JP2020154292A - toner - Google Patents

Abstract

To provide a toner which excels in low temperature fixability, and with which high transfer efficiency is maintained even at an initial use time and in a long-term use.SOLUTION: Provided is a toner including a toner particle containing a toner base particle containing a mold release agent and containing an organic silicone polymer on the surface of the toner base particle and an external additive A. The toner is characterized in that the organic silicone polymer has a T3 unit structure, R represents C1-6 alkyl group or phenyl group, the organic silicone polymer forms a protrusion on the toner base particle surface, the number average value of protrusion height H is 30 nm to 300 nm, a ratio to the number average value of protrusion height H of maximum dimeter R of the external additive A is 1.00 to 4.00, the maximum diameter R is 30 nm to 1200 nm, and, when a 1.5 μm square reflection electron image of toner surface is acquired and an image is obtained by binarization of the reflection electron image, by surface observation of the toner with a scanning electron microscope, the area ratio of light part area of the image to the total area of the image is 30.0% to 75.0%.SELECTED DRAWING: Figure 2

Description

The present disclosure relates to toners used in image forming methods such as electrophotographic methods.

The electrophotographic image forming apparatus is required to be miniaturized and have a long life, and in order to meet these demands, the toner is also required to be further improved in various performances.
Attempts have been made to save space in various units from the viewpoint of miniaturization. In particular, if the transferability of the toner is improved, the waste toner container for collecting the transfer residual toner on the photoconductor drum can be miniaturized, and various attempts have been made to improve the transferability.
In the transfer step, the toner on the photoconductor drum is transferred to a medium such as paper. In order to improve the transferability, it is important to reduce the adhesive force between the photoconductor drum and the toner so that the toner can be easily separated from the photoconductor drum. As a technique for that purpose, a technique of externally adding a large particle size external additive having a particle size of about 100 nm to 300 nm is known.

However, although the above is an effective technique as a method for improving the transfer efficiency, the function of the large particle size external additive as a spacer is deteriorated by movement, desorption, and burial due to long-term image output. Therefore, it is difficult to stably obtain the expected effect of improving the transfer efficiency.
Therefore, Patent Document 1 proposes a method of semi-embedding a large particle size external additive to suppress the movement / detachment of the external additive.

JP-A-2009-036980 Japanese Unexamined Patent Publication No. 2016-021041

The method described in Patent Document 1 has a problem that movement / detachment can be suppressed, but burial is accelerated.
In order to improve transferability by a method other than external addition, a method of covering the surface of toner particles with an organosilicon compound is also being studied.
For example, Patent Document 2 discloses a toner containing an organosilicon polymer having a partial structure represented by R—Si (O _1/2 ) ₃ in the surface layer.
This toner seems to have excellent durability against burial of an external additive as an effect of the organosilicon compound covering the surface of the toner particles.

However, it was found that there is still room for improvement in order to further extend the life of the toner.
In Patent Document 1, as a result of semi-burial, burial in the latter half of durability is likely to be accelerated.
On the other hand, in Patent Document 2, when the coverage of the organic silicon polymer covering the surface of the toner particles is high, the contained wax for demolding is less likely to precipitate on the surface of the toner particles. Therefore, the low temperature fixability tends to decrease.
On the contrary, when the coverage of the organosilicon polymer covering the surface of the toner particles is low, the spacer effect at the initial stage of use is not sufficiently exhibited. In addition, it is difficult to maintain the spacer effect for a long period of time, and there is room for improvement in maintaining high transfer efficiency.
Further, when a large particle size external additive is used for a toner having a low coverage of an organosilicon polymer, abrasion is likely to occur when cleaning the transfer residual toner on the intermediate transfer material.
That is, the present disclosure provides a toner that is excellent in low-temperature fixability and maintains high transfer efficiency even in the initial stage of use and long-term use.

As a result of diligent studies, the present inventors have found that a toner that solves the above problems can be obtained by forming a convex portion on the surface of the toner particles and controlling the shape of the convex portion and the diameter of the external additive A. It was.
That is, the present disclosure is
Toner mother particles containing a release agent, toner particles containing an organosilicon polymer on the surface of the toner mother particles, and
External agent A and
Toner with
The organosilicon polymer has a T3 unit structure represented by R-Si (O _1/2 ) ₃ .
The R represents an alkyl group or a phenyl group having 1 or more and 6 or less carbon atoms.
The organosilicon polymer forms a convex portion on the surface of the toner mother particle,
When a cross-sectional image of the toner obtained by a scanning transmission electron microscope is developed by linearly developing a line along the circumference of the toner mother particle surface to obtain a developed image of the cross-sectional image,
In the developed image,
The length of the line along the circumference in the portion where the convex portion and the toner mother particle form a continuous interface is defined as the convex width w.
The maximum length of the convex portion in the normal direction of the convex width w is defined as the convex diameter D.
When the length from the apex of the convex portion to the line along the circumference of the line segment forming the convex diameter D is defined as the convex height H,
The number average value of the convex height H is 30 nm or more and 300 nm or less.
The ratio of the number average particle diameter R of the primary particles of the external additive A to the number average value of the convex height H is 1.00 or more and 4.00 or less.
The number average particle size R of the primary particles of the external additive A is 30 nm or more and 1200 nm or less.
By observing the surface of the toner with a scanning electron microscope,
When a 1.5 μm square backscattered electron image of the toner surface was obtained and an image was binarized so that the organosilicon polymer portion in the backscattered electron image became a bright part,
The present invention relates to a toner characterized in that the area ratio of the bright area of the image to the total area of the image is 30.0% or more and 75.0% or less.

According to the present disclosure, it is possible to provide a toner which is excellent in low temperature fixability and maintains high transfer efficiency even in the initial stage of use and long-term use.

Schematic diagram of cross-sectional observation of toner by STEM Schematic diagram showing a method for measuring the convex shape of toner Schematic diagram showing a method for measuring the convex shape of toner Schematic diagram showing a method for measuring the convex shape of toner

In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.

Hereinafter, embodiments will be described, but the present disclosure is not limited to the following aspects.
The toner has a toner mother particle containing a mold release agent, a toner particle containing an organosilicon polymer on the surface of the toner mother particle, and an external additive A.

The organosilicon polymer has a T3 unit structure represented by R—Si (O _1/2 ) ₃ , and R represents an alkyl group or a phenyl group having 1 to 6 carbon atoms.

The organosilicon polymer forms a convex portion on the surface of the toner mother particle, and forms a convex portion.
When a cross-sectional image of the toner obtained by a scanning transmission electron microscope is developed by linearly developing a line along the circumference of the toner mother particle surface to obtain a developed image of the cross-sectional image,
In the developed image,
The length of the line along the circumference in the portion where the convex portion and the toner mother particle form a continuous interface is defined as the convex width w.
The maximum length of the convex portion in the normal direction of the convex width w is defined as the convex diameter D.
When the length from the apex of the convex portion to the line along the circumference of the line segment forming the convex diameter D is defined as the convex height H,
The number average value of the convex height H is 30 nm or more and 300 nm or less.

The ratio of the number average particle diameter R of the primary particles of the external additive A to the number average value of the convex height H is 1.00 or more and 4.00 or less.
The number average particle size R of the primary particles of the external additive A is 30 nm or more and 1200 nm or less.

By observing the surface of the toner with a scanning electron microscope,
When a 1.5 μm square backscattered electron image of the toner surface was obtained and an image was binarized so that the organosilicon polymer portion in the backscattered electron image became a bright part,
The area ratio of the bright area of the image to the total area of the image is 30.0% or more and 75.0% or less.

The convex portion is characterized in that it is in surface contact with the surface of the toner mother particles, and the surface contact can be expected to have a remarkable effect of suppressing the movement, detachment, and burial of the convex portion.
In order to show the degree of surface contact, the cross section of the toner was observed with a scanning transmission electron microscope (hereinafter, also referred to as STEM). FIGS. 1, 2, 3 and 4 show a schematic view of the convex portion.
1 shown in FIG. 1 is a STEM image, which is an image showing about 1/4 of the toner particles, 2 is the toner particles, 3 is the surface of the toner mother particles, and 4 is the convex portion. 5 shown in FIGS. 2 to 4 is a convex width w, 6 is a convex diameter D, and 7 is a convex height H.

Observe the cross-sectional image of the toner and draw a line along the circumference of the toner matrix particle surface. A developed image is obtained by developing a straight line along the circumference. In the developed image, the length of the line along the circumference in the portion where the convex portion and the toner mother particle form a continuous interface is defined as the convex width w.
Further, the maximum length of the convex portion in the normal direction of the convex width w is defined as the convex diameter D, and the length from the apex of the convex portion to the line along the circumference in the line segment forming the convex diameter D is defined as the convex diameter D. The convex height is H.

In FIGS. 2 and 4, the convex diameter D and the convex height H are the same, and in FIG. 3, the convex diameter D is larger than the convex height H.
Further, FIG. 4 schematically shows a fixed state of particles similar to bowl-shaped particles in which the central portion of the hemispherical particles is recessed, which is obtained by crushing or breaking the hollow particles.
In FIG. 4, the convex width w is the total length of the organosilicon polymer in contact with the surface of the toner matrix particles. That is, the convex width w in FIG. 4 is the sum of w1 and w2.

The number average value of the convex height H is 30 nm or more and 300 nm or less, preferably 30 nm or more and 200 nm or less, more preferably 30 nm or more and 100 nm or less, and further preferably 30 nm or more and 80 nm or less.
When the number average value of the convex height H is 30 nm or more, a spacer effect is generated between the surface of the toner mother particles and the transfer member, and the transferability is remarkably improved.
On the other hand, when the number average value of the convex height H is 300 nm or less, the effect of suppressing movement / detachment / burial is remarkable, and high transferability is maintained even in long-term use.

The number average particle size R of the primary particles of the external additive A is 30 nm or more and 1200 nm or less.
When the R is 30 nm or more, a spacer effect is exhibited between the R and the transfer member, and high transferability is exhibited. Further, the larger the R, the better the transfer performance tends to be.
On the other hand, when R exceeds 1200 nm, the fluidity of the toner is lowered and image unevenness is likely to occur. In addition, poor scraping of the transfer residual toner on the photosensitive drum is likely to occur.
The number average particle size R of the primary particles of the external additive A is preferably 30 nm or more and 1000 nm or less, more preferably 30 nm or more and 500 nm or less, and further preferably 30 nm or more and 300 nm or less.

The ratio of the number average particle diameter R of the primary particles of the external additive A to the number average value of the convex height H is 1.00 or more and 4.00 or less. When the ratio [(the number average particle size R of the primary particles of the external additive A) / (the number average value of the convex height H)] is within the above range, excellent transferability and low temperature fixing that can withstand a long life It is possible to achieve both sex.
The ratio is preferably 1.00 or more and 3.80 or less, more preferably 1.00 or more and 3.70 or less, and further preferably 1.00 or more and 3.00 or less.
When the average number of convex heights H is 30 nm, which is the minimum value, if R is 30 nm or more, a spacer effect can be exhibited between the convex height H and the transfer member, and the transferability can be improved. It is considered that the external additive A is substituted in a place where the convex portion does not exist due to the influence of desorption and the like, and the spacer effect is exhibited. That is, if R is less than 30 nm, the spacer effect is unlikely to be exhibited.

The adhesion rate of the external additive A to the surface of the toner particles is preferably 0% or more and 20% or less, and more preferably 0% or more and 10% or less.
When the adhesion rate is in the above range, the external additive A can easily move on the surface of the toner particles, and the transferability can be further improved by the convex portion substitution action.
The adhesion rate can be controlled in the above range by adjusting, for example, the rotation speed of the mixer used when adding and mixing the external additive A to the toner particles and the processing temperature.

When the cumulative distribution of the convex height H is taken in the convex portion where the convex height H is 30 nm or more and 300 nm or less, and the convex height corresponding to 80% of the convex height H is taken as H80. , H80 is preferably 65 nm or more and 120 nm or less, and more preferably 75 nm or more and 100 nm or less.
When H80 is in the above range, transferability can be further improved.
The H80 can be prepared in the above range by, for example, a method for controlling the characteristics of the convex portion described later.

In the fixing step of fixing the toner to the fixing member, an appropriate amount of the release agent exudes from the toner mother particles, thereby improving the separation performance between the fixing member and the paper.
A 1.5 μm square backscattered electron image of the toner surface was obtained by observing the surface of the toner with a scanning electron microscope, and binarized so that the organic silicon polymer portion in the backscattered electron image became a bright part. When an image is obtained, the area ratio of the bright area of the image to the total area of the image (hereinafter, also simply referred to as the area ratio of the bright area) is 30.0% or more and 75.0% or less. Further, the area ratio of the bright area of the image is preferably 35.0% or more and 70.0% or less.
The higher the area ratio of the bright area, the higher the abundance ratio of the organosilicon polymer on the surface of the toner matrix particles.
When the area ratio of the bright area is higher than 75.0%, the presence ratio of the component derived from the toner matrix particles on the surface of the toner matrix particles is small, and the release agent is less likely to exude from the toner matrix particles, resulting in a low temperature. Thin paper wrapping around the fuser tends to occur during fixing.
On the other hand, when the area ratio of the bright area of the image is less than 30.0%, the presence ratio of the component derived from the toner matrix particles is large on the surface of the toner matrix particles. That is, the exposed area of the component derived from the toner mother particles on the surface of the toner mother particles is large, and the transferability at the initial stage of use is lowered.
The area ratio of the bright area of the image is also referred to as the coverage of the organosilicon polymer on the surface of the toner matrix particles.
The area ratio of the bright area of the image can be adjusted to the above range by, for example, a method of controlling the characteristics of the convex portion described later.

The external additive A is not particularly limited as long as the number average particle size R of the primary particles is 30 nm or more and 1200 nm or less, and various organic fine particles or inorganic fine particles can be used.
The external additive A preferably contains silica fine particles from the viewpoint of easily imparting fluidity and being easily negatively charged like the toner mother particles. The content of the silica fine particles in the external additive A is preferably 50% by mass or more, and more preferably the external agent A is silica fine particles.
The content of the external additive A in the toner is preferably 0.02% by mass or more and 5.00% by mass or less, and more preferably 0.05% by mass or more and 3.00% by mass or less.

Examples of the organic fine particles or the inorganic fine particles other than the silica fine particles include the following.
(1) Fluidity-imparting agent: alumina fine particles, titanium oxide fine particles, carbon black and carbon fluoride.
(2) Abrasive: Fine particles of metal oxide (fine particles such as strontium titanate, cerium oxide, alumina, magnesium oxide, and chromium oxide), fine particles of nitride (fine particles such as silicon nitride), fine particles of carbide (silicon carbide) Fine particles such as), fine particles of metal salts (fine particles such as calcium sulfate, barium sulfate, and calcium carbonate).
(3) Lubricants: Fine particles of fluororesin (fine particles such as vinylidene fluoride and polytetrafluoroethylene) and fine particles of fatty acid metal salts (fine particles such as zinc stearate and calcium stearate).
(4) Charge-controllable fine particles: Fine particles of metal oxide (fine particles such as tin oxide, titanium oxide, zinc oxide, and alumina), carbon black.
As the silica fine particles and the organic fine particles or the inorganic fine particles, those which have been subjected to a hydrophobic treatment for improving the fluidity of the toner and making the charge of the toner particles uniform may be used.
Examples of the treatment agent for the hydrophobization treatment include unmodified silicone varnish, various modified silicone varnish, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. Can be mentioned. These treatment agents may be used alone or in combination.

As the silica fine particles, known silica fine particles can be used, and either dry silica fine particles or wet silica fine particles may be used. It is preferable that the particles are wet silica fine particles (hereinafter, also referred to as sol-gel silica) obtained by the sol-gel method.
Sol-gel silica exists in a spherical and monodisperse, but some are partially united.
When the half width of the peak of the primary particles in the volume-based particle size distribution chart is 25 nm or less, the number of such coalesced particles is small, the uniform adhesion of the silica fine particles on the toner particle surface is increased, and higher fluidity is obtained. Will be able to.
Further, it is preferable that the saturated water adsorption amount of the silica fine particles at 32.5 ° C. and 80.0% relative humidity is 0.4% by mass or more and 3.0% by mass or less. By controlling within the above range, the sol-gel silica having pores is less likely to adsorb water even in a high temperature and high humidity environment, and it becomes easy to maintain high chargeability. Therefore, it is possible to obtain a higher quality image with less fog through the durable output.

The method for producing sol-gel silica will be described below.
First, in an organic solvent in which water is present, alkoxysilane is hydrolyzed and condensed with a catalyst to obtain a silica sol suspension. Then, the solvent is removed from the silica sol suspension and dried to obtain silica fine particles.
The average particle size of the number of primary particles of silica fine particles obtained by the sol-gel method can be controlled by the reaction temperature in the hydrolysis and condensation reaction steps, the dropping rate of alkoxysilane, the mass ratio of water, an organic solvent and a catalyst, and the stirring rate. Is.
The silica fine particles thus obtained are usually hydrophilic and have many surface silanol groups. Therefore, when used as an external additive for toner, it is preferable to hydrophobize the surface of the silica fine particles.
As a method of hydrophobizing treatment, a method of removing the solvent from the silica sol suspension, drying it, and then treating it with a hydrophobizing treatment agent, or adding a hydrophobizing treatment agent directly to the silica sol suspension. Examples thereof include a method of treating at the same time as drying. From the viewpoint of controlling the half width of the peak of the primary particles in the volume-based particle size distribution chart and controlling the saturated water adsorption amount, a method of directly adding the hydrophobizing agent to the silica sol suspension is preferable.

Examples of the hydrophobizing agent include the following.
γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ -Aminopropyltrimethoxysilane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltoerymethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyl Trimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, methyltriethoxysilane, butyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, Phenyltriethoxysilane, o-methylphenyltriethoxysilane, p-methylphenyltriethoxysilane.
Further, the silica fine particles may be crushed in order to facilitate monodisperse of the silica fine particles on the surface of the toner particles and to exert a stable spacer effect.

The apparent density of the silica fine particles is preferably 150 g / L or more and 300 g / L or less. The fact that the apparent density of the silica fine particles is in the above range indicates that the silica fine particles are hard to be clogged tightly and exist with a large amount of air intervening between the fine particles, and the apparent density is very low. Therefore, the mixing property of the toner particles and the silica fine particles is improved during the external addition step, and a uniform coating state can be easily obtained. Further, this phenomenon is more remarkable when the average circularity of the toner particles is high, and the coverage of the silica fine particles tends to be higher. As a result, the toners of the externally added toners are less likely to be clogged tightly with each other, so that the adhesive force between the toners and toners tends to decrease.
As a means for controlling the apparent density of the silica fine particles within the above range, the strength of the hydrophobization treatment in the silica sol suspension or the crushing treatment after the hydrophobization treatment is adjusted, and the amount of the hydrophobization treatment is adjusted. Can be mentioned. By applying a uniform hydrophobization treatment, relatively large aggregates themselves can be reduced. Alternatively, by adjusting the strength of the crushing treatment, the relatively large aggregates contained in the silica fine particles after drying can be loosened into relatively small particles, and the apparent density can be reduced.

The organosilicon polymer has a T3 unit structure represented by R—Si (O _1/2 ) _{3. The} R represents an alkyl group or a phenyl group having 1 to 6 carbon atoms.
In the organosilicon polymer having the T3 unit structure, 1 out of 4 valences of Si atoms
One is bonded to R and the remaining three are bonded to O atom. The O atom constitutes a state in which both of the two valences are bonded to Si, that is, a siloxane bond (Si—O—Si). Considering the Si atom and the O atom as the organosilicon polymer, since two Si atoms have three O atoms, it is expressed as −Si (O _1/2 ) ₃ . It is considered that the −Si (O _1/2 ) ₃ structure of this organosilicon polymer has properties similar to those of silica (SiO ₂ ) composed of a large number of siloxane bonds.

The R is preferably an alkyl group having 1 or more and 6 or less carbon atoms, and more preferably an alkyl group having 1 or more and 3 or less carbon atoms.
As the alkyl group having 1 or more and 3 or less carbon atoms, a methyl group, an ethyl group and a propyl group can be preferably exemplified. More preferably, R is a methyl group.
The organosilicon polymer is preferably a polycondensation polymer of an organosilicon compound having a structure represented by the following formula (Z).

In formula (Z), R ₁ represents a hydrocarbon group (preferably an alkyl group) having 1 or more carbon atoms and 6 or less carbon atoms, and R ₂ , R ₃ and R ₄ are independently halogen atoms and hydroxy groups, respectively. Represents an acetoxy group or an alkoxy group.
R ₁ is preferably an aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms, and more preferably a methyl group.

R ₂ , R ₃ and R ₄ are independently halogen atoms, hydroxy groups, acetoxy groups, or alkoxy groups (hereinafter, also referred to as reactive groups). These reactive groups are hydrolyzed, addition polymerized and polycondensed to form a crosslinked structure.
The hydrolyzability is mild at room temperature, and from the viewpoint of the precipitation property of the toner matrix particles on the surface, an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.
Further, the hydrolysis, addition polymerization and condensation polymerization of R ₂ , R ₃ and R ₄ can be controlled by the reaction temperature, reaction time, reaction solvent and pH. To obtain an organosilicon polymer, an organosilicon compound having three reactive groups in a molecule, except for R ₁ in the formula (Z) shown above (R _2, R ₃ and R ₄₎ (hereinafter, trifunctional (Also referred to as sex silane) may be used alone or in combination of two or more.

Examples of the compound represented by the above formula (Z) include the following.
Methyltrimethoxysilane, Methyltriethoxysilane, Methyldiethoxymethoxysilane, Methylethoxydimethoxysilane, Methyltrichlorosilane, Methylmethoxydichlorosilane, Methylethoxydichlorosilane, Methyldimethoxychlorosilane, Methylmethoxyethoxychlorosilane, Methyldiethoxychlorosilane, Methyl Triacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxy Trifunctional methylsilanes such as hydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane.
Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltri Trifunctional such as methoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane Sexual silane.
Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

Further, an organosilicon polymer obtained by using the following in combination with an organosilicon compound having a structure represented by the formula (Z) may be used to the extent that the effects of the present disclosure are not impaired. Organosilicon compound having 4 reactive groups in one molecule (tetrafunctional silane), organosilicon compound having 2 reactive groups in one molecule (bifunctional silane) or organosilicon compound having one reactive group (bifunctional silane) Monofunctional silane). For example, the following can be mentioned.
Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriemethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-amino Ethyl) Aminopropyltriethoxysilane, Vinyltriisocyanasilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyldiethoxymethoxysilane, Vinylethoxydimethoxysilane, Vinylethoxydihydroxysilane, Vinyldimethoxyhydroxysilane, Vinylethoxymethoxyhydroxysilane, Trifunctional vinylsilane, such as vinyldiethoxyhydroxysilane.

The content of the organosilicon polymer in the toner is preferably 1.0% by mass or more and 10.0% by mass or less.

The adhesion rate of the organosilicon polymer to the surface of the toner matrix particles is preferably 80% or more and 100% or less, and 90% or more and 100% or less, from the viewpoint of reducing the adhesive force to the member and improving the transfer efficiency associated therewith. It is more preferable that it is 95% or more and 100% or less.
The adhesion rate can be set within the above range by adjusting, for example, the addition rate of the organosilicon compound, the reaction temperature, the reaction time, the pH at the time of reaction, the timing of pH adjustment, etc. when the organosilicon compound is added and polymerized. Can be controlled to.

As a preferable method for forming the specific convex portion on the surface of the toner mother particle, the toner particle is formed by adding an organic silicon compound to the toner mother particle dispersion liquid obtained by dispersing the toner mother particle in an aqueous medium. It is preferable to obtain a dispersion.
It is preferable to adjust the solid content concentration of the toner mother particle dispersion liquid to 25% by mass or more and 50% by mass or less. The temperature of the toner mother particle dispersion is preferably adjusted to 35 ° C. or higher. Further, it is preferable to adjust the pH of the toner mother particle dispersion to a pH at which condensation of the organosilicon compound does not easily proceed. Since the pH at which condensation of the organosilicon polymer is difficult to proceed differs depending on the substance, the pH at which the reaction is most difficult to proceed is preferably within ± 0.5.

On the other hand, it is preferable to use an organosilicon compound that has been hydrolyzed. For example, it is hydrolyzed in a separate container as a pretreatment for the organosilicon compound. When the amount of the organic silicon compound is 100 parts by mass, the concentration of 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 and RO water, and more preferably 100 parts by mass of water. It is 400 parts by mass or less. The conditions for hydrolysis are preferably a pH of 2 to 7, a temperature of 15 ° C to 80 ° C, and a time of 30 to 600 minutes.

The obtained hydrolyzed solution and the toner matrix particle dispersion are mixed to adjust the pH to a pH suitable for condensation (preferably 5 to 12, or 1 to 3, more preferably 8 to 12). By adjusting the amount of the hydrolyzed liquid to 5.0 parts by mass or more and 30.0 parts by mass or less of the organosilicon compound with respect to 100 parts by mass of the toner mother particles, it becomes easy to form a convex portion.
Further, it is preferable to condense the pH in two steps. For example, the condensed pH of the first stage may be 4.0 to 6.0, and the condensed pH of the second stage may be 8.0 to 11.0.
The temperature and time for forming and condensing the protrusions are preferably maintained at 35 ° C. to 99 ° C. for 60 minutes to 72 hours.

Further, in order to control the characteristics of the convex portion on the surface of the toner mother particles, the holding time before adjusting to the first-stage condensed pH and the holding time before adjusting to the second-stage condensed pH are appropriately adjusted. You may. By adjusting the holding time, it is easy to control the characteristics of the convex portion on the surface of the toner mother particles. For example, the retention time before adjusting the first stage condensation pH is 0.10 hours to 1.50 hours, and the retention time before adjusting the second stage condensation pH is 3.0 hours to 5.0 hours. It is good to do.
The characteristics of the convex portion can also be controlled by adjusting the condensation temperature of the organosilicon compound in the range of 35 ° C. to 80 ° C.
For example, the convex width w can be controlled by the amount of the organosilicon compound added, the reaction temperature, the first-stage condensation pH, the reaction time, and the like. For example, as the condensation time in the first step becomes longer, the convex width tends to increase.
The convex diameter D and the convex height H can be controlled by the amount of the organosilicon polymer added, the reaction temperature, the condensation pH of the second step, and the like. For example, when the condensed pH in the second step is high, the convex diameter D and the convex height H tend to be large.

Hereinafter, a method for producing toner will be described, but the method is not limited thereto.
As the toner particles, it is preferable that the toner mother particles are produced in an aqueous medium and a convex portion containing an organic silicon polymer is formed on the surface of the toner mother particles. Further, it is preferable to add and mix the external additive A to the toner particles by a known method (for example, Henschel mixer, Nippon Coke Industries, Ltd. FM10C type, etc.) to produce the toner.
Examples of the method for producing the toner matrix particles include a method for producing resin particles in an aqueous medium such as a suspension polymerization method, a dissolution suspension method, and an emulsion aggregation method. Of these, the suspension polymerization method is preferable.
When the suspension polymerization method is used, the organosilicon polymer is easily precipitated uniformly on the surface of the toner matrix particles, the adhesion of the organosilicon polymer is excellent, the environmental stability, the effect of suppressing the charge amount reversal component, and their effects. Durability is improved. Hereinafter, the suspension polymerization method will be further described.

In the suspension polymerization method, a polymerizable monomer composition containing a polymerizable monomer and a mold release agent capable of producing a resin and, if necessary, other additives is granulated in an aqueous medium, and the mixture is granulated. This is a method for obtaining toner matrix particles by polymerizing the polymerizable monomer contained in the polymerizable monomer composition.
After the polymerization step is completed, the produced particles may be recovered by washing and filtration by a known method and dried to obtain toner matrix particles.
The temperature may be raised in the latter half of the polymerization step. Further, in order to remove the unreacted polymerizable monomer or by-product, it is also possible to distill off a part of the dispersion medium from the reaction system in the latter half of the polymerization step or after the completion of the polymerization step.
It is preferable to use the toner mother particles thus obtained to form convex portions of the organosilicon polymer by the above method.

The release agent is not particularly limited, and known ones shown below can be used.
Paraffin wax, microcrystallin wax, petroleum wax and its derivatives such as petrolatum, Montan wax and its derivatives, hydrocarbon wax and its derivatives by the Fisher Tropsch method, polyolefin wax and its derivatives such as polyethylene and polypropylene, carnauba wax, Natural waxes and derivatives thereof such as candelilla waxes, fatty acids such as higher aliphatic alcohols, stearic acids, palmitic acids and their compounds, acid amide waxes, ester waxes, ketones, hardened castor oil and derivatives thereof, plant waxes, Animal wax, hydrocarbon resin.
Derivatives include oxides, block copolymers with vinyl-based monomers, and graft-modified products. These can be used alone or in combination.
The content of the release agent is preferably 2.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the resin or the polymerizable monomer that produces the resin.

The toner mother particles may contain a resin. Examples of the resin include the following.
Monopolymers of styrene and its substituents such as polystyrene and polyvinyltoluene; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methylacrylate 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-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Styrene-based copolymers such as coalesced, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethylmethacrylate, polybutylmethacrylate, poly Vinyl 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 type Styrene. These can be used alone or in combination.
Among these, styrene homopolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, dimethyl styrene-acrylate Styrene-acrylic copolymer such as aminoethyl copolymer, or styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate A styrene-methacryl copolymer such as a copolymer is preferable.

Examples of the polymerizable monomer include the following vinyl-based polymerizable monomers.
Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexylstyrene, pn-octyl, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene; methylacrylate, 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, Methacrylate-based polymerizable monomers such as diethyl phosphate ethyl methacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, formic acid Vinyl esters such as vinyl; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone. These may be used alone or in combination.

Further, a polymerization initiator may be added when the polymerizable monomer is polymerized. Examples of the polymerization initiator include the following.
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, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxycarbonate, cumene hydroperoxide, 2,4- Peroxide-based polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide. These may be used alone or in combination.
The amount of the polymerization initiator added is preferably 0.5% by mass or more and 30.0% by mass or less with respect to the polymerizable monomer.

Further, in order to control the molecular weight of the resin, a chain transfer agent may be added when the polymerizable monomer is polymerized.
The amount of the chain transfer agent added is preferably 0.001% by mass or more and 15,000% by mass or less with respect to the polymerizable monomer.
Further, in order to control the molecular weight of the resin, a cross-linking agent may be added when the polymerizable monomer is polymerized.
Examples of the crosslinkable monomer include the following.
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 diacrylate (MANDA Nihonkayaku), and the above acrylate converted to methacrylate.
Examples of the polyfunctional crosslinkable monomer include the following.
Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylic phthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl chlorendate. These may be used alone or in combination.
The amount of the cross-linking agent added is preferably 0.001% by mass or more and 15,000% by mass or less with respect to the polymerizable monomer.

When the medium used in the suspension polymerization is an aqueous medium, the following can be used as a dispersion stabilizer for the particles of the polymerizable monomer composition.
Tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina ..
In addition, examples of the organic dispersant include the following.
Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch.
It is also possible to use commercially available nonionic, anionic and cationic surfactants.
Examples of the surfactant include the following.
Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.

The toner mother particles may contain a colorant. The colorant is not particularly limited and known ones can be used.
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 parts by mass of the resin or the polymerizable monomer that produces the resin.
The toner mother particles may contain a charge control agent. The charge control agent is not particularly limited, and known ones can be used.
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 parts by mass of the resin or the polymerizable monomer that produces the resin.

Hereinafter, various measurement methods will be described.
<Method of observing the cross section of toner with a scanning transmission electron microscope (STEM)>
The cross section of the toner observed with a scanning transmission electron microscope (STEM) is prepared as follows.
The procedure for producing the cross section of the toner will be described below.
When organic fine particles or inorganic fine particles are externally attached to the toner, the toner from which the organic fine particles or inorganic fine particles have been removed by the following method or the like is used as a sample.
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved while boiling to prepare a sucrose concentrate. In a centrifuge tube (capacity 50 mL), 31 g of the above sucrose concentrate and Contaminone N (nonionic surfactant, anionic surfactant, organic builder, pH 7 precision measuring instrument cleaning neutral detergent Add 6 mL of 10 mass% aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.). Add 1.0 g of toner to this and loosen the toner lumps with a spatula or the like. The centrifuge tube is shaken with a shaker (sold by AS-1N AS ONE Corporation) at 300 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube (50 mL) for a swing rotor, and separated by a centrifuge (manufactured by Kokusan Co., Ltd., H-9R) at 3500 rpm for 30 minutes.
By this operation, the toner particles and the external additive are separated. Visually confirm that the toner particles and the aqueous solution are sufficiently separated, and collect the toner particles separated in the uppermost layer with a spatula or the like. The collected toner particles are filtered through a vacuum filter and then dried in a dryer for 1 hour or more to obtain a sample for measurement. Perform this operation multiple times to secure the required amount.
Whether or not the convex portion contains an organosilicon polymer is confirmed by combining elemental analysis by energy dispersive X-ray analysis (EDS).

Toner is sprayed on a cover glass (Matsunami Glass Co., Ltd., square cover glass; square No. 1) so as to form a single layer, and an osmium plasma coater (filgen Co., Ltd., OPC80T) is used to apply an Os film (Os film) to the toner as a protective film. 5 nm) and a naphthalene film (20 nm) are applied.
Next, a PTFE tube (outer diameter 3 mm (inner diameter 1.5 mm) x 3 mm) is filled with a photocurable resin D800 (JEOL Ltd.), and the cover glass is placed on the tube with toner photocurable resin D800. Place it quietly so that it touches the surface. After irradiating light in this state to cure the resin, the cover glass and the tube are removed to form a cylindrical resin in which toner is embedded on the outermost surface.
4 when the radius of the toner (for example, weight average particle size (D4)) from the outermost surface of the cylindrical resin is 8.0 μm at a cutting speed of 0.6 mm / s by an ultrasonic ultramicrotome (Leica, UC7). Cut by a length of .0 μm) to obtain a cross section of the toner center.
Next, cutting is performed so that the film thickness is 100 nm, and a flaky sample of the cross section of the toner is prepared. By cutting by such a method, a cross section of the toner center portion can be obtained.

As a scanning transmission electron microscope (STEM), JEM-2800 manufactured by JEOL Ltd. was used. Images are acquired with a STEM probe size of 1 nm and an image size of 1024 x 1024 pixels. Further, the contrast of the director control panel of the bright field image is adjusted to 1425, the contrast control is adjusted to 3750, the contrast of the image control panel is adjusted to 0.0, the brightness control is adjusted to 0.5, and the Gammma is adjusted to 1.00 to acquire an image.
The image magnification is 100,000 times, and the image is acquired so as to fit in about one-fourth to one-half of the circumference of the cross section in one toner particle as shown in FIG.
The obtained STEM image is image-analyzed using image processing software (image J (available from https://imagej.nih.gov/ij/)), and the convex portion containing the organic silicon polymer is measured. .. The measurement is performed on 30 convex portions arbitrarily selected from the STEM image.
Whether or not the convex portion contains an organic silicon polymer is confirmed by a combination of elemental analysis by a scanning electron microscope (SEM) and an energy dispersive X-ray analysis (EDS).
First, draw a line along the circumference of the toner matrix particle with the line drawing tool (select the Segmented line on the Strat tab). The portion where the convex portion of the organosilicon polymer is buried in the toner mother particles is connected with the line assuming that the convex portion is not buried so as to maintain the curvature of the contour line of the toner mother particles.
Based on the line, the development is performed on the developed image (select the Selection on the Edit tab, change the line width to 500 pixels in the properties, select the Selection on the Edit tab, and perform Strugger).
In the developed image, the following measurement is carried out for one of the convex portions containing the organosilicon polymer.
The length of the line along the circumference in the portion where the convex portion and the toner mother particle form a continuous interface is defined as the convex width w.
In the normal direction of the convex width w, the maximum length of the convex portion is defined as the convex diameter D, and the length from the apex of the convex portion to the line along the circumference of the line segment forming the convex diameter D is the convex height. Let's say H.
The measurement is carried out for 30 arbitrarily selected convex portions, and the arithmetic mean value of each measured value is defined as the number average value of the convex height H.

<Calculation method of H80>
In the STEM image of the cross section of the toner using the scanning transmission electron microscope (STEM),
In the convex portion where the convex height H is 30 nm or more and 300 nm or less, the cumulative distribution of the convex height H is taken, and the convex height corresponding to 80% by integration from the smaller convex height H is H80 (unit). : Nm).

<Calculation method of area ratio of bright area in 1.5 μm square reflected electron image of toner surface>
For the area ratio of the bright area, the surface of the toner is observed using a scanning electron microscope. Then, a 1.5 μm square backscattered electron image of the toner surface was obtained, and an image subjected to binarization treatment so that the organic silicon polymer portion in the backscattered electron image became a bright part was obtained, and the entire area of the image was obtained. The ratio of the bright area of the image is obtained.
A 1.5 μm square reflected electron image of the toner surface is obtained by a scanning electron microscope (SEM).
When organic fine particles or inorganic fine particles are externally attached to the toner, the toner from which the organic fine particles or inorganic fine particles have been removed by the following method or the like is used as a sample.
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved while boiling to prepare a sucrose concentrate. In a centrifuge tube (capacity 50 mL), 31 g of the above sucrose concentrate and Contaminone N (nonionic surfactant, anionic surfactant, organic builder, pH 7 precision measuring instrument cleaning neutral detergent Add 6 mL of 10 mass% aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.). Add 1.0 g of toner to this and loosen the toner lumps with a spatula or the like. The centrifuge tube is shaken with a shaker (sold by AS-1N AS ONE Corporation) at 300 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube (50 mL) for a swing rotor, and separated by a centrifuge (manufactured by Kokusan Co., Ltd., H-9R) at 3500 rpm for 30 minutes.
By this operation, the toner particles and the external additive are separated. Visually confirm that the toner particles and the aqueous solution are sufficiently separated, and collect the toner particles separated in the uppermost layer with a spatula or the like. The collected toner particles are filtered through a vacuum filter and then dried in a dryer for 1 hour or more to obtain a sample for measurement. Perform this operation multiple times to secure the required amount.
Further, whether or not the convex portion contains an organosilicon polymer is confirmed by combining elemental analysis by energy dispersive X-ray analysis (EDS) described later.

The SEM device and observation conditions are as follows.
Equipment used: ULTRA PLUS manufactured by Carl Zeiss Microscopy Co., Ltd.
Acceleration voltage: 1.0kV
WD: 2.0mm
Aperture Size: 30.0 μm
Detection signal: EsB (energy selective reflected electron)
EsB Grid: 800V
Observation magnification: 50,000 times Contrast: 63.0 ± 5.0% (reference value)
Brightness: 38.0 ± 5.0% (reference value)
Resolution: 1024 x 768
Pretreatment: Toner particles are sprayed on carbon tape (no vapor deposition)
The accelerating voltage and EsB Grid are set to achieve items such as acquisition of structural information on the outermost surface of toner particles, prevention of charge-up of undeposited sample, and selective detection of high-energy reflected electrons. For the observation field of view, select the vicinity of the apex where the curvature of the toner particles is the smallest.

The fact that the bright part of the reflected electron image is derived from the organic silicon polymer can be determined by superimposing the element mapping image obtained by the energy dispersive X-ray analysis (EDS) obtained by the scanning electron microscope (SEM) and the reflected electron image. confirmed.
The SEM / EDS equipment and observation conditions are as follows.
Equipment used (SEM): ULTRA PLUS manufactured by Carl Zeiss Microscopy Co., Ltd.
Equipment used (EDS): NORAN manufactured by Thermo Fisher Scientific Co., Ltd.
System 7, Ultra Dry EDS Detector
Acceleration voltage: 5.0 kV
WD: 7.0 mm
Aperture Size: 30.0 μm
Detection signal: SE2 (secondary electrons)
Observation magnification: 50,000 times Mode: Spectral Imaging
Pretreatment: Toner particles are sprayed on carbon tape, and platinum sputtering. The mapping image of the silicon element obtained by this method and the reflected electron image are superposed, and the silicon atom part of the mapping image and the bright part of the reflected electron image match. Make sure you do.

The area ratio of the bright area to the total area of the reflected electron image is calculated by analyzing the reflected electron image on the surface of the toner particles obtained by the above method using the image processing software ImageJ (developer Wayne Rashand). Obtained. The procedure is shown below.
First, the reflected electron image is converted into 8-bit from the Type of the Image menu. Next, from Filters in the Process menu, set the Median diameter to 2.0 pixels to reduce image noise.
Estimate the center of the image after excluding the observation condition display area displayed at the bottom of the backscattered electron image, and use the rectangle tool (Rectangle Tool) on the toolbar to select a range 1.5 μm square from the center of the backscattered electron image. ..
Next, select Thrashold from Adjust in the Image menu. Select Value, click Auto, then click Apply to get a binarized image. By this operation, the bright part of the reflected electron image is displayed in white.
Estimate the image center again after removing the observation condition display part displayed at the bottom of the reflected electron image, and use the rectangle tool (Rectangle Tool) on the toolbar to measure the area 1.5 μm square from the image center of the reflected electron image. select.
Next, select Histogram from the Analyze menu. Read the Count value from the newly opened Histogram window (corresponding to the total area of the reflected electron image). Also, click List and read the Count value when the brightness is 0 (corresponding to the bright area of the reflected electron image). From the above values, the area ratio of the bright area to the total area of the reflected electron image is calculated. The above procedure is performed for 10 fields of view of the toner particles to be evaluated, the number average value is calculated, and the total area of the image obtained by binarizing the organic silicon polymer portion in the backscattered electron image so that it becomes a bright part. The area ratio (%) of the bright area of the image to the image.

<Method for identifying organosilicon polymers>
The method for identifying the organic silicon polymer is a combination of observation with a scanning electron microscope (SEM) and elemental analysis with energy dispersive X-ray analysis (EDS).
Using a scanning electron microscope "Hitachi ultra-high resolution field emission scanning electron microscope S-4800" (Hitachi High Technologies America, Inc.), the toner is observed in a field magnified up to 50,000 times. Focus on the surface of the toner particles and observe the surface.
EDS analysis is performed on the particles and the like existing on the surface, and it is determined whether or not the analyzed particles and the like are organosilicon polymers from the presence or absence of the Si element peak.
When the surface of the toner particles contains both an organosilicon polymer and silica fine particles, compare the ratio (Si / O ratio) of the element content (atomic%) of Si and O with the standard. The organosilicon polymer is identified in.
EDS analysis is performed on each of the organosilicon polymer and silica fine particle preparations under the same conditions to obtain the element content (atomic%) of each of Si and O.
Let A be the Si / O ratio of the organosilicon polymer and B be the Si / O ratio of the silica fine particles. Select a measurement condition in which A is significantly larger than B.
Specifically, the standard is measured 10 times under the same conditions, and the arithmetic mean values of A and B are obtained. Select the measurement conditions for which the obtained average value is A / B> 1.1.
When the Si / O ratio of the particles to be discriminated is on the A side of [(A + B) / 2], the particles are judged to be an organosilicon polymer.
Tospearl 120A (Momentive Performance Materials Japan GK) as a standard for organosilicon polymer particles, HDK V1 as a standard for silica fine particles
5 (Asahi Kasei) is used.

<Method of measuring the average particle size R of the number of primary particles of the external additive>
Elemental analysis by scanning electron microscope "Hitachi ultra-high resolution field emission scanning electron microscope S-4800" (Hitachi High Technologies America, Inc.) and energy dispersive X-ray analysis (EDS) is performed.
In a field of view magnified up to 50,000 times, the external additive particles are randomly photographed in combination with the above-mentioned elemental analysis method using EDS.
100 external additive particles are randomly selected from the captured image, the major axis of the primary particles of the target external additive particles is measured, and the arithmetic mean value thereof is defined as the number average particle size R.
The observation magnification is appropriately adjusted according to the size of the external additive particles.

<Method for identifying the composition and ratio of constituent compounds of organosilicon polymers>
NMR is used to identify the composition and ratio of the constituent compounds of the organosilicon polymer contained in the toner.
If the toner contains an external additive such as silica fine particles in addition to the organosilicon polymer, perform the following operations.
1 g of toner is placed in a vial, dissolved in 31 g of chloroform, and dispersed. For dispersion, an ultrasonic homogenizer is used for 30 minutes to prepare a dispersion.
Sonic processing device: Ultrasonic homogenizer VP-050 (manufactured by TIETECH Co., Ltd.)
Microchip: Step type microchip, tip diameter φ2 mm
Microchip tip position: Central part of glass vial and height 5 mm from bottom of vial Ultrasonic conditions: Intensity 30%, 30 minutes At this time, ultrasonic waves while cooling the vial with ice water so that the dispersion liquid does not rise. Multiply.
The dispersion is replaced with a glass tube for a swing rotor (50 mL), and a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) is used to perform centrifugation under the conditions of 58.33S- ¹ for 30 minutes. In the glass tube after centrifugation, particles having a heavy specific gravity, for example, silica fine particles, are contained in the lower layer. A chloroform solution containing the upper layer organosilicon polymer is collected, and chloroform is removed by vacuum drying (40 ° C./24 hours) to prepare a sample.
Using the above sample or the organosilicon polymer, the abundance ratio of the constituent compounds of the organosilicon polymer and the ratio of the T3 unit structure represented by R-Si (O _1/2 ) ₃ in the organosilicon polymer are determined. , Solid ²⁹ Measured and calculated by Si-NMR.

First, the hydrocarbon group represented by R is confirmed by ¹³ C-NMR.
«Measurement conditions ¹³ C-NMR (solid)»
Equipment: JNM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample: Sample or organosilicon polymer 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
Number of integrations: 1024 times By this method, a methyl group (Si-CH ₃ ), an ethyl group (Si-C ₂ H ₅ ), a propyl group (Si-C ₃ H ₇ ), and a butyl group bonded to a silicon atom. (Si-C ₄ H ₉ ), pentyl group (Si-C ₅ H ₁₁ ), hexyl group (Si-C ₆ H ₁₃ ) or phenyl group (Si-C ₆ H)
_The hydrocarbon group represented by R is confirmed by the presence or absence of a signal caused by ₅ ) or the like.
On the other hand, in solid ²⁹ Si-NMR, peaks are detected in different shift regions depending on the structure of the functional group bonded to Si of the constituent compound of the organosilicon polymer.
The structure bonded to Si can be specified by specifying each peak position using a standard sample. In addition, the abundance ratio of each constituent compound can be calculated from the obtained peak area. The ratio of the peak area of the T3 unit structure to the total peak area can be calculated.

Specifically, the measurement conditions for solid ²⁹ Si-NMR are as follows.
Equipment: JNM-ECX5002 (JEOL RESONANCE)
Temperature: Room temperature Measurement method: DDMAS method ²⁹ Si 45 °
Sample tube: Zirconia 3.2 mmφ
Sample: Filled in a test tube in powder form Sample rotation speed: 10 kHz
relaxation delay: 180s
Scan: 2000
After the measurement, a plurality of silane components having different substituents and bonding groups of the sample or organosilicon polymer are peak-separated into the following X1 structure, X2 structure, X3 structure, and X4 structure by curve fitting, and the peak areas are respectively. Is calculated.
The following X3 structure is a T3 unit structure.
X1 structure: (Ri) (Rj) (Rk) SiO _1/2 (A1)
X2 structure: (Rg) (Rh) Si (O _1/2 ) ₂ (A2)
X3 structure: RmSi (O _1/2 ) ₃ (A3)
X4 structure: Si (O _1/2 ) ₄ (A4)

Ri, Rj, Rk, Rg, Rh and Rm in the formulas (A1), (A2) and (A3) are organic groups such as hydrocarbon groups having 1 to 6 carbon atoms and halogen atoms bonded to silicon. , Hydroxy group, acetoxy group or alkoxy group.
When it is necessary to confirm the structure in more detail, it may be identified by the measurement result of ¹ H-NMR together with the measurement result of ¹³ C-NMR and ²⁹ Si-NMR.

<Method for quantifying organosilicon polymer or silica fine particles contained in toner>
The toner is dispersed in chloroform as described above, and then centrifugation is used to separate an external agent such as an organic silicon polymer and silica fine particles by a difference in specific gravity, and each sample is obtained to obtain an organic silicon polymer or silica. Obtain the content of an external additive such as fine particles.
Hereinafter, the case where the external additive is silica fine particles will be illustrated. Even other fine particles can be quantified by the same method.
First, the pressed toner is measured by fluorescent X-rays, and the content of silicon in the toner is determined by performing an analysis process such as a calibration curve method or an FP method.
Next, for each constituent compound forming the organosilicon polymer and silica fine particles, the solid ²⁹
The structure is specified by using Si-NMR, thermal decomposition GC / MS, etc., and the silicon content in the organosilicon polymer and the silica fine particles is determined.
From the relationship between the silicon content in the toner determined by fluorescent X-ray and the silicon content in the organosilicon polymer and silica fine particles determined by solid ²⁹ Si-NMR and thermal decomposition GC / MS, the toner is calculated. The content of the organosilicon polymer and the silica fine particles of the above is determined.

<Method of measuring the adhesion rate to toner matrix particles or toner particles by washing with an external agent such as an organosilicon polymer or silica fine particles>
(Washing process)
Weigh 20 g of "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a pH 7 precision instrument consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) in a vial having a capacity of 50 mL, and 1 g of toner. Mix with.
Set in "KM Shaker" (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd., set speed to 50, and shake for 120 seconds. As a result, depending on the state in which the organic silicon polymer or the silica fine particles are fixed, the external agent such as the organic silicon polymer or the silica fine particles moves from the toner mother particles or the surface of the toner particles to the dispersion liquid side.
Then, in a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) (16.67S-1 for 5 minutes), an external agent such as an organosilicon polymer or silica fine particles transferred to the toner and the supernatant was applied. To separate.
The precipitated toner is dried by vacuum drying (40 ° C./24 hours), washed with water, and used as toner.

Next, using a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation), a toner that does not undergo the water washing step (toner before washing) and a toner obtained through the water washing step. Take a picture of the toner (toner after washing with water).
In addition, the measurement target is identified by elemental analysis using energy dispersive X-ray analysis (EDS).
Then, the captured toner surface image is converted into the image analysis software Image-Pro Plus.
ver. Analysis is performed using 5.0 (Nippon Roper Co., Ltd.), and the coverage is calculated.
The image capturing conditions of S-4800 are as follows.
(1) Sample preparation A thin layer of conductive paste is applied to a sample table (aluminum sample table 15 mm x 6 mm), and toner is sprayed onto the sample table. Further air blow to remove excess toner from the sample table and allow it to dry sufficiently. Set the sample table in the sample holder and adjust the sample table height to 36 mm with the sample height gauge.
(2) Setting of S-4800 observation conditions When measuring the coverage, elemental analysis by the above-mentioned energy dispersive X-ray analysis (EDS) is performed in advance, and an external agent such as an organic silicon polymer or silica fine particles on the toner surface is used. The measurement is performed after distinguishing between.
Inject liquid nitrogen into the anti-contamination trap attached to the housing of S-4800 until it overflows, and leave it for 30 minutes. The "PC-SEM" of S-4800 is started to perform flushing (cleaning of the FE chip which is an electronic source). Click the accelerating voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2, and execute. Confirm that the emission current due to flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.
Click the accelerating voltage display to open the HV setting dialog, and set the accelerating voltage to [1.1 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [Up (U)] and [+ BSE] for the SE detector, and select [+ BSE] in the selection box to the right of [+ BSE]. L. A. 100] is selected to set the mode for observing with a reflected electron image. Similarly, in the [Basic] tab of the operation panel, set the probe current of the electron optics condition block to [Normal], the focus mode to [UHR], and the WD to [4.5 mm]. Press the [ON] button on the accelerating voltage display of the control panel to apply the accelerating voltage.
(3) Calculation of number of toners, average particle size (D1) Drag the inside of the magnification display section of the control panel to set the magnification to 5000 (5k) times. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is adjusted to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and use autofocus to focus. Repeat this operation twice more to focus.
Then, the particle size of 300 toners is measured to obtain the number average particle size (D1). The particle size of each particle is the maximum diameter when the toner particles are observed.
(4) Focus adjustment For particles with a number average particle size (D1) of ± 0.1 μm obtained in (3), the inside of the magnification display section of the control panel is displayed with the midpoint of the maximum diameter aligned with the center of the measurement screen. Drag to set the magnification to 10000 (10k) times.
Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is adjusted to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and use autofocus to focus. After that, the magnification is set to 50,000 (50k) times, the focus is adjusted using the focus knob and the STIGMA / ALIGNMENT knob in the same manner as above, and the focus is adjusted again by autofocus. Repeat this operation again to focus. Here, if the inclination angle of the observation surface is large, the measurement accuracy of the coverage tends to be low, so by selecting the one that focuses on the entire observation surface at the same time when adjusting the focus, select the one with the least inclination of the surface. And analyze.
(5) Image saving Perform brightness adjustment in ABC mode, take a picture with a size of 640 x 480 pixels, and save it. The following analysis is performed using this image file. One photograph is taken for each toner to obtain an image of 25 toner particles.
(6) Image analysis The coverage is calculated by binarizing the image obtained by the above method using the following analysis software. At this time, the above screen is divided into 12 squares and analyzed.
Image analysis software Image-Pro Plus ver. The analysis conditions for 5.0 are as follows. However, if an organosilicon polymer having a particle size of less than 30 nm and more than 300 nm or an external additive such as silica fine particles having a particle size of less than 30 nm and more than 1200 nm is contained in the divided compartment, the coverage is calculated in that compartment. Will not be done.
In the image analysis software Image-Pro Plus 5.0,
Select "Measurement", "Count / Size", and "Options" on the toolbar to set the binarization conditions. Select 8 concatenations in the object extraction options and set the smoothing to 0. In addition, pre-sort, fill holes, do not select envelopes, and set "exclude borders" to "none". Select "Measurement item" from "Measurement" on the toolbar, and enter 2 to ⁷ in the area selection range.
The coverage is calculated by enclosing a square area. At this time, the area (C) of the area is set to 24,000 to 26,000 pixels. "Treatment" -Automatically binarizes by binarization, and calculates the total area (D) of the area without an external agent such as an organosilicon polymer or silica fine particles.
From the area C of the square area and the total area D of the area without an external additive such as an organosilicon polymer or silica fine particles, the coverage can be obtained by the following formula.
Coverage (%) = 100- (D / C x 100)
The arithmetic mean value of all the obtained data is used as the coverage ratio.
Then, the coverage of each of the pre-wash toner and the post-wash toner is calculated.
[Coverage of toner after washing with water] / [Coverage of toner before washing with water] × 100 is defined as the “adhesion rate” of the present disclosure.

The present disclosure will be described in more detail with reference to Examples and Comparative Examples, but the present disclosure is not limited thereto. Unless otherwise specified, "parts" and "%" used in the examples are based on mass.

An example of manufacturing toner will be described.
<Production example of toner particles 1>
(Preparation of aqueous medium 1)
650.0 parts of ion-exchanged water and 14.0 parts of sodium phosphate (12-hydrate manufactured by Rasa Industries, Ltd.) were put into a reaction vessel equipped with a stirrer, a thermometer, and a return pipe, and nitrogen was purged. However, it was kept warm at 65 ° C. for 1.0 hour.
T. K. Using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.), while stirring at 15,000 rpm, a calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) is dissolved in 10.0 parts of ion-exchanged water is collectively added. Then, an aqueous medium containing a dispersion stabilizer was prepared. Further, 10% by mass hydrochloric acid was added to the aqueous medium to adjust the pH to 5.0 to obtain the aqueous medium 1.

(Preparation of polymerizable monomer composition)
・ Styrene: 60.0 parts ・ C.I. I. Pigment Blue 15: 3: 6.5 parts After putting the material into an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.) and further dispersing it at 220 rpm for 5.0 hours using zirconia particles with a diameter of 1.7 mm. Zirconia particles were removed to prepare a colorant dispersion.
on the other hand,
-Styrene: 20.0 parts-n-butyl acrylate: 20.0 parts-Crosslinking agent (divinylbenzene): 0.3 parts-Saturated polyester resin: 5.0 parts (propylene oxide-modified bisphenol A (2 mol adduct) Polycondensate of 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.): 7.0 parts The material was added to the above colorant dispersion, heated to 65 ° C., and then T.I. K. A polymerizable monomer composition was prepared by uniformly dissolving and dispersing at 500 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.).

(Granulation process)
The temperature of the aqueous medium 1 was adjusted to 70 ° C., and T.I. K. While maintaining the rotation speed of the homomixer at 15,000 rpm, the polymerizable monomer composition was put into the aqueous medium 1 and 10.0 parts of t-butylperoxypivalate as a polymerization initiator was added. As it is, 15,000 with the stirring device
Granulation was performed for 10 minutes while maintaining rpm.

(Polymerization process and distillation process)
After the granulation step, the stirrer is replaced with a propeller stirring blade, and the mixture is polymerized at 70 ° C. for 5.0 hours while stirring at 150 rpm, and further heated to 85 ° C. and held for 2.0 hours to polymerize. Was done.
After that, the return pipe of the reaction vessel was replaced with a cooling pipe, and the obtained slurry was heated to 100 ° C. to carry out distillation for 6 hours to distill off the unreacted polymerizable monomer, and to distill off the unreacted polymerizable monomer. Got

(Forming process of organosilicon polymer)
60.0 parts of ion-exchanged water was weighed in a reaction vessel equipped with a stirrer and a thermometer, and the pH was adjusted to 4.0 with 10% by mass hydrochloric acid. This was heated with stirring to bring the temperature to 40 ° C. Then, 40.0 parts of methyltriethoxysilane, which is an organosilicon compound, was added and stirred for 2 hours or more for hydrolysis.
The end point of the hydrolysis was visually confirmed that the oil and water did not separate and became one layer, and the mixture was cooled to obtain a hydrolyzed solution of an organosilicon compound.
After adjusting the temperature of the resin particle dispersion obtained above to 55 ° C., 25.0 parts (the amount of the organosilicon compound added is 10.0 parts) of the hydrolyzed solution of the organosilicon compound is added to make it organic. The polymerization of the silicon compound was started. After holding as it was for 0.25 hours, the pH was adjusted to 5.5 with a 3.0% aqueous sodium hydrogen carbonate solution. After holding for 1.0 hour (condensation reaction 1) while continuing stirring at 55 ° C., adjust the pH to 9.5 with a 3.0% aqueous sodium hydrogen carbonate solution, and hold for another 4.0 hours (condensation). Reaction 2) was carried out to obtain a toner particle dispersion.

(Washing process and drying process)
After the step of forming the organic silicon polymer was completed, the toner particle dispersion was cooled, hydrochloric acid was added to the toner particle dispersion to adjust the pH to 1.5 or less, and the mixture was allowed to stand for 1.0 hour with stirring.
Then, solid-liquid separation was performed with a pressure filter to obtain a toner cake.
The obtained toner cake was reslurried with ion-exchanged water to form a dispersion liquid again, and then solid-liquid separated with the above-mentioned filter to obtain a toner cake.
The obtained toner cake was transferred to a constant temperature bath at 40 ° C., dried and classified over 72 hours to obtain toner particles 1. Table 1 shows the conditions for producing the toner particles 1.

<Production Examples of Toner Particles 2-11 and Comparative 2-9>
Toner particles 2 to 11 and comparisons 2 to 9 were obtained in the same manner as in the production example of toner particles 1, except that the conditions shown in Table 1 were changed. Table 1 shows the production conditions of the toner particles 2-11 and the comparison 2-9.

<Production examples of external additives A1 to 6 and A8 to 11>
The external additives A1 to 6 and A8 to 11 were produced as follows.
150 parts of 5% ammonia water was placed in a 1.5 L glass reaction vessel equipped with a stirrer, a dropping nozzle and a thermometer to prepare an alkaline catalyst solution.
After adjusting the alkali catalyst solution to 50 ° C., 100 parts of tetraethoxysilane and 50 parts of 5% aqueous ammonia were added dropwise at the same time with stirring, and the mixture was reacted for 8 hours to obtain a silica fine particle dispersion. Then, the obtained silica fine particle dispersion was dried by spray drying and crushed with a pin mill to obtain silica fine particles.
Here, by appropriately changing the above production conditions, external additives A1 to 6 and A8 to 11 having different number average particle diameters R of the primary particles were obtained. Table 2 shows the physical properties of the external additives A1 to 6 and A8 to 11.

<Production example of external additive A7>
As the external additive A7, alumina and AKP-30 (Sumitomo Chemical Co., Ltd.) were used. Table 2 shows the physical properties of the external preparation A7.

<Manufacturing example of toner 1>
100.00 parts of toner particles 1 and 1.00 parts of external additive A1 were put into a Henschel mixer (FM10C type manufactured by Nippon Coke Industries, Ltd.) in which water at 7 ° C. was passed through the jacket. Next, after the water temperature in the jacket became stable at 7 ° C. ± 1 ° C., the rotary blades were mixed for 10 minutes at a peripheral speed of 38 m / sec. In the mixing, the amount of water flowing through the jacket was appropriately adjusted so that the temperature inside the tank of the Henschel mixer did not exceed 25 ° C.
The obtained mixture was sieved with a mesh having an opening of 75 μm to obtain toner 1. Table 3 shows the manufacturing conditions and physical properties of the toner 1.

<Production examples of toners 2 to 11 and comparisons 2 to 9>
Toners 2 to 11 and comparisons 2 to 9 were obtained in the same manner as in the production example of toner 1, except that the external additive A shown in Table 3 was changed and the external addition conditions by the Henschel mixer were appropriately changed. Table 3 shows the manufacturing conditions and physical properties of the toners 2 to 11 and the comparisons 2 to 9.

表中、「Ｘ」は、外添剤Ａの一次粒子の個数平均粒径Ｒの凸高さＨの個数平均値に対する比を表す。

In the table, "X" represents the ratio of the number average particle diameter R of the primary particles of the external additive A to the number average value of the convex height H.

<Manufacturing example of toner particle comparison 1>
In the production example of the toner particles 1, the toner particle comparison 1 was obtained in the same manner except that the “step of forming the organosilicon polymer” was not carried out. Table 1 shows the production conditions of the toner particle comparison 1.

<Manufacturing example of toner comparison 1>
100.00 parts of the comparative toner particles 1 and 1.00 parts of the external additive A8 were put into a Henschel mixer (FM10C type manufactured by Nippon Coke Industries Co., Ltd.) in which water at 7 ° C. was passed through the jacket. Next, after the water temperature in the jacket became stable at 7 ° C. ± 1 ° C., the rotary blades were mixed at a peripheral speed of 38 m / sec for 10 minutes. In the mixing, the amount of water flowing through the jacket was appropriately adjusted so that the temperature inside the tank of the Henschel mixer did not exceed 25 ° C.
The obtained mixture was sieved with a mesh having an opening of 75 μm to obtain Comparative Toner 1. Table 3 shows the production conditions and physical properties of the comparative toner 1.

<Example 1>
The following evaluation was performed on the toner 1. The results are shown in Table 4.

<Evaluation of transferability>
As an evaluation machine, a modified machine of a commercially available Canon laser beam printer LBP7700C was used. The modification point was that the rotation speed of the developing roller was 360 mm / sec by changing the evaluation machine body and software.
Toner was loaded into the LBP7700C toner cartridge, and the toner cartridge was left to stand in a normal temperature and humidity environment (25 ° C., 50% RH; hereinafter also referred to as N / N) for 24 hours.
After leaving the toner cartridge for 24 hours in the environment, the toner cartridge is attached to the above, and in the N / N environment, a margin of 50 mm is provided on each side, and an image with a printing rate of 5.0% is printed in the center in the horizontal direction of A4 paper. I printed out up to 500 sheets.
For evaluation, a solid image is output at the initial stage of use (after printing the first sheet) and after printing 7,500 sheets (after long-term use), and the transfer residual toner on the photoconductor at the time of forming the solid image is made of transparent polyester. It was taped and peeled off using an adhesive tape.
The concentration difference was calculated by subtracting the concentration of the adhesive tape only attached on the paper from the concentration of the peeled adhesive tape attached on the paper.
The concentration was measured at 5 points, and the arithmetic mean value was calculated. Then, from the value of the concentration difference, the determination was made as follows.
The density was measured with an X-Rite color reflection densitometer (X-Rite 500 Series, manufactured by X-rite).
(Evaluation criteria)
A: Concentration difference is less than 0.030 B: Concentration difference is 0.030 or more and less than 0.050 C: Concentration difference is 0.050 or more and less than 0.100 D: Concentration difference is 0.100 or more

<Evaluation of low temperature fixability>
As an evaluation machine, a modified machine was used in which the fixing unit of the Canon laser beam printer LBP9600C was modified so that the fixing temperature could be adjusted.
Using the modified machine, the fixing temperature was changed from 140 ° C. to 5 ° C. in a normal temperature and humidity environment (25 ° C., 50% RH; hereinafter also referred to as N / N) at a process speed of 300 mm / sec. ..
Further, as another condition, a solid image having a toner loading amount of 0.40 mg / cm ^{2 was formed on} the image receiving paper, and heating and pressurizing was performed without oil.
Printing is executed under the above conditions, the paper passing condition is visually confirmed, the minimum temperature of the fixing unit when the paper is passed without wrapping is checked, and the wrapping property (low temperature) at low temperature fixing is based on the following criteria. Fixability) was verified.
The image-receiving paper, GF-600 (怦量60g / ^{m 2,} sold by Canon Marketing Japan Inc.) was used.
(Evaluation criteria)
A: 140 ° C or 145 ° C
B: 150 ° C
C: 155 ° C
D: 160 ° C or 165 ° C
E: 170 ° C or higher

<Evaluation of liquidity (solid followability)>
The solid followability in a high temperature and high humidity environment was evaluated by the following method.
As the evaluation machine, a modified machine of the above-mentioned commercially available Canon laser beam printer LBP7700C was used.
The toner-filled cartridge and the main body were left in a high temperature and high humidity environment (temperature 32.5 ° C., humidity 80% RH) for 24 hours or more. Then, three solid images were output as sample images in succession, and the solid followability of the third solid image obtained was visually evaluated.
Further, after continuously passing 10,000 sheets a day at a printing rate of 1%, the paper was left in the machine for one day, and after being left to stand, the solid followability was evaluated. The evaluation criteria are as follows.
It is known that the higher the fluidity of the toner, the better the evaluation can be obtained.
Evaluation was performed every 10,000 sheets, and up to 30,000 sheets were continuously evaluated.
The following evaluation criteria are the criteria when continuously evaluating up to 30,000 sheets.
(Evaluation criteria)
A: Image density is uniform without unevenness B: Image density is slight unevenness but does not cause a problem in use C: Image density is uneven but does not cause a problem in use D: Image density Level that is uneven and does not result in a uniform solid image

<Examples 2 to 11 and Comparative Examples 1 to 9>
In Example 1, the evaluation was carried out in the same manner except that the toner 1 was changed to toners 2 to 11 and comparative toners 1 to 9. The results are shown in Table 4.

1: STEM image 2: Toner particles 3: Toner mother particle surface 4: Convex part, 5: Convex width w, 6: Convex diameter D, 7: Convex height H

Claims (5)

Toner mother particles containing a release agent, toner particles containing an organosilicon polymer on the surface of the toner mother particles, and
External agent A and
Toner with
The organosilicon polymer has a T3 unit structure represented by R-Si (O _1/2 ) ₃ .
The R represents an alkyl group or a phenyl group having 1 or more and 6 or less carbon atoms.
The organosilicon polymer forms a convex portion on the surface of the toner mother particle,
When a cross-sectional image of the toner obtained by a scanning transmission electron microscope is developed by linearly developing a line along the circumference of the toner mother particle surface to obtain a developed image of the cross-sectional image,
In the developed image,
The length of the line along the circumference in the portion where the convex portion and the toner mother particle form a continuous interface is defined as the convex width w.
The maximum length of the convex portion in the normal direction of the convex width w is defined as the convex diameter D.
When the length from the apex of the convex portion to the line along the circumference of the line segment forming the convex diameter D is defined as the convex height H,
The number average value of the convex height H is 30 nm or more and 300 nm or less.
The ratio of the number average particle diameter R of the primary particles of the external additive A to the number average value of the convex height H is 1.00 or more and 4.00 or less.
The number average particle size R of the primary particles of the external additive A is 30 nm or more and 1200 nm or less.
By observing the surface of the toner with a scanning electron microscope,
When a 1.5 μm square backscattered electron image of the toner surface was obtained and an image was binarized so that the organosilicon polymer portion in the backscattered electron image became a bright part,
The area ratio of the bright area of the image to the total area of the image is 30.0% or more and 75.0% or less.
Toner characterized by that. The toner according to claim 1, wherein the adhesion ratio of the external additive A to the surface of the toner particles is 0% or more and 20% or less. The toner according to claim 1 or 2, wherein the external additive A contains silica fine particles. The toner according to any one of claims 1 to 3, wherein the adhesion rate of the organosilicon polymer to the surface of the toner matrix particles is 80% or more and 100% or less. In the convex portion where the convex height H is 30 nm or more and 300 nm or less.
When the cumulative distribution of the convex height H is taken and the convex height corresponding to 80% by total from the smaller convex height H is taken as H80,
The toner according to any one of claims 1 to 4, wherein the H80 is 65 nm or more and 120 nm or less.

Images