JP6573387B2 - toner - Google Patents

Description

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

Typical examples of electrophotographic systems that use toner include machines such as laser printers and copiers. In recent years, in order to achieve cleaner-less and waste toner reduction, improvement in toner transferability has been demanded.
In the electrophotographic system, positively or negatively charged toner is carried on a toner carrier, and the electrostatic image carrier is charged to create a potential difference between the image area and the non-image area. Development is performed on the image portion of the carrier. The developed toner on the electrostatic image bearing member is fixed to the transfer material by heat and pressure after being transferred to a transfer material such as paper or transferred to an intermediate transfer member and further transferred to the transfer material (transfer process) Is done.
In the transfer process, the toner on the electrostatic image bearing member receives a transfer bias, and is transferred to the transfer material by electrostatic attraction. Sometimes. By finely controlling the transfer current, it is often possible to reduce the amount of toner that remains on the electrostatic charge image carrier without being transferred in various environments and situations, so-called residual toner is often reduced. The demerit that occurs. Therefore, there is a demand for a small amount of residual toner (good transferability) in a wide transfer current region. In this specification, the fact that there is little residual toner in a wide transfer electric energy region is expressed as a wide transfer latitude.

In order to improve toner transferability, it is generally known that it is effective to reduce the adhesion of the toner to the electrostatic image carrier.
As a means for reducing the adhesion force of the toner, a method of attaching an external additive to the surface of the toner particles can be mentioned. A typical example of the external additive is silica fine particles. Silica is composed of silicon dioxide and the chemical structure is SiO ₂ . Therefore, it was thought that if the surface of the toner particles can be uniformly covered with a silicon compound, the adhesive force can be further reduced. Furthermore, if the silicon compound covering the surface of the toner particles covers the toner without deterioration even after durable use, it is considered that a toner that can maintain the effect of reducing the adhesive force can be obtained, and has been studied. .
As an example of the idea of covering the surface of toner particles with a silicon compound, a method for producing a polymerized toner characterized by adding a silane coupling agent to a reaction system is disclosed (see Patent Document 1).
Alternatively, a polymerized toner containing a silicon compound applied to the surface portion in the form of a continuous thin film is disclosed (see Patent Document 2).

Japanese Patent Laid-Open No. 03-089361 JP 09-179341 A

However, in the method of Patent Document 1, the amount of silane compound deposited on the toner surface is probably insufficient, so that a large transferability improvement effect cannot be obtained. In addition, the toner of Patent Document 2 continues to stay on the toner carrier as the toner is charged up, particularly under low temperature and low humidity. It may increase and transferability may decrease. Further, the deteriorated toner is likely to generate particles with insufficient charge amount or particles (charge amount reversal component) charged with a polarity opposite to the design concept, and there is a possibility that the transfer latitude becomes narrow.
For the reasons described above, a toner having a toner particle surface covered with a silicon compound that is excellent in transferability under a low temperature and low humidity environment is desired.
An object of the present invention is to provide a toner that improves transferability more than ever in a low-temperature and low-humidity environment, and that the effect lasts through durable use. In particular, an object of the present invention is to provide a toner capable of obtaining high transfer efficiency under a wide range of transfer current conditions.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following toner.
That is, the present invention is a toner having toner particles having a surface layer containing an organosilicon polymer and a resin having an ionic functional group,
The organosilicon polymer has a partial structure represented by the following formula (1) or (2):
In the X-ray photoelectron spectroscopic analysis of the surface of the toner particle, when the total of the carbon atom concentration dC, oxygen atom concentration dO, and silicon atom concentration dSi on the toner particle surface is 100.0 atomic%, the silicon The atomic concentration dSi is 1.0 atomic% or more and 22.2 atomic% or less,
The toner has a pKa (acid dissociation constant) of the resin having an ionic functional group of 6.0 or more and 9.0 or less.

（式（２）中のＬは、メチレン基、エチレン基又はフェニレン基を表す。）

(L in the formula (2) represents a methylene group, an ethylene group or a phenylene group.)

  According to the present invention, it is possible to provide a toner in which high transfer efficiency can be obtained under a wide range of transfer current conditions in a low temperature and low humidity environment, and the effect can be sustained through durable use.

Conceptual diagram that defines the surface thickness of toner surfaces containing organosilicon compounds An example of an electrophotographic apparatus to which the present invention can be applied

Hereinafter, the present invention will be described in detail. The present invention is a toner having toner particles having a surface layer containing a resin having an organosilicon polymer and an ionic functional group,
The organosilicon polymer has a partial structure represented by the following formula (1) or (2):
In the X-ray photoelectron spectroscopic analysis of the toner particle surface, when the total of the carbon atom concentration dC, oxygen atom concentration dO, and silicon atom concentration dSi on the toner particle surface is 100.0 atomic%, silicon atoms Concentration dSi of 1.0 atomic% or more and 22.2a
tomic% or less,
The toner has a pKa (acid dissociation constant) of 6.0 to 9.0 in the resin having an ionic functional group.

(L in the formula (2) represents a methylene group, an ethylene group or a phenylene group.)
In the toner of the present invention, high transfer efficiency is obtained in a wide transfer current region in a low temperature and low humidity environment, and the effect is maintained through durable use.
The inventors of the present invention have focused on reducing the adhesive force of the toner in order to improve the transferability, and have continued to study to uniformly cover the toner particle surface with a silicon compound. However, under low temperature and low humidity, as described above, the toner may be charged up and remain on the toner carrier. The toner that remains on the toner carrier increases the load, so that the uniformity of the toner surface is impaired when the silicon compound on the surface of the toner particles is partially peeled off or the silicon compound that has been peeled off adheres to the toner surface again. It is thought that it will be.
As a result, it was speculated that the adhesion force of the toner increased through durable use, and at the same time, particles with insufficient charge amount and charge amount reversal components also increased, resulting in a narrow transfer latitude.
Therefore, it was thought that if toner charge-up can be suppressed, toner deterioration can be suppressed even under low temperature and low humidity, and high transfer efficiency can be maintained under a wide range of transfer current conditions.
As a result of intensive studies, the toner particles have a surface layer containing a specific organosilicon polymer and a resin having a pKa (acid dissociation constant) having an ionic functional group of 6.0 or more and 9.0 or less. Thus, it has been found that charge transfer is suppressed in a low-temperature and low-humidity environment, and that high transfer efficiency is maintained under a wide range of transfer current conditions through durable use.

Hereinafter, the toner configuration of the present invention will be described.
The toner of the present invention contains an organosilicon polymer having a partial structure represented by the above formula (1) or (2) in the surface layer. In the organosilicon polymer, one of the four valences of Si atoms is bonded to the following formula (iii) or (iv), and the remaining three are bonded to O atoms.

(* Is a bond with a silicon atom. L in formula (iv) represents a methylene group, an ethylene group or a phenylene group.)
O atoms constitute a state in which two valences are both bonded to Si, that is, a siloxane bond (Si—O—Si). Considering Si atoms and O atoms as an organosilicon polymer, two Si atoms and three O atoms are expressed as —SiO _3/2 . The —SiO _3/2 structure of this organosilicon polymer is considered to have properties similar to silica (SiO ₂ ) composed of a large number of siloxane bonds. Therefore, the toner of the present invention is considered to create a situation similar to the case where silica is added to the surface. Thereby, it is considered that the surface of the toner particles can be strengthened.
On the other hand, by including the structure of the formula (iii) or (iv), it can react with various polymerizable monomers including a vinyl polymerizable monomer to form a crosslinked structure. Therefore, the toner of the present invention can increase the adhesion between the inside of the toner particles and the surface layer, and the toner is less likely to deteriorate due to rubbing or pressure during durable use. Therefore, it is considered that the effect of the present invention can be maintained through durable use.

The toner of the present invention is also characterized in that the surface layer contains a resin having a pKa having an ionic functional group of 6.0 or more and 9.0 or less.
It has been clarified that the resin having the ionic functional group is negatively charged and can maintain a state in which the adhesion force of the toner is reduced under low temperature and low humidity when it coexists with the organosilicon polymer. Although details are unknown, it is presumed that the resin having the ionic functional group is excellent in humidity control and has an effect of moderately suppressing the charge-up of the organosilicon polymer under low temperature and low humidity.
It was also found that the toner charge amount is stabilized through durable use, and the charge amount reversal component is reduced. Although details in this respect are also unclear, since the organosilicon polymer has an organic network having a partial structure represented by the formula (iii) or (iv), the organosilicon polymer has the ionic functional group-containing resin. It is considered that the affinity is high. Therefore, the adhesiveness between the two becomes strong. As a result, toner deterioration due to rubbing and pressure during durable use hardly occurs. In other words, even if the printing process speed is increased or the number of printed sheets is increased in durable use (this is expressed as severe durable use in this specification), the toner of the present invention is deteriorated more than before. It is suppressed. From the above, it is considered that the toner of the present invention can stabilize the charge amount of the toner and can maintain the effect of suppressing the charge amount reversal component through severe endurance use.

When pKa (acid dissociation constant) is less than 6.0, the charging performance is too high, so that charge-up occurs under low humidity. When pKa (acid dissociation constant) exceeds 9.0, the charging ability is low and the charge amount reversal component increases.
The pKa of the resin having an ionic functional group is preferably in the range of 7.0 or more and 8.5 or less.
Although the method of calculating pKa (acid dissociation constant) will be described later, it can be determined from the neutralization titration result.
Any resin having an ionic functional group may be used as long as it satisfies the above pKa (acid dissociation constant).
For example, a resin having a hydroxyl group bonded to an aromatic ring or a carboxy group bonded to an aromatic ring tends to have a pKa (acid dissociation constant) in the above range.
For example, those obtained by polymerizing vinyl salicylic acid, 1 vinyl phthalate, vinyl benzoic acid, 1-vinyl naphthalene-2-carboxylic acid are preferable.

In order to facilitate the inclusion of the organosilicon polymer in the surface layer, the silicon polymer preferably has a small number of carbon atoms. Specifically, among the partial structures represented by the formula (2), L is preferably a methylene group, more preferably a partial structure represented by the formula (1). When the number of carbon atoms per unit of the organosilicon polymer is 3 or more, the surface precipitation property of the organosilicon polymer is lowered, and the coverage of the toner particles tends to be lowered accordingly. Moreover, it is important that L is a hydrocarbon group among the partial structures represented by Formula (2). For example, when an ester group is included, the durability tends to decrease because the bonding strength of the ester bond is weak.

In the present invention, in the X-ray photoelectron spectroscopic analysis of the surface of the toner particles, the total of the carbon atom concentration dC, oxygen atom concentration dO, and silicon atom concentration dSi on the toner particle surface is 100.0 atomic%. In some cases, the silicon atom concentration dSi must be 1.0 atomic% or more and 22.2 atomic% or less.
The main atoms of toner particles that are usually considered are carbon (C) and oxygen (O). In the present invention, when silicon (Si) atoms are present on the toner particle surfaces, a —SiO _3/2 structure derived from the partial structure represented by the formula (1) or (2) is present. The X-ray photoelectron spectroscopic analysis is an elemental analysis of the outermost surface of several nm. The higher the silicon atom concentration dSi, the more the organosilicon polymer of the present invention is present on the toner particle surface.
When dSi is less than 1.0 atomic%, a sufficient amount of the organosilicon polymer does not exist on the toner particle surface. For this reason, the adhesion force of the toner cannot be lowered, and it is difficult to obtain the effects of the present invention as described above. When dSi is more than 22.2 atomic%, the resin having the ionic functional group is hardly present on the toner particle surface. For this reason, it is difficult to maintain the effect of the present invention due to the occurrence of charge-up through severe endurance use. The effect of the present invention is effectively exhibited when the silicon atom concentration dSi is 1.0 atomic% or more and 22.2 atomic% or less. The silicon atom concentration dSi is preferably 9.0 atomic% or more and 21.0 atomic% or less. The dSi can be controlled by the method for producing toner particles at the time of forming the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH at the time of forming the organosilicon polymer. It can also be controlled by the monomer type and amount of the organosilicon polymer.
As described above, due to the toner configuration, the transfer latitude is wide in a low temperature and low humidity environment, and the effect is maintained through durable use.

Various methods are conceivable as means for allowing the organosilicon polymer and the resin having the ionic functional group to coexist. In order to effectively exhibit the effects of the present invention, the ionic functional group is formed on the outermost surface of the toner. It is preferable that a resin having
Therefore, a method of fixing the resin having an ionic functional group from the outside after producing toner base particles containing the organosilicon polymer is preferable.
Specifically, the toner base particles and the resin are mixed by a dry method and fixed by mechanical treatment, or the toner base particles and the resin having the ionic functional group are dispersed in a resin particle state in an aqueous medium. And a method of heating or adding a flocculant.
In the present invention, it is preferable that the resin particles are fixed to the surface of the toner base particles by heating in an aqueous medium. This is because the resin particles are dispersed in an aqueous medium in a charged state, so that the resin having the ionic functional group can be uniformly fixed on the surface of the toner base particles without aggregation. Further, since the unevenness of the toner particle surface can be increased, the adhesion force of the toner can be further reduced.

The production method of the resin particles may be any method. For example, those produced by a known method such as an emulsion polymerization method, a soap-free emulsion polymerization method, a phase inversion emulsion method, or a mechanical emulsion method can be used. Among these production methods, the phase inversion emulsification method is preferable because it does not require an emulsifier and a dispersion stabilizer and resin particles having a smaller particle diameter can be easily obtained.
In the phase inversion emulsification method, a resin having self-dispersibility or a resin capable of developing self-dispersibility by neutralization is used. Here, self-dispersibility in an aqueous medium is exhibited in a resin having a hydrophilic group in the molecule. Specifically, good self-dispersibility is exhibited in a resin having a polyether group or an ionic functional group.

For the production of the resin particles, for example, a resin having an ionic functional group that exhibits self-emulsifying properties by neutralization is used. Specifically, a resin having an ionic functional group and a pKa (acid dissociation constant) of 6.0 or more and 9.0 or less is used.
By neutralizing the ionic functional group in the resin, the hydrophilicity is increased and self-dispersion in an aqueous medium becomes possible. When the resin is dissolved in an organic solvent, a neutralizing agent is added, and the resin is mixed with an aqueous medium while stirring, the resin solution causes phase inversion emulsification to produce fine particles. The organic solvent is removed using a method such as heating or decompression after phase inversion emulsification. Thus, according to the phase inversion emulsification method, a stable aqueous dispersion of resin particles can be obtained without substantially using an emulsifier or a dispersion stabilizer.

  In the present invention, the average particle diameter of the resin particles is preferably in the range of 5 nm to 300 nm in terms of volume-based median diameter (D50) determined by particle size distribution measurement by a laser scattering method. More preferably, it is the range of 20 nm or more and 200 nm or less. Sufficient durability can be easily obtained when the volume-based median diameter (D50) is 5 nm or more. In addition, when the volume-based median diameter (D50) is 300 nm or less, it is easy to fix uniformly.

  The content of the resin having an ionic functional group is preferably 0.1 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer. More preferably, they are 0.2 mass part or more and 1.0 mass part or less.

The thickness of the surface layer of the toner particles used in the present invention can be defined in cross-sectional observation using a transmission electron microscope (TEM), and details will be described later. Average thickness Dav. Of the surface layer containing the organosilicon polymer and the resin having the ionic functional group. However, it is preferable that it is 5.0 nm or more. By the thickness of the surface layer, the toner particles can be more firmly protected from rubbing and pressure in severe use. Therefore, the effect of the present invention is further maintained, that is, it is possible to further maintain a wide transcription latitude.
More preferably, the average thickness is 10.0 nm or more. On the other hand, the average thickness is preferably 150.0 nm or less, and more preferably 100.0 nm or less, from the viewpoint of low-temperature fixability.

It is further possible that the ratio of the number of split axes in which the thickness of the surface layer of the toner particles is 2.5 nm or less (hereinafter also referred to as the ratio of the thickness of the surface layer of 2.5 nm or less) is 20.0% or less. It is a good condition. This condition approximates that at least 80.0% or more of the area of the surface layer of toner particles is composed of the surface layer of 2.5 nm or more. That is, when this condition is satisfied, there are few gaps between the surface layers, and the toner particle surfaces are sufficiently covered. Therefore, the effect of the present invention that effectively suppresses the charge amount reversal component through harsh endurance and exhibits a wide range of transfer latitude can be made more stable.
The ratio of the thickness of the surface layer of 2.5 nm or less is more preferably 10.0% or less.

  Average thickness Dav. The ratio of the surface layer thickness of 2.5 nm or less can be controlled by the method for producing toner particles during the formation of the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH during the formation of the organosilicon polymer. it can. It can also be controlled by the amount of monomer of the organosilicon polymer. Furthermore, the amount of the resin having an ionic functional group and, when the resin having an ionic functional group is used in the state of resin particles, can also be controlled by the particle size of the resin particles.

In the chart obtained by measuring ²⁹ Si-NMR of the THF-insoluble matter of the toner particles of the present invention, the ratio of the peak area attributed to the structure of the following formula (5) to the total peak area of the organosilicon polymer is 40%. This is another favorable condition. The ratio is more preferably 50% or more and 100% or less.
Rf-SiO _3/2 formula (5)
(In formula (5), Rf is the following formula (iii) or (iv))

(* Is a bond with a silicon atom. L in formula (iv) represents a methylene group, an ethylene group or a phenylene group.)
The detailed measurement method will be described later. This is represented by the partial structure represented by —SiO _3/2 and the above formula (iii) or (iv) in the organosilicon polymer contained in the toner particles. It is approximated to have 40.0% or more of both of the partial structures.
As described above, it is the meaning of the partial structure of —SiO _3/2 that three of the four valences of the Si atom are bonded to an oxygen atom, and these oxygen atoms are bonded to another Si atom. If one of the oxygens is a silanol group, the partial structure of the organosilicon polymer is represented by Rf—SiO _2/2 —OH. Further, if two oxygens are silanol groups, the partial structure is Rf—SiO _1/2 (—OH) ₂ . When these structures are compared, it is closer to the silica structure represented by SiO ₂ when more oxygen atoms form a crosslinked structure with Si atoms. Therefore, it is considered that the more the —SiO _3/2 skeleton, the harder the properties and the higher the durability. On the other hand, if the oxygen atom remains in the form of a silanol group and does not form a cross-linked structure, the resin-like properties become dominant and the durability tends to be lowered.

Moreover, the partial structure of the said formula (iii) or (iv) means reacting with various polymerizable monomers including a vinyl-type polymerizable monomer, and forming the crosslinked structure. Therefore, it can be said that the structure of Formula (5) has both the inorganic network by -SiO3 _{/ 2} and the organic network by the said Formula (iii) or (iv). Therefore, the toner has a strong binding force between the inorganic structure and the organic structure, and the durability is further improved.
Therefore, the ratio of the peak area attributed to the structure of the above formula (5) is preferably 40% or more in order to further improve the durability and the environmental stability.
The ratio of the peak area can be controlled by the method for producing toner particles during the formation of the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent, and the pH during the formation of the organosilicon polymer.

The toner particles of the present invention are produced by granulating a polymerizable monomer composition containing an organosilicon compound and a polymerizable monomer in an aqueous medium and polymerizing the polymerizable monomer. More preferably.
When the toner particles are produced in an aqueous medium, the organosilicon compound is likely to be present on the surface of the toner particles due to the hydrophilicity of a hydrophilic group such as a silanol group of the organosilicon compound. Therefore, it is easy to control the core-shell structure that the organosilicon polymer forms the surface layer, and the effects of the present invention are further exhibited.
The organosilicon compound forming the organosilicon polymer is represented by the above formula (iii) or (iv) by polymerizing in a water-based medium together with a polymerizable monomer that serves as a binder resin for toner particles. It becomes easy to form a crosslinked structure. As a result, the adhesion between the inside of the toner particles and the surface layer becomes stronger, and the durability of the effect of suppressing the charge amount reversal component in the present invention is further improved.

  In addition, it is preferable that the organosilicon polymer used for this invention is a polymer of the polymerizable monomer containing the organosilicon compound which has a structure represented by following formula (3).

（式（３）中、Ｒｆは下記式（ｉ）又は（ｉｉ）を表し、Ｒ１、Ｒ２及びＲ３は、それぞれ独立して、ハロゲン原子、水酸基、アセトキシ基又は炭素数１〜６（好ましくは１〜３）のアルコキシ基を表す。）

(In the formula (3), Rf represents the following formula (i) or (ii), and R1, R2, and R3 each independently represent a halogen atom, a hydroxyl group, an acetoxy group, or a carbon number of 1 to 6 (preferably 1 -Represents the alkoxy group of 3).)

※は、ケイ素原子との結合部である。Ｌは、メチレン基、エチレン基又はフェニレン基を表す。

* Indicates a bond with a silicon atom. L represents a methylene group, an ethylene group or a phenylene group.

The reactive group of R1 to R3 undergoes hydrolysis, addition polymerization, and condensation polymerization to form a crosslinked structure with a siloxane bond (Si—O—Si). In view of the controllability of polymerization conditions and the ease of forming a siloxane structure, the reactive groups R1 to R3 are preferably alkoxy groups having mild hydrolyzability at room temperature. Furthermore, a methoxy group or an ethoxy group is more preferable from the viewpoints of the precipitation property of the organosilicon polymer on the toner particle surface and the covering property. The hydrolysis, addition polymerization and condensation polymerization of R1 to R3 can be controlled by the reaction temperature, reaction time, reaction solvent and pH.
The addition amount of the organosilicon compound is preferably 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the binder resin or polymerizable monomer.

A typical production example of the organosilicon polymer includes a production method called a sol-gel method. In the sol-gel method, a metal alkoxide M (OR) n (M: metal, O: oxygen, R: hydrocarbon, n: oxidation number of metal) is used as a starting material, and hydrolysis and condensation polymerization are performed in a solvent. It is a method of gelling through a state, and is used for the synthesis of glass, ceramics, organic-inorganic hybrids, and nanocomposites. According to this production method, functional materials having various shapes such as surface layers, fibers, bulk bodies, and fine particles can be produced from a liquid phase at a low temperature.
Specifically, the surface layer of the toner particles is preferably generated by hydrolysis polycondensation of an organosilicon compound typified by alkoxysilane. By providing this surface layer uniformly on the surface of the toner particles, the toner performance is less likely to deteriorate during long-term use without the need for fixing and adhering inorganic fine particles as is done with conventional toners. A toner having excellent storage stability can be obtained.

  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, they are likely to be present on the surface of the toner particles due to hydrophilicity due to hydrophilic groups such as silanol groups of the organosilicon compound. However, when the hydrophobicity of the organosilicon compound is too high (for example, when the organosilicon compound has a highly hydrophobic functional group), it becomes difficult to deposit the organosilicon compound on the surface layer of the toner particles. As a result, the toner particles are difficult to form a surface layer containing an organosilicon polymer. On the other hand, when the hydrophobicity of the organosilicon compound is too low, the charging stability of the toner tends to be lowered even if the organosilicon polymer is contained in the surface layer of the toner particles. The microstructure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH, type and amount of the organosilicon compound, and the like.

In order to obtain the organosilicon polymer, it is preferable to use at least one organosilicon compound having a structure represented by the formula (3). Examples of the compound having the structure represented by the formula (3) include the following.
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane, vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyl Triacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyldimethoxy Hydroxysilane, vinylethoxymethoxyhydroxysila Trifunctional vinyl silanes, such as vinyldiethoxyhydroxysilane; allyltrimethoxysilane, allyltriethoxysilane, allyldiethoxymethoxysilane, allylethoxydimethoxysilane, allyltrichlorosilane, allylmethoxydichlorosilane, allylethoxydichlorosilane , Allyldimethoxychlorosilane, allylmethoxyethoxychlorosilane, allyldiethoxychlorosilane, allyltriacetoxysilane, allyldiacetoxymethoxysilane, allyldiacetoxyethoxysilane, allylacetoxydimethoxysilane, allylacetoxymethoxyethoxysilane, allylacetoxydiethoxysilane, allyl Trihydroxysilane, allylmethoxydihydroxysilane, allylethoxydihydroxysilane, Lil dimethoxy hydroxy silane, allyl ethoxymethoxy hydroxy silane, allyl diethoxy hydroxy silane, trifunctional allylsilanes like; p-styryl trimethoxysilane. The organosilicon compound may be used alone or in combination of two or more.

The content of the monomer unit derived from the organosilicon compound satisfying the formula (3) (that is, the unit represented by the formula (1) or (2)) is 50 based on the total monomer units of the organosilicon polymer. It is preferably from mol% to 100 mol%, more preferably from 60 mol% to 100 mol%. By setting the content of the organosilicon compound satisfying the formula (3) to 50 mol% or more, it is possible to further improve the durability and durability of the toner adhesive force reduction effect.
In addition to the organosilicon compound having the structure of the formula (3), an organosilicon compound having four reactive groups in one molecule (tetrafunctional silane), and an organosilicon compound having three reactive groups in one molecule ( Trifunctional silane), organosilicon compound obtained by using together an organosilicon compound having two reactive groups in one molecule (bifunctional silane) or an organosilicon compound having one reactive group (monofunctional silane) A polymer may be used. Examples of the organosilicon compound that may be used in combination include the following.

Methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyl Triacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxy Hydroxysilane, methylethoxymethoxyhydroxysila Trifunctional methylsilanes, such as methyldiethoxyhydroxysilane, trifunctional ethylsilanes such as ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyl Trifunctional propylsilanes such as trimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane; butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxy Trifunctional butylsilanes such as silane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyl Trifunctional hexylsilanes such as acetoxysilane, hexyltrihydroxysilane; Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltrihydroxysilane Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycid Xylpropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxy Sisilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltri Methoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3 -Ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxy Lan, bis (triethoxysilylpropyl) tetrasulfide, trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, t-butyldimethylsilyl chloride, N, N′-bis (trimethylsilyl) urea, N, O-bis (trimethylsilyl) Trifluoroacetamide, trimethylsilyltrifluoromethanesulfonate, 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane, trimethylsilylacetylene, hexamethyldisilane, 3-isocyanatopropyltriethoxysilane, tetraisocyanatesilane, methyltri Isocyanate silane, vinyl triisocyanate 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 hydroxy 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 that the content of H + in the medium and the reactive group are increased as the reaction proceeds. When it decreases, the substitution reaction to the hydroxy group becomes slow. Therefore, a polycondensation reaction occurs before all of the reactive groups attached to the silane are hydrolyzed, and a one-dimensional linear polymer or a two-dimensional polymer is easily generated relatively easily.

On the other hand, when the medium is alkaline, hydroxide ions are added to silicon and go through a pentacoordinate intermediate. Therefore, all the reactive groups (for example, alkoxy group-OR group) are easily removed, and are easily substituted with silanol groups. In particular, when a silicon compound having three or more reactive groups on the same silane is used, hydrolysis and polycondensation occur three-dimensionally to form an organosilicon polymer having a large number of three-dimensional crosslinks. . The reaction is also completed in a short time.
Therefore, in order to form the organosilicon polymer, it is preferable to proceed the sol-gel reaction with the reaction medium being in an alkaline state. Specifically, when producing in an aqueous medium, the pH should be 8.0 or more. preferable. As a result, an organosilicon polymer having higher strength and superior durability can be formed. The sol-gel reaction is preferably performed at a reaction temperature of 85 ° 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.

  The resin having an ionic functional group preferably contains a polymer A having a monovalent group a represented by the following formula (4). The content of the polymer A in the resin having an ionic functional group is preferably 10% by mass or more and 100% by mass or less.

(In Formula (4), each R ¹ is independently a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms), or 1 to 18 carbon atoms (preferably Represents an alkoxy group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms (preferably 1 to 4 carbon atoms), or 1 to 18 carbon atoms (preferably Represents an alkoxy group of 1 to 4), g represents an integer of 1 to 3 and h represents an integer of 0 to 3).
Examples of the alkyl group in R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. Examples of the alkoxy group Includes a methoxy group, an ethoxy group, a propoxy group, and the like.

  The main chain structure of the polymer A is not particularly limited. Examples thereof include vinyl polymers, polyester polymers, polyamide polymers, polyurethane polymers, polyether polymers, and the like. Moreover, the hybrid type polymer which combined these 2 or more types is also mentioned. Among these, a vinyl polymer is preferable in consideration of adhesion to the toner base particles. The polymer A can be synthesized, for example, by using, as a monomer, a compound having a polymerizable functional group such as a vinyl group at the bonding position of the monovalent group a represented by the formula (4). For example, it is preferable that the group represented by the formula (4) is represented by the following formula (4-1).

[In Formula (4-1), each R ³ independently represents an alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms), or 1 to 18 carbon atoms (preferably 1 or more). 4 or less). R ⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms (preferably 1 to 4 carbon atoms), or an alkoxy group having 1 to 18 carbon atoms (preferably 1 to 4 carbon atoms). R ⁵ represents a hydrogen atom or a methyl group, i represents an integer of 1 to 3, and j represents an integer of 0 to 3. ]
The content of the monovalent group a represented by the structural formula (4) contained in the polymer A is preferably 50 μmol / g or more and 1000 μmol / g or less. By setting it to 50 μmol / g or more, good chargeability and durability can be exhibited. Moreover, charge-up can be suppressed by setting it as 1000 mol / g or less.

The content of the monovalent group a represented by the structural formula (4) in the polymer A can be determined by the method described later. First, the acid value of the polymer A is quantified by titrating the polymer A by the method described later, and the amount of the carboxy group derived from the monovalent group a represented by the structural formula (4) of the polymer A Is calculated. And based on this, content (micromol / g) of the monovalent group a shown by Structural formula (4) in the polymer A is computable.
In addition, when the polymer A has a carboxy group at a site other than the monovalent group a represented by the structural formula (4), 1 represented by the structural formula (4) is produced when the polymer A is produced. The acid value of the compound (for example, polyester resin) immediately before the addition reaction of the valent group a is measured in advance. The addition amount of the monovalent group a represented by the structural formula (4) can be calculated by the difference from the acid value of the polymer A after the addition reaction.
In addition, NMR is measured, the molar ratio of each component is calculated from the integral value derived from the characteristic chemical shift value of each monomer component, and the content (μmol / g) can be calculated based on that. it can.

Hereinafter, specific methods for producing the toner of the present invention will be described, but the present invention is not limited thereto.
As the first manufacturing method, a polymerizable monomer composition containing a polymerizable monomer and an organosilicon compound is granulated in an aqueous medium, and the polymerizable monomer and the organosilicon compound are polymerized (hereinafter referred to as “the polymerizable monomer composition”). In this method, toner mother particles that are polymer particles are obtained by a suspension polymerization method, and then a resin having a pKa having an ionic functional group of 6.0 or more and 9.0 or less is added and fixed. . Since the toner base particles are polymerized in a state where the organosilicon compound is deposited on the surface of the toner base particles, a layer containing the organosilicon polymer can be formed on the surface of the toner base particles. In addition, there is an advantage that the organosilicon compound is easily precipitated uniformly. On the other hand, the resin having an ionic functional group exists outside the organosilicon polymer. That is, the toner particles according to the present invention preferably have a surface layer containing an organosilicon polymer and a resin having an ionic functional group, and a binder resin.

More preferably, toner particles are obtained through the following steps (i), (ii) and (iii) in this order.
(I) A step of forming particles of a polymerizable monomer composition containing a polymerizable monomer and an organosilicon compound in an aqueous medium.
(Ii) A step of polymerizing at least a part of the polymerizable monomer and the organosilicon compound contained in the particles of the polymerizable monomer composition to obtain a dispersion of polymer particles.
(Iii) The process of adding the resin particle containing resin whose pKa which has an ionic functional group is 6.0 or more and 9.0 or less to the dispersion liquid of the said polymer particle.
After (iii), it is more preferable to fix the resin particles attached on the surface of the polymer particles by various methods. A method of fixing will be described later.

  In the second production method, after obtaining toner mother particles, a surface layer of a resin having an organosilicon polymer and an ionic functional group is formed in an aqueous medium. The toner base particles may be obtained by melt-kneading a binder resin and, if necessary, a colorant, and pulverizing. The binder resin particles and optionally the colorant particles are aggregated in an aqueous medium, You may get it by meeting. Alternatively, the organic phase dispersion prepared by dissolving the binder resin and, if necessary, the colorant in an organic solvent may be suspended and granulated in an aqueous medium, and then the organic solvent may be removed.

  As the third production method, an organic phase dispersion prepared by dissolving a binder resin, an organosilicon compound and, if necessary, a colorant in an organic solvent is suspended, granulated and polymerized in an aqueous medium, and then organically produced. In this method, after removing the solvent to obtain toner mother particles, a resin having an ionic functional group is added and fixed. Also in this method, the organic silicon compound is polymerized in the state where the toner particles are deposited on the surface of the toner particles, and the resin having an ionic functional group exists outside the organosilicon polymer.

  As the fourth production method, binder resin particles, sol or gel-containing organosilicon compound-containing particles, resin particles having an ionic functional group, and, if necessary, colorant particles are aggregated and associated in an aqueous medium. This is a method for forming toner particles.

As the fifth production method, a solvent having an organosilicon compound and a resin having an ionic functional group is sprayed onto the surface of the toner base particles by spray drying, and the surface is polymerized or dried by hot air and cooling. And forming a surface layer containing an organosilicon polymer and a resin having an ionic functional group. The toner base particles may be obtained by melt-kneading a binder resin and, if necessary, a colorant, and pulverizing. The binder resin particles and optionally the colorant particles are aggregated in an aqueous medium, You may get it by meeting. Alternatively, the organic phase dispersion prepared by dissolving the binder resin and, if necessary, the colorant in an organic solvent may be suspended and granulated in an aqueous medium, and then the organic solvent may be removed.
Examples of the preferable aqueous medium in the present invention include the following. Examples thereof include water, alcohols such as methanol, ethanol and propanol, and mixed solvents thereof.

As the method for producing toner particles, 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 of the toner base particles, has excellent adhesion between the surface layer of the toner particles and the inside thereof, has an effect of suppressing the charge amount reversal component, and has durability durability. Become good. Hereinafter, the suspension polymerization method will be further described.
You may add a mold release agent, a coloring agent, and other 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.

Examples of the release agent include the following. 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 acid such as higher aliphatic alcohol, stearic acid and palmitic acid, or compound thereof, acid amide wax, Ester wax, ketone, hydrogenated castor oil and derivatives thereof, vegetable wax, animal wax, silicone resin. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. These can be used alone or in combination.

As the above-mentioned other resins, the following resins can be used as long as the effects of the present invention are not affected. Styrene such as polystyrene and polyvinyltoluene, and homopolymers of substituted styrene; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene -Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methacrylic acid Ethyl copolymer, styrene-butyl methacrylate copolymer, styrene-dimethyl methacrylate ethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Coalescence, styrene-pig Styrene copolymers such as ene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene , Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. These can be used alone or in combination.
A polyester resin is preferable, and a polyester resin containing a urea group is more preferable.

As the polymerizable monomer or the polymerizable monomer used for the binder resin in the suspension polymerization method, the following vinyl polymerizable monomers can be preferably exemplified.
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- Noni Acrylic polymerizable monomers such as methyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, Diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as methacrylate; methylene aliphatic monocarboxylic esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether Vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.
Among these vinyl polymerizable monomers, styrene, styrene derivatives, acrylic polymerizable monomers, and methacrylic polymerizable monomers are preferable. That is, the binder resin is preferably a styrene polymer, a styrene-acrylic copolymer or a styrene-methacrylic copolymer. Adhesiveness with the organosilicon polymer having a structure represented by the above formula (1) or (2) is improved, and durability is 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-based or diazo-based polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxycarbonate, cumene hydroperoxide, 2,4- Peroxide-based polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 30.0 parts by mass with respect to 100 parts by mass of 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. A preferable addition amount is 0.001 part by mass or more and 15.000 parts by mass or less with respect to 100 parts 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 crosslinkable monomer. 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 monomer. 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. A preferable addition amount is 0.001 part by mass or more and 15.000 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

When the medium used in the suspension polymerization is an aqueous medium, the following can be used as the 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.

A colorant can also be used in the toner of the present invention. It does not specifically limit as a coloring agent, The well-known thing 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 thereof 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 the form of a solid solution.
In addition, it is preferable that content of a coloring agent is 3.0 to 15.0 mass parts with respect to 100 mass parts of binder resin or a polymerizable monomer.

A charge control agent can be used at the time of toner production, and known ones can be used. The addition amount of these charge control agents is preferably 0.01 parts by mass or more and 10.00 parts by mass or less with respect to 100 parts by mass of the binder resin or polymerizable monomer.
In the toner of the present invention, various organic or inorganic fine powders may be externally added to the toner particles as necessary. 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.

As organic or inorganic fine powder, the following are used, for example.
(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black, and carbon fluoride.
(2) Abrasive: metal oxide (for example, strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitride (for example, silicon nitride), carbide (for example, silicon carbide), metal salt (for example, calcium sulfate, sulfuric acid) Barium, calcium carbonate).
(3) Lubricant: fluororesin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
(4) Charge controllable particles: metal oxide (for example, tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.
The organic or inorganic fine powder can also treat 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. As treatment agents for hydrophobic treatment of organic or inorganic fine powders, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, An organic titanium compound is mentioned. These treatment agents may be used alone or in combination.

A method of fixing resin particles containing a resin having an ionic functional group and having a pKa of 6.0 or more and 9.0 or less to the toner base particles in an aqueous medium will be described.
In the step of fixing the resin particles containing the resin having an ionic functional group to the surface of the toner base particles in the aqueous medium (fixing step), the pH of the aqueous medium is pKa-2.0 or more of the resin particles. Is preferred.

Since the pKa of the resin particles used in the present invention is 6.0 or more and 9.0 or less, the dissociation of the ionic functional groups of the resin particles depends on the pH in the aqueous medium. When the pH of the aqueous medium is low and the dissociation of the ionic functional group is small, the surface of the resin particles is considered to have many portions that are not charged, and the resin particles easily come into contact with each other and aggregate on the surface of the toner base particles It will stick. In the fixed state, the aggregates of the resin particles are easily detached from the toner base particles due to contact between the toners or between the toner and the charging member, so that the charging stability tends to be lowered. Furthermore, the aggregates of the detached resin particles themselves may cause member contamination, and the durability tends to decrease.
When the pH of the aqueous medium is pKa-2.0 or more of the resin particles, the aggregation of the resin particles is suppressed, and the resin particles are uniformly and firmly fixed to the toner base particles. Can keep. Preferably, the pH of the aqueous medium is not less than the pKa of the resin particles. Furthermore, in order to suppress excessive dissociation of the ionic functional group, it is preferable that the pH of the aqueous medium is pKa + 4.0 or less of the resin particles.

As a method for fixing the resin particles, a known method can be applied as long as the pH of the aqueous medium is adjusted to pKa-2.0 or more of the resin particles. For example, resin particles may be added to a dispersion of toner base particles and then embedded in the base particles by a mechanical impact force, or the aqueous medium may be fixed by heating. Further, a flocculant may be added and fixed, or the above methods may be combined. In any case, it is preferable to stir the aqueous medium.
More preferably, from the viewpoint of firmly fixing the resin particles to the toner base particles, the aqueous medium is heated to a glass transition temperature of the resin particles of −20 ° C. or higher and a glass transition temperature of + 30 ° C. or lower.

In the fixing step, it is preferable that the zeta potential of the toner base particles is 10 mV or more larger than the zeta potential of the resin particles. When the zeta potential of the toner base particles is 10 mV or more larger than the zeta potential of the resin particles, the resin particles are electrostatically fixed to the toner base particles, so that the toner particles can be fixed in a short time, and there is no variation between the toners. Can be suppressed.
The zeta potential of the toner base particles can be controlled using the above dispersion stabilizer. Specifically, it can be controlled by the type and amount of the dispersion stabilizer adhering to the surface of the toner base particles and the adhering method.
After fixing the resin particles on the surface of the toner base particles, the toner particles are obtained by filtration, washing and drying by a known method. When an inorganic dispersion stabilizer is used, it is preferably removed after dissolving with an acid or a base.

The measurement method used in the present invention will be described below.
<Concentration of silicon atoms existing on the toner particle surface (atomic%)>
The concentration (atomic%) of silicon atoms present on the toner particle surface in the present invention was calculated by performing surface composition analysis by X-ray photoelectron spectroscopy (ESCA).
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
Sweep number: Si 15 times, C 10 times, O 10 times In the present invention, from the measured peak intensity of each atom, the silicon atoms present in the surface layer of the toner particles using the relative sensitivity factor provided by PHI are used. The concentration [dSi], the carbon atom concentration [dC], and the oxygen atom concentration [dO] (all atomic%) were calculated.
Then, the ratio (atomic%) of the silicon atom concentration dSi when the total of the carbon atom concentration dC, oxygen atom concentration dO and silicon atom concentration dSi (dC + dO + dSi) in the toner particle surface layer is 100.0 atomic%. )

<Average thickness Dav. Of the surface layer of the toner particles measured by cross-sectional observation of the toner particles using a transmission electron microscope (TEM). And measuring method in which the thickness of the surface layer is 2.5 nm or less>
In the present invention, cross-sectional observation of toner particles is performed by the following method.
As a specific method for observing the cross section of the toner particles, the toner particles are sufficiently dispersed in a room temperature curable epoxy resin and then cured in an atmosphere of 40 ° C. for 2 days. A flaky sample is cut out from the obtained cured product using a microtome equipped with diamond teeth. This sample is magnified by a magnification of 10,000 to 100,000 times with a transmission electron microscope (Electron microscope Tecnai TF20XT manufactured by FEI) (TEM), and the cross section of the toner particles is observed.
In the present invention, the difference between the atomic weights of the resin used and the organosilicon compound is utilized, and the confirmation is performed utilizing the fact that the contrast becomes brighter when the atomic weight is large. Further, a ruthenium tetroxide staining method and an osmium tetroxide staining method may be used in order to provide contrast between materials.
For the particles used for the measurement, the equivalent circle diameter Dtem was determined from the cross-section of the toner particles obtained from the TEM micrograph, and the value was ± 10% of the weight average particle diameter D4 of the toner particles determined by the method described later. It was included in the width.
As described above, a bright field image of the cross section of the toner particles is obtained with an acceleration voltage of 200 kV using the FEI electron microscope Tecnai TF20XT. Next, using an EELS detector GIF Tridiem manufactured by Gatan, an EF mapping image at the Si-K end (99 eV) is obtained by the Three Window method, and it is confirmed that the organosilicon polymer is present in the surface layer.
Next, for one toner particle in which the equivalent circle diameter Dtem falls within a width of ± 10% of the weight average particle diameter D4 of the toner particles, the major axis L that is the maximum diameter of the toner particle cross section and the center of the major axis L are passed. In addition, the toner particle cross section is equally divided into 16 with the intersection of the vertical axes L90 as the center (see FIG. 1). That is, from the midpoint by drawing 16 straight lines that cross the cross section so that the midpoint of the long axis L passes and the crossing angle at the midpoint is equal (crossing angle is 11.25 °). 32 line segments are formed to the surface of the toner particles. Next, the segment (division axis) from the center to the surface layer of the toner particles is An (n = 1 to 32), the length of the segment (division axis) is RAn, the organosilicon polymer and the ionic functional group. The thickness of the surface layer of toner particles containing a group-containing resin is FRAn.
Then, the average thickness Dav. Of the surface layer of the toner particles containing the organosilicon polymer at 32 locations on the line segment (dividing axis) and the resin having an ionic functional group. Ask for. Furthermore, on each of the 32 existing line segments (dividing axis), the thickness of the surface layer of the toner particles containing the organosilicon polymer and the resin having an ionic functional group is 2.5 nm or less (segmented axis). Find the percentage of numbers.
In the present invention, in order to average, 10 toner particles were measured, and an average value per toner particle was calculated.

[Equivalent circle diameter (Dtem) obtained from cross section of toner particle obtained from transmission electron microscope (TEM) photograph]
The equivalent circle diameter (Dtem) obtained from the cross section of the toner particles obtained from the TEM photograph is obtained by the following method. First, for one toner particle, a circle equivalent diameter Dtem obtained from a cross section of the toner particle obtained from the TEM photograph is obtained according to the following formula.
[Equivalent circle diameter (Dtem) obtained from cross section of toner particles obtained from TEM photograph] = (RA1 + RA2 + RA3 + RA4 + RA5 + RA6 + RA7 + RA8 + RA9 + RA10 + RA11 + RA12 + RA13 + RA14 + RA15 + RA16 + RA17 + RA18 + RA21 + RA22 + RA23 + RA24 + RA22 + RA24 + RA24 + RA24 + RA24 + RA24 + RA24 + RA24 +
The equivalent circle diameter of 10 toner particles is obtained, and the average value per one particle is calculated to obtain the equivalent circle diameter (Dtem) obtained from the cross section of the toner particles.

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

[Ratio of surface layer thickness of 2.5 nm or less]
[Ratio in which surface layer thickness (FRAn) is 2.5 nm or less] = [{number of split axes in which surface layer thickness (FRAn) is 2.5 nm or less} / 32] × 100
This calculation is performed on 10 toner particles, and the average value of the ratio of the obtained 10 surface layer thicknesses (FRAn) is 2.5 nm or less is obtained, and the surface layer thickness (FRAn) of the toner particles is determined. The ratio was 2.5 nm or less.

<Method for Measuring Weight Average Particle Size (D4) of Toner Particles>
The weight average particle diameter (D4) of the toner particles is measured with a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. Measured data with 25,000 effective measurement channels using the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for condition setting and measurement data analysis Analyze and calculate.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner particles are added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolytic solution (5) in which the toner particles are dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. 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. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<The confirmation method of the partial structure represented by Formula (5)>
In the present invention, the Rf unit in the partial structure represented by the formula (5) was confirmed by ¹³ C-NMR (solid) measurement. The measurement conditions and the sample preparation method are shown below. "Measurement conditions for ¹³ C-NMR (solid)"
Device: AVANCE III 500 manufactured by BRUKER
Probe: 4mm MAS BB / 1H
Measurement temperature: room temperature Sample rotation speed: 6 kHz
Sample: 150 mg of a measurement sample (THF insoluble matter of toner particles for NMR measurement, preparation method is described below) is put in a sample tube having a diameter of 4 mm.
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

`` Sample preparation method ''
Preparation of measurement sample: 10.0 g of toner particles are weighed, placed in a cylindrical filter paper (No. 86R manufactured by Toyo Roshi), passed through a Soxhlet extractor, extracted for 20 hours using 200 ml of tetrahydrofuran (THF) as a solvent, and in a cylindrical filter paper. The filtrate obtained by vacuum drying at 40 ° C. for several hours is used as a sample for NMR measurement.
In the present invention, when the organic fine powder or inorganic fine powder is externally added to the toner, the organic fine powder or inorganic fine powder is removed by the following method to obtain toner particles.
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water, and dissolved with a water bath to prepare a sucrose concentrate. 31 g of the above sucrose concentrate in a centrifuge tube, and 10% by weight aqueous solution of neutral detergent for cleaning a precision measuring instrument having a pH of 7, comprising non-ionic surfactant, anionic surfactant and organic builder, 6 mL of Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. To this dispersion, 1.0 g of toner is added, and the mass of toner is loosened with a spatula or the like.
The centrifuge tube is shaken with a shaker at 350 spm (strokes per min) for 20 min. After shaking, the solution is replaced with a glass tube for swing rotor (50 mL) and separated by a centrifuge at 3500 rpm for 30 min. By this operation, the toner particles are separated from the detached external additive. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the toner separated in the uppermost layer is collected with a spatula or the like. The collected toner is filtered with a vacuum filter and then dried with a dryer for 1 hour or longer to obtain toner particles. Perform this operation multiple times to ensure the required amount.
When Rf is the above formula (iii), the presence of the unit represented by the above formula (iii) was confirmed by the presence or absence of a signal due to the methine group (> CH—Si) bonded to the silicon atom.
When Rf is the above formula (iv), a methylene group (Si—CH ₂ —), an ethylene group (Si—C ₂ H ₄ —), or a phenylene group (Si—C ₆ H ₄ —) bonded to a silicon atom. ), The presence of the unit represented by the above formula (iv) was confirmed.

<Measurement method of ratio of peak area attributed to structure of formula (5), measured in ²⁹ Si-NMR of THF-insoluble matter in toner particles>
In the present invention, ²⁹ Si-NMR (solid) measurement of the THF insoluble content of the toner particles was performed under the following measurement conditions.
"Measurement conditions for ²⁹ Si-NMR (solid)"
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
29Si 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 above measurement, a plurality of silane components having different substituents and bonding groups of toner particles are peak-separated into the following X1 structure, X2 structure, X3 structure, and X4 structure by curve fitting. Calculate mol% of ingredients.
X1 structure: (Ri) (Rj) (Rk) SiO _1/2 formula (6)
X2 structure: (Rg) (Rh) Si (O _1/2 ) ₂ formula (7)
X3 structure: RmSi (O _1/2 ) Formula ₃ (8)
X4 structure: Si (O _1/2 ) Formula ₄ (9)

（式（ｉ）〜（ｉｖ）において、※は、ケイ素原子との結合手を表す。式（ｉｉ）及び式（ｉｖ）において、Ｌは、それぞれメチレン基、エチレン基またはフェニレン基を表す。）
なお、本発明では化学シフト値でシランモノマーを特定して、トナー粒子の^２９Ｓｉ−ＮＭＲの測定において全ピーク面積から未反応のモノマー成分を取り除いたＸ１構造の面積とＸ２構造の面積とＸ３構造の面積とＸ４構造の面積の合計を重合体の全ピーク面積とした。ＳＸ１＋ＳＸ２＋ＳＸ３＋ＳＸ４＝１．００
ＳＸ１＝｛Ｘ１構造の面積／（Ｘ１構造の面積＋Ｘ２構造の面積＋Ｘ３構造の面積＋Ｘ４構造の面積）｝
ＳＸ２＝｛Ｘ２構造の面積／（Ｘ１構造の面積＋Ｘ２構造の面積＋Ｘ３構造の面積＋Ｘ４構造の面積）｝
ＳＸ３＝｛Ｘ３構造の面積／（Ｘ１構造の面積＋Ｘ２構造の面積＋Ｘ３構造の面積＋Ｘ４構造の面積）｝
ＳＸ４＝｛Ｘ４構造の面積／（Ｘ１構造の面積＋Ｘ２構造の面積＋Ｘ３構造の面積＋Ｘ４構造の面積）｝
本発明においては、トナー粒子のＴＨＦ不溶分の^２９Ｓｉ−ＮＭＲの測定で得られるチャートにおいて、前記有機ケイ素重合体の全ピーク面積に対する上記式（５）の構造に帰属されるピーク面積の割合が、４０％以上であることが好ましい。この測定方法において
、−ＳｉＯ_３／２構造を示す値は上記ＳＸ３である。この値が、０．４０以上であることが好ましい。
なお、式（５）表される部分構造をさらに詳細に確認する必要がある場合、上記^１３Ｃ−ＮＭＲ及び^２９Ｓｉ−ＮＭＲの測定結果と共に^１Ｈ−ＮＭＲの測定結果によって同定してもよい。 (In the formulas (6), (7) and (8), Ri, Rj, Rk, Rg, Rh and Rm each represent a substituent selected from the following formulas (i) to (iv)).

(In formulas (i) to (iv), * represents a bond with a silicon atom. In formulas (ii) and (iv), L represents a methylene group, an ethylene group, or a phenylene group, respectively).
In the present invention, the area of the X1 structure, the area of the X2 structure, and the area of the X3 structure are obtained by specifying the silane monomer by the chemical shift value and removing unreacted monomer components from the total peak area in the ²⁹ Si-NMR measurement of the toner particles. And the total area of the X4 structure was defined as the total peak area of the polymer. SX1 + SX2 + SX3 + SX4 = 1.00
SX1 = {area of X1 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX2 = {area of X2 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX3 = {area of X3 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX4 = {area of X4 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
In the present invention, the ratio of the peak area attributed to the structure of the above formula (5) to the total peak area of the organosilicon polymer in the chart obtained by measurement of ²⁹ Si-NMR of the THF-insoluble matter of the toner particles is 40% or more is preferable. In this measurement method, the value indicating the —SiO _3/2 structure is SX3. This value is preferably 0.40 or more.
In the case where it is necessary to confirm a partial structure represented formula (5) in more detail, it may be identified by measurement results of ¹ H-NMR together with the measurement results of the ¹³ C-NMR and ²⁹ Si-NMR.

<Volume-based median diameter of resin particles (D50)>
The volume-based median diameter (D50) of the resin particles is calculated by measuring the particle diameter by a dynamic light scattering method (DLS: Dynamic Light Scattering) using a Zetasizer Nano-ZS (manufactured by MALVERN).
First, turn on the device and wait 30 minutes for the laser to stabilize. Thereafter, the Zetasizer software is started.
Select Manual from the Measurement menu and enter the measurement details as shown below.
Measurement mode: Particle diameter Material: Polystyrene latex (RI: 1.59, Absorption: 0.01)
Dispersant: Water (Temperature: 25 ° C., Viscosity: 0.8872 cP, RI: 1.330)
Temperature: 25.0 ° C
Cell: Clear disposable zeta cell
Measurement duration: Automatic
The sample is prepared by diluting with water so as to be 0.50% by mass, filled in a disposable capillary cell (DTS1060), and the cell is loaded into the cell holder of the apparatus.
When the above preparation is completed, the measurement is started by pressing the Start button on the measurement display screen.
D50 is calculated based on the volume-based particle size distribution data obtained by converting the light intensity distribution obtained from the DLS measurement by Mie theory.

<Zeta potential>
The zeta potential is measured using a Zetasizer Nano-ZS (manufactured by MALVERN). In the preparation of the sample, the dispersion is diluted with water so as to be 0.50% by mass. Next, it adjusts with 0.1 mol / L sodium hydroxide aqueous solution or 0.1 mol / L hydrochloric acid aqueous solution so that it may become equal to pH of the adhering process. The sample with adjusted pH is filled into a disposable capillary cell (DTS1060), and the cell is loaded into the cell holder of the apparatus. When the preparation is completed, the temperature is set to the temperature at the time of fixation.

<Glass transition temperature (Tg)>
The glass transition temperature (Tg) of the resin particles containing the toner base particles and the resin having an ionic functional group is determined using a differential scanning calorimeter (DSC) M-DSC (trade name: Q2000, manufactured by TA Instruments). Then, measure according to the following procedure. Weigh accurately 3 mg of the sample 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.

<Acid value>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
Titration is performed using a 0.1 mol / l potassium hydroxide ethyl alcohol solution (Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.). 100 ml of 0.100 mol / l hydrochloric acid is placed in a 250 ml tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 0.100 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
The measurement conditions for the acid value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are as follows.
Titration parameters Titration mode: Blank titration Titration style: Total titration Maximum titration: 20 ml
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter end point determination potential: 30 dE
End point determination potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 ml
main exam;
0.100 g of the measurement sample is precisely weighed in a 250 ml tall beaker, 150 ml of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.
Blank test;
Titration is performed in the same manner as described above, except that no sample is used (that is, only a mixed solution of toluene / ethanol (3: 1)).
The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.611] / S
(In the formula, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide ethyl alcohol solution in blank test (ml), C: addition amount (ml) of potassium hydroxide ethyl alcohol solution in this test, f: Factor of potassium hydroxide solution, S: Sample (g))

<Acid value, pKa>
0.100 g of the measurement sample is precisely weighed in a 250 ml tall beaker, 150 ml of THF is added and dissolved over 30 minutes. A pH electrode is placed in this solution and the pH of the sample in THF is read. Thereafter, 10 μl of 0.1 mol / l potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.) is added, and the pH is read and titrated each time. A 0.1 mol / l potassium hydroxide ethyl alcohol solution is added until the pH becomes 10 or more and there is no change in pH even when 30 μl is added. From the obtained results, the pH is plotted against the addition amount of 0.1 mol / l potassium hydroxide ethyl alcohol solution to obtain a titration curve. From the obtained titration curve, the place where the slope of the pH change is the greatest is taken as the neutralization point, and the acid value (mgKOH / g) is calculated from the amount of added potassium hydroxide. Since pKa is the same value as the pH in half of the 0.1 mol / l potassium hydroxide ethyl alcohol solution required up to the neutralization point, the pH in half is read from the titration curve.

<Content of structure a contained in polymer A>
The content of the structure a contained in the polymer A is performed using nuclear magnetic resonance spectroscopy ( ¹ H-NMR) [400 MHz, CDCl ₃ , room temperature (25 ° C.)].
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Number of integrations: 64 times From the integrated value of the obtained spectrum, the molar ratio of each monomer component is obtained, and the mol% of the structure a contained in the polymer A is calculated based on this.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples. “Part” means “part by mass”.

<Synthesis Example of Polymerizable Monomer M-1>
(Process 1)
100 g of 2,5-dihydroxybenzoic acid and 1441 g of 80% sulfuric acid were heated and mixed at 50 ° C. To this dispersion, 144 g of tert-butyl alcohol was added and stirred at 50 ° C. for 30 minutes. Thereafter, 144 g of tert-butyl alcohol was added to this dispersion and stirring was performed for 30 minutes three times. The reaction solution was cooled to room temperature and poured slowly into 1 kg of ice water. The precipitate was filtered, washed with water, and then washed with hexane. This precipitate was dissolved in 200 mL of methanol and reprecipitated in 3.6 L of water. After filtration, 74.9 g of a salicylic acid intermediate represented by the following structural formula (10) was obtained by drying at 80 ° C.

(Process 2)
25.0 g of the obtained salicylic acid intermediate was dissolved in 150 mL of methanol, 36.9 g of potassium carbonate was added, and the mixture was heated to 65 ° C. To this reaction solution, a mixed solution of 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol was added dropwise, and reacted at 65 ° C. for 3 hours. The reaction solution was cooled and then filtered, and the filtrate was concentrated to obtain a crude product. The crude product was dispersed in 1.5 L of water at pH = 2 and extracted by adding ethyl acetate. Thereafter, it was washed with water and dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and purified by recrystallization from toluene and ethyl acetate to obtain 20.1 g of a polymerizable monomer M-1 represented by the following structural formula (11).

<Synthesis Example of Polymerizable Monomer M-2>
Except for changing the salicylic acid intermediate of the structural formula (10) to 18 g of 2,4-dihydroxybenzoic acid, in the same manner as the synthesis of the polymerizable monomer M-1 (step 2), the following structural formula (12) A polymerizable monomer M-2 was obtained.

<Synthesis Example of Polymerizable Monomer M-3>
Except for changing the salicylic acid intermediate of the structural formula (10) to 18 g of 2,3-dihydroxybenzoic acid, in the same manner as the synthesis of the polymerizable monomer M-1 (step 2), the following structural formula (13) A polymerizable monomer M-3 was obtained.

<Synthesis Example of Polymerizable Monomer M-4>
Except for changing the salicylic acid intermediate of the structural formula (10) to 18 g of 2,6-dihydroxybenzoic acid, in the same manner as the synthesis of the polymerizable monomer M-1 (step 2), the following structural formula (14) A polymerizable monomer M-4 was obtained.

<Synthesis example of polymerizable monomer M-5>
A salicylic acid intermediate was obtained by the same method as the synthesis of the polymerizable monomer M-1 (Step 1) except that 144 g of tert-butyl alcohol was changed to 253 g of 2-octanol. A polymerizable monomer M-5 represented by the following structural formula (15) was obtained by the same method as the synthesis of the polymerizable monomer M-1 (step 2) except that 32 g of the salicylic acid intermediate obtained here was used. .

<Synthesis Example of Polymerizable Monomer M-6>
Except for changing the salicylic acid intermediate of the structural formula (10) to 2,5-dihydroxy-3-methoxybenzoic acid 22 g, the following structural formula is used in the same manner as the synthesis of the polymerizable monomer M-1 (step 2). The polymerizable monomer M-6 of (16) was obtained.

<Synthesis Example of Polymer A-1>
Polymerizable monomer M-1 represented by Structural Formula (11): 10.7 g and styrene: 59.2 g were dissolved in 42.0 ml of DMF, stirred for 1 hour while bubbling nitrogen, and then heated to 110 ° C. To this reaction solution, a mixture of tert-butyl peroxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation) and 42 ml of toluene was added dropwise as an initiator. Furthermore, it reacted at 110 degreeC for 4 hours. Then, it cooled and it was dripped at methanol 1L, and the deposit was obtained. The obtained precipitate was dissolved in 120 ml of THF and then added dropwise to 1.80 L of methanol to precipitate a white precipitate, which was filtered and dried at 90 ° C. under reduced pressure to obtain 57.6 g of polymer A-1. It was. NMR and acid value of the obtained polymer A-1 were measured, and the content of components derived from the polymerizable monomer M-1 was confirmed.

<Synthesis Example of Polymers A-2 to A-8>
Except having changed the preparation amount of a raw material like Table 1, it carried out similarly to the synthesis example of the polymer A-1, and obtained the polymer A-2-the polymer A-8.

<Synthesis Example of Polymer B-1>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.
next,
5-vinylsalicylic acid 9.0 parts by mass Styrene 75.0 parts by mass 2-ethylhexyl acrylate 16.0 parts by mass Dimethyl-2,2'-azobis (2-methylpropionate) 5.0 parts by mass The reaction vessel was added dropwise with stirring and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to obtain a polymer B-1.

<Synthesis example of polymer B-2>
Of the synthesis examples of polymer B-1, synthesis was performed in the same manner except for the following changes.
The polymer B-2 was obtained by changing 9.0 parts by mass of 5-vinylsalicylic acid to 10.9 parts by mass of 1-vinylnaphthalene-2-carboxylic acid.

<Synthesis Example of Polymer B-3>
In a reaction vessel equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple,
Bisphenol A propylene oxide 2 mol adduct 500 parts by weight terephthalic acid 154 parts by weight Fumaric acid 45 parts by weight Tin octylate 2 parts by weight are charged, a polycondensation reaction is performed at 230 ° C. for 8 hours, and further at 8 kPa for 1 hour. After continuing the polycondensation reaction, the polyester resin was formed by cooling to 160 ° C., and then 10 parts by weight of acrylic acid was added at a temperature of 160 ° C., mixed and held for 15 minutes,
142 parts by mass of styrene
35 parts by mass of n-butyl acrylate
Polymerization initiator (di-t-butyl peroxide) 10 parts by mass
The mixture was added dropwise with a dropping funnel over 1 hour, followed by addition polymerization reaction for 1 hour while maintaining the temperature at 160 ° C., and then heated to 200 ° C. and held at 10 kPa for 1 hour. Combined B-3 was obtained.
Table 1 shows the physical properties of the obtained polymers A-1 to A-8, B-1 to B-3.

Ｓｔ：スチレン
２ＥＨＡ：２−エチルヘキシルアクリレート
ＢＡ：ブチルアクリレート
ＨＥＭＡ：２−ヒドロキシエチルメタクリレート

St: Styrene 2EHA: 2-ethylhexyl acrylate BA: Butyl acrylate HEMA: 2-hydroxyethyl methacrylate

<Production Example of Water Dispersion of Resin Particle E-1>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200.0 parts by mass of methyl ethyl ketone was charged, and 100.0 parts by mass of Polymer A-1 was added and dissolved.
Subsequently, 1.0N potassium hydroxide aqueous solution was slowly added, and after stirring for 10 minutes, 500.0 parts by mass of ion-exchanged water was slowly dropped and emulsified.
The obtained emulsion was distilled under reduced pressure to remove the solvent, and ion-exchanged water was added to prepare the resin concentration to be 20%, thereby obtaining an aqueous dispersion of resin particles E-1.
Table 2 shows the physical property values of the obtained aqueous dispersion of resin particles.

<Production example of aqueous dispersion of resin particles E2-12>
Resin particle E-2 to resin particle E- are the same as in the production example of resin particle E-1, except that the amounts of polymer A-1 and 1.0N potassium hydroxide aqueous solution are changed as shown in Table 2. 12 aqueous dispersions were obtained.
Table 2 shows the physical property values of the aqueous dispersions of the obtained resin particles E-2 to E-12.

<Examples of polyester resin synthesis>
(Synthesis of isocyanate group-containing prepolymer)
-Bisphenol A ethylene oxide 2 mol adduct 725 parts by mass-290 parts by mass of phthalic acid-3.0 parts by mass of dibutyltin oxide The above materials were stirred at 220 ° C for 7 hours and further reacted under reduced pressure for 5 hours. Then, it cooled to 80 degreeC and reacted with 190 mass parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the isocyanate group containing polyester resin was obtained. 25 parts by mass of an isocyanate group-containing polyester resin and 1 part by mass of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a polyester-based resin composed mainly of a polyester containing a urea group. The weight average molecular weight (Mw) of the obtained polyester resin was 22300, the number average molecular weight (Mn) was 2980, and the peak molecular weight was 7200.

[Example 1]
<Production Example of Toner 1>
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 700 parts by mass of ion-exchanged water and 1000 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution and 1.0 mol / liter 24.0 parts by mass of an aqueous HCl 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 (manufactured by Tokushu Kika Kogyo Co., Ltd.). To this, 85 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . Thereafter, a polymerizable monomer composition was prepared using the following raw materials.
-Styrene monomer 75.0 parts by mass-n-butyl acrylate 25.0 parts by mass-1,6-hexanediol diacrylate 0.1 parts by mass-Organosilicon compound (vinyltriethoxysilane) 10.0 parts by mass-Copper phthalocyanine Pigment (Pigment Blue 15: 3) 6.5 parts by weight, mold release agent (behenyl behenate) 10.0 parts by weight, polyester resin 5.0 parts by weight Time-dispersed to obtain a polymerizable monomer composition. Next, this polymerizable monomer composition was transferred to another container and kept at 60 ° C. for 20 minutes with stirring. Thereafter, 16.0 parts by mass of t-butyl peroxypivalate as a polymerization initiator (toluene) 50% solution) was added and held for 5 minutes with stirring. Next, the polymerizable monomer composition was put into an aqueous dispersion medium and granulated for 10 minutes while stirring with a high-speed stirring device. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring (reaction 1 step). The pH was 5.1. Next, 1.0N-NaOH was added to adjust the pH to 8.1, and the temperature inside the container was raised to 90 ° C. and maintained for 6.5 hours (reaction step 2). Thereafter, 1.0 N hydrochloric acid was added to bring the pH to 5.1. Next, 300 parts by mass of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. Distillation at a temperature of 100 ° C. in the container was performed for 5 hours to remove residual monomer and toluene, and a dispersion of toner mother particles was obtained (distillation step). The dispersion of the toner base particles is set to 90 ° C., and 1.0 N-NaOH is added to adjust the pH to 9.0, and 2.5 parts by mass of an aqueous dispersion of resin particles E-1 (solid content: 0.5 parts by mass) Was added slowly. Furthermore, the inside of the container was maintained at 90 ° C. for 1.0 hour (adhering step).
The dispersion stabilizer was dissolved by adding 10% hydrochloric acid to the container containing the dispersion after cooling to 30 ° C., adjusting the pH to 1.0, and stirring for 2 hours. Further, the toner particles 1 were obtained by filtration, washing and drying. Fine powder was cut by air classification to obtain toner 1. The formulation and conditions of the obtained particles are shown in Table 3, and the physical properties are shown in Table 6.

[Examples 2 to 21, Comparative Examples 1 to 4]
Toners 2 to 21 and 24 to 27 were obtained in the same manner as in Example 1 except that the formulations and conditions shown in Table 3, Table 4, and Table 5 were changed.
The physical properties of the obtained particles are shown in Tables 6, 7 and 8.

[Example 22]
<Production Example of Toner 22>
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 700 parts by mass of ion-exchanged water and 1000 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution and 1.0 mol / liter 24.0 parts by mass of an aqueous HCl 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 (manufactured by Tokushu Kika Kogyo Co., Ltd.). To this, 85 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . Thereafter, a polymerizable monomer composition was prepared using the following raw materials.
-Styrene monomer 75.0 parts by mass-n-butyl acrylate 25.0 parts by mass-1,6-hexanediol diacrylate 0.1 parts by mass-Organosilicon compound (vinyltriethoxysilane) 10.0 parts by mass-Copper phthalocyanine Pigment (Pigment Blue 15: 3) 6.5 parts by mass, mold release agent (behenyl behenate) 10.0 parts by mass, polyester resin 5.0 parts by mass Time-dispersed to obtain a polymerizable monomer composition. Next, this polymerizable monomer composition was transferred to another container and kept at 60 ° C. for 20 minutes with stirring. Thereafter, 16.0 parts by mass of t-butyl peroxypivalate as a polymerization initiator (toluene) 50% solution) was added and held for 5 minutes with stirring. Next, the polymerizable monomer composition was put into an aqueous dispersion medium and granulated for 10 minutes while stirring with a high-speed stirring device. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring (reaction 1 step). The pH was 5.1. Next, 1.0N-N
aOH was added to pH 8.1, and the temperature in the container was raised to 90 ° C. and maintained for 6.5 hours (reaction 2 step). Thereafter, 1.0 N hydrochloric acid was added to bring the pH to 5.1. Next, 300 parts by mass of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. Distillation at a temperature of 100 ° C. in the container was performed for 5 hours to remove residual monomer and toluene, and a dispersion of toner mother particles was obtained (distillation step). The dispersion stabilizer was dissolved by adding 10% hydrochloric acid to the container containing the dispersion after cooling to 30 ° C., adjusting the pH to 1.0, and stirring for 2 hours. Further, the toner mother particles were obtained by filtration, washing and drying. 0.5 part by mass of the polymer A-2 was added to the total amount of the toner base particles, and the resulting mixture was put into a dry particle composite apparatus (Nobilta NOB-130 manufactured by Hosokawa Micron). Processing temperature 30 ° C., rotary processing blade 90 m / sec. The toner particles 22 were obtained by fixing under the above conditions. Thereafter, fine coarse powder was cut by air classification to obtain toner 22.
The physical properties are shown in Table 8.

Example 23
<Production Example of Toner Particles 23>
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 700 parts by mass of ion-exchanged water and 1000 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution and 1.0 mol / liter 24.0 parts by mass of an aqueous HCl 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 (manufactured by Tokushu Kika Kogyo Co., Ltd.). To this, 85 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . Thereafter, a polymerizable monomer composition was prepared using the following raw materials.
-Styrene monomer 75.0 parts by mass-n-butyl acrylate 25.0 parts by mass-1,6-hexanediol diacrylate 0.1 parts by mass-Organosilicon compound (vinyltriethoxysilane) 10.0 parts by mass-Copper phthalocyanine Pigment (Pigment Blue 15: 3) 6.5 parts by mass, mold release agent (behenyl behenate) 10.0 parts by mass, polyester resin 5.0 parts by mass Time-dispersed to obtain a polymerizable monomer composition. Next, this polymerizable monomer composition was transferred to another container and kept at 60 ° C. for 20 minutes with stirring. Thereafter, 16.0 parts by mass of t-butyl peroxypivalate as a polymerization initiator (toluene) 50% solution) was added and held for 5 minutes with stirring. Next, the polymerizable monomer composition was put into an aqueous dispersion medium and granulated for 10 minutes while stirring with a high-speed stirring device. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring (reaction 1 step). The pH was 5.1. Next, 1.0N-NaOH was added to adjust the pH to 9.0, and 2.5 parts by mass of an aqueous dispersion of resin particles E-2 (solid content of 0.5 parts by mass) was slowly added. The inside of the vessel was heated to 90 ° C. and maintained for 6.5 hours (reaction 2 step). Thereafter, 1.0 N hydrochloric acid was added to bring the pH to 5.1. Next, 300 parts by mass of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. Distillation at a temperature of 100 ° C. in the container was carried out for 5 hours to remove residual monomers and toluene, thereby obtaining a dispersion of toner particles (distillation step). The dispersion stabilizer was dissolved by adding 10% hydrochloric acid to the container containing the dispersion after cooling to 30 ° C., adjusting the pH to 1.0, and stirring for 2 hours. Further, the toner particles 23 were obtained by filtration, washing and drying. Thereafter, the fine coarse powder was cut by air classification to obtain toner 23. The physical properties are shown in Table 8.

Each toner obtained in Examples 1 to 23 and Comparative Examples 1 to 4 was evaluated for performance according to the following method. The results are shown in Table 9.
A tandem Canon laser beam printer LBP9510C having the configuration shown in FIG. 2 has been modified to enable printing only with the cyan station. Also, the transfer current was modified so that it could be set arbitrarily. Using this toner cartridge for LBP9510C, 200 g of toner was filled. The toner cartridge was left for 3 days in an environment of low temperature and low humidity L / L (10 ° C./15% RH). After being left for 3 days in this low temperature and low humidity L / L environment, the toner cartridge is attached to the LBP9510C, and an image with a printing ratio of 1.0% is printed out to 15,000 sheets in the A4 paper lateral direction. Evaluation of transfer latitude, image density, and chargeability during sheet output (after endurance) was performed. The results are shown in Table 5.

<Transcription latitude>
At the initial stage and after printing 15000 sheets, the transfer current is changed in increments of 2 μA between 2 to 20 μA, a solid image is output at each, and the transfer residual toner on the photoconductor after the solid image transfer is taped with Mylar tape. I stripped it off. After that, the tape and the tape that was not taped were transferred to LETTER size XEROX 4200 paper (XEROX, 75 g / m
² ). Transferability was evaluated by a value obtained by subtracting the reflectance Dr (%) of the tape attached without taping from the reflectance Ds (%) of the tape.
The transfer current range in which the numerical value of transferability is 2.0 or less was defined as transfer latitude.
The reflectance was measured using “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku) with an amber filter.

<Image density>
Initially and after outputting 15,000 sheets, a sample image in which a solid black image of 20 mm square was printed at the four corners and the center of the paper surface was output, and the average density of the five points was measured. The image density was measured by using “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.

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 (6)

A toner having toner particles having a surface layer containing an organosilicon polymer and a resin having an ionic functional group,
The organosilicon polymer has a partial structure represented by the following formula (1) or (2):
In the X-ray photoelectron spectroscopic analysis of the surface of the toner particle, when the total of the carbon atom concentration dC, oxygen atom concentration dO, and silicon atom concentration dSi on the toner particle surface is 100.0 atomic%, the silicon The atomic concentration dSi is 1.0 atomic% or more and 22.2 atomic% or less,
A toner wherein the pKa (acid dissociation constant) of the resin having an ionic functional group is 6.0 or more and 9.0 or less.

(L in the formula (2) represents a methylene group, an ethylene group or a phenylene group.)   In cross-sectional observation of the toner particles using a transmission electron microscope (TEM), the crossing angle at the midpoint passes through the midpoint of the long axis L which is the maximum diameter of the cross section of the toner particles (crossing angle). When 32 lines are formed from the midpoint to the surface of the toner particles by drawing 16 straight lines crossing the cross section so that the angle is 11.25 °, The average thickness Dav. The toner according to claim 1, wherein the toner is 5.0 nm or more.   The toner according to claim 2, wherein a ratio of the number of the line segments having a thickness of the surface layer of 2.5 nm or less is 20.0% or less.   The toner according to claim 1, wherein the resin having an ionic functional group has a pKa (acid dissociation constant) of 7.0 or more and 8.5 or less. The toner according to claim 1, wherein the organosilicon polymer is a polymer of a polymerizable monomer containing an organosilicon compound represented by the following formula (3).

(In the formula (3), Rf represents a partial structure represented by the following formula (i) or (ii), and R1, R2, and R3 each independently represent a halogen atom, a hydroxyl group, an acetoxy group, or a carbon number of 1 to 3. 6 represents an alkoxy group.)

(* Is a bonding part with a silicon atom. L in the formula (ii) represents a methylene group, an ethylene group or a phenylene group.) The toner according to claim 1, wherein the resin having an ionic functional group contains a polymer A having a monovalent group a represented by the following formula (4).

(In the formula (4), ^{R 1} is, each independently, a hydroxyl group, a carboxyl group, 1 to 18 alkyl group carbon atoms, or represents a 1 to 18 alkoxy group carbon atoms, ^{R 2} is A hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, g represents an integer of 1 to 3 and h represents an integer of 0 to 3 Represents.)

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