stirring blade, 12: driving roller, 13: transfer roller, 14: bias power source, 15: tension roller, 16: transfer conveying belt, 17: driven roller, 18: paper, 19: paper feeding roller, 20: Adsorption roller, 21: fixing device

Claims (10)

A surface layer containing an organosilicon polymer which is a polymer of an organosilicon compound ;
A binder resin, a pigment and a pigment dispersant ;
What manufacturing method der toner having toner particles having,
The manufacturing method comprises:
A polymerizable monomer constituting the binder resin,
The pigment,
The pigment dispersant, and
The organosilicon compound
A step of producing the toner particles by granulating a polymerizable monomer composition containing an aqueous medium and polymerizing the polymerizable monomer;
Organosilicon polymer has a unit represented by the following formula (1),

(In the formula (1), R is more than 6 hydrocarbon group having a carbon also is an aryl group.)
The pigment dispersant is
An adsorbing component adsorbing to the pigment;
A polymer component having affinity for the binder resin and the polymerizable monomer, and
Connecting portion for binding the polymer component and the adsorbing component
Consists of
In the measurement using X-ray photoelectron spectroscopy (ESCA) on the surface of the toner particles, the silicon element concentration dSi is 0 with respect to the total concentration (dC + dO + dSi) of the carbon element concentration dC, oxygen element concentration dO and silicon element concentration dSi on the toner surface. .5 atomic% or more,
The SP value difference between the binder resin of the pigment dispersing agent is at ± 2.0 or less, the production method of the toner adsorption rate to said pigment is characterized in that 30% or more. The pigment dispersing agent, method for producing a toner according to 請 Motomeko 1 Ru der azo compound. In the chart obtained by the measurement of ²⁹ Si-NMR in THF-insoluble matter of the toner particles, the above formula (1) percentage ST3 of the peak area attributed to the unit represented by to the total peak area of the organic silicon polymer ST3 ≧ 0.40 satisfying the following formula (a) (a)
Method for producing a toner according to 請 Motomeko 1 or 2. In the measurement of ²⁹ Si-NMR in THF-insoluble matter of the toner particles, the peak area of the structure of the total peak area of the organic silicon polymer, the number of siloxy groups bonded to silicon is 3.0 (SX3) the ratio S (SX3) of the the number of O _1/2 bonded to silicon is 2.0 peak area S of the structure (SX2) (SX2) but, S (SX3) / S ( SX2) ≧ 1 method for producing a toner according to any one of 請 Motomeko 1-3 that meet the .00. In the cross section observation of the toner particles using transmission electron microscopy (TEM), evenly around the long axis L and the center intersection of streets and perpendicular axis L90 of the long axis L of the cross section of the toner particles 16 when divided shaft from the center of the case was RAn (n = 1~32), respectively, the average thickness Dav of the surface layer of 32 places on the shaft. Method for producing a toner according to but any one of 請 Motomeko 1-4 Ru der least 2.5 nm. The organic silicon compound, method for producing a toner according to any one of Ah Ru請 Motomeko 1-5 in which Ru of compounds represented by the following formula (2).

(In the formula (2), R ₁ is a hydrocarbon group having 6 or less carbon atoms, R _2, R ₃ and R ₄ are each independently a halogen atom, a hydroxyl group or an alkoxy group.) Formula (2) R ₁ in the method for producing a toner according to 請 Motomeko 6 Ru Oh a methyl group, an ethyl group or a propyl group. Formula ₍₂₎ R 2, R ₃ and R ₄ are in each, independently, method for producing a toner according to 請 Motomeko 6 or 7 Ru alkoxy der. The pigment dispersing agent, method for producing a toner according to any one of claims 1 to 8 having a structure represented by the following formula (3).

(In the formula (3), it is one of R _5, R ₆ or Ar, to have a structure that binds to the polymer component via a single bond or a linking group.
R ₅ is an alkyl group, a phenyl group, OR ₉ group, or NR ₁₀ R ₁₁ group, R ₉ to R ₁₁ are each independently a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
However, when R ₅ has a structure that binds to the polymer component, it is bonded via a single bond or a linking group, and the linking group bonded to R ₅ is an amide group, an ester group, a urethane group, a urea group, an alkylene group, phenylene group, -O -, - NR ₇ - and -NHCH (CH ₂ OH) - is a divalent linking group selected from the group consisting of, R ₇ is a hydrogen atom, an alkyl group, phenyl or an aralkyl group There is .
R ₆ is an alkyl group, a phenyl group, OR ₁₃ group or NR ₁₄ R ₁₅ radical, R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
However, when R ₆ has a structure bonded to the polymer component, the bonding group bonded via a single bond or a linking group and bonded to R ₆ is an alkylene group, a phenylene group, —O—, —NR ₁₂ —, -NHCOC (CH _{3) 2} - and -NHCH (CH ₂ OH) - is a divalent linking group selected from the group consisting of, R ₁₂ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
Ar is an aryl group .
However, when Ar has a structure that binds to a polymer component, it is bonded via a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, an alkylene group, or a phenylene group , -O -, - NR ₇ - and -NHCH (CH ₂ OH) - is a divalent linking group selected from the group consisting of, R ₇ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
The single bond or the linking group, if R _5, R ₆ or which bind to Ar is, R _5, R ₆ or bonded substituted with hydrogen atom in Ar. ) It said polymer component, method for producing a toner according to any one of the polymers or copolymers der Ru請 Motomeko 1-9 having the unit represented by the following formula (4).

(In the formula (4), R ₁₆ is .R ₁₇ hydrogen atom or a carbon number is 1 or 2 alkyl groups, a phenyl group, a carboxyl group, a carboxylic acid ester group or a carboxylic acid amide group.)

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