JP7199830B2 - toner - Google Patents

Description

The present invention relates to toners for developing electrostatic images used in imaging processes such as electrophotography and electrostatic printing.

In recent years, copiers and printers have been used in new market areas, and high speed printing and high image stability are required for use in various environments. For example, printers and the like, which were conventionally used mainly in offices where the temperature and humidity were controlled, are now being used in harsh environments of high temperature and high humidity.

Patent Document 1 discloses a toner in which surface-treated inorganic fine particles are externally added to control the wettability of the toner in order to maintain good developability in a high-temperature, high-humidity environment.
Patent Document 2 discloses a toner in which the force between two particles of the toner is controlled.

JP 2011-064868 A Japanese Patent Application Laid-Open No. 2016-103005

The toner disclosed in Japanese Patent Application Laid-Open No. 2002-200001 has problems such as poor control due to charge-up in a low-temperature and low-humidity environment, and a decrease in solid-color followability due to a decrease in fluidity of the toner. Here, the regulation defect means an image defect caused by toner adhering to the toner carrier.
On the other hand, the toner disclosed in Patent Document 2 suppresses fogging in a high-temperature, high-humidity environment. there were.
For the above reasons, there is a demand for the development of a toner that exhibits excellent solid followability in high-temperature and high-humidity environments and in low-temperature and low-humidity environments and that suppresses defective regulation.
SUMMARY OF THE INVENTION The present invention provides a toner exhibiting excellent solid followability in a high-temperature and high-humidity environment and a low-temperature and low-humidity environment, and in which defective regulation is suppressed.

The present invention provides a toner containing a colorant and a binder resin,
the toner has a surface layer containing an organosilicon polymer;
The organosilicon polymer is a polymer having a structure represented by the following formula (R ^a T3),
R ^a —SiO _3/2 (R ^a T3)
[In the formula (R ^a T3), R ^a represents a hydrocarbon group having 1 or more and 6 or less carbon atoms. ]
In a methanol/water mixed solvent wettability test, the toner has a methanol concentration of 5.0% by volume or more and 30.0% by volume or less when the transmittance of light having a wavelength of 780 nm is 50%;
A toner characterized by having an interparticle force of 1.0 nN or more and 25.0 nN or less, which is measured by breaking a compacted body of the toner formed by compressing the toner with a load of 78.5 N. be.

According to the present invention, it is possible to provide a toner exhibiting excellent solid followability in a high-temperature and high-humidity environment and a low-temperature and low-humidity environment and in which defective regulation is suppressed.

Graph showing an example of a methanol drop transmittance curve in a wettability test (A) and (B) are diagrams showing an example of a device used to measure the force between two particles. A diagram showing an example of a jig used to measure the amount of charge on the developing roller.

In the present invention, unless otherwise specified, the descriptions of "○○ or more and XX or less" and "○○ to XX", which represent numerical ranges, mean numerical ranges including the lower and upper limits that are endpoints.
The present invention provides a toner containing a colorant and a binder resin,
In a methanol/water mixed solvent wettability test, the toner has a methanol concentration of 5.0% by volume or more and 30.0% by volume or less when the transmittance of light having a wavelength of 780 nm is 50%;
The toner is characterized in that the force between two particles measured by breaking a compact body of the toner formed by compressing the toner with a load of 78.5 N is 1.0 nN or more and 25.0 nN or less. .

In a high-temperature and high-humidity environment, the toner or the external additive adsorbs moisture, resulting in a decrease in charge amount and fluidity of the toner. As a result, fogging may occur, and solid followability may deteriorate. Therefore, conventionally, the problem has been solved by applying a hydrophobic treatment to the external additive.
Water adsorption can be suppressed by using a hydrophobized external additive, but on the other hand, the charge imparted to the toner does not leak, and regulation failure due to charge build-up occurs especially in a low temperature and low humidity environment.
Therefore, the present inventors believe that these problems can be solved in high-temperature and high-humidity environments and in low-temperature and low-humidity environments if the charge amount and fluidity of the toner do not decrease while the hydrophilicity of the toner is increased. I came to the idea that there is no.
As a result of earnest studies by the inventors, the following findings were obtained.
The hydrophilicity of the toner can be controlled by the wettability to methanol/water mixed solvent.
On the other hand, the fluidity of toner should be improved by reducing the force between two toner particles.
The reduction in the force between the two particles suppresses aggregation of the toner in the developing device, so that the toner can be quickly loosened. As a result, it should exhibit excellent chargeability.
That is, the inventors have found that the above problem can be solved by adjusting the force between two toner particles while the hydrophilicity of the toner is increased.

In a methanol/water mixed solvent wettability test, the toner has a methanol concentration (TA; hereinafter also referred to as wettability) of 5.0% by volume or more and 30.0% when the transmittance of light having a wavelength of 780 nm is 50%. % by volume or less. Moreover, the methanol concentration is preferably 5.0% by volume or more and 20.0% by volume or less.
When the methanol concentration is within the above range, the hydrophilicity of the toner is high, and charge-up can be prevented in a low-temperature, low-humidity environment. The details of the method for measuring the methanol concentration will be described later.

On the other hand, the force between two particles measured by breaking a compacted body of toner formed by compressing the toner with a load of 78.5 N is 1.0 nN or more and 25.0 nN or less. The force between two particles is preferably 3.0 nN or more and 20.0 nN or less, more preferably 3.0 nN or more and 17.0 nN or less.
Here, the force between the two particles applies a vertical load of 78.5N to the toner accommodated in the upper and lower cylindrical cells to form a toner compact. It is calculated based on the maximum tensile breaking force obtained when the compacted body of the toner is pulled and the compacted body of the toner is broken.
The compression condition at 78.5N is a value assuming the load applied when the compacted toner in the cartridge passes through the regulating portion.
When the force between the two particles is within the above range, the toner does not agglomerate at the regulating portion in the cartridge even in a high-temperature and high-humidity environment, resulting in good solid followability. The details of the method for measuring the force between two particles will be described later.
Further, by satisfying the methanol concentration (TA) and the force between two particles, electrostatic aggregation can be suppressed, and solid followability in a low-temperature and low-humidity environment is also improved.

Means for adjusting the methanol concentration (TA) and the force between two particles within the above ranges are not particularly limited. However, it is difficult to achieve this by externally adding an organic resin surface layer and a surface-treated inorganic fine particle, which are used in general toners.
As one means for adjusting the methanol concentration (TA) and the force between two particles within the above ranges, for example, a mode in which the toner has a surface layer containing an organosilicon polymer can be mentioned.
By including the organosilicon polymer in the surface layer of the toner, the wettability of the toner surface can be suitably controlled. On the other hand, the more the force between two particles is increased, the more the surface layer and the inside of the toner can be prevented from absorbing moisture.
As for material selection, it is possible to adjust the wettability and the force between two particles by adjusting the number of carbon atoms and the number of carbon chains of the functional groups directly bonded to the silicon atoms of the organosilicon polymer.
In addition, it is possible to control the wettability and the force between two particles by adjusting the uneven shape of the surface layer containing the organosilicon polymer and the network structure connecting the protrusions.
These adjustments depend on the timing and form of addition of the organosilicon polymer in the step of forming the surface layer containing the organosilicon polymer on the toner; the pH, temperature, and time when the organosilicon polymer is pretreated; Adjustable.

A specific example will be described below, but it is not limited to this.
First, toner core particles containing a binder resin and a colorant are prepared and dispersed in an aqueous medium to obtain a core particle dispersion. At this time, the core particle concentration is preferably such that the solid content of the core particles is 10% by mass or more and 40% by mass or less with respect to the total amount of the core particle dispersion. The temperature of the core particle dispersion is preferably adjusted to 35° C. or higher. Further, it is preferable to adjust the pH of the core particle dispersion to a pH at which condensation of the organosilicon compound does not easily proceed. Since the pH at which the condensation of the organosilicon polymer is difficult to proceed differs depending on the substance, it is preferably within ±0.5 around the pH at which the reaction is most difficult to proceed.
On the other hand, it is preferable to use the organosilicon compound that has been hydrolyzed.
For example, as a pretreatment of the organosilicon compound, hydrolysis may be carried out in a separate container. When the amount of the organosilicon compound is 100 parts by mass, the charge concentration for hydrolysis is preferably 40 parts by mass or more and 500 parts by mass or less of water from which ions have been removed, such as ion-exchanged water or RO water, and more preferably water. It is 100 mass parts or more and 400 mass parts or less.
The hydrolysis conditions are preferably pH 2 or more and 7 or less, temperature 15° C. or more and 80° C. or less, and time 30 minutes or more and 600 minutes or less.
The obtained hydrolyzate of the organosilicon compound and the core particle dispersion are mixed and adjusted to a pH suitable for condensation of the organosilicon compound (preferably 6 or more and 12 or less, or 1 or more and 3 or less, more preferably 8 or more and 12 below), the organosilicon compound can be condensed to form a surface layer on the surface of the core particles of the toner. Condensation and surface layering are preferably carried out at 35° C. or higher for 60 minutes or longer. In addition, the surface macrostructure can be adjusted by adjusting the holding time at 35° C. or higher before adjusting the pH to a suitable one for condensation, and the holding time is preferably 3 minutes or more and 120 minutes or less.
It is believed that the above method reduces reactive residues in the organosilicon polymer and increases the ratio of the —Si—O—Si— structure, thereby increasing the hydrophilicity.
Furthermore, it is believed that the obtained surface layer has an uneven shape and a network is formed between the protrusions, so that the resin portion of the core particles is less likely to be exposed and the force between the two particles can be reduced.

When a surface layer containing an organosilicon polymer is used, the content of the organosilicon polymer in the toner is preferably 0.5% by mass or more and 5.0% by mass or less, and preferably 1.5% by mass or more. It is more preferably 5.0% by mass or less.
When the content of the organosilicon polymer is within the above range, durability of the toner can be improved. The content of the organosilicon polymer can be controlled by the type and amount of the organosilicon compound used to form the organosilicon polymer, the production method for the formation of the organosilicon polymer, reaction temperature, reaction time, reaction solvent and pH. . A method for measuring the content of the organosilicon polymer will be described later.

When a surface layer containing an organosilicon polymer is used, the fixation rate of the organosilicon polymer to the toner is preferably 90.0% or more and 100.0% or less, and preferably 92.0% or more and 99.0%. The following are more preferable.
When the fixation rate is within the above range, the organosilicon polymer is less likely to peel off or detach, and is not fused to the members in the cartridge, so development streaks are suppressed even when a durable output is performed. A method for measuring the fixation rate of the organosilicon polymer to the toner will be described later.
The fixation rate can be adjusted within the above range depending on the production method, reaction temperature, reaction time, reaction solvent, pH, etc. during formation of the organosilicon polymer.

The organosilicon polymer is preferably a polymer having a structure represented by the following formula (R ^a T3).
R ^a —SiO _3/2 (R ^a T3)
[In the formula (R ^a T3), R ^a is a hydrocarbon group having 1 to 6 carbon atoms, or a vinyl-based polymer moiety containing a partial structure represented by the following formula (i) or the following formula (ii): show. ]

［式（ｉ）及び式（ｉｉ）において、＊は該（Ｒ^ａＴ３）で表される構造中のＳｉ元素との結合部位を表し、式（ｉｉ）におけるＬは、アルキレン基又はアリーレン基を表す。］
該アルキレン基はメチレン基が好ましく、該アリーレン基はフェニレン基が好ましい。

[In formulas (i) and (ii), * represents a bonding site with the Si element in the structure represented by (R ^a T3), and L in formula (ii) represents an alkylene group or an arylene group. show. ]
The alkylene group is preferably a methylene group, and the arylene group is preferably a phenylene group.

When the organosilicon polymer has the structure described above, the charge on the surface of the toner flows quickly, and the charge rising property of the toner is improved. As a result, the toner on the toner carrier is supplied even immediately after the solid image is output, and the solid followability is further improved.
Of the four valence electrons of the Si atom in formula (R ^a T3), one participates in bonding with R ^a and the remaining three participate in bonding with the O atom. The O atom constitutes a state in which both valence electrons are involved in bonding with the Si atom, that is, a siloxane bond (Si—O—Si).
Considering Si atoms and O atoms as an organosilicon polymer, it is expressed as —SiO _3/2 because it has two Si atoms and three O atoms.
The presence of the siloxane polymer moiety (--SiO _3/2 ) in the formula (R ^a T3) can be confirmed by ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble portion of the toner.
The existence of the structures represented by formulas (i) and (ii) can be confirmed by ¹³ C-NMR measurement of the tetrahydrofuran-insoluble matter of the toner.

In the chart obtained by ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble matter of the toner, the ratio of the peak area attributed to the structure of the formula (R ^a T3) to the total peak area of the organosilicon polymer is 20% or more. is preferred.

Examples of the production of the organosilicon polymer include a sol-gel method.
The sol-gel method is a method in which a liquid raw material is used as a starting material, hydrolyzed and condensation-polymerized, and gelled through a sol state, and is used in a method for synthesizing glasses, ceramics, organic-inorganic hybrids, and nanocomposites. By using this production method, functional materials in various shapes such as surface layers, fibers, bulk bodies, and fine particles can be produced from the liquid phase at low temperatures.
Specifically, the organosilicon polymer present in the surface layer of the toner is preferably produced by hydrolysis and polycondensation of a silicon compound represented by alkoxysilane.
By providing the toner with the surface layer containing the organosilicon polymer, it is possible to obtain a toner with improved environmental stability, less deterioration in toner performance during long-term use, and excellent storage stability.
Furthermore, the sol-gel method starts from a liquid and forms a material by gelling the liquid, so various microstructures and shapes can be produced. In particular, when the toner is produced in an aqueous medium, it is easily deposited on the surface of the toner due to the hydrophilicity of the hydrophilic group such as the silanol group of the organosilicon compound. The fine structure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH, the type and amount of the organometallic compound, and the like.

The organosilicon polymer contained in the surface layer is preferably a polycondensation product of an organosilicon compound having a structure represented by the following formula (Z).

［式（Ｚ）中、Ｒ_１は、炭化水素基を表し、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して、ハロゲン原子、ヒドロキシ基、アセトキシ基、又は、アルコキシ基を表す。］
尚、Ｒ_１は、式（Ｒ^ａＴ３）中のＲ^ａとなる官能基であり、下記式（Ａ）若しくは下記式（Ｂ）で表される構造も含む。

［式（Ａ）及び（Ｂ）において、＊は式（Ｚ）で表される構造中のＳｉ元素との結合部位を表し、式（Ｂ）におけるＬは、アルキレン基又はアリーレン基を表す。］
該アルキレン基はメチレン基が好ましく、該アリーレン基はフェニレン基が好ましい。

[In formula (Z), R ₁ represents a hydrocarbon group, and R ₂ , R ₃ and R ₄ each independently represent a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group. ]
R ₁ is a functional group that becomes R ^a in the formula (R ^a T3), and includes structures represented by the following formula (A) or the following formula (B).

[In the formulas (A) and (B), * represents a bonding site with the Si element in the structure represented by the formula (Z), and L in the formula (B) represents an alkylene group or an arylene group. ]
The alkylene group is preferably a methylene group, and the arylene group is preferably a phenylene group.

Hydrophobicity can be improved by the hydrocarbon group of _R1 , and a toner excellent in environmental stability can be obtained. An aryl group, which is an aromatic hydrocarbon group, such as a phenyl group, can also be used as the hydrocarbon group. When the hydrophobicity of R ₁ is large, the charge amount tends to increase in various environments. Therefore, in view of environmental stability, R ₁ is preferably an aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms. More preferably, it is an alkyl group having 1 or more and 3 or less carbon atoms.
R ₂ , R ₃ and R ₄ are each independently a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups form a crosslinked structure through hydrolysis, addition polymerization, and condensation polymerization, and a toner excellent in member contamination resistance and development durability can be obtained.
An alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable, from the viewpoints of mild hydrolyzability at room temperature and deposition and coating properties on the surface of the toner.
Also, the hydrolysis, addition polymerization and condensation polymerization of R ₂ , R ₃ and R ₄ can be controlled by reaction temperature, reaction time, reaction solvent and pH.

To obtain an organosilicon polymer, an organosilicon compound ₍ hereinafter referred to as _{a trifunctional silane} (also referred to as ) may be used singly or in combination.
Examples of organosilicon compounds having a structure represented by formula (Z) include the following.
Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyldiethoxymethoxysilane, Vinylethoxydimethoxysilane, Vinyltrichlorosilane, Vinylmethoxydichlorosilane, Vinylethoxydichlorosilane, Vinyldimethoxychlorosilane, Vinylmethoxyethoxychlorosilane, Vinyldiethoxychlorosilane, Vinyl Triacetoxysilane, Vinyldiacetoxymethoxysilane, Vinyldiacetoxyethoxysilane, Vinylacetoxydimethoxysilane, Vinylacetoxymethoxyethoxysilane, Vinylacetoxydiethoxysilane, Vinyltrihydroxysilane, Vinylmethoxydihydroxysilane, Vinylethoxydihydroxysilane, Vinyldimethoxysilane trifunctional vinylsilanes such as hydroxysilane, vinylethoxymethoxyhydroxysilane, vinyldiethoxyhydroxysilane; allyltrimethoxysilane, allyltriethoxysilane, allyldiethoxymethoxysilane, allylethoxydimethoxysilane, allyltrichlorosilane, allyl Methoxydichlorosilane, allylethoxydichlorosilane, allyldimethoxychlorosilane, allylmethoxyethoxychlorosilane, allyldiethoxychlorosilane, allyltriacetoxysilane, allyldiacetoxymethoxysilane, allyldiacetoxyethoxysilane, allylacetoxydimethoxysilane, allylacetoxymethoxyethoxysilane , allylacetoxydiethoxysilane, allyltrihydroxysilane, allylmethoxydihydroxysilane, allylethoxydihydroxysilane, allyldimethoxyhydroxysilane, allylethoxymethoxyhydroxysilane, allyldiethoxyhydroxysilane; p- styryltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyl Diethoxychlorosilane, Methyltriacetoxysilane, Methyldiacetoxymethoxysilane, Methyldiacetoxyethoxysilane, Methylacetoxydimethoxysilane, Methylacetoxymethoxyethoxysilane, Methylacetoxydiethoxysilane trifunctional methylsilanes such as trifunctional methylsilanes, such as silane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane; ethyltrimethoxysilane, ethyltrihydroxysilane; trifunctional ethylsilanes such as ethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane; propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, trifunctional propylsilanes such as; trifunctional butylsilanes such as butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane; hexyltrimethoxysilane, hexyltri trifunctional hexylsilanes such as ethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane; phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltrihydroxysilane; Trifunctional phenylsilanes such as. An organosilicon compound may be used alone or in combination of two or more.

As a result of hydrolysis and polycondensation, the content of the organosilicon compound having the structure represented by formula (Z) in the organosilicon polymer is preferably 50 mol% or more, more preferably 60 mol% or more. .
In addition to the organosilicon compound having the structure represented by the formula (Z), an organosilicon compound having four reactive groups in one molecule (tetrafunctional silane) and three reactive groups in one molecule An organosilicon compound (trifunctional silane), an organosilicon compound having two reactive groups in one molecule (bifunctional silane), or an organosilicon compound having one reactive group (monofunctional silane) may be used in combination. good. For example:
dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy propyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- Acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3 -aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane Silane, 3-anilinopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 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, tetraisocyanatosilane, methyltriisocyanatosilane, vinyltriisocyanatosilane.

It is preferable that the surface layer containing the organosilicon polymer and the core particles of the toner are in contact with each other without a gap. As a result, bleeding due to the resin component, release agent, and the like inside the toner can be suppressed, and a toner excellent in storage stability, environmental stability, and development durability can be obtained.
In addition to the organosilicon polymer, the surface layer may contain resins such as styrene-acrylic copolymer resins, polyester resins and urethane resins, various additives, and the like.

[Binder resin]
The toner contains a binder resin. The binder resin is not particularly limited, and conventionally known ones can be used. Preferred examples of the binder resin include vinyl-based resins and polyester resins. Examples of vinyl resins, polyester resins and other binder resins include the following resins or polymers.
Homopolymers of styrene and substituted products thereof such as polystyrene and polyvinyltoluene; styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, 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-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Styrenic copolymers such as coalescence, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, poly Vinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. These binder resins can be used alone or in combination.

The binder resin preferably contains a carboxy group from the viewpoint of chargeability, and is preferably a resin produced using a polymerizable monomer containing a carboxy group.
Examples of the polymerizable monomer include acrylic acid; α-alkyl unsaturated carboxylic acids or β-alkyl unsaturated carboxylic acids such as methacrylic acid, α-ethylacrylic acid and crotonic acid; fumaric acid, maleic acid, citracone; Acids, unsaturated dicarboxylic acids such as itaconic acid; unsaturated dicarboxylic acid monoesters such as succinic acid monoacryloyloxyethyl ester, succinic acid monoacryloyloxyethylene ester, phthalic acid monoacryloyloxyethyl ester, phthalic acid monomethacryloyloxyethyl ester derivatives, etc.
As the polyester resin, a polycondensation product of a carboxylic acid component and an alcohol component listed below can be used.
Carboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid.
Alcohol components include bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.
Moreover, the polyester resin may be a polyester resin containing a urea group. As for the polyester resin, it is preferable not to cap carboxyl groups such as terminals.
In the toner, the binder resin may have a polymerizable functional group for the purpose of improving the viscosity change of the toner at high temperatures. Polymerizable functional groups include vinyl groups, isocyanate groups, epoxy groups, amino groups, carboxy groups, and hydroxy groups.

[Crosslinking agent]
In order to control the molecular weight of the binder resin, a cross-linking agent may be added during the polymerization of the polymerizable monomer.
For example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, divinylbenzene, bis(4 -acryloxypolyethoxyphenyl)propane, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate , polyethylene glycol #200, #400, and #600 diacrylates, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Nippon Kayaku), and methacrylates obtained by converting the above acrylates.
The amount of the cross-linking agent to be added is preferably 0.001 parts by mass or more and 15.000 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

[Release agent]
The toner may contain a release agent. Examples of the release agent include paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and its derivatives, montan wax and its derivatives, hydrocarbon waxes produced by the Fischer-Tropsch process and its derivatives, and polyolefin waxes such as polyethylene and polypropylene. and derivatives thereof, natural waxes such as carnauba wax and candelilla wax and derivatives thereof, higher fatty alcohols, fatty acids such as stearic acid, palmitic acid, or derivatives thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, and silicone resins. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products.
The content of the release agent is preferably 5.0 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or polymerizable monomer.

[Coloring agent]
A toner contains a colorant. Colorants are not particularly limited, and for example, known ones shown below can be used.
Yellow pigments include yellow iron oxide, navels yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, condensed azo compounds such as 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, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180.
Examples of orange pigments include the following.
Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Benzidine Orange G, Indanthrene Brilliant Orange RK, Indanthrene Brilliant Orange GK.
Red pigments include condensation of red iron oxide, permanent red 4R, lithol red, pyrazolone red, watching red calcium salt, lake red C, lake red D, brilliant carmine 6B, brilliant carmine 3B, eosin lake, rhodamine lake B, and alizarin lake. azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following.
C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254.
Blue pigments include copper phthalocyanine compounds and their derivatives such as alkali blue lake, victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, and indanthrene blue BG, anthraquinone compounds, and basic dye lakes. compound and the like. Specific examples include the following.
C. I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, 66.
Purple pigments include Fast Violet B and Methyl Violet Lake.
Examples of green pigments include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. White pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of black pigments include carbon black, aniline black, non-magnetic ferrite, magnetite, and those toned black using the above yellow, red, and blue colorants. These colorants can be used singly or in combination, or in the form of a solid solution.
If necessary, the colorant may be surface-treated with a substance that does not inhibit polymerization to modify the surface.
The content of the colorant is preferably 3.0 parts by mass or more and 15.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or polymerizable monomer.

[Charge control agent]
The toner may contain a charge control agent. A known charge control agent can be used. In particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferred. Furthermore, when the toner is produced by a direct polymerization method, a charge control agent that has a low polymerization inhibitory property and substantially no solubilized substances in an aqueous medium is preferred.
Examples of charge control agents that control the toner to be negatively charged include the following.
Metal compounds such as monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acids as organometallic compounds and chelate compounds. Others include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, or esters, phenol derivatives such as bisphenol, and the like. Furthermore, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, and calixarenes are included.
On the other hand, the charge control agent for controlling the toner to be positively chargeable includes the following.
nigrosine and nigrosine modifications such as fatty acid metal salts; guanidine compounds; imidazole compounds; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate; and their lake pigments; triphenylmethane dyes and their lake pigments (the lake agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; resin charge control agents.
The charge control agent can be contained alone or in combination of two or more.
The content of the charge control agent is preferably 0.01 parts by mass or more and 10.00 parts by mass or less with respect to 100.00 parts by mass of the binder resin.

[External Additive]
The toner may be prepared without containing an external additive. agents, cleaning aids, and the like.
Examples of external additives include inorganic oxide fine particles such as silica fine particles, alumina fine particles and titanium oxide fine particles, inorganic stearic acid compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, or strontium titanate and zinc titanate. and inorganic titanate compound fine particles such as These can be used individually by 1 type or in combination of 2 or more types.
The inorganic fine particles may be treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil, or the like in order to improve heat-resistant storage stability and environmental stability.
The BET specific surface area of the external additive is preferably 10 m ² /g or more and 450 m ² /g or less.
The BET specific surface area can be determined by a low temperature gas adsorption method using a dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, using a specific surface area measuring device (trade name: Gemini 2375 Ver.5.0, manufactured by Shimadzu Corporation), nitrogen gas is adsorbed on the surface of the sample, and the BET multipoint method is used for measurement. BET specific surface area (m ² /g) can be calculated.
The total amount of these various external additives added is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 part by mass, relative to 100 parts by mass of the particles before external addition. It is at least 3 parts by mass and no more than 3 parts by mass. In addition, various external additives may be used in combination.

[Developer]
The toner can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a magnetic carrier and used as a two-component developer.
As the magnetic carrier, for example, magnetic particles made of known materials such as metals such as iron, ferrite and magnetite; alloys of these metals with metals such as aluminum and lead can be used. Among these, it is preferable to use ferrite particles.
As the magnetic carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as a resin, or a resin-dispersed carrier in which magnetic particles are dispersed in a binder resin may be used.
The volume average particle size of the magnetic carrier is preferably 15 μm or more and 100 μm or less, more preferably 25 μm or more and 80 μm or less.

A known means can be used for the method for producing the toner. Examples thereof include a kneading pulverization method and a wet manufacturing method.
A wet manufacturing method is preferable from the viewpoint of uniformity of toner particle size and shape controllability. Examples of wet production methods include a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, an emulsion aggregation method, and the like.
The suspension polymerization method will be described below, but the method is not limited thereto.
In the suspension polymerization method, a polymerizable monomer for forming a binder resin, a colorant, and optionally other additives are dispersed using a dispersing machine such as a ball mill or an ultrasonic dispersing machine. A polymerizable monomer composition is prepared by uniformly dissolving or dispersing (preparation step of a polymerizable monomer composition).
The other additives include polyfunctional monomers, chain transfer agents, waxes as release agents, charge control agents, and plasticizers.
As the polymerizable monomer, the following vinyl polymerizable monomers can be suitably 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-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene; methyl acrylate; , ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n - acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate , n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate , diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate, methacrylic polymerizable monomers; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl formate, etc. vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone.

Next, the polymerizable monomer composition is put into an aqueous medium prepared in advance, and the polymerizable monomer composition is dispersed by a stirrer or disperser having a high shear force so that the toner has a desired size. Form droplets of the polymer composition (granulation step).
It is preferable that the aqueous medium in the granulation step contain a dispersion stabilizer in order to control the particle size of the toner, sharpen the particle size distribution, and suppress coalescence of the toner in the production process.
Dispersion stabilizers are generally classified broadly into macromolecules that generate a repulsive force due to steric hindrance and poorly water-soluble inorganic compounds that stabilize dispersion by electrostatic repulsive force. Fine particles of poorly water-soluble inorganic compounds are preferably used because they are dissolved by acid or alkali and can be dissolved and easily removed by washing with acid or alkali after polymerization.
As the dispersion stabilizer for the sparingly water-soluble inorganic compound, one containing any one of magnesium, calcium, barium, zinc, aluminum and phosphorus is preferably used. More preferably, it contains any one of magnesium, calcium, aluminum and phosphorus. Specifically, the following are mentioned.
Magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, hydroxyapatide.
As the dispersion stabilizer, an organic compound such as polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, and starch may be used in combination.
The content of the dispersion stabilizer is preferably 0.01 parts by mass or more and 2.00 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.
Further, a surfactant of 0.001% by mass or more and 0.1% by mass or less may be used in combination to make the dispersion stabilizer finer. Specifically, commercially available nonionic, anionic, and cationic surfactants can be used. Examples include sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate.

After the granulation step or while performing the granulation step, the temperature is set to about 50° C. or more and 90° C. or less to polymerize the polymerizable monomer contained in the polymerizable monomer composition and disperse the toner. It is preferable to obtain a liquid (polymerization step).
In the polymerization step, it is preferable to perform a stirring operation so that the temperature distribution in the container becomes uniform. When a polymerization initiator is added, it can be added at any desired time and required time. Further, the temperature may be raised in the second half of the polymerization reaction for the purpose of obtaining a desired molecular weight distribution. Furthermore, in order to remove unreacted polymerizable monomers, by-products and the like out of the system, part of the aqueous medium may be distilled off in the latter half of the reaction or after the completion of the reaction. The distillation operation can be performed under normal pressure or reduced pressure.

An oil-soluble initiator is generally used as the polymerization initiator. For example:
2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4 - azo compounds such as methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropyl peroxycarbonate, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert- Butyl peroxy-2-ethylhexanoate, benzoyl peroxide, tert-butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl hydroperoxide, di-tert-butylperoxide peroxide initiators such as oxide, tert-butyl peroxypivalate and cumene hydroperoxide;
If necessary, a water-soluble initiator may be used in combination with the polymerization initiator, and examples thereof include the following.
ammonium persulfate, potassium persulfate, 2,2'-azobis(N,N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis(2-amidinopropane) hydrochloride, azobis(isobutylamidine) hydrochloride salt, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.
The polymerization initiators can be used alone or in combination, and chain transfer agents, polymerization inhibitors and the like can be further added and used to control the degree of polymerization of the polymerizable monomers.

The weight-average particle size of the toner is preferably 3.0 μm or more and 10.0 μm or less from the viewpoint of obtaining high-definition and high-resolution images.
The weight average particle diameter of the toner can be measured by a pore electrical resistance method. For example, it can be measured using "Coulter Counter Multisizer 3" (manufactured by Beckman Coulter, Inc.).
The obtained toner dispersion is sent to a filtration step for solid-liquid separation of the toner and the aqueous medium.
The solid-liquid separation can be performed by a common filtration method.
After that, it is preferable to wash the surface of the toner with reslurry or washing water in order to remove the foreign matter that has not been completely removed from the surface of the toner.
After sufficient washing is performed, solid-liquid separation is performed again to obtain a toner cake. After that, it is preferable to dry by a known drying means, and if necessary, to separate a particle group having a particle size outside the predetermined size by classification to obtain a toner.
In the case of forming a surface layer having an organosilicon polymer on the surface of the toner, the obtained toner dispersion is used as the core particle dispersion, and the hydrolyzate of the organosilicon compound is added as described above to form the surface layer. should be formed.

<Method of Wettability Test for Methanol/Water Mixed Solvent>
The wettability test of the toner to a methanol/water mixed solvent was performed using a powder wettability tester "WET-100P" (manufactured by Lesca) under the following conditions and procedures. calculate.
A fluororesin-coated spindle rotor having a length of 25 mm and a maximum barrel diameter of 8 mm is placed in a cylindrical glass container having a diameter of 5 cm and a thickness of 1.75 mm.
60 mL of reverse osmosis membrane-treated water (RO water) is put into the cylindrical glass container, and dispersed for 5 minutes with an ultrasonic disperser to remove bubbles and the like.
To this, 0.1 g of toner is accurately weighed and added to prepare a sample solution for measurement.
While stirring the spindle-shaped rotor in the cylindrical glass container at a speed of 300 rpm using a magnetic stirrer, 0.8 mL / min of methanol is passed through the powder wettability tester into the measurement sample liquid. Add continuously at a drop rate.
The transmittance is measured with light having a wavelength of 780 nm, and a methanol dropping transmittance curve as shown in FIG. 1 is created. From the methanol dropping transmittance curve, the methanol concentration (TA) is read when the transmittance shows 50%.
In addition, the methanol concentration (TA; volume %) is
(volume of methanol present in cylindrical glass container/volume of mixture of methanol and water present in cylindrical glass container) x 100
It is a value calculated by

<Method for measuring force between two particles>
The force between two toner particles is measured using a Hosokawa Micron Aggrobot according to the instructions for the apparatus.
Specific measurement methods and measurement conditions are as follows.
(Sample conditions)
Charged mass of powder: 9.2 (g) for magnetic toner, 7.7 (g) for non-magnetic toner Binder mass: 0 (g)
True density of powder: True density of toner (kg/m ³ )
Density of liquid binder: 0 (kg/m ³ )
Body area average diameter of powder: Weight average particle diameter of toner (D4) (μm)
Specific surface area shape factor: 6 (-)
Minimum void ratio of dry powder: 0.26 (-)
(Measurement condition)
Environmental temperature: 25°C
Humidity: 50%
Cell inner diameter: 25mm
In-cell height: 37.5mm
Cell temperature: 25°C
Spring wire diameter: 1.0mm
Compression speed: 1.0mm/sec
Compression holding time: 0.0 sec
Compressive stress: 8 kg/cm ²
Tensile speed: 0.40mm/sec
Tensile sampling start time: 0.0 sec
Tensile sampling time: 25 sec
(1) Magnetic Toner Under the environment of 25° C./50%, 9.2 g of toner is filled into the upper and lower cylindrical cells shown in FIG. 2(A). After that, the compressing rod is lowered at 1.0 mm/sec to apply a vertical load of 78.5 N to form a toner compact.
After that, as shown in FIG. 2B, the upper cell was lifted by a spring at a speed of 0.40 mm/sec to pull the compacted toner, and the maximum tensile breaking force obtained when the compacted toner was broken. to calculate the force between two particles (nN). Note that the force between two particles (nN) is automatically calculated.
(2) Non-Magnetic Toner Under an environment of 25° C./50%, 7.7 g of toner is filled into the upper and lower cylindrical cells shown in FIG. 2(A). After that, the compressing rod is lowered at 1.0 mm/sec to apply a vertical load of 78.5 N to form a toner compact.
After that, as shown in FIG. 2B, the upper cell was lifted by a spring at a speed of 0.40 mm/sec to pull the compacted toner, and the maximum tensile breaking force obtained when the compacted toner was broken. to calculate the force between two particles (nN). Note that the force between two particles (nN) is automatically calculated.

<Method for Measuring Content of Organosilicon Polymer>
The content of the organosilicon polymer in the toner was measured using a wavelength dispersive X-ray fluorescence spectrometer "Axios" (manufactured by PANalytical) and dedicated software "SuperQ ver.4" for setting measurement conditions and analyzing measurement data. 0F" (manufactured by PANalytical).
Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds.
A proportional counter (PC) is used to measure light elements, and a scintillation counter (SC) is used to measure heavy elements.
As a measurement sample, 4 g of toner was placed in a special aluminum ring for press and leveled, and a tablet press "BRE-32" (manufactured by Mayekawa Test Instruments Co., Ltd.) was used at 20 MPa for 60 seconds. Pellets that are pressed and molded to a thickness of 2 mm and a diameter of 39 mm are used.
Silica (SiO ₂ ) fine powder was added to 0.5 parts by mass to 100 parts by mass of a toner containing no organosilicon polymer (to which an external additive was not added), and a coffee mill was used. Mix well with Similarly, 5.0 parts by mass and 10.0 parts by mass of fine silica powder were mixed with the toner, respectively, and these were used as samples for the calibration curve.
For each sample, a pellet of the sample for the calibration curve was prepared as described above using a tablet press, and when PET was used as the analyzing crystal, the diffraction angle (2θ) was observed at 109.08°. Measure the count rate (unit: cps) of Si-Kα rays.
At this time, the acceleration voltage and current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A linear function calibration curve is obtained with the obtained X-ray count rate on the vertical axis and the amount of SiO ₂ added in each calibration curve sample on the horizontal axis.
Next, the toner to be analyzed is made into pellets as described above using a tablet press, and the Si--Kα ray count rate of the pellets is measured. Then, the content of the organosilicon polymer in the toner is determined from the above calibration curve.

<Method for Confirming Structure Represented by Formula (R ^a T3)>
Among the structures represented by the formula (R ^a T3), structures such as hydrocarbon groups bonded to silicon atoms are confirmed by ¹³ C-NMR (solid).
Further, the detailed structure of formula (R ^a T3) is ¹³ C-NMR (solid) and ²⁹ Si-NMR
Confirm by
The apparatus, measurement conditions, and sample preparation method used are shown below.
" ¹³ C-NMR (solid) measurement conditions"
Device: JNM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran-insoluble matter of toner for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP/MAS
Measurement nuclear frequency: 123.25 MHz ( ¹³ C)
Reference substance: adamantane (external standard: 29.5 ppm)
Sample rotation speed: 20 kHz
Contact time: 2ms
Delay time: 2s
Accumulated times: 1024 times

"Sample preparation method"
Preparation of measurement sample: 10.0 g of toner was weighed, placed in a filter paper thimble (No. 86R manufactured by Toyo Roshi Kaisha Ltd.), put in a Soxhlet extractor, and extracted with 200 mL of tetrahydrofuran as a solvent for 20 hours. A sample obtained by vacuum drying at 40° C. for several hours is used as a sample for NMR measurement.
When the toner contains an external additive or the like, the toner is obtained by removing the external additive by the following method.
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a concentrated sucrose solution. In a centrifugation tube, 31 g of concentrated sucrose and Contaminon N (a 10% by mass aqueous solution of a neutral detergent for washing precision measuring instruments with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, 6 mL of Kojunyaku Kogyo Co., Ltd.) is added to prepare a dispersion liquid. 1.0 g of toner is added to this dispersion, and clumps of toner are loosened with a spatula or the like.
The centrifuge tube is shaken on a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced in a swing rotor glass tube (50 mL) and separated in a centrifuge at 3500 rpm for 30 minutes.
This operation separates the toner from the external additive. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the separated toner on the uppermost layer is collected with a spatula or the like. After the collected toner is filtered with a vacuum filter, it is dried with a dryer for 1 hour or more to obtain a toner. This operation is carried out multiple times to ensure the required amount.

In formula (R ^a T3), when R ^a has a structure represented by formula (i) above, the presence or absence of a signal due to a methine group (>CH—Si) bonded to a silicon atom determines Confirm the existence of the structure represented by (i).
In the formula (R ^a T3), when R ^a has a structure represented by the above formula (ii), a methylene group (Si—CH ₂ —) or an ethylene group (Si—C ₂ H _4- ) or an arylene group (for example, a phenylene group (Si--C ₆ H ₄ --)) or the like, the presence or absence of a signal resulting from such a structure confirms the presence of the structure represented by the above formula (ii).
In the formula (R ^a T3), when R ^a is a hydrocarbon group having 1 to 6 carbon atoms, a methyl group (Si—CH ₃ ) or an ethyl group (Si—C ₂ H ₅ ) bonded to a silicon atom , propyl group (Si—C ₃ H ₇ ), butyl group (Si—C ₄ H ₉ ), pentyl group (Si—C ₅ H ₁₁ ), hexyl group (Si—C ₆ H ₁₃ ), phenyl group (Si— C ₆ H ₅ ) or the like confirms its presence.

<Method for Measuring Peak Area Assigned to Structure of Formula (R ^a T3), Measured by ²⁹ Si-NMR of Tetrahydrofuran-Insoluble Content of Toner>
The ²⁹ Si-NMR (solid) measurement of the tetrahydrofuran-insoluble portion of the toner is performed under the following measurement conditions.
" ²⁹ Si-NMR (solid) measurement conditions"
Device: JNM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran-insoluble matter of toner for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP/MAS
Measured nuclear frequency: 97.38 MHz ( ²⁹ Si)
Reference substance: DSS (external standard: 1.534 ppm)
Sample rotation speed: 10 kHz
Contact time: 10ms
Delay time: 2s
Cumulative number of times: 2000 to 8000 times After the above measurement, multiple silane components with different substituents and bonding groups in the tetrahydrofuran-insoluble portion of the toner are subjected to curve fitting to separate the peaks into the following X1 structure, X2 structure, X3 structure, and X4 structure. and calculate the peak area.
X1 structure: (Ri) (Rj) (Rk) SiO _1/2 formula (12)
X2 structure: (Rg)(Rh)Si(O _1/2 ) ₂ Formula (13)
X3 structure: RmSi(O _1/2 ) ₃ formula (14)
X4 structure: Si(O _1/2 ) ₄ formula (15)

［式（１２）、（１３）及び（１４）中のＲｉ、Ｒｊ、Ｒｋ、Ｒｇ、Ｒｈ、及びＲｍはケイ素原子に結合している炭素数が１以上６以下の炭化水素基などの有機基、ハロゲン原子、ヒドロキシ基、アセトキシ基又はアルコキシ基を示す。］

[Ri, Rj, Rk, Rg, Rh, and Rm in formulas (12), (13) and (14) are organic groups such as hydrocarbon groups having 1 to 6 carbon atoms bonded to a silicon atom; , a halogen atom, a hydroxy group, an acetoxy group or an alkoxy group. ]

In the chart obtained by ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble matter of the toner, a plurality of silane components having different substituents and bonding groups in the X3 structure are identified by chemical shift values.
These are peak-separated by curve fitting so that the difference between the measurement result and the synthesized peak is minimized, and the peak area is obtained.
By this method, the ratio of the peak area attributed to the structure of the formula (R ^a T3) to the total peak area of the organosilicon polymer is calculated.

<Method for calculating fixation ratio of organic silicon polymer to toner>
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a concentrated sucrose solution. In a centrifugation tube (capacity: 50 mL), 31 g of the concentrated sucrose solution and Contaminon N (a pH 7 neutral detergent for cleaning precision measuring instruments consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) were added. 6 mL of a mass % aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. 1 g of toner is added to this dispersion, and clumps of toner are loosened with a spatula or the like.
The centrifugation tube is shaken on a shaker at 350 spm (strokes per min) for 20 minutes and washed with water.
After shaking, the solution is replaced in a swing rotor glass tube (50 mL) and separated in a centrifuge (H-9R manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 minutes.
It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the separated toner on the uppermost layer is collected with a spatula or the like. After the collected aqueous solution containing the toner is filtered with a vacuum filter, it is dried with a dryer for 1 hour or more.
The dried product is pulverized with a spatula, and the amount of organosilicon polymer is measured with fluorescent X-rays. The fixation rate (%) is calculated from the ratio of the amount of element to be measured between the toner after water washing and the initial toner.
Fluorescent X-ray measurement of each element conforms to JIS K 0119-1969, but is specifically as follows.
As a measurement device, a wavelength dispersive X-ray fluorescence spectrometer "Axios" (manufactured by PANalytical) and attached dedicated software "SuperQ ver.4.0F" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data ) is used.
Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 10 seconds. A proportional counter (PC) is used to measure light elements, and a scintillation counter (SC) is used to measure heavy elements.
As a measurement sample, about 1 g of the toner after washing with water and the initial toner was placed in a dedicated press aluminum ring with a diameter of 10 mm, and the toner was flattened. ), pressurized at 20 MPa for 60 seconds, and used pellets molded to a thickness of about 2 mm.
Measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and the concentration is calculated from the count rate (unit: cps), which is the number of X-ray photons per unit time.
As a method for quantifying the amount of silicon in the toner, for example, 0.5 parts by mass of silica (SiO ₂ ) fine powder is added to 100 parts by mass of the toner, and the mixture is thoroughly mixed using a coffee mill. Similarly, 2.0 parts by mass and 5.0 parts by mass of fine silica powder were mixed with the toner, respectively, and these were used as samples for the calibration curve.
For each sample, a pellet of the sample for the calibration curve was prepared as described above using a tablet press, and when PET was used as the analyzing crystal, the diffraction angle (2θ) was observed at 109.08°. Measure the count rate (unit: cps) of Si-Kα rays. At this time, the acceleration voltage and current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A linear function calibration curve is obtained with the obtained X-ray count rate on the vertical axis and the amount of SiO ₂ added in each calibration curve sample on the horizontal axis.
Next, the toner to be analyzed is made into pellets as described above using a tablet press, and the Si--Kα ray count rate of the pellets is measured. Then, the content of the organosilicon polymer in the toner is determined from the above calibration curve. The ratio of the elemental amount of the toner after washing with water to the elemental amount of the initial toner calculated by the above method was obtained and defined as the fixation rate (%) to the toner.

<Method for Measuring Weight Average Particle Diameter (D4) of Toner>
The weight average particle diameter (D4) of toner is calculated as follows. As a measuring device, a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. The attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) is used for setting the measurement conditions and analyzing the measurement data. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special-grade sodium chloride dissolved in ion-exchanged water to a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used.
Before performing measurement and analysis, the dedicated software is set as follows.
On the "Change standard measurement method (SOMME)" screen of the dedicated software, set the total count number in control mode to 50000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter (manufactured by Co., Ltd.) is used to set the value obtained. By pressing the "threshold/noise level measurement button", the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and put a check in the “Flush aperture tube after measurement” box.
On the "pulse-to-particle size conversion setting" screen of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.
A specific measuring method is as follows.
(1) About 200 mL of the electrolytic aqueous solution is placed in a 250 mL glass round-bottomed beaker exclusively for Multisizer 3, set on a sample stand, and stirred counterclockwise at 24 rpm with a stirrer rod. Then, remove dirt and air bubbles inside the aperture tube using the dedicated software's "Flush Aperture" function.
(2) About 30 mL of the electrolytic aqueous solution is placed in a 100 mL flat-bottom glass beaker. As a dispersant, "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for cleaning precision measuring instruments at pH 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersant. ) is diluted with ion-exchanged water to about 3 times the mass, and about 0.3 mL of the diluted solution is added.
(3) Prepare an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) having an electric output of 120 W and incorporating two oscillators with an oscillation frequency of 50 kHz with a phase shift of 180 degrees. About 3.3 L of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminon 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. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker in (4) above is being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water in the water tank is appropriately adjusted to 10°C or higher and 40°C or lower.
(6) The electrolytic aqueous solution of (5) above, in which the toner is dispersed, is dropped into the round-bottomed beaker of (1) above set in the sample stand, and adjusted so that the measured concentration is about 5%. . The measurement is continued until the number of measured particles reaches 50,000.
(7) Analyze the measurement data with the dedicated software attached to the apparatus, and calculate the weight average particle size (D4). Incidentally, the weight average particle diameter (D4) is the "average diameter" on the "analysis/volume statistical value (arithmetic mean)" screen when graph/vol% is set in the dedicated software.

<Method for Measuring True Density of Toner>
The true density of the toner is measured by a dry automatic densitometer Accupic II 1340 series (manufactured by Shimadzu Corporation). Measurement is performed with a cell size of 10 mL and a toner mass of 5.0 g.

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these. All "parts" and "%" of each material in Examples and Comparative Examples are based on mass unless otherwise specified.

[Example 1]
(Preparation step of aqueous medium 1)
To 1000.0 parts of ion-exchanged water in a reaction vessel, 14.0 parts of sodium phosphate (12 hydrate, manufactured by Rasa Kogyo Co., Ltd.) was added, and the mixture was kept at 65° C. for 1.0 hour while purging with nitrogen.
T. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12000 rpm, a calcium chloride aqueous solution obtained by dissolving 9.2 parts of calcium chloride (dihydrate) in 10.0 parts of ion-exchanged water is mixed together. to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 10% by mass hydrochloric acid was added to the aqueous medium to adjust the pH to 6.0, and an aqueous medium 1 was obtained.

(Preparation step of polymerizable monomer composition)
・Styrene: 60.0 parts ・C.I. I. Pigment Blue 15:3: 6.5 parts The above material was placed in an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.), and further dispersed using zirconia particles with a diameter of 1.7 mm at 220 rpm for 5.0 hours, A pigment dispersion was prepared.
The following materials were added to the pigment dispersion.
・Styrene: 15.0 parts ・n-Butyl acrylate: 25.0 parts ・Divinylbenzene (crosslinking agent): 0.3 parts ・Saturated polyester resin: 4.0 parts (propylene oxide-modified bisphenol A (2 mol adduct) and terephthalic acid (molar ratio 10:12), glass transition temperature (Tg) = 68 ° C., weight average molecular weight (Mw) = 10000, molecular weight distribution (Mw / Mn) = 5.12)
Fischer-Tropsch wax (melting point 78°C): 9.0 parts K. A homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used to uniformly dissolve and disperse at 500 rpm to prepare a polymerizable monomer composition.

(Hydrolysis step of organosilicon compound for surface layer)
60.0 parts of ion-exchanged water was weighed into a reactor equipped with a stirrer and a thermometer, and the pH was adjusted to 3.0 using 10% by mass hydrochloric acid. This was heated with stirring to bring the temperature to 70°C.
Thereafter, 40.0 parts of methyltriethoxysilane was added and stirred for 2 hours to hydrolyze the organosilicon compound for the surface layer. The end point of the hydrolysis was visually confirmed by checking that the oil and water did not separate into a single layer, and after cooling, a hydrolyzate 1 of the organosilicon compound for surface layer was obtained.

(Granulation process)
The temperature of the aqueous medium 1 is set at 70°C, T.E. K. While maintaining the rotation speed of the homomixer at 12000 rpm, the polymerizable monomer composition was charged into the aqueous medium 1, and 9.0 parts of t-butyl peroxypivalate as a polymerization initiator was added. The mixture was granulated for 10 minutes while maintaining 12000 rpm with the stirring device.

(Polymerization process)
After the granulation step, the stirrer was changed to a propeller stirring blade, and the mixture was stirred at 150 rpm while maintaining the temperature at 70°C for 5.0 hours to polymerize, and then heated to 95°C for 2.0 hours to polymerize. A reaction was carried out to obtain a slurry of core particles.
After that, the temperature of the slurry was cooled to 60° C. and the pH was measured to be pH=5.0. While stirring was continued at 60° C., 20.0 parts of the hydrolyzate 1 of the organosilicon compound for the surface layer was added to start forming the surface layer of the toner. After holding for 30 minutes as it is, the slurry was adjusted to pH=9.0 for completion of condensation using an aqueous sodium hydroxide solution and held for an additional 300 minutes to form a surface layer.

(Washing and drying process)
After completion of the polymerization process, the obtained toner slurry is cooled, and hydrochloric acid is added to the toner slurry to adjust the pH to 1.5 or less, and the mixture is left with stirring for 1 hour and then solid-liquid separated by a pressurized filter to obtain toner. got cake.
This was reslurried with ion-exchanged water to form a dispersion again, and then subjected to solid-liquid separation with the aforementioned filter. After reslurry and solid-liquid separation were repeated until the electrical conductivity of the filtrate became 5.0 μS/cm or less, solid-liquid separation was finally performed to obtain a toner cake.
The resulting toner cake was dried with a flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.).
The drying conditions were as follows: the blowing temperature was 90°C, the outlet temperature of the dryer was 40°C, and the feeding speed of the toner cake was adjusted so that the outlet temperature did not deviate from 40°C according to the moisture content of the toner cake.
In this example, the obtained Toner 1 was used as it is as Toner 1 without adding an external additive.
Toner 1 was confirmed by the method described above to have a surface layer containing an organosilicon polymer. Table 2 shows the physical properties of Toner 1 obtained. The evaluation method for Toner 1 is described below. Moreover, the results are shown in Table 3.

<Evaluation of developability of toner using laser beam printer>
A commercially available Canon laser beam printer "LBP7600C" modified was used.
The modifications were made by changing the gears and software of the main body of the evaluation machine so that the number of revolutions of the developing roller was twice that of the drum. A toner cartridge of LBP7600C was loaded with 40 g of toner.

(1) Evaluation under low-temperature and low-humidity environment (solid followability, poor regulation, development streaks)
Under a low-temperature and low-humidity environment (15° C./10% RH), five solid images were printed on LETTER-size XEROX4200 paper (manufactured by XEROX, 75 g/m ² ) (initial evaluation).
Furthermore, one halftone image was output (initial evaluation).
After that, 5,000 sheets of images with a print rate of 1% were output.
Thereafter, 5 solid images (evaluation after durability) and 1 halftone image (evaluation after durability) were output in the same manner.
All solid images and halftone images obtained were evaluated for solid followability, poor regulation, and development streaks.
The image density is measured by using a Macbeth reflection densitometer RD918 (manufactured by Macbeth Co.) according to the attached instruction manual and measuring the relative density of the white background portion with an image density of 0.00. and the obtained relative density was used as the value of the image density.

[Evaluation criteria]
(Solid followability)
Evaluation was made on the basis of the difference between the image density at the leading edge of the first solid image and the trailing edge of the third solid image.
A: Image density difference is less than 0.10 B: Image density difference is 0.10 or more and less than 0.20 C: Image density difference is 0.20 or more and less than 0.30 D: Image density difference is 0.30 or more

(poor regulation)
The amount of spot streaks and toner lumps appearing on the halftone image was evaluated.
A: Not occurred.
B: There are no spotty streaks, but there are two or three small toner lumps.
C: Slight spotty streaks at edges, or 4 or 5 small toner lumps.
D: There are spotty streaks on the entire surface, or there are 5 or more small toner masses or obvious toner masses.

(Development streak)
Evaluation was made by the number of vertical streaks appearing on the developing roller and on the halftone image.
A: No vertical streaks in the paper ejection direction are observed on the developing roller or on the image.
B: Five or less thin streaks in the circumferential direction are observed on both ends of the developing roller. Alternatively, a slight vertical streak in the paper discharge direction can be seen on the image.
C: 6 or more and 20 or less thin streaks in the circumferential direction are observed on both ends of the developing roller. Or a few fine streaks can be seen on the image.
D: 21 or more thin streaks in the circumferential direction are observed on both ends of the developing roller. Or conspicuous streaks are seen on the image.

(2) Evaluation under high-temperature and high-humidity environment (solid followability, fogging, development streaks)
The process cartridge filled with toner was stored for 3 days in a high-temperature and high-humidity environment (35° C./80% RH). After that, one solid white image with a 0% print ratio (initial evaluation) and 5 sheets of all solid images were output on Canon color laser copy paper (A4: 81.4 g/m ² , manufactured by Canon Inc.) (initial evaluation).
Furthermore, one halftone image was output (initial evaluation).
After that, 5,000 sheets of images with a print rate of 1% were output.
Thereafter, one solid white image (evaluation after running), five solid images (evaluation after running), and one halftone image (evaluation after running) were output in the same manner.
All solid images and halftone images obtained were evaluated for solid followability and development streaks based on the same criteria as those used for evaluation under a low-temperature, low-humidity environment.
Further, fogging was evaluated for the obtained solid white image.
The fogging density (%) was measured using "REFLECTMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.). %). An amber filter was used as the filter.
(Evaluation criteria)
A: Fogging density less than 0.5% B: Fogging density 0.5% to less than 1.0% C: Fogging density 1.0% to less than 2.0% D: Fogging density 2.0% or more

(3) Evaluation of Charge Rise A process cartridge filled with toner was stored for 3 days under a high temperature and high humidity environment (35° C./80% RH). After that, 15 images are output. The machine is forcibly stopped during the output of the 15th sheet, and the toner charge amount on the developing roller immediately after passing through the regulation blade is measured.
A Faraday cage shown in FIG. 3 was used to measure the amount of charge on the developing roller.
The inside (the right side of the figure) was made to be in a decompressed state so that the toner on the developing roller was sucked in, and a toner filter 33 was provided to collect the toner (31 and 32 respectively represent a suction portion and a holder). .
From the mass (M) of the collected toner and the charge (Q) directly measured with a coulomb meter, the charge amount Q/M (μC/g) per unit mass is calculated, and the toner charge amount (Q/M) is calculated. were ranked as follows.
A: Less than -40 μC/g B: -40 μC/g or more and less than -30 μC/g C: -30 μC/g or more and less than -25 μC/g D: -25 μC/g or more and less than -20 μC/g E: -20 μC/g or more

<Examples 2 to 14, Comparative Example 4>
In Example 1, the type of the organosilicon compound used in the "hydrolysis step of the organosilicon compound for the surface layer" and the conditions for adding the hydrolyzate 1 in the "polymerization step" were changed as shown in Table 1. Toners 2 to 14 and Toner 18 were produced in the same manner as in Example 1 except for the above.
It was confirmed by the method described above that the obtained toner had a surface layer containing an organosilicon polymer. Table 2 shows the physical properties of the obtained toner, and Table 3 shows the evaluation results.

<Comparative Example 1>
In Example 1, instead of performing the "hydrolysis step of the organosilicon compound for the surface layer", 15 parts of methyltriethoxysilane of the organosilicon compound for the surface layer was used as a monomer in the "preparation of the polymerizable monomer composition." added in the process.
In addition, in the "polymerization step", the hydrolyzate was not added after the core particle slurry was obtained, and only pH adjustment and subsequent maintenance were carried out.
Toner 15 was produced in the same manner as in Example 1 except for the above.
It was confirmed by the method described above that the obtained toner had a surface layer containing an organosilicon polymer. Table 2 shows the physical properties of the obtained toner, and Table 3 shows the evaluation results.

<Comparative Example 2>
In Example 1, instead of performing the "hydrolysis step of the organosilicon compound for the surface layer", 8 parts of methyltriethoxysilane of the organosilicon compound for the surface layer was used as a monomer in the "preparation of the polymerizable monomer composition." added in the process.
In addition, in the "polymerization step", the hydrolyzate was not added after the core particle slurry was obtained, and only pH adjustment and subsequent maintenance were carried out.
Toner 16 was produced in the same manner as in Example 1 except for the above.
It was confirmed by the method described above that the obtained toner had a surface layer containing an organosilicon polymer. Table 2 shows the physical properties of the obtained toner, and Table 3 shows the evaluation results.

<Comparative Example 3>
In Example 1, the "step of hydrolyzing the organosilicon compound for the surface layer" was not carried out.
In addition, in the "polymerization step", the hydrolyzate was not added after the core particle slurry was obtained, and only pH adjustment and subsequent maintenance were carried out.
Toner 17 (before addition of external additives) was produced in the same manner as in Example 1 except for the above.
To 100.0 parts of the toner 17 (before adding external additives), untreated silica fine particles synthesized by a dry method (trade name: Aerosil #200, specific surface area: about 200 m ² /g, manufactured by Aerosil Co.) 2 0 part was mixed at 3000 rpm for 15 minutes using a Mitsui Henschel mixer (Mitsui Miike Kakoki Co., Ltd.) to obtain Toner 17. Table 2 shows the physical properties of the obtained toner, and Table 3 shows the evaluation results.

<Comparative Example 5>
To 100.0 parts of Toner 17 (before adding external additives) produced in Comparative Example 3, 2.0 parts of hydrophobic silica fine particles were added at 3000 rpm using a Mitsui Henschel mixer (Mitsui Miike Kakoki Co., Ltd.). Toner 19 was obtained after mixing for 15 minutes.
The hydrophobic silica fine particles used as the fluidity improver were treated with dimethylsilicone oil (20% by mass) and had a BET specific surface area of 170 m ² /g.
Table 2 shows the physical properties of the obtained toner, and Table 3 shows the evaluation results.

<Comparative Example 6>
To 100.0 parts of Toner 17 (before adding external additives) produced in Comparative Example 3, 2.0 parts of hydrophobic silica fine particles were added at 3000 rpm using a Mitsui Henschel mixer (Mitsui Miike Kakoki Co., Ltd.). Toner 20 was obtained after mixing for 15 minutes.
The hydrophobic silica fine particles used as the fluidity improver were treated with dimethylsilicone oil (20% by mass) and had a BET specific surface area of 50 m ² /g.
Table 2 shows the physical properties of the obtained toner, and Table 3 shows the evaluation results.

31: suction unit, 32: holder, 33: toner filter

Claims (4)

A toner containing a colorant and a binder resin,
the toner has a surface layer containing an organosilicon polymer;
The organosilicon polymer is a polymer having a structure represented by the following formula (R ^a T3),
R ^a —SiO _3/2 (R ^a T3)
[In the formula (R ^a T3), R ^a represents a hydrocarbon group having 1 or more and 6 or less carbon atoms. ]
In a methanol/water mixed solvent wettability test, the toner has a methanol concentration of 5.0% by volume or more and 30.0% by volume or less when the transmittance of light having a wavelength of 780 nm is 50%;
The toner is compressed with a load of 78.5 N, and the force between the two particles is 1.0 nN or more and 25.0 nN or less .
A toner characterized by: 2. The toner according to claim 1, wherein the methanol concentration is 5.0% by volume or more and 20.0% by volume or less. 3. The toner according to claim 1, wherein the content of said organosilicon polymer in said toner is 0.5% by mass or more and 5.0% by mass or less. 4. The toner according to any one of claims 1 to 3, wherein the fixation rate of the organosilicon polymer to the toner is 90.0% or more and 100.0% or less.

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