JP6643121B2 - toner - Google Patents

Description

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

  A representative device of an electrophotographic system using a toner includes a laser printer and a copying machine. In recent years, colorization has rapidly progressed, and higher image quality has been demanded. As a problem of electrophotography using toner, there is an improvement in transferability. When a toner image formed on a photoconductor, which is an electrostatic image carrier, is transferred to a transfer material in a transfer process, transfer residual toner that leaves toner on the photoconductor may occur. In that case, the transfer residual toner is cleaned in a cleaning step and stored in a waste toner container. However, since a cleaning device for performing the cleaning process is provided, the size of the device is inevitably increased, which is a bottleneck in miniaturizing the device. Also, in a system that does not have a cleaning step and collects the transfer residual toner at the same time as the development, it is necessary to satisfy a sufficient cleaning property and a sufficient transfer property in the long term, and the surface shape of the toner particles is extremely high. It is necessary to control.

  Further, the amount of the transfer residual toner changes with respect to the transfer current, and there is generally an optimum range of the transfer current at which the amount of the transfer residual toner is minimized. If the transfer current is lower than the optimum current range, the transfer electric field is small with respect to the attraction between the toner and the photoconductor, so that the toner does not move and the transfer residual toner amount increases. On the other hand, when the transfer current is larger than the optimum current range, discharge occurs in the toner layer and the transfer electric field is rather weakened, so that the transfer residual toner increases. Therefore, it is desirable to set the transfer current at the lowest position in the optimum current range.

  However, the optimum current range also changes depending on the charge amount of the toner. In particular, when printing is not performed for a long time under high humidity, the optimal range of the transfer current is liable to change because the charge amount is easily reduced and the attractive force between the toner and the photosensitive member is easily changed. To cope with this change, there is a method of determining the transfer current from environment detecting means such as a temperature and humidity sensor. However, there is a concern that various control devices may become complicated and large. Therefore, there is a demand for a toner that does not change its charge amount even under high temperature and high humidity and has good transferability in a wide transfer current range.

It is generally known that in order to improve the transferability of the toner, it is effective to reduce the adhesion of the toner to the electrostatic image carrier. As a means for reducing the adhesion of the toner, an external additive may be attached to the surface of the toner particles. A typical example of the external additive is silica fine particles. The silica fine particles are composed of silicon dioxide, and have a chemical structure of SiO ₂ . Therefore, it was considered that if the surface of the toner particles could be uniformly covered with the silicon compound, the adhesion of the toner could be further reduced. Further, studies have been made on the assumption that if the silicon compound covering the surface of the toner particles coats the toner without deterioration even after the durability, it is possible to obtain a toner that maintains the effect of lowering the adhesive force.

  As an example of a technical concept of covering the surface of a toner particle with a silicon compound, a method for producing a polymerized toner characterized by adding a silane coupling agent to a reaction system is disclosed (see Patent Document 1). However, according to this method, the amount of the silane compound deposited on the toner surface is insufficient, so that a large transferability improving effect cannot be obtained. Alternatively, a polymerized toner containing a silicon compound applied on the surface in the form of a continuous thin film has been disclosed (see Patent Document 2). However, particularly at low temperature and low humidity, the toner is charged up and stays on the electrostatic image carrier, resulting in accelerated deterioration of the toner, and an increase in the adhesive force during the running, resulting in a decrease in transferability. May be. In addition, the deteriorated toner is likely to have particles with an insufficient charge amount or particles charged with a polarity opposite to the design concept (charge amount inversion component), and the transfer latitude may be narrowed.

  As another method for increasing the transfer efficiency of toner, it has been proposed to add a spherical external additive having a large particle diameter (see Patent Document 3). In this proposal, a large particle size external additive is added to lower the physical adhesion between the toner and the electrostatic image carrier, thereby improving transfer efficiency. Although it is an effective technique as a method for improving transfer efficiency, the external additive having a large spherical particle may move to a concave portion on the toner surface due to long-term image output. Depending on the particle size of the large particle size external additive and the depth of the concave portion, the large particle size external additive moved to the concave portion can no longer function as a spacer. Therefore, the expected effect of improving the transfer efficiency may not be obtained. Conversely, in the case of a toner having a smooth surface, the adhesion between the external additive and the toner particles is insufficient, and the external additive having a large particle diameter may be released from the toner. For this reason, the fluidity and developability greatly fluctuate due to the long-term image output, and the liberated large-diameter external additive may be scattered. This proposal does not actively control the surface irregularities of the toner particles. In order for the large particle external additive to function effectively, it is important to control the surface shape of the toner according to the external additive.

  On the other hand, as a proposal which defines the surface shape of the toner, there is a proposal in which the irregularity period of the toner surface is measured by a scanning probe microscope (SPM) to define the surface shape of the toner (see Patent Document 4).

JP 03-089361 A JP-A-09-179341 JP 2002-108001 A JP-A-2004-85850

  The proposal disclosed in Patent Document 4 proposes that when a large period of irregularities and a small irregularity on a toner fall within a predetermined range, the fluidity of the toner is improved, a uniform toner brush can be realized, and a high dot reproducibility is achieved. That is, image quality can be obtained. However, in this proposal, the detailed definition of the large uneven period and the small uneven period is ambiguous, and a toner obtained by externally adding silica (30 nm) to toner particles pulverized by a jet mill is used. It cannot be said that the surface properties of the particles were actively controlled. In addition, stress is applied to the toner due to the optimal surface shape and the long-term image output for allowing the large particle external additive to uniformly and stably exist on the toner particle surface, and the external additive moves on the toner particle. However, it does not suggest a surface shape that can provide the effect of addition. Further, embedding of the external additive due to image output over a long period of time and localization of the external additive due to movement of the external additive on the toner particles when using a large particle size external additive are not considered.

  SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner having improved transferability more than before. Specifically, the present invention is to provide a toner that has a low transfer residual toner and a high transfer efficiency under a wide range of transfer current conditions throughout the entire durability even in a severe environment such as a high-temperature high-humidity environment or a low-temperature low-humidity environment. With the goal.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found the following toner. That is, the present invention is a toner including toner particles having a surface layer containing an organosilicon polymer,
The organosilicon polymer has a partial structure represented by the following formula (1) or (2),
In X-ray photoelectron spectroscopic analysis of the surface of the toner particles, wherein the surface of the toner particles, the concentration of carbon atoms dC, the concentration of oxygen atoms dO, and the total concentration dSi of the silicon atoms when the 100.0 atomic% , the concentration dSi of the silicon atoms is at 22.2 atomic% or less 1.0 atomic% or more,
In the roughness curve measured with a scanning probe microscope of the toner particles, JIS B0601: Arithmetic Average Roughness Ra (nm) measured on the basis of 2001, is a 10nm or more 300nm or less,
When the standard deviation of the Ra and σRa (nm), σRa / Ra is, it is 0.60 or less,
In the roughness curve, the toner particles JIS B0601: average length of roughness curve element to be measured on the basis of the 2001 RSm (nm) is, is at 20nm or more 500nm or less,
When the standard deviation of the RSm and σRSm (nm), σRSm / RSm is a toner which is characterized in that 0.60 or less.

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

  According to the present invention, it is possible to provide a toner having improved transferability more than before. Specifically, it is possible to provide a toner capable of suppressing transfer residual toner in a wide transfer current region throughout the entire durability in any of a low-temperature low-humidity environment and a high-temperature high-humidity environment.

FIG. 4 is a diagram illustrating a method for calculating an arithmetic average roughness Ra of a toner particle and a standard deviation σRa of Ra according to the present invention. FIG. 4 is a diagram illustrating a method for calculating an average length RSm of a roughness curve element of a toner particle and a standard deviation σRSm of RSm according to the present invention. 1 is an example of an image forming apparatus using the toner of the present invention. FIG. 3 is a diagram illustrating a relationship between back contrast and fog in the first embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The toner of the present invention is a toner including toner particles having a surface layer containing an organosilicon polymer, wherein the organosilicon polymer has a partial structure represented by the following formula (1) or (2). And
In X-ray photoelectron spectroscopic analysis of the surface of the toner particles, the surface of the toner particles, the concentration of carbon atoms dC, the concentration of oxygen atoms dO, and the total concentration dSi of the silicon atoms when the 100.0 atomic% , the concentration dSi of the silicon atoms is at 22.2 atomic% or less 1.0 atomic% or more,
In the roughness curve measured with a scanning probe microscope of the toner particles, JIS B0601: Arithmetic Average Roughness Ra (nm) measured on the basis of 2001, is a 10nm or more 300nm or less,
When the standard deviation of the Ra and σRa (nm), σRa / Ra is, it is 0.60 or less,
In the roughness curve, the toner particles JIS B0601: average length of roughness curve element to be measured on the basis of the 2001 RSm (nm) is, is at 20nm or more 500nm or less,
When the standard deviation of the RSm and σRSm (nm), σRSm / RSm, characterized in that it is 0.60 or less.

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

  Hereinafter, each of the above requirements will be described in detail.

  The toner particles according to the present invention contain an organosilicon polymer having a partial structure represented by the above formula (1) or (2) in the surface layer. In the organosilicon polymer, one of the four valences of a silicon atom is bonded to a partial structure represented by the following formula (iii) or (iv), and the remaining three are bonded to an oxygen atom.

  (In the formulas (iii) and (iv), * represents a bonding portion to a silicon atom. In the formula (iv), L represents a methylene group, an ethylene group, or a phenylene group.)

The oxygen atom forms a state in which both valences are bonded to a silicon atom, that is, a siloxane bond (Si-O-Si). Considering a silicon atom and an oxygen atom as an organosilicon polymer, it has two oxygen atoms and three oxygen atoms, and thus is expressed as —SiO _3/2 . It is considered that the —SiO _3/2 structure in this organosilicon polymer has properties similar to silica (SiO ₂ ) composed of a large number of siloxane bonds. Therefore, it is considered that the toner of the present invention creates a situation similar to the case where silica is added to the surface, and as a result, the surface of the toner particles can be strengthened. On the other hand, by containing the partial structure represented by the above formula (iii) or (iv), it reacted with various polymerizable monomers including a vinyl polymerizable monomer to form a crosslinked structure. An organosilicon polymer is obtained. Therefore, in the toner of the present invention, the adhesion between the inside of the toner particles and the surface layer is improved, and the toner is hardly deteriorated due to rubbing or pressure in durability. Therefore, it is considered that the effects of the present invention can be maintained through durability.

  From the viewpoint of facilitating the inclusion of the organosilicon polymer in the surface layer of the toner particles, the silicon polymer preferably has a small carbon number. Specifically, in the partial structure represented by the formula (2), L is preferably a methylene group. Further, it is more preferable that the organosilicon polymer has a partial structure represented by the formula (1). In the above formula (2), when L is an alkylene chain having 3 or more carbon atoms, the surface precipitation of the organosilicon polymer is reduced, and accordingly, the coverage of the toner particles is reduced. As the number of carbon atoms in the silicon polymer increases, the decrease in surface precipitation becomes remarkable, and the coatability becomes insufficient. Therefore, it is difficult to sufficiently exert the effects of the present invention. In the partial structure represented by the formula (2), it is important that L is a hydrocarbon group. For example, when L includes an ester group, the bond strength of the ester bond is weak, so that the durability is reduced. It tends to be easy.

  In the toner particles according to the present invention, in the X-ray photoelectron spectroscopy analysis of the surface of the toner particles, the total of the concentration dC of carbon atoms, the concentration dO of oxygen atoms, and the concentration dSi of silicon atoms on the surface of the toner particles is 100.0. When the atomic percentage is defined as atomic%, the concentration dSi of the silicon atom is 1.0 atomic% or more and 22.2 atomic% or less.

Usually, the main atoms of the toner particles that are envisaged are carbon atoms (C) and oxygen atoms (O). In the present invention, a silicon atom (Si), that is, a —SiO _3/2 structure derived from the partial structure represented by the formula (1) or (2) exists on the surface of the toner particle. The X-ray photoelectron spectroscopy is to perform elemental analysis on the outermost surface of a few nm, and the higher the silicon atom concentration dSi, the more the organosilicon polymer of the present invention is present on the toner particle surface. When the dSi is less than 1.0 atomic%, a sufficient amount of the organosilicon polymer does not exist on the surface of the toner particles. Therefore, the adhesion of the toner cannot be reduced, and it is difficult to obtain the effects of the present invention as described above. When the concentration dSi of the silicon atom is 1.0 atomic% or more and 22.2 atomic%, the effect of the present invention is effectively exhibited. The dSi is preferably at least 9.0 atomic% and at least 22.2 atomic%. The dSi can be controlled by a method for producing toner particles when forming an organosilicon polymer, a reaction temperature, a reaction time, a reaction solvent, and a pH when forming an organosilicon polymer. It can also be controlled by the type and amount of the monomer of the organosilicon polymer.
With the above-described configuration, the toner of the present invention has a wide transfer latitude in a high-temperature and high-humidity environment or a low-temperature and low-humidity environment, and its effect is maintained through durability.

  The toner particles according to the present invention have an arithmetic average roughness Ra (nm) measured based on JIS B0601: 2001 of 10 nm or more and 300 nm or less in a roughness curve measured by a scanning probe microscope. When the standard deviation is σRa (nm), σa / Ra is 0.60 or less.

  A scanning probe microscope (hereinafter, also referred to as “SPM”) includes a probe, a cantilever that supports the probe, and a displacement measurement system that detects bending of the cantilever, and an atomic force between the probe and the sample. (Attraction or repulsion) is detected and the shape of the sample surface is observed. The arithmetic average roughness Ra measured by the SPM is a three-dimensional extension of the center line average roughness Ra defined in JIS B0601: 2001 so that it can be applied to a measurement surface. It is a value obtained by averaging the absolute values of the deviations from the reference plane to the designated plane, and is expressed by the following equation. The arithmetic average roughness Ra is an index indicating the roughness of the particle surface, and can obtain information on the unevenness of the toner particle surface on a nanometer scale. Further, there is a feature that the influence of one scratch on the measured value is very small, and a stable result is obtained.

F (X, Y): surface indicated by all measured data S ₀ : area when the specified surface is assumed to be ideally flat Z ₀ : average value of Z data in the specified surface In the present invention, it means a 1 μm square measurement area.

  When the arithmetic average roughness Ra of the toner particles measured by SPM is 10 nm or more and 300 nm or less, a convex portion having an appropriate size is formed on the surface of the toner particles, and in a state where no external additive or the like is added. Also, the physical adhesion of the toner to the photoconductor can be sufficiently reduced. As a result, it is possible to provide a toner having good transfer efficiency in a wide transfer current region and having a small amount of untransferred toner. Further, by the presence of the protrusions in the organosilicon polymer, the protrusions are firmly adhered to the toner surface, and the toner is less likely to be peeled or embedded even by long-term image output. Can be provided. As a result, it is possible to maintain initial transferability and fogging ability even after durability.

  When Ra is less than 10 nm, the height of the projection formed on the surface of the toner particles is too small, so that the projection cannot exhibit a sufficient spacer effect. Therefore, the physical adhesion of the toner to the photoconductor is hard to decrease, and the transfer efficiency of the toner is likely to decrease. In addition, the toner tends to be easily deteriorated due to long service life. On the other hand, when Ra is larger than 300 nm, the projections on the surface of the toner particles receive greater resistance when subjected to stress such as rubbing or pressure, and thus are easily detached from the toner particles. Therefore, when image output is performed for a long period of time, the chargeability of the toner is likely to decrease, and fog or the like due to poor charging is likely to occur.

  Ra is preferably from 20 nm to 200 nm, more preferably from 40 nm to 100 nm. The formation of the protrusions is controlled by adding relatively large particles such as silica particles (hereinafter, also referred to as "large particles") together with the organosilicon polymer during the production of the toner particles. It is possible. Further, Ra can also be controlled by the particle size of the large-diameter particles and the like.

  In the toner particles according to the present invention, σRa / Ra is 0.60 or less, where σRa is the standard deviation of the Ra measured by SPM. σRa / Ra indicates the degree of variation in the height of the projections on the surface of the toner particles. The smaller the value, the smaller the variation in the height of the projections. When the σRa / Ra is 0.60 or less, it is possible to reduce the variation in the height of the projections formed on the surface of the toner particles. Therefore, the distribution of the physical adhesion of each toner is reduced, and the physical adhesion of each toner to the photoconductor becomes uniform. As a result, the transfer efficiency is further improved in a wide transfer current region. When σRa / Ra is greater than 0.60, the variation in the height of the projections on the surface of the toner particles becomes large. For this reason, the physical adhesive force at the portion in contact with the photoreceptor tends to vary for each toner, and the transfer efficiency tends to decrease. The σRa / Ra can be controlled by adjusting the coefficient of variation in the volume particle size distribution of the large particle added at the time of manufacturing the toner particles.

  In the toner particles according to the present invention, in the roughness curve, an average length RSm (nm) of a roughness curve element of the toner particles measured based on JIS B0601: 2001 is 20 nm or more and 500 nm or less, and the RSm Is the standard deviation of σRSm (nm), σRSm / RSm is 0.60 or less.

  The average length RSm of the roughness curve element measured by SPM is defined in JIS B0601: 2001. RSm is a value obtained by extracting a reference length in the direction of the average line from the roughness curve, and averaging the length of one period of unevenness included in the roughness curve at a certain reference length 1; It is expressed by the following equation.

RSm _i : length of each concavo-convex portion for one cycle included in the roughness curve n: total number of all concavo-convex portions included in reference length l Note that reference length l in the present invention is 1 μm.

  By measuring the RSm of the toner particles, it is possible to accurately obtain information on the interval between the convex portions formed on the surface of the toner particles. Further, from the ratio between the standard deviations σRSm and RSm, it is possible to obtain information on the degree of variation in the interval between the projections. When the average length RSm of the roughness curve element is 20 nm or more and 500 nm or less, convex portions having an appropriate density are formed on the surface of the toner particles, and the physical adhesion of each toner to the photoconductor is stabilized. Further, when a stress such as rubbing or pressure is applied, the convex portion easily exerts a spacer effect, and it is possible to provide a toner in which deterioration of the toner is suppressed. As a result, it is possible to provide a toner that maintains a wide transfer latitude through long life and durability. Further, it is possible to provide a toner in which the projections are hardly peeled off or embedded even by long-term image output. On the other hand, when the RSm is less than 20 nm, the density of the protrusions is too high, and the electrostatic adhesion of the toner tends to increase. As a result, the fluidity of the toner tends to decrease, and the transfer efficiency may decrease. When the RSm is larger than 500 nm, the density of the projections is too small, and the physical adhesion of each toner to the photoreceptor may be increased particularly in a low-temperature and low-humidity environment. For this reason, there is a case where an adverse effect that the transfer residual toner increases is caused. The RSm can be controlled in the above range by adjusting the amount of particles added together with the organosilicon polymer during the production of toner particles.

  When the σRSm / RSm is 0.60 or less, the intervals between the convex portions on the surface of the toner particles become uniform. As a result, the variation in the physical adhesion of the toner surface in contact with the photoconductor is reduced, and the transferability of the toner is further improved. On the other hand, when σRSm / RSm is larger than 0.60, the unevenness of the protrusions formed on the toner particle surfaces is not uniform, so that the non-electrostatic adhesion of the toner surface in contact with the photoconductor varies. In particular, and in a low-temperature and low-humidity environment, the amount of transfer residual toner may increase. In addition, since there is a region where the density of the protrusions is low, when a stress such as rubbing or pressure is applied, the protrusions are less likely to exhibit a spacer effect, and the toner may be likely to deteriorate. The σRSm / RSm can be controlled in the above range by adjusting the addition timing of the particles added together with the organosilicon polymer during the production of the toner particles, the production temperature of the toner particles, and the like.

  In the present invention, as the means for controlling the arithmetic average roughness Ra to 10 nm or more and 300 nm or less, a relatively large particle (large particle) together with the organosilicon compound constituting the organosilicon polymer is used as a toner. The technique of immobilization on the particle surface is suitably used. According to such a method, it is possible to efficiently form a surface layer containing an organosilicon polymer having a moderately-sized convex portion on the surface of the toner particles, and to form the large-diameter particles into toner particles. It can be firmly fixed to the surface. The particles to be added preferably have a relatively large particle diameter having a volume average particle diameter of about 20 nm to 700 nm. The particle size distribution of the particles is preferably sharp, and the coefficient of variation in the volume particle size distribution is preferably 30% or less.

  The particles to be added are not particularly limited, but the following materials are exemplified. First, as the inorganic fine particles, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, Examples include chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like. It is preferable that the inorganic fine particles have a hydrophobic property by using a surface treatment agent in order to prevent the flow characteristics and the charging characteristics of the toner under high humidity from being deteriorated. Examples of preferred surface treatment agents include silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like. it can. Further, polymer fine particles produced by soap-free emulsion polymerization of metal salts of fatty acids such as stearic acid such as zinc stearate and calcium stearate, and polymethyl methacrylate fine particles and polystyrene fine particles are also preferably used.

Among the particles, it is preferable to use silica particles from the viewpoint of affinity with the organosilicon polymer. By using the silica particles, a more firmly adhered projection is formed on the surface layer of the toner particles formed by the organosilicon polymer. Examples of the method for producing silica particles include the following methods.
A combustion method for obtaining silica particles by burning a silane compound (that is, a method for producing fumed silica)
-Explosive combustion method to obtain silica particles by burning metal silicon powder explosively-Wet method to obtain silica particles by neutralization reaction of sodium silicate and mineral acid (of which, those synthesized under alkaline conditions, sedimentation method, Those synthesized under acidic conditions are called gel methods.)
A sol-gel method for obtaining silica particles by hydrolysis of an alkoxysilane such as hydrocarbyloxysilane (so-called Stoeber method)
Among these, the sol-gel method is preferred from the viewpoint that the particle size distribution of the silica particles can be made relatively sharp. Further, in order to sharpen the particle size distribution of the silica particles and to exert a more effective spacer effect, it is preferable to subject the silica particles to a crushing treatment.

  It is preferable that the particles added for forming the projections have been subjected to a hydrophobic treatment in order to suppress a decrease in the charge amount in a high-temperature and high-humidity environment. Various methods can be used as a method for subjecting the particles to a hydrophobic treatment. For example, a method in which the particles are treated with a hydrophobizing agent in a dry manner, and a method in which the particles are treated with a hydrophobizing agent in a wet manner are exemplified. Among these, a dry-type hydrophobic treatment method is preferred from the viewpoint that excellent fluidity can be imparted to the toner while suppressing the aggregation of the particles. Examples of the dry-type hydrophobic treatment method include, for example, a method of spraying a hydrophobic treatment agent while stirring the particles, and a method of spraying a hydrophobic treatment agent vapor onto silica particles on a fluidized bed or the particles under stirring. There is a method to introduce.

Examples of the agent for hydrophobizing the particles include the following.
Chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, t-butyldimethylchlorosilane, and vinyltrichlorosilane;
Tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxy Silane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, i-butyltrisilane Ethoxysilane, decyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-amino Alkoxysilanes such as ethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane,
Hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, hexabutyldisilazane, hexapentyldisilazane, hexahexyldisilazane, hexacyclohexyldisilazane, hexaphenyldisilazane, divinyltetramethyldisilazane, dimethyltetravinyl Silazane such as disilazane,
Dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, alkyl-modified silicone oil, chloroalkyl-modified silicone oil, chlorophenyl-modified silicone oil, fatty acid-modified silicone oil, polyether-modified silicone oil, alkoxy-modified silicone oil, carbinol-modified Silicone oils such as silicone oil, amino-modified silicone oil, fluorine-modified silicone oil, and terminal-reactive silicone oil;
Siloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane,
Long chain fatty acids such as undecylic acid, lauric acid, tridecylic acid, dodecylic acid, myristic acid, palmitic acid, pentadecylic acid, stearic acid, heptadecylic acid, arachidic acid, montanic acid, oleic acid, linoleic acid, arachidonic acid,
Salts of the above fatty acids with metals such as zinc, iron, magnesium, aluminum, calcium, sodium, lithium and the like.
Among these hydrophobizing agents, alkoxysilanes, silazanes, and silicone oil (particularly, straight silicone oil) are preferable in that the hydrophobizing treatment of the particles is easily performed. As the hydrophobizing agent, one type may be used alone, or two or more types may be used in combination.

  Examples of a method for incorporating the particles into the toner particles include a method in which the particles are added in a powder state in a suspension polymerization method or a solution suspension method, and a method in which the particles are dispersed in a liquid. Method. Among them, a method in which the particles are added in a state of being dispersed in a solvent of an organosilicon compound is preferable. The timing of adding the particles may be before the particles of the toner composition (polymerizable monomer composition or resin solution) are formed in the aqueous medium, or after the polymerization of the toner composition has progressed to some extent. May be. From the viewpoint of efficiently forming the irregularities derived from the particles on the toner surface, a method of adding the toner composition after the polymerization of the toner composition has progressed to some extent is preferable.

In the toner particles according to the present invention, the average length of a roughness curve element measured according to JIS B0601: 2001 is set to RSm1, and the toner particles are subjected to centrifugal separation in a sucrose solution to apply the toner particles to the surface of the toner particles. when the toner particles where the particles-adhesive strength is less separated was removed, and the average length of roughness curve element and RSM2, RSM2 / RSm1 is preferably 1.20 or less.

  Usually, various kinds of fine particles such as an external additive externally arranged on the surface of the toner particles include particles having a small adhesive force on the surface of the toner particles. Such particles having a small adhesive force may be released from the surface of the toner particles during running, and may cause a decrease in transferability of the toner. Therefore, it is preferable that the particles adhered to the surface of the toner particles maintain the initial state of adhesion as much as possible, and the present inventor indicates that the index capable of catching the easiness of the change in the state of adhesion is RSm2 / RSm1. Found them. That is, RSm1 is an index representing the average length of a roughness curve element formed on the surface of toner particles immediately after toner production, and RSm2 gives mechanical stress to the toner, and the adhesive force to the toner particle surface is reduced. It is an index representing the average length of the roughness curve element on the surface of the toner particles after removing small particles. RSm2 is an index that simulates the state of the toner particle surface after endurance subjected to stress such as rubbing and pressure.

Here, a method for separating and removing particles having a small adhesive force to the toner particle surface is specifically as follows.
160 g of sucrose (manufactured by Kishida Chemical) is added to 100 mL of ion-exchanged water and dissolved in a water bath to prepare a concentrated sucrose solution. In a centrifuge tube, 31 g of the sucrose concentrated solution and Contaminone (registered trademark) N (a neutral detergent for washing a precision measuring instrument having a pH of 7 consisting of a nonionic surfactant, an anionic surfactant and an organic builder). A 6% by mass aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. 1.0 g of the toner is added to this dispersion, and the lump of the toner is loosened with a spatula or the like.
The centrifuge tube is shaken with a shaker at 350 spm (strokes per min) for 20 min. After shaking, the solution is replaced with a swing rotor glass tube (50 mL), and separated by a centrifuge at 3500 rpm for 30 minutes. By this operation, the toner particles are separated from the particles having a small adhesive force on the surface of the toner particles separated from the toner particles. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the toner separated in the uppermost layer is collected with a spatula or the like. The collected toner is filtered with a reduced pressure filter and then dried for one hour or more with a dryer to obtain toner particles from which toner particles having small adhesion to the surface are separated and removed. Perform this operation several times to secure the required amount.

Usually, the value of RSm2 in a state where particles on the toner surface are partially removed is larger than RSm1. The larger the value of RSm2 / RSm1, the more easily the particles on the surface of the toner particles are peeled off, indicating that the transferability of the toner is likely to change. The toner particles of the present invention, this RSM2 / RSm1 thereof is preferably 1.20 or less, more preferably 1.10 or less. RSM2 / RSm1 is, by 1.20 or less, the ratio of particles adhesion is less on the toner particle surfaces is small, it is possible to provide a toner smaller transfer of the change through the durability. Further, RSM2 / RSm1 is, by 1.10 or less, the ratio of particles adhesion is less on the toner particle surfaces can be further reduced to 10% or less, not only the transfer of the change is small Thus, a toner having excellent durability can be obtained even under a wide range of environments and severe use conditions. RSm2 / RSm1 is in the above range by adjusting the method for producing toner particles during the formation of the organosilicon polymer, the hydrolysis during the formation of the organosilicon polymer, the reaction temperature during the polymerization, the reaction time, the reaction solvent and the pH, and the like. Can be controlled. It can also be controlled by the content of the organosilicon polymer. Further, it can also be controlled by adjusting the timing of adding the organosilicon polymer and the fine particles for forming unevenness in the step of forming unevenness on the surface of the toner particles.

In a chart obtained by ²⁹ Si-NMR measurement of a THF (tetrahydrofuran) insoluble content of the toner particles according to the present invention, a peak attributed to a structure represented by the following formula (4) with respect to the total peak area of the organosilicon polymer. A further favorable condition is that the area ratio is 40% or more.
Rf-SiO _3/2 (4)
(In the formula (4), Rf represents a partial structure represented by the following formula (iii) or (iv).)

  (In the formulas (iii) and (iv), * represents a bonding portion to a silicon atom. In the formula (iv), L represents a methylene group, an ethylene group, or a phenylene group.)

Although a detailed measurement method will be described later, the favorable condition is that the organosilicon polymer contained in the toner particles has a partial structure represented by —SiO _3/2 and a partial structure represented by the above formula (iii) or (iv). Approximately, it has 40% or more of both of the substructures.

As described above, the partial structure of —SiO _3/2 means that among the four valences of a silicon atom, three are bonded to an oxygen atom, and furthermore, those oxygen atoms are bonded to another silicon atom. . If one of the oxygen atoms is a silanol group, the partial structure of the organosilicon polymer is represented by Rf-SiO _2/2 -OH. Furthermore, if two oxygen atoms are silanol groups, the partial structure will be Rf-SiO1 _{/ 2} (-OH) ₂ . Comparing these structures, the case where more oxygen atoms form a crosslinked structure with silicon atoms is closer to the silica structure represented by SiO ₂ . Therefore, it is considered that the more the -SiO _3/2 skeleton, the harder the property and the higher the durability. On the other hand, when the oxygen atoms remain in the form of a silanol group and do not form a crosslinked structure, it is considered that the resinous properties are dominant and the durability is reduced.

In addition, the partial structure represented by the above formula (iii) or (iv) means that it reacts with various polymerizable monomers including a vinyl polymerizable monomer to form a crosslinked structure. I do. Therefore, it can be said that the structure represented by the formula (4) has both an inorganic network based on —SiO _{3/2 and} an organic network based on the above formula (iii) or (iv). As a result, the toner according to the present invention has a strong bonding force between the inorganic structure and the organic structure, and the durability is further improved. From the above, in order to further improve the durability and environmental stability, the ratio of the peak area attributed to the structure represented by the above formula (4) to the total peak area of the organosilicon polymer is 40% or more. Is preferred. The ratio of the peak area can be controlled by the method for producing the toner particles at the time of forming the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH at the time of forming the organosilicon polymer.

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

  The organosilicon polymer contained in the surface layer of the toner particles is specifically produced by hydrolytic polycondensation of an organosilicon compound represented by alkoxysilane. In the present invention, the organosilicon polymer is preferably an organosilicon polymer obtained by polymerizing a polymerizable monomer composition containing an organosilicon compound represented by the following formula (3). That is, a polymer having a unit derived from an organosilicon compound represented by the following formula (3) is preferable. By uniformly providing the surface layer formed in this way on the surface of the toner particles, the performance of the toner is deteriorated during long-term use without fixing or adhering the inorganic fine particles as in the conventional method. And a toner having excellent storage stability can be obtained.

  (In the formula (3), Rf represents a partial structure represented by the following formula (i) or (ii), and R1, R2 and R3 each independently represent a halogen atom, a hydroxy group, an acetoxy group or an alkoxy group. Represents a group.)

  (In the formulas (i) and (ii), * represents a bonding portion to a silicon atom. In the formula (ii), L represents a methylene group, an ethylene group, or a phenylene group.)

  The crosslinked structure by the siloxane bond (Si-O-Si) is formed by the hydrolysis, addition polymerization and condensation polymerization of the reactive groups R1 to R3 in the above formula (3). From the viewpoint of controllability of polymerization conditions and ease of forming a siloxane structure, R1 to R3 are preferably alkoxy groups. Alkoxy groups have mild hydrolyzability at room temperature. Further, from the viewpoints of the precipitability of the organosilicon polymer on the surface of the toner particles and the coating property, R1 to R3 are more preferably methoxy groups or ethoxy groups. The hydrolysis, addition polymerization and condensation polymerization of R1 to R3 can be controlled by the reaction temperature, reaction time, reaction solvent and pH.

  A typical production example of the organosilicon polymer according to the present invention is a production method called a sol-gel method. In the sol-gel method, hydrolysis and condensation polymerization are carried out in a solvent using a metal alkoxide M (OR) n (M: metal, O: oxygen atom, R: hydrocarbon, n: oxidation number of metal) as a starting material. This is a method of gelling through a sol state. The sol-gel method is used for synthesizing glass, ceramics, organic-inorganic hybrid, and nanocomposite. According to this production method, functional materials having various shapes such as a surface layer, a fiber, a bulk body, and fine particles can be produced from a liquid phase at a low temperature.

  Furthermore, the sol-gel method starts with a solution and forms a material by gelling the solution, so that various microstructures and shapes can be produced. In particular, when the toner particles are produced in an aqueous medium, the toner particles are likely to be present on the surface of the toner particles due to the hydrophilicity due to the hydrophilic group such as a silanol group in the organosilicon compound. However, when the organosilicon compound is too hydrophobic (for example, when the organosilicon compound has a highly hydrophobic functional group), it becomes difficult to deposit the organosilicon compound on the surface layer of the toner particles. It becomes difficult to form a surface layer containing a silicon polymer. On the other hand, when the hydrophobicity of the organosilicon compound is too small, the charge stability of the toner tends to decrease even if the organosilicon polymer is contained in the surface layer of the toner particles. The microstructure and shape can be adjusted by the reaction temperature, the reaction time, the reaction solvent, the pH, the type and the amount of the organosilicon compound, and the like.

  In order to obtain the organosilicon polymer, it is preferable to use one or more kinds of organosilicon compounds having a structure represented by the formula (3). Examples of the organosilicon compound having the structure represented by the formula (3) include the following. Vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane, vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyl Triacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyldimethoxy Hydroxysilane, vinylethoxymethoxyhydroxysila And trifunctional vinyl silanes such as vinyldiethoxyhydroxysilane; allyltrimethoxysilane, allyltriethoxysilane, allyldiethoxymethoxysilane, allylethoxydimethoxysilane, allyltrichlorosilane, allylmethoxydichlorosilane, allylethoxydichlorosilane, allyl Dimethoxychlorosilane, allylmethoxyethoxychlorosilane, allyldiethoxychlorosilane, allyltriacetoxysilane, allyldiacetoxymethoxysilane, allyldiacetoxyethoxysilane, allylacetoxydimethoxysilane, allylacetoxymethoxyethoxysilane, allylacetoxydiethoxysilane, allyltrihydroxy Silane, allyl methoxy dihydroxy silane, allyl ethoxy dihydroxy silane, allyl Methoxy hydroxy silane, allyl ethoxymethoxy hydroxy silane, trifunctional allylsilanes and allyl diethoxy hydroxy silane; p-styryltrimethoxysilane. As the organosilicon compound, one type may be used alone, or two or more types may be used in combination.

  In the organosilicon compound used for the synthesis of the organosilicon polymer, the proportion of the organosilicon compound represented by the formula (3) is preferably at least 50 mol%, more preferably at least 60 mol%. By setting the proportion of the organosilicon compound represented by the formula (3) to 50 mol% or more, the durability of the toner can be further reduced.

  Further, together with the organosilicon compound represented by the formula (3), an organosilicon compound having four reactive groups in one molecule (tetrafunctional silane), an organosilicon compound having three reactive groups in one molecule ( Trifunctional silane), an organosilicon compound having two reactive groups in one molecule (difunctional silane) or an organosilicon compound having one reactive group in one molecule (monofunctional silane) The obtained organosilicon polymer may be used. The following may be mentioned as the organosilicon compound that may be used in combination. Methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyl Triacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxy Hydroxysilane, methylethoxymethoxyhydroxysila , Trifunctional methylsilane such as methyldiethoxyhydroxysilane; trifunctional ethylsilane such as ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane; propyltrimethoxysilane; Trifunctional propylsilanes such as propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, and propyltrihydroxysilane; butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, and butyltrihydroxysilane Trifunctional butylsilane such as hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyl Trifunctional hexylsilanes such as tritrihydroxysilane; trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane and phenyltrihydroxysilane; dimethyldiethoxysilane, tetra Ethoxysilane, hexamethyldisilazane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl Rutriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriemethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilyl propyl) Pill) tetrasulfide, trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, t-butyldimethylsilyl chloride, N, N'-bis (trimethylsilyl) urea, N, O-bis (trimethylsilyl) trifluoroacetamide, trimethylsilyltrifluoro Methanesulfonate, 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane, trimethylsilylacetylene, hexamethyldisilane, 3-isocyanatopropyltriethoxysilane, tetraisocyanatesilane, methyltriisocyanatesilane, vinyltriisocyanatesilane .

In general, it is known that in a sol-gel reaction, the bonding state of siloxane bonds generated varies depending on the acidity of a reaction medium. Specifically, when the reaction medium is acidic, a hydrogen ion electrophilically attaches to an oxygen atom of one reactive group (for example, an alkoxy group (—OR group)). Next, the oxygen atom in the water molecule is coordinated to the silicon atom, and becomes a hydroxy group by a substitution reaction. When water is sufficiently present, one H ⁺ (proton) attacks one oxygen atom of a reactive group (for example, an alkoxy group or an OR group), so that H ^{+ in} the medium is increased as the reaction proceeds. When the content and the number of the reactive groups are reduced, the substitution reaction with the hydroxy group becomes slow. Therefore, a polycondensation reaction occurs before all the reactive groups of the silane are hydrolyzed, and a one-dimensional linear polymer or a two-dimensional polymer is relatively easily generated. On the other hand, when the medium is alkaline, hydroxide ions are added to silicon atoms and pass through a pentacoordinate intermediate. Therefore, all the reactive groups (for example, an alkoxy group or an OR group) are easily desorbed, and are easily replaced with silanol groups. In particular, when an organosilicon compound having three or more reactive groups in the same silane is used, hydrolysis and polycondensation occur three-dimensionally to form an organosilicon polymer having a large number of three-dimensional cross-linking bonds. Is done. In addition, the reaction is completed in a short time.

  Therefore, in order to form an organosilicon polymer, it is preferable that the sol-gel reaction proceed while the reaction medium is in an alkaline state, and specifically, when the reaction medium is produced in an aqueous medium, the pH is 8.0 or more. preferable. As a result, an organosilicon polymer having higher strength and excellent durability can be formed. The sol-gel reaction is preferably performed at a reaction temperature of 85 ° C. or more and a reaction time of 5 hours or more. By performing the sol-gel reaction at the above-described reaction temperature and reaction time, it is possible to suppress the formation of coalesced particles in which organosilicon compounds in a sol or gel state are bonded on the surface of the toner particles.

  Hereinafter, a specific method for producing the toner particles of the present invention will be described, but the present invention is not limited thereto.

  As the first production method, a polymerizable monomer for a binder resin, a colorant, and a polymerizable monomer composition containing an organosilicon compound are suspended and granulated in an aqueous medium, and a polymerizable monomer is prepared. This is a method (suspension polymerization method) of obtaining toner particles by polymerizing the polymer. If necessary, additives such as a charge control agent and a release agent may be added to the toner particles. The toner particles thus obtained are polymerized in a state where the organosilicon compound is deposited on the toner surface in the vicinity of the toner surface, so that a layer containing the organosilicon polymer can be formed on the toner particle surface. Another advantage is that the organosilicon compound is easily deposited uniformly. The suspension polymerization method is the most preferable production method from the viewpoint of uniformity of the layer containing the organosilicon polymer on the surface of the toner particles.

  The second production method is a method of forming a surface layer containing an organosilicon polymer in an aqueous medium after obtaining a toner base. The toner matrix may be obtained by melt-kneading and pulverizing a binder resin and a colorant, or may be obtained by aggregating and associating binder resin particles and colorant particles in an aqueous medium. Alternatively, a binder resin, an organosilicon compound and a colorant may be dissolved in an organic solvent to produce an organic phase dispersion, suspended in an aqueous medium, granulated, and obtained by removing the organic solvent after polymerization. Good. If necessary, additives such as a charge control agent and a release agent may be added to the toner particles.

  As a third production method, a binder resin, an organic silicon compound and a colorant are dissolved in an organic solvent, and an organic phase dispersion produced is suspended in an aqueous medium, granulated, polymerized, and then the organic solvent is removed. This is a method of obtaining toner particles by removing. If necessary, additives such as a charge control agent and a release agent may be added to the toner particles. Also in this method, the organic silicon compound is polymerized in a state where it is deposited on the toner surface in the vicinity of the toner particle surface.

  Preferred aqueous media in the present invention include water, alcohols such as methanol, ethanol and propanol, and mixed solvents thereof.

  Preferable examples of the polymerizable monomer in the suspension polymerization method include vinyl polymerizable monomers shown below. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p-methylstyrene Styrene derivatives such as n-hexylstyrene, pn-octyl, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene and p-phenylstyrene; methyl acrylate, ethyl Acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate Acrylic polymerizable monomers such as acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n- Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethylphos Phthate ethyl methacrylate, dibutyl phosphate ethyl methacrylate Methacrylic polymerizable monomers such as acrylates; methylene aliphatic monocarboxylic esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  In addition, the following may be mentioned as the polymerization initiator used in the polymerization. 2,2′-azobis- (2,4-divaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxy carbonate, cumene hydroperoxide, 2,4-dichloro Peroxide polymerization initiators such as benzoyl peroxide and lauroyl peroxide; These may be used alone or in combination of two or more. It is preferable that these polymerization initiators are added in an amount of 0.5 to 30.0% by mass based on the polymerizable monomer.

  The following resins can be used as a binder resin for the toner particles or as other additives for exhibiting a function, as long as the effects of the present invention are not affected. Styrenes such as polystyrene and polyvinyltoluene and their substituted homopolymers; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer , Styrene-butadier Styrene-based copolymers such as copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene , Polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacryl resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, and aromatic petroleum resin. One of these resins may be used alone, or two or more thereof may be used in combination.

  Further, in order to control the molecular weight of the binder resin constituting the toner particles, a chain transfer agent may be added at the time of polymerization. A preferable addition amount is 0.001 to 15,000 mass% based on the polymerizable monomer.

On the other hand, a crosslinking agent may be added at the time of polymerization in order to control the molecular weight of the binder resin constituting the toner particles. 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 type diacrylate (neopentyl glycol diacrylate hydroxypivalate, trade name: Kaya Head MANDA, manufactured by Nippon Kayaku Co., Ltd.), and more acrylate what was changed to methacrylate.
The following are mentioned as a polyfunctional crosslinkable monomer. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy / polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diarylchlorendate.
The crosslinking agent is preferably added in an amount of 0.001 to 15,000 mass% based on the polymerizable monomer.

  When the medium used in the suspension polymerization method 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 . The following are examples of the organic dispersant. Polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, starch. It is also possible to use commercially available nonionic, anionic, or cationic surfactants. Examples of such a surfactant include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.

The colorant used for the toner particles of the present invention is not particularly limited, and the following known colorants can be used.
As the yellow pigment, condensed azo compounds such as yellow iron oxide, Navels Yellow, Naphthol Yellow S, Hanza Yellow G, Hanza Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake, Isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, the following are mentioned. C. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment Yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment Yellow 180.
The orange pigments include the following. Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Benzidine Orange G, Indaslen Brilliant Orange RK, Indaslen Brilliant Orange GK.
Examples of red pigments include condensation of Bengala, Permanent Red 4R, Risor Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brirant Carmine 3B, Eoxin Lake, Rhodamine Lake B, Alizarin Lake, etc. Examples include azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following are mentioned. C. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 23, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 48: 4, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 81: 1, C.I. I. Pigment Red 122, C.I. I. Pigment red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 166, C.I. I. Pigment Red 169, C.I. I. Pigment Red 177, C.I. I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 202, C.I. I. Pigment Red 206, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221, C.I. I. Pigment Red 254.
Examples of blue pigments include copper phthalocyanine compounds such as alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, and indathrene blue BG, and derivatives thereof, anthraquinone compounds, and basic dyes. Lake compounds and the like. Specifically, the following are mentioned. C. I. Pigment Blue 1, C.I. I. Pigment Blue 7, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 62, C.I. I. Pigment Blue 66.
Examples of purple pigments include Fast Violet B and Methyl Violet Lake.
Examples of green pigments include Pigment Green B, Malachite Green Lake, and Final Yellow Green G.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of black pigments include carbon black, aniline black, non-magnetic ferrite, magnetite, and black tones using the above-mentioned yellow, red and blue colorants.
These colorants can be used singly or as a mixture of two or more, and further in the form of a solid solution. In addition, it is preferable that content of a coloring agent is 3.0-15.0 mass parts with respect to 100 mass parts of binder resins or polymerizable monomers.

  A charge control agent may be added to the toner particles according to the present invention, and known toners can be used. The charge control agent is preferably added in an amount of 0.01 to 10.00 parts by mass based on 100 parts by mass of the binder resin or the polymerizable monomer.

  A releasing agent may be added to the toner particles according to the present invention, and known toner particles can be used. The amount of the release agent to be added is preferably 1 to 30 parts by mass based on 100 parts by mass of the binder resin or the polymerizable monomer.

  In the toner of the present invention, various organic or inorganic fine powders may be externally added to the toner particles as needed. The particle size of the organic or inorganic fine powder is preferably 1/10 or less of the weight average particle size of the toner particles from the viewpoint of durability when added to the toner particles.

As the organic or inorganic fine powder, for example, the following are used.
(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black and carbon fluoride.
(2) Abrasives: metal oxides (eg, strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitrides (eg, silicon nitride), carbides (eg, silicon carbide), metal salts (eg, calcium sulfate, sulfuric acid) Barium, calcium carbonate).
(3) Lubricant: fluororesin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
(4) Charge controllable particles: metal oxides (eg, tin oxide, titanium oxide, zinc oxide, silica, alumina), and carbon black.

  As the organic or inorganic fine powder, a powder whose surface has been subjected to a hydrophobic treatment may be used in order to improve the fluidity of the toner and make the charge of the toner particles uniform. Examples of the treating agent for hydrophobizing the organic or inorganic fine powder include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, Organic titanium compounds may be mentioned. One of these treatment agents may be used alone, or two or more thereof may be used in combination.

  FIG. 3 is an example of an image forming apparatus capable of forming an image using the toner particles according to the present invention. The outline of the image forming process is as follows. An electrostatic latent image is formed on the photoconductor 1. The electrostatic latent image formed on the photoconductor is developed using the toner 4 on the developing roller 2 to form a toner image. The toner image is transferred to the transfer conveyance belt 16. By the action of the transfer bias applied to the transfer means, the toner image transferred on the transfer / conveyance belt 16 is transferred to a recording medium 18 such as paper. Then, the toner image transferred onto the recording medium 18 is fixed by the fixing device 21.

  Hereinafter, various measurement methods according to the present invention will be described.

<Concentration of silicon atoms present on the surface of toner particles (atomic%)>
The concentration (atomic%) of silicon atoms present on the surface of the toner particles according to the present invention was calculated by performing a surface composition analysis using X-ray photoelectron spectroscopy (ESCA).
In the present invention, the ESCA apparatus and measurement conditions are as follows.
Device used: Quantum2000, manufactured by ULVAC-PHI
X-ray photoelectron spectrometer measurement conditions: X-ray source Al Kα
X-ray: 100 μm 25 W 15 kV
Raster: 300 μm × 200 μm
PassEnergy: 58.70 eV StepSize: 0.125 eV
Neutralizing electron gun: 20 μA, 1 V Ar ion gun: 7 mA, 10 V
Sweep number: Si 15 times, C 10 times In the present invention, the surface atomic concentration (atomic%) was calculated from the measured peak intensity of each atom using a relative sensitivity factor provided by PHI.

<Method for confirming partial structure represented by formula (4)>
In the present invention, among the partial structures represented by the formula (4), the presence of the unit of Rf was confirmed by ¹³ C-NMR (solid) measurement. The measurement conditions and the sample preparation method are described below.

[Measurement conditions of ¹³ C-NMR (solid)]
Apparatus: manufactured by BRUKER, AVANCE III 500
Probe: 4mm MAS BB / 1H
Measurement temperature: room temperature Sample rotation speed: 6 kHz
Sample: 150 mg of a measurement sample (THF-insoluble content of toner particles for NMR measurement, preparation method is as described below) is placed in a sample tube having a diameter of 4 mm.
Measurement core frequency: 125.77 MHz
Reference substance: Glycine (external standard: 176.03 ppm)
Observation width: 37.88 kHz
Measurement method: CP / MAS
Contact time: 1.75ms
Repetition time: 4s
Number of integration: 2048 times LB value: 50 Hz

[Method for preparing measurement sample]
10.0 g of the toner particles were weighed, placed in a cylindrical filter paper (No. 86R, manufactured by Toyo Roshi Kaisha), subjected to a Soxhlet extractor, and extracted with 200 ml of tetrahydrofuran (THF) as a solvent for 20 hours. The product obtained by vacuum drying at a temperature of ° C for several hours is used as a sample for NMR measurement.

In the present invention, when the organic fine powder or the inorganic fine powder is externally added to the toner, the organic fine powder or the inorganic fine powder is removed by the following method to obtain toner particles.
160 g of sucrose (manufactured by Kishida Chemical) is added to 100 mL of ion-exchanged water and dissolved in a water bath to prepare a concentrated sucrose solution. In a centrifuge tube, 31 g of the above sucrose concentrate and 10% of a neutral detergent for washing a precision measuring instrument of pH 7 consisting of Contaminone (registered trademark) N (a nonionic surfactant, an anionic surfactant and an organic builder). A 6% by mass aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. 1.0 g of the toner is added to the dispersion, and the clumps of the toner particles are loosened with a spatula or the like.
The centrifuge tube is shaken with a shaker at 350 spm (strokes per min) for 20 min. After shaking, the solution is replaced with a swing rotor glass tube (50 mL), and separated by a centrifuge at 3500 rpm for 30 minutes. By this operation, the toner particles and the external additives separated from the toner particles are separated. It is visually confirmed that the toner particles and the aqueous solution are sufficiently separated, and the toner particles separated in the uppermost layer are collected with a spatula or the like. The collected toner particles are filtered by a reduced pressure filter, and then dried by a dryer for 1 hour or more to obtain toner particles. Perform this operation several times to secure the required amount.

When Rf is represented by the formula (iii), the presence or absence of a signal derived from a methine group (> CH—Si) bonded to a silicon atom confirms the presence of the unit represented by the formula (iii). I do. Also, if Rf is represented by the formula (iv), a methylene group bonded to the silicon atom _(Si-CH 2 -), ethylene group _{(Si-C 2 H 4 -} ), or a phenylene group (Si- The presence of the unit represented by the formula (iv) is confirmed by the presence or absence of a signal derived from C ₆ H ₄ −).

<Method of Measuring Ratio of Peak Area Attributable to Structure of Formula (4) Measured in ²⁹ Si-NMR of THF Insoluble Content of Toner Particles>
In the present invention, ²⁹ Si-NMR (solid) measurement of the THF-insoluble portion of the toner particles was performed under the following measurement conditions.

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

After the above measurement, a plurality of silane components having different substituents and bonding groups in the toner particles are separated into peaks by the curve fitting into the following X1, X2, X3, and X4 structures, and the peak area ratio is determined. The mole% of each component is calculated from the following.
X1 structure: (Ri) (Rj) (Rk) SiO _1/2 (6)
X2 structure: (Rg) (Rh) Si (O _1/2 ) ₂ (7)
X3 structure: RmSi (O _1/2 ) ₃ (8)
X4 structure: Si (O _1/2 ) ₄ (9)

  (In the formulas (6), (7) and (8), Ri, Rj, Rk, Rg, Rh and Rm represent an organic group, a halogen atom, a hydroxy group or an alkoxy group bonded to a silicon atom.)

In the present invention, the silane monomer is specified from the chemical shift value, and the area of the X1 structure, the area of the X2 structure and the area of the X3 structure obtained by removing the unreacted monomer component from the entire peak area in the ²⁹ Si-NMR measurement of the toner particles are determined. The total of the area of the structure and the area of the X4 structure was defined as the total peak area of the organosilicon polymer.
SX1 + SX2 + SX3 + SX4 = 1.00
SX1 = {area of X1 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX2 = {area of X2 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX3 = {area of X3 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX4 = {area of X4 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}

As described above, in the present invention, in the chart obtained by measuring ²⁹ Si-NMR of the THF-insoluble portion of the toner particles, it is assigned to the structure represented by the above formula (4) with respect to the total peak area of the organosilicon polymer. The ratio of the peak area to be obtained is preferably 40% or more. In this measurement method, the value indicating the -SiO3 _{/ 2} structure is SX3. That is, it is a preferable condition of the present invention that SX3 is 0.40 or more. When it is necessary to confirm the partial structure represented by the formula (4) in more detail, the partial structure is identified using the measurement results of ¹ H-NMR together with the measurement results of ¹³ C-NMR and ²⁹ Si-NMR. You may.

<Method for measuring arithmetic mean roughness (Ra) of toner particle surface by SPM, standard deviation of Ra (σRa), average length of roughness curve element (RSm), standard deviation of RSm (σRSm)>
The arithmetic average roughness (Ra), standard deviation of Ra (σRa), average length of a roughness curve element (RSm), and standard deviation of RSm (σRSm) by SPM are as follows. Was measured by
Scanning probe microscope: Hitachi High-Tech Science Corporation Measurement unit: E-sweep
Measurement mode: DFM (resonance mode) shape image Resolution: 256 X data, 128 Y data
Measurement area: 1 μm square

In the present invention, when the organic fine powder or the inorganic fine powder is externally added to the toner, a method similar to the method described in the method of preparing the measurement sample in the above ¹³ C-NMR (solid) measurement is used. The organic fine powder or the inorganic fine powder is removed to obtain toner particles.
As the toner particles, toner particles having a particle diameter equal to the weight average particle diameter (D4) measured by the Coulter counter method described later were selected and measured. In addition, ten different toner particles were measured.

[Calculation method of arithmetic average roughness (Ra)]
The measured data was analyzed on a “surface roughness analysis” screen in a “three-dimensional inclination correction” mode, and the average value of the obtained data was calculated to be the average surface roughness (Ra) of the toner particles.

[Definition and calculation method of Ra standard deviation (σRa)]
The standard deviation σRa of Ra was defined as follows. First, ten cross sections (cross section 1 to cross section 10) were arbitrarily selected from the measured 1 μm square measurement area. Here, the cross section 1 will be described as an example. As shown in FIG. 1, the area S _{i of} each area surrounded by each peak and each valley and the reference line length l of each area surrounded by each peak and each valley with reference to the average line of the roughness curve. _i was measured. Then, the height (depth) Ra _i of each peak and each valley from the reference line was calculated by the following equation.

For all peaks and valleys present on the reference line direction section 1, after calculating the Ra _i from the above equation, and the average value thereof was calculated Ra 'by the following equation.

  n: total number of peaks and valleys in section 1

  Subsequently, a standard deviation σRa ′ of Ra ′ in the cross section 1 was calculated by the following equation.

  n: total number of peaks and valleys in section 1

  After calculating all the above-mentioned σRa ′ in the cross section 1 to the cross section 10, the average value thereof was calculated and defined as the standard deviation σRa of Ra of the toner particles.

[Method of calculating average length (RSm) of roughness curve element]
The average length RSm of the roughness curve element was calculated as follows. First, ten cross sections (cross section 1 to cross section 10) were arbitrarily selected from the measured 1 μm square measurement area. Here, the cross section 1 will be described as an example. As in Figure 2, based on the average line of the roughness curve, the length RSm _i of the part one cycle of irregularities has occurred, it was measured for all of the irregularities cycles. Then, the average length RSm ′ of the roughness curve element in the cross section 1 was calculated by the following equation.

  n: total number of irregularity periods in section 1

  After calculating all of the above RSm's in the cross section 1 to the cross section 10, the average value was calculated and defined as the average length RSm of the roughness curve element of the toner particles.

[Method for calculating standard deviation of RSm (σRSm)]
The standard deviation σRSm of RSm was defined as follows. First, in the method for calculating the RSm 'of the cross section 1, the standard deviation σRSm' of the RSm 'in the cross section 1 was calculated by the following equation.

  n: total number of irregularity periods in section 1

  After calculating all of the above? RSm 'in the cross section 1 to the cross section 10, the average value thereof was calculated and defined as the standard deviation? RSm of the RSm of the toner particles.

<Method of Measuring Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner Particles>
The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner particles are measured by a precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, Beckman) using a pore electric resistance method equipped with a 100 μm aperture tube. -Coulter Corporation) and the dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (Beckman Coulter) for setting measurement conditions and analyzing measurement data, and the number of effective measurement channels is 2,500. Measure with 1000 channels, analyze the measured data and calculate. As the electrolytic aqueous solution used for the measurement, a solution prepared by dissolving a special grade sodium chloride in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter) can be used.

Before performing the measurement and analysis, the dedicated software is set as follows.
In the “Change standard measurement method (SOM) screen” of the dedicated software, set the total count number in the control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained by using the following method. Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, the current is set to 1600 μA, the gain is set to 2, and the electrolytic solution is set to ISOTON II, and a check mark is placed in the flash of the aperture tube after the measurement.
On the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measuring method is as follows.
(1) Approximately 200 ml of the aqueous electrolytic solution is placed in a glass 250 ml round bottom beaker dedicated to Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 revolutions / second. Then, the dirt and air bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat bottom glass beaker, and “Contaminon (registered trademark) N” (a nonionic surfactant, an anionic surfactant, and an organic builder) is contained therein as a dispersant. About 0.3 ml of a diluting solution obtained by diluting a 10% by mass aqueous solution of a neutral detergent for washing a precision measuring instrument with a pH of 7 (manufactured by Wako Pure Chemical Industries, Ltd.) three times by mass with ion-exchanged water is added.
(3) Two oscillators having an oscillation frequency of 50 kHz are built in a state shifted by 180 degrees, and are placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetra 150” (manufactured by Nikkaki Bios) having an electric output of 120 W. A predetermined amount of ion-exchanged water is charged, and about 2 ml of the contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the aqueous electrolytic solution in the beaker becomes maximum.
(5) About 10 mg of toner particles are added little by little to the aqueous electrolytic solution in the beaker of (4) while irradiating the aqueous electrolytic solution with ultrasonic waves, and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. The ultrasonic dispersion is appropriately adjusted so that the water temperature in the water tank is 10 ° C. or more and 40 ° C. or less.
(6) The electrolytic solution of (5) in which toner particles are dispersed is dropped using a pipette into the round bottom beaker of (1) installed in the sample stand, and adjusted so that the measured concentration is about 5%. I do. Then, measurement is performed until the number of particles to be measured reaches 50,000.
(7) Analyze the measured data with the dedicated software attached to the device, and calculate the weight average particle size (D4). The “average diameter” of the analysis / volume statistical value (arithmetic average) screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4), and the graph / number% is set by the dedicated software. The “average diameter” on the “analysis / number statistical value (arithmetic average)” screen at this time is the number average particle diameter (D1).

  Hereinafter, the present invention will be described in more detail with reference to specific production methods, examples, and comparative examples, but this does not limit the present invention in any way. All parts in the following formulations are parts by mass.

<Production Example of Silica Particle 1>
To a 3 L glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 589.6 g of methanol, 42.0 g of water, and 47.1 g of 28% by mass aqueous ammonia were added and mixed. The obtained solution was adjusted to 35 ° C., and 1100.0 g (7.23 mol) of tetramethoxysilane and 395.2 g of 5.4 mass% aqueous ammonia were simultaneously added with stirring. Tetramethoxysilane was added dropwise over 6 hours, and ammonia water was added over 5 hours. After completion of the dropwise addition, the mixture was further stirred for 0.5 hour to carry out hydrolysis to obtain a methanol-water dispersion of hydrophilic spherical sol-gel silica fine particles. Next, an ester adapter and a cooling tube were attached to a glass reactor, and the dispersion was dried sufficiently at 80 ° C. under reduced pressure. The obtained silica particles were heated in a thermostat at 400 ° C. for 10 minutes.
The above steps were performed a plurality of times, and the obtained silica particles were subjected to a crushing treatment with a pulverizer (manufactured by Hosokawa Micron Corporation).
Then, as a surface treatment step, first, 500 g of silica particles were charged into a polytetrafluoroethylene inner cylinder stainless steel autoclave having an inner volume of 1000 mL. Next, the inside of the autoclave was replaced with nitrogen gas. Thereafter, 3.5 g of HMDS (hexamethyldisilazane (surface treatment agent)) and 1.0 g of water were atomized with a two-fluid nozzle while the stirring blade attached to the autoclave was rotated at 400 rpm to form silica particles. Sprayed to make it even. After stirring for 30 minutes, the autoclave was sealed and heated at 200 ° C. for 2 hours. Subsequently, deammonia treatment was performed by reducing the pressure in the system while heating, and silica particles 1 were obtained.

  The average primary particle size of the silica particles 1 was measured as follows. The silica particles were observed with a transmission electron microscope, and the average value of the major axes was calculated for 300 primary particles having a major axis of 1 nm or more in a visual field enlarged to 30,000 to 50,000 times. When the sampled particles are too small to measure the particle size even at a magnification of 50,000 times, the photograph is further enlarged and measured so that the primary particle size of the particles in the photograph is 5 mm or more. Was. Table 1 shows the physical properties of the silica particles 1.

<Production Example of Silica Particles 2 and 3>
In the production example of silica particles 1, silica particles 2 were prepared in the same manner as silica particles 1 except that the amount of methanol initially used was changed from 589.6 g to 835.4 g and 277.6 g, respectively. And 3 were produced. By this change, the volume average particle diameter (Dv) of the silica particles and the coefficient of variation in the volume particle size distribution were adjusted. Table 1 shows the physical properties of the silica particles 2 and 3.

<Production example of silica particles 4>
In the production example of the silica particles 1, except that the dropping time of tetramethoxysilane was changed from 6 hours to 3 hours and the dropping time of the 5.4 mass% aqueous ammonia was changed from 5 hours to 3 hours, Silica particles 4 were produced in the same manner as in 1. By this change, the coefficient of variation in the volume particle size distribution of the silica particles was adjusted. Table 1 shows the physical properties of the silica particles 4.

<Production example of silica particles 5>
Silica particles 5 were produced in the same manner as the silica particles 1 except that the HMDS treatment was not performed in the production example of the silica particles 1. Table 1 shows the physical properties of the silica particles 5.

<Production Example of Silica Particles 6 and 7>
In the production example of silica particles 1, silica particles 6 were prepared in the same manner as silica particles 1 except that the amount of methanol used first was changed from 589.6 g to 1004.5 g and 187.3 g, respectively. , 7 were produced. By this change, the volume average particle diameter (Dv) of the silica particles and the coefficient of variation in the volume particle size distribution were adjusted. Table 1 shows the physical properties of the silica particles 6 and 7.

<Production example of silica particles 8>
In the production example of the silica particles 1, the dropping time of tetramethoxysilane was changed from 6 hours to 1 hour, and the dropping time of 5.4 mass% aqueous ammonia was changed from 5 hours to 1 hour. A silica particle 8 was prepared in the same manner as the silica particle 1 except that the process was not performed. By this change, the coefficient of variation in the volume particle size distribution of the silica particles was adjusted. Table 1 shows the physical properties of the silica particles 8.

<Production example of titania particles 1>
The ilmenite ore containing 50% by mass of TiO ₂ equivalent was dried at 150 ° C. for 3 hours, and then dissolved by adding sulfuric acid to obtain an aqueous solution of TiOSO ₄ . After concentrating the obtained aqueous solution, 10 parts by mass of titania sol having rutile crystals as a seed was added, and then hydrolysis was performed at 170 ° C. to obtain a slurry of metatitanic acid (TiO (OH) ₂ ) containing impurities. . This slurry was repeatedly washed at pH 5 to 6 to sufficiently remove sulfuric acid, FeSO ₄ and impurities to obtain a highly pure slurry of metatitanic acid. After the slurry was filtered, 0.5 parts by mass of lithium carbonate (Li ₂ CO ₃ ) was added, and the mixture was calcined at 240 ° C. for 4 hours. Fine particles were obtained.
While dispersing the obtained titanium oxide fine particles in ethanol and stirring, 5 parts by mass of isobutyltrimethoxysilane as a surface treatment agent was dropped and mixed with 100 parts by mass of the titanium oxide fine particles and reacted. After drying, the mixture was heat-treated at 170 ° C. for 3 hours, and repeatedly subjected to a crushing treatment with a jet mill until the aggregates of titanium oxide disappeared, whereby titania particles 1 were obtained. Table 1 shows the physical properties of the titania particles 1.

<PMMA particles 1>
As the PMMA particles 1, polymethyl methacrylate resin fine particles (cross-linked PMMA particles, MP1451, manufactured by Soken Chemical Co., Ltd.) were used. Table 1 shows the physical properties of PMMA particles 1.

<Production example of polyester resin 1>
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirrer, the following monomers were charged, and the mixture was reacted at 220 ° C. for 15 hours under a nitrogen atmosphere under normal pressure. Further, the reaction was carried out under a reduced pressure of 10 to 20 mmHg for 1 hour to obtain a polyester resin 1. Polyester resin 1 had a Tg (glass transition temperature) of 75.0 ° C. and an acid value of 8.1.
21 parts by mass of terephthalic acid 21 parts by mass of isophthalic acid 89.5 parts by mass of bisphenol A-propylene oxide 2 mol adduct 23.0 parts by mass of bisphenol A-propylene oxide 3 mol adduct 20.0 parts by mass of potassium oxalate 0. 030 parts by mass

<Production example of polyester resin 2>
・ 11.0 mol of terephthalic acid ・ 2 mol of bisphenol A-propylene oxide adduct (PO-BPA) 10.9 mol The above monomers are charged into an autoclave together with an esterification catalyst, and then a decompression device, a water separation device, and a nitrogen gas introduction device are used. , A temperature measuring device and a stirring device were attached to an autoclave. The reaction was carried out at 210 ° C. under a reduced pressure under a nitrogen atmosphere at 210 ° C. until the Tg reached 68 ° C., to obtain a polyester resin 2. The polyester resin 2 had a weight average molecular weight (Mw) of 7,360 and a number average molecular weight (Mn) of 2,980.

<Production example of polyester resin 3>
-725 parts by mass of bisphenol A ethylene oxide 2 mol adduct-290 parts by mass of phthalic acid-3.0 parts by mass of dibutyltin oxide The above materials are stirred at 220 ° C and reacted for 7 hours, and further reacted under reduced pressure for 5 hours. Thereafter, the mixture was cooled to 80 ° C. and reacted with 190 parts by mass of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate group-containing prepolymer. Next, 25 parts by mass of an isocyanate group-containing prepolymer and 1 part by mass of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a polyester resin 3 containing a urea group-containing polyester as a main component. The obtained polyester resin 3 had a weight average molecular weight (Mw) of 21,600, a number average molecular weight (Mn) of 3,040, and a peak molecular weight of 7,100.

<Production Example of Toner Particle 1>
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen inlet tube, 700 parts by mass of ion-exchanged water, 1000 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, 1.0 part by mass 22.0 parts by weight of a molar / liter aqueous HCl solution were added. The mixture was maintained at 60 ° C. while stirring at 12,000 rpm using a high-speed stirrer TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Here, 85 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . Thereafter, a polymerizable monomer composition was prepared using the following raw materials.
75.0 parts by mass of styrene monomer 25.0 parts by mass of n-butyl acrylate 0.1 part by mass of divinylbenzene 8.0 parts by mass of organosilicon compound (vinyltriethoxysilane) 8.0 parts by mass of copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 parts by mass, polyester resin 1 5.0 parts by mass, charge control agent (Bontron E-88, manufactured by Orient Chemical Co.) 0.7 parts by mass, release agent (paraffin wax, HNP-5, Japan) 9.0 parts by mass The above raw materials were dispersed with an attritor (manufactured by Nippon Coke Industry Co., Ltd.) for 3 hours to obtain a polymerizable monomer composition. Next, this polymerizable monomer composition was transferred to another container, and kept at 60 ° C. for 20 minutes with stirring. Then, 16.0 parts by mass of t-butyl peroxypivalate as a polymerization initiator (toluene (50% solution) and held for 5 minutes with stirring. Next, the polymerizable monomer composition was charged into the aqueous dispersion medium, and granulated for 10 minutes while stirring with a high-speed stirring device. Thereafter, the high-speed stirring device was changed to a propeller-type stirrer, the internal temperature was raised to 70 ° C., and the mixture was reacted for 4 hours while stirring slowly to obtain a polymer slurry (1 reaction step). pH was 5.5.
On the other hand, 1.5 parts by mass of silica particles 1 and 3.0 parts of vinyltriethoxysilane were charged into an autoclave equipped with a nitrogen gas introducing device, a temperature measuring device and a stirring device, and were charged under a nitrogen atmosphere under normal pressure. The reaction was performed at 5 ° C. for 5 hours to prepare a silica particle dispersion. After the silica particle dispersion was added to the polymer slurry after the completion of the first reaction step, the temperature in the vessel was raised to 85 ° C. and maintained for 3.0 hours (second reaction step).
Next, 300 parts by mass of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. The distillation in which the temperature in the vessel was 100 ° C. was performed for 4 hours to remove the residual monomer and toluene, thereby obtaining a polymer slurry (3 reaction steps).
Next, after cooling the inside of the vessel to 85 ° C., 13.0 parts by mass of 1.0 mol / liter NaOH was added to maintain the temperature at 9.0 while maintaining the temperature. Thereafter, the reaction was further carried out at 85 ° C. for 4 hours (4 reaction steps). Dilute hydrochloric acid was added to the vessel containing the polymer slurry after cooling to 30 ° C. to remove the dispersion stabilizer. Further, after filtering, washing and drying, fine coarse powder was cut by air classification to obtain toner particles 1. Tables 2 and 3 show the formulation and conditions of the toner particles 1, and Table 4 shows the physical properties.

<Production Examples of Toner Particles 2 to 12, 14, and 15>
Except for changing the composition amount and the production conditions of the polymerizable monomer composition shown in Table 2, and the organosilicon compound and the large-diameter particles shown in Table 3, the toner was manufactured according to the production example of the toner particles 1. Particles 2, 4 to 12, 14, and 15 were obtained. Table 4 shows the physical properties of the obtained particles. The method of vacuum distillation in the three reaction steps is as follows.
In a propeller-type stirring apparatus, distillation was performed under reduced pressure at 80 ° C. and a pressure of 13.3 kPa (100 Torr) or less while stirring at 100 r / min to remove residual monomers and terminate the reaction. Thereafter, the remaining monomer and toluene were removed.

<Production Example of Toner Particle 13>
In the production example of the toner particles 1, the method of adding the silica particle dispersion was changed as follows. First, 1.5 parts by mass of silica particles 1 and 3.0 parts of vinyltriethoxysilane were charged into an autoclave equipped with a nitrogen gas introducing device, a temperature measuring device, and a stirring device, and heated at 70 ° C. under a nitrogen atmosphere under normal pressure. For 5 hours to prepare a silica particle dispersion. This silica particle dispersion was divided into two equal portions in two containers to obtain a silica particle dispersion A and a silica particle dispersion B. First, the silica particle dispersion liquid A was added to the polymer slurry after one step of the reaction. Thereafter, the silica particle dispersion liquid B was added to the polymer slurry in which the three reaction steps were completed, and the four reaction steps were allowed to proceed. Except for this, toner particles 13 were obtained in the same manner as for toner particles 1. Table 4 shows the physical properties of the obtained particles.

<Production Example of Toner Particle 16>
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen inlet tube, 700 parts by mass of ion-exchanged water, 1000 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, 1.0 part by mass 22.0 parts by weight of a molar / liter aqueous HCl solution were added. The mixture was maintained at 60 ° C. while stirring at 12,000 rpm using a high-speed stirrer TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Here, 85 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . Thereafter, a polymerizable monomer composition was prepared using the following raw materials.
・ Styrene monomer 75.0 parts by mass ・ N-butyl acrylate 25.0 parts by mass ・ Divinylbenzene 0.1 parts by mass ・ Organic silicon compound (vinyl triethoxysilane) 8.0 parts by mass ・ Silica particles 5 1.5 parts by mass 6.5 parts by mass of copper phthalocyanine pigment (Pigment Blue 15: 3) 5.0 parts by mass of polyester resin 1 0.7 parts by mass of charge control agent (Bontron E-88, manufactured by Orient Chemical Company) 0.7 part by mass (Paraffin wax, HNP-5, manufactured by Nippon Seiro, melting point: 60 ° C.) 9.0 parts by mass The above raw materials were dispersed for 3 hours with an attritor (manufactured by Nippon Coke Industries, Ltd.) to obtain a polymerizable monomer composition. Next, this polymerizable monomer composition was transferred to another container, and kept at 60 ° C. for 20 minutes with stirring. Then, 16.0 parts by mass of t-butyl peroxypivalate as a polymerization initiator (toluene (50% solution) and held for 5 minutes with stirring. Next, the polymerizable monomer composition was charged into the aqueous dispersion medium, and granulated for 10 minutes while stirring with a high-speed stirring device. Thereafter, the high-speed stirring device was changed to a propeller-type stirrer, the internal temperature was raised to 70 ° C., and the reaction was carried out for 4 hours while stirring slowly (reaction one step). pH was 5.5.
Thereafter, the temperature in the vessel was raised to 85 ° C. and maintained for 3.0 hours (reaction 2 step).
Next, 300 parts by mass of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. The distillation in which the temperature in the vessel was 100 ° C. was performed for 4 hours to remove the residual monomer and toluene, thereby obtaining a polymer slurry (3 reaction steps).
Next, after cooling the inside of the vessel to 85 ° C., 13.0 parts by mass of 1.0 mol / liter NaOH was added to maintain the temperature at 9.0 while maintaining the temperature. Thereafter, the reaction was further carried out at 85 ° C. for 4 hours (4 reaction steps). Dilute hydrochloric acid was added to the vessel containing the polymer slurry after cooling to 30 ° C. to remove the dispersion stabilizer. Further, after filtering, washing and drying, fine coarse powder was cut by air classification to obtain toner particles 16. The formulations and conditions of the toner particles 16 are shown in Tables 2 and 3, and the physical properties are shown in Table 4.

<Production Example of Toner Particle 17>
60.0 parts by mass of polyester resin 2 40.0 parts by mass of polyester resin 3 6.5 parts by mass of copper phthalocyanine pigment (Pigment Blue 15: 3) 5.0 parts by mass of organosilicon compound (vinyltriethoxysilane) Parts: charge control agent (Bontron E-88, manufactured by Orient Chemical Co.) 0.7 parts by mass Release agent (paraffin wax, HNP-5, manufactured by Nippon Seiro, melting point 60 ° C.) 9.0 parts by mass And 400 parts by mass of toluene to obtain a solution.
In a four-necked container equipped with a Liebig reflux tube, 700 parts by mass of ion-exchanged water, 1000 parts by mass of a 0.1 mol / L aqueous solution of Na ₃ PO _4, and 22.0 parts of a 1.0 mol / L aqueous HCl solution were added. Parts by weight were added. The mixture was maintained at 60 ° C. while stirring at 12,000 rpm using a high-speed stirrer TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Here, 85 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .
Next, 100 parts by mass of the above-mentioned solution was added with stirring at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and the mixture was stirred for 5 minutes. Next, the mixture was kept at 70 ° C. for 5 hours to obtain a polymer slurry. pH was 5.5.
On the other hand, 1.5 parts by mass of silica particles 1 and 3.0 parts of vinyltriethoxysilane were charged in an autoclave equipped with a nitrogen gas introducing device, a temperature measuring device, and a stirring device, and were charged under a nitrogen atmosphere under normal pressure. The reaction was performed at 5 ° C. for 5 hours to prepare a silica particle dispersion. The prepared silica particle dispersion was charged into the polymer slurry, and the inside of the vessel was heated to 85 ° C. and held for 3 hours. Thereafter, 300 parts by mass of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. Next, distillation at a temperature in the container of 100 ° C. was performed for 4 hours to obtain a polymer slurry. Thereafter, the temperature in the vessel was adjusted to 85 ° C., and 13.0 parts by mass of 1.0 mol / liter NaOH was added to adjust the pH to 9.0. The reaction was allowed to proceed at 85 ° C. for another 4 hours. Dilute hydrochloric acid was added to the vessel containing the polymer slurry to remove the dispersion stabilizer. Further, the resultant was filtered, washed, dried, and cut into fine coarse powder by air classification to obtain toner particles 17. Table 4 shows the physical properties of the obtained toner particles.

<Production Examples of Comparative Toner Particles 1 and 3 to 7>
A comparison was made according to the production example of the toner particles 1 except that the composition amount and the production conditions of the polymerizable monomer composition shown in Table 2 and the organosilicon compound and the large-diameter particles shown in Table 3 were changed. Toner particles 1 and comparative toner particles 3 to 7 were obtained. Table 4 shows the physical properties of the obtained toner particles.

<Production Example of Comparative Toner Particle 2>
The composition amount and production conditions of the polymerizable monomer composition shown in Table 2 were changed to the organosilicon compound and large-diameter particles shown in Table 3, and an aqueous NaOH solution was added in four steps of the reaction. Comparative toner particles 2 were obtained in the same manner as in the preparation of toner particles 1 except that the addition of dilute hydrochloric acid after the completion of the four reaction steps was not performed. Table 4 shows the physical properties of the obtained toner particles.

<Production Example of Comparative Toner Particle 8>
In the production example of the toner particles 1, the method of adding the silica particle dispersion was changed as follows. First, 1.5 parts by mass of silica particles 1 and 3.0 parts of vinyltriethoxysilane were charged into an autoclave equipped with a nitrogen gas introducing device, a temperature measuring device, and a stirring device. The reaction was performed at 5 ° C. for 5 hours to prepare a silica particle dispersion. This silica particle dispersion was divided into three equal portions in three containers to obtain a silica particle dispersion C, a silica particle dispersion D, and a silica particle dispersion E. First, the silica particle dispersion C was added to the polymer slurry after one step of the reaction. Next, after the completion of the third reaction step, the temperature in the vessel was set at 65 ° C., the silica particle dispersion D was added to the polymer slurry, and the fourth reaction step was started. Further, 2.0 hours after the start of the four reaction steps, the silica particle dispersion E was added to the polymer slurry. Except for this, comparative toner particles 8 were obtained in the same manner as in the production example of toner particles 1. Table 4 shows the physical properties of the obtained toner particles.

[Example 1]
A laser beam printer LBP9510C of tandem type having a configuration shown in FIG. 3 made by Canon was modified to enable printing only with a cyan station. The process speed was set to 300 mm / sec by changing gears and software of the evaluation machine main body. In addition, it was modified so that the back contrast and transfer current could be set arbitrarily. Here, the back contrast is a potential difference for providing a difference between the potential of the toner carrier and the potential of the electrostatic image carrier in the non-image portion, and controlling the toner so as not to be developed to the non-image portion as much as possible.
As a cartridge used for evaluation, a cyan cartridge was used. That is, the product toner was extracted from a commercially available cyan cartridge, the inside was cleaned by air blowing, and then the toner particles according to the present invention obtained above were filled, and the toner was evaluated. In each of the magenta, yellow, and black stations, product toner was extracted, and magenta, yellow, and black cartridges with the toner remaining amount detection mechanism disabled were inserted and evaluated.

  Using this toner cartridge for LBP9510C, 200 g of toner particles 1 were filled (toner 1). Then, the toner cartridge was left for 24 hours under a high temperature and high humidity (32.5 ° C./85% RH) environment (HH environment). After standing for 24 hours in a high-temperature, high-humidity environment, the toner cartridge is mounted on the LBP9510C, and an image with a printing ratio of 1.0% is printed in A4 paper lateral direction, intermittent mode (that is, the developing unit is stopped for 10 seconds every time two sheets are printed out). Then, printing was performed up to 20,000 sheets in a mode in which the deterioration of the toner is promoted by the preliminary operation of the developing device at the time of restarting. Evaluation of fog latitude, transfer latitude, charging uniformity, and toner deterioration at the initial stage and at the time of output of 20,000 sheets (after endurance) were performed by the following methods. Table 5 shows the results.

<Evaluation of cabriolet latitude>
The back contrast was changed in steps of 10 V from 40 V to 400 V, and a white background image (image with a printing ratio of 0%) was printed on each of them, and an amber filter was attached to “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.). Fog was measured. The operation was performed at the initial stage and after printing 20,000 sheets. The measured value of fog is a fog density (%) obtained by subtracting the measured value of the image of the entire white background from the measured value of unused paper. FIG. 4 shows a measurement example of Example 1. The range in which the fog concentration was within 2.0% was defined as fog latitude. Approximately, when the fog density exceeds 3.5%, it tends to be recognized as an image defect. Therefore, when the fog latitude within which the fog density falls within 2.0% is 90 V or more, it was determined that the superiority of the fog control design was exhibited. The evaluation criteria are shown below.
A: fog latitude 250 V or more B: fog latitude 150 V to less than 250 V C: fog latitude 90 V to less than 150 V D: fog latitude 50 V to less than 90 V E: fog less than 50 V

<Evaluation of transfer latitude>
At the initial stage and after printing 20,000 sheets, the transfer current is changed in steps of 2 μA between 2 and 20 μA, a solid image is output in each case, and the transfer residual toner on the photoreceptor after the solid image transfer is taped with Mylar tape. And stripped off. Thereafter, the tape and the untaped tape were affixed to LETTER size XEROX 4200 paper (XEROX, 75 g / m ² ). The value obtained by subtracting the reflectance Dr (%) of the tape affixed without taping from the reflectance Ds (%) of the tape was used as a value representing the transferability. The transfer current range where the value of the transfer property was 2.0 or less was defined as the transfer latitude. The reflectance was measured using "REFLECMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.) with an amber filter attached. The evaluation criteria are shown below.
A: Transcription latitude 13 μA or more B: Transcription latitude 10 μA or more and less than 13 μA C: Transcription latitude 7 μA or more and less than 10 μA D: Transcription latitude 4 μA or more and less than 7 μA E: Transcription latitude 4 μA or less

<Evaluation of charging uniformity>
The particle size distribution of the toner in the cartridge at the initial stage and after printing 20,000 sheets is measured in accordance with the above-mentioned method of measuring the weight average particle diameter (D4). From the obtained weight average particle diameters (D4), the following equation is obtained. A particle size change index was calculated based on the above, and the evaluation was performed based on the following criteria. The more uniform the charge distribution of each toner, the more uniformly the toner of each particle size is consumed by the endurance use. Therefore, the change index of the weight average particle size (D4) approaches 100.
Particle size change index (%) = (initial weight average particle size (D4) / weight average particle size after printing 20,000 sheets (D4)) × 100
A: 95 ≦ particle size change index (%) ≦ 100
B: 85 ≦ particle size change index (%) <95
C: 75 ≦ particle size change index (%) <85
D: Particle size change index (%) <75

<Evaluation of toner deterioration>
Evaluation of toner deterioration was performed by calculating the rate of change in solid image density at the initial stage and after printing 20,000 sheets. That is, from each of the obtained concentrations, the rate of change in the concentration was calculated based on the following equation, and the evaluation was performed based on the following criteria.
Density change rate (%) = (solid image density after printing 20,000 sheets / initial solid image density) × 100
A: 95 ≦ density change rate (%) ≦ 100
B: 85 ≦ density change rate (%) <95
C: 75 ≦ concentration change rate (%) <85
D: Concentration change rate (%) <75

[Examples 2 to 17, Comparative Examples 1 to 8]
The toners 2 to 17 and the comparative toners 1 to 8 were evaluated in the same manner as in Example 1 using the toner particles 2 to 17 and the comparative toner particles 1 to 8. Table 5 shows the results.

1: photosensitive member, 2: developing roller, 3: toner supply roller, 4: toner, 5: regulating blade, 6: developing device, 7: laser beam, 8: charging device, 9: cleaning device, 10: charging for cleaning Apparatus, 11: stirring blade, 12: drive roller, 13: transfer roller, 14: bias power supply, 15: tension roller, 16: transfer conveyance belt, 17: driven roller, 18: paper, 19: paper feed roller, 20: Suction roller, 21: fixing device

Claims (6)

A toner comprising toner particles having a surface layer containing an organosilicon polymer,
The organosilicon polymer has a partial structure represented by the following formula (1) or (2),
In X-ray photoelectron spectroscopic analysis of the surface of the toner particles, wherein the surface of the toner particles, the concentration of carbon atoms dC, the concentration of oxygen atoms dO, and the total concentration dSi of the silicon atoms when the 100.0 atomic% , the concentration dSi of the silicon atoms is at 22.2 atomic% or less 1.0 atomic% or more,
In the roughness curve measured with a scanning probe microscope of the toner particles, JIS B0601: Arithmetic Average Roughness Ra (nm) measured on the basis of 2001, is a 10nm or more 300nm or less,
When the standard deviation of the Ra and σRa (nm), σRa / Ra is, it is 0.60 or less,
In the roughness curve, the toner particles JIS B0601: average length of roughness curve element to be measured on the basis of the 2001 RSm (nm) is, is at 20nm or more 500nm or less,
When the standard deviation of the RSm and σRSm (nm), the toner, wherein the ShigumaRSm / RSm is 0.60 or less.

(In the formula (2), L represents a methylene group, an ethylene group, or a phenylene group.) The average length of a roughness curve element measured based on JIS B0601: 2001 of the toner particles is set to RSm1, and the toner particles are subjected to centrifugal separation in a sucrose solution to obtain particles having a small adhesive force to the surface of the toner particles. the separating off the toner particles, when the average length of the roughness curve element and RSM2, RSM2 / RSm1 is 1.20 or less, toner according to claim 1. The RSM2 / RSm1 is 1.10 or less, toner according to claim 2. The toner according to any one of claims 1 to 3, wherein the organosilicon polymer is a polymer containing a unit derived from an organosilicon compound represented by the following formula (3).

(In the formula (3), Rf represents a partial structure represented by the following formula (i) or (ii), and R1, R2 and R3 each independently represent a halogen atom, a hydroxy group, an acetoxy group or an alkoxy group. Represents a group.)

(In the formulas (i) and (ii), * represents a bonding portion to a silicon atom. In the formula (ii), L represents a methylene group, an ethylene group, or a phenylene group.) The toner according to any one of claims 1 to 4, wherein the concentration dSi of the silicon atom is 9.0 atom% or more and 22.2 atom%. Tetrahydrofuran insoluble content of the toner particles ²⁹ In a chart obtained by Si-NMR measurement, a ratio of a peak area attributed to a structure represented by the following formula (4) to a total peak area of the organosilicon polymer is 40% or more. The toner according to claim 1.
Rf-SiO _3/2     (4)
(In the formula (4), Rf represents a partial structure represented by the following formula (iii) or (iv).)

(In the formulas (iii) and (iv), * represents a bonding portion to a silicon atom. In the formula (iv), L represents a methylene group, an ethylene group, or a phenylene group.)

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