JP7614925B2 - toner - Google Patents

Description

The present invention relates to a toner used in an electrophotographic image forming device.

In recent years, as full-color electrophotographic copying machines have become widespread, there has been a demand for higher image quality and energy saving. In particular, due to the increased process speed and high durability, there has been a demand for toners with more stable charging performance and fluidity than ever before. Toners contain external additives to impart charging performance and fluidity. In general, to increase the fluidity of toners, it is better to use external additives with small primary particle diameters, but after long-term use, small-particle external additives are embedded in toner particles and cannot function as external additives. In addition, with long-term use, external additives are detached from the surface of toner particles, causing changes in fluidity and charging performance, which causes contamination of components such as photosensitive drums and charging rollers.
Patent Document 1 proposes that by incorporating polyorganosilsesquioxane microparticles into an external additive and specifying the particle size and the state of the binder resin contained in the toner base particles, the polyorganosilsesquioxane microparticles will not be detached, thereby preventing image defects and contamination inside the image forming device for a long period of time.

JP 2017-122873 A

However, as a result of the inventors' investigation of the toner described in Patent Document 1, it was found that image defects and changes in image density may occur easily when images are output for a long period of time in a high-temperature and high-humidity environment.
The present invention provides a toner that solves these problems, does not cause image defects even in long-term image output, and has excellent density stability and suppression of member contamination even under high temperature and high humidity conditions.Furthermore, the present invention provides a toner that has development stability even under low humidity conditions.

The present invention provides a toner having toner particles and an external additive,
The external additive contains organosilicon polymer particles,
the organosilicon polymer particles have an absolute charge quantity Q (mC/kg) of 200 (mC/kg) or less;
the organosilicon polymer particles have a number average particle size S (nm) of 25 nm or more and 250 nm or less;
the toner particles have an arithmetic average roughness Ra (nm) measured by a scanning probe microscope of 15 nm or more and 200 nm or less;
The toner is characterized in that the relationship between the number average particle size S (nm) of the organosilicon polymer particles and the arithmetic mean roughness Ra of the toner particles satisfies the following formula (1):
Ra≦S (1)

The present invention provides a toner that can achieve both excellent density stability and contamination suppression even under high temperature and high humidity conditions. Furthermore, it provides a toner that has development stability even under low humidity conditions.

FIG. 2 is an explanatory diagram illustrating an example of a charge amount measuring device. FIG. 2 is an explanatory diagram showing an example of a heat treatment apparatus used in the present invention. FIG. 2 is an explanatory diagram of the embedding rate of resin fine particles in the present invention. FIG. 2 is an explanatory diagram of a method for measuring ten-point average roughness (Rzjis).

When a numerical range is expressed as "xx or more and xx or less" or "xx to xx", it means that the numerical range includes the lower and upper limit endpoints, unless otherwise specified.

The toner of the present invention is a toner comprising toner particles and an external additive, wherein the external additive contains organosilicon polymer particles, the organosilicon polymer particles have an absolute value of charge quantity Q (mC/kg) of 200 (mC/kg) or less, the organosilicon polymer particles have a number average particle size S (nm) of 25 nm or more and 250 nm or less, the toner particles have an arithmetic mean roughness Ra (nm) measured by a scanning probe microscope of 15 nm or more and 200 nm or less, and the relationship between the number average particle size S (nm) of the organosilicon polymer particles and the arithmetic mean roughness Ra of the toner particles satisfies the relationship of the following formula (1):
Ra≦S (1)

In the present invention, when the toner satisfies the above conditions, the detachment of the organosilicon polymer particles used as an external additive is suppressed, even when multiple sheets are printed, so the fluidity of the toner does not change. As a result, no image defects occur and the image density is stable. In addition, because the detachment of the organosilicon polymer particles is suppressed, contamination of the image forming device is also suppressed.

The inventors believe the reason for this is as follows:

The organosilicon polymer particles of the present invention are believed to be difficult to charge due to the uniform charge density, and therefore are unlikely to develop large electrostatic adhesion forces. For this reason, the organosilicon polymer particles are believed to adhere to the toner particles not by electrostatic adhesion forces, but by van der Waals forces, which are non-electrostatic adhesion forces.

The toner particles of the present invention are characterized by having a surface roughness within the above-mentioned range, and the irregularities that form this roughness increase the number of contact points between the organosilicon polymer particles and the toner particles, increasing the number of points at which van der Waals forces act. As a result, it is believed that detachment of the organosilicon polymer particles is suppressed.

The organosilicon polymer particles of the present invention are particles that have organic groups and are composed of polyorganosiloxanes with siloxane bonds (Si-O-) as the main polymer backbone.

The amount of organosilicon polymer contained in the toner is preferably 0.1% by mass or more and 30.0% by mass or less, and more preferably 0.5% by mass or more and 10.0% by mass or less.

Also, unlike particles composed only of silicon and oxygen atoms, such as polysiloxane skeletons, organosilicon polymer particles tend to have excellent elasticity because they have an organic portion represented by R. For this reason, when organosilicon polymer particles are used as an external additive, their elasticity allows them to absorb stress applied within the developing device. As a result, the organosilicon polymer particles do not become embedded in the toner particles even when multiple sheets are output, and the initial toner state is maintained for a long period of time. As a result, it is believed that image defects do not occur over a long period of time, and density is stable.

The absolute value of the charge quantity Q (mC/kg) of the organosilicon polymer particles of the present invention is 200 (mC/kg) or less, preferably 150 (mC/kg) or less, and more preferably 140 (mC/kg) or less.

By using an organosilicon polymer with a charge amount within the above range as an external additive, the adhesion of the toner is reduced (i.e., the fluidity of the toner is improved) and the toner's ability to follow the electric field (development stability, developability after durability) is improved, resulting in improved developability.

Furthermore, the number average particle size S (nm) of the organosilicon polymer particles is 25 nm or more and 250 nm or less, and preferably 80 nm or more and 170 nm or less.

If the particle size is 25 nm or more, it is believed that when the toner is subjected to stress in the developing device with long-term use, the particles are less likely to be embedded. Therefore, it is preferable that the particle size is 25 nm or more, and more preferable that the particle size is 80 nm or more. Also, if the particle size is 250 nm or less, it is believed that the organosilicon polymer particles are less likely to detach from the toner particle surface. Therefore, it is preferable that the particle size is 250 nm or less, and more preferable that the particle size is 170 nm or less.

In the present invention, the arithmetic mean roughness Ra (nm) of the toner particles measured by a scanning probe microscope is 15 nm or more and 200 nm or less.

In the present invention, a scanning probe microscope (hereinafter also referred to as "SPM") is equipped with a probe, a cantilever that supports the probe, and a displacement measurement system that detects the bending of the cantilever, and detects the atomic force (attractive or repulsive force) between the probe and the sample to observe the shape of the sample surface. The arithmetic mean roughness Ra measured by an SPM is a three-dimensional extension of the center line mean roughness Ra defined in JIS B0601:2001 so that it can be applied to the measurement surface, and is the average absolute value of the deviation from the reference surface to the specified surface (the measurement method will be described in detail later). Equation 1

The arithmetic mean roughness Ra is an index that represents the roughness of the particle surface, and can provide information on the unevenness of the toner particle surface on a nanometer scale. Another advantage is that the effect of a single scratch on the measurement value is extremely small, allowing for stable results to be obtained.

When the Ra of the toner particles is within the above range, there are more contact points with the organosilicon polymer particles, and van der Waals forces act at these contact points, strengthening the adhesion between the toner particles and the organosilicon polymer particles, making it difficult for the organosilicon polymer particles to detach.

In the present invention, the relationship between the number average particle size S (nm) of the organosilicon polymer particles and the arithmetic mean roughness Ra of the toner particles satisfies the following formula (1).
Ra≦S (1)

In the present invention, when the relationship between the number-average particle size S (nm) of the organosilicon polymer particles and the arithmetic mean roughness Ra of the toner particles satisfies formula (1), the organosilicon polymer particles are present on the outermost surface of the toner. In other words, since the particle size of the organosilicon polymer particles used as an external additive is larger than the unevenness of the toner particles, the contact points between the toner particles and between the toner and the components are organosilicon polymer particles.

In this state, the presence of organosilicon polymer on the outermost surface of the toner reduces the toner's adhesive strength, which in turn reduces its adhesive strength to components and improves developability. Furthermore, the presence of organosilicon polymer particles on the outermost surface of the toner means that even when stress is applied inside the developing machine, embedding does not occur due to their elasticity, so the toner state does not change, and density changes are unlikely to occur even when output is performed over a long period of time.

In the present invention, the arithmetic mean roughness Ra (nm) of the toner particles is preferably 70 nm or more and 150 nm or less. When the toner particles have an Ra of 70 nm or more, the unevenness of the toner particles becomes large, increasing the chance of contact with the organosilicon polymer particles, and van der Waals forces act at the contact points, strengthening the adhesive force between the toner particles and the organosilicon polymer particles, making it difficult for the organosilicon polymer particles to detach. In addition, when the Ra is 150 nm or less, the organosilicon polymer particles tend to be present on the outermost surface of the toner, reducing the adhesive force as a toner, improving developability, which is preferable.

Furthermore, the ten-point average roughness Rzjis (nm) of the toner particles measured by a scanning probe microscope is preferably 70 nm or more and 250 nm or less, and more preferably 110 nm or more and 200 nm or less.

The ten-point average roughness (Rzjis) was measured according to the definition in JIS B0601 (1994). That is, a reference length was extracted from the roughness curve in the direction of the average line, and the sum of the average of the absolute values of the elevations (Yp) from the highest peak to the fifth peak, and the average of the absolute values of the elevations (Yv) from the lowest valley bottom to the fifth valley bottom, measured in a direction perpendicular to the average line of the extracted portion, was calculated (the measurement method is described in detail later).

In the present invention, by having the ten-point average roughness Rzjis of the toner particles within the above range, as with Ra, the unevenness of the toner particles is appropriate, increasing the opportunities for contact with the organosilicon polymer particles. This prevents the organosilicon polymer particles from being detached, and at the same time makes it easier for the organosilicon polymer particles to exist on the outermost surface of the toner, reducing the toner's adhesive strength and improving developability.

In the present invention, the toner is shaken for 10 minutes at a shaking speed of 14.5 cm/sec and a shaking width of 3.0 cm, the toner after shaking is dispersed in ion-exchanged water containing a surfactant, and the resulting dispersion is shaken for 5 minutes at a shaking speed of 46.7 cm/sec and a shaking width of 4.0 cm. The adhesion rate A (%) of the organosilicon polymer particles to the toner particles is preferably 75% or more, as measured using a sample obtained by this method.

When a toner using conventional toner particles and organosilicon polymer particles is mixed with a standard carrier for negatively charged toners (manufactured by Nippon Imaging Co., Ltd.) and shaken under the above conditions, the organosilicon polymer particles are liberated and the adhesion rate decreases. In the present invention, it is preferable that the adhesion rate after shaking under the above conditions is 75% or more. If the adhesion rate is 75% or more, the detachment of the organosilicon polymer particles from the toner is suppressed, so the fluidity of the toner does not decrease, image defects do not occur even when output is performed over a long period of time, image density is stable, and component contamination is suppressed.

The method for measuring the adhesion rate A will be described in detail later.

In the present invention, the toner particles have convex portions that form the roughness of the toner particles, and the convex portions are formed by the embedding of the resin fine particles in the toner mother particles, and it is preferable that the embedding rate of the resin fine particles is 15% or more and less than 50%, the coverage rate of the resin fine particles in the toner particles is 20% or more and 50% or less, and the number average particle diameter R (nm) of the resin fine particles is equal to or less than the number average particle diameter S (nm) of the organosilicon polymer particles.

In the present invention, the unevenness of the toner particles is preferably formed by resin fine particles. The resin fine particles preferably have a number average particle diameter of 10 nm or more and 500 nm or less. More preferably, the number average particle diameter is 80 nm or more and 130 nm or less. By using resin fine particles with a number average particle diameter of 10 nm or more, the unevenness is formed by being embedded in the toner mother particle. In addition, when the resin fine particles have a number average particle diameter of 500 nm or less, the convex parts derived from the resin fine particles are not too high, so that the convex parts are prevented from coming off.

In addition, the type of resin microparticles in the present invention is not particularly limited, but examples include polymer-based resin microparticles such as polymethyl methacrylate resin microparticles, urethane resin microparticles, phenol resin microparticles, melamine resin microparticles, and polystyrene resin microparticles.

The resin microparticles in the present invention are preferably thermoplastic microparticles. By using thermoplastic microparticles, the convex portions derived from the resin microparticles are less likely to come off the toner base particles. This is believed to be because the thermoplastic resin microparticles are more likely to be integrated with the toner base particles, which are also thermoplastic. Furthermore, the fixing properties of the toner are improved by using thermoplastic microparticles. This is believed to be because the thermoplastic resin is more likely to melt during fixing.

Examples of thermoplastic fine particles include vinyl resins, polyester resins, polyamide resins, and fluororesins. In addition, as the vinyl resin, it is possible to use polymers or copolymers of monomers such as ethylene, propylene, isobutylene, styrene, and α-methylstyrene, unsaturated carboxylic acid esters such as methyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as maleic acid, unsaturated dicarboxylic anhydrides such as maleic anhydride, nitrile vinyl monomers such as acrylonitrile, halogen-containing vinyl monomers such as vinyl chloride, and nitro vinyl monomers such as nitrostyrene.

The content of the resin particles in the toner base particles is preferably 0.1 parts by mass or more and 15.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 7.0 parts by mass or less, per 100.0 parts by mass of the toner base particles.

In the present invention, it is preferable that the embedment rate of the resin fine particles is 15% or more and less than 50%. When the embedment rate of the resin fine particles is in the above range, the unevenness of the toner particles becomes appropriate, the contact points with the organosilicon polymer particles increase, and the detachment of the organosilicon polymer particles is suppressed. When the embedment rate is 15% or more, unevenness of the resin fine particles is formed, and when it is less than 50%, the detachment of the convex parts is suppressed.

The method for calculating the embedding rate of resin microparticles will be described later.

In the present invention, the coverage of the resin fine particles on the toner particles is preferably 20% or more and 50% or less. With the coverage of the resin fine particles in the above range, the contact opportunity between the toner particles and the organosilicon polymer particles is optimized, and detachment of the organosilicon polymer particles is suppressed. If the coverage is 20% or more, the contact opportunity between the resin fine particles and the organosilicon polymer particles increases. If it is 50% or less, there is space for the organosilicon polymer to be externally added to the toner particles, which is preferable.

Furthermore, in the present invention, it is preferable that the number average particle diameter R (nm) of the resin microparticles is equal to or less than the number average particle diameter S (nm) of the organosilicon polymer particles.

In the present invention, when the number average particle size R (nm) of the resin microparticles is equal to or smaller than the number average particle size S (nm) of the organosilicon polymer particles, the organosilicon polymer particles are present on the outermost surface of the toner. In other words, the particle size of the organosilicon polymer particles used as an external additive is larger than the unevenness of the toner particles, and as described above, the adhesion of the toner is reduced, the adhesion to the components is reduced, and the developability is improved. In addition, the presence of the organosilicon polymer particles on the outermost surface of the toner prevents embedding due to their elasticity even when stress is applied in the developing machine, and the state of the toner does not change, and the density is less likely to change even when output is performed over a long period of time.

The resin microparticles according to the present invention preferably have a carbonyl group.

In addition, in the present invention, it is preferable that the organosilicon polymer particles contain silanol groups, and that the amount of moisture adsorption at a relative humidity of 80% in the moisture adsorption isotherm at 30°C is 5 mg/g or more and 35 mg/g or less.

When the resin microparticles contain carbonyl groups, the oxygen atoms in the double bonds of the carbonyl groups interact with the hydrogen atoms of the silanol groups of the organosilicon polymer particles to form hydrogen bonds. This prevents the organosilicon polymer particles from detaching.

In addition, the water adsorption amount of the organosilicon polymer particles at a relative humidity of 80% is preferably 5 mg/g or more and 35 mg/g or less, and more preferably 18 mg/g or more and 25 mg/g or less.

In the present invention, the above-mentioned moisture adsorption amount can be controlled by the OH group concentration of the organosilicon polymer. By keeping the moisture adsorption amount of the organosilicon polymer contained in the toner within the above-mentioned range, the interaction between the hydrogen atoms of the silanol of the organosilicon polymer particles and the oxygen atoms of the carbonyl groups of the resin fine particles is enhanced, suppressing the detachment of the organosilicon polymer particles.

<Method of Producing Organosilicon Polymer Particles>
There are no particular limitations on the method for producing the organosilicon polymer particles, and they can be obtained, for example, by dropping a silane compound into water, carrying out hydrolysis and condensation reactions in the presence of a catalyst, and then filtering and drying the resulting suspension. The number average particle size of the primary particles of the organosilicon polymer particles can be controlled by the type of catalyst, the compounding ratio, the reaction start temperature, the dropping time, etc.

Catalysts include acidic and basic catalysts. This is because the use of an acidic catalyst makes it easier for the hydrolysis reaction to proceed, while the use of a basic catalyst makes it easier for the condensation reaction to proceed.

Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide.

The organosilicon polymer particles can be obtained by polymerizing the following monomer raw materials:

Monomer raw material: A monomer raw material containing an organosilicon compound represented by the following formula (4), in which R ⁷ in the following formula (4) is an alkyl group or a phenyl group having 1 to 6 carbon atoms, and R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrolyzable group.

Hereinafter, the above organosilicon compound will also be referred to as a trifunctional silane. The monomer raw material may contain one type of trifunctional silane alone, or two or more types of trifunctional silanes.

The hydrolyzable group means a functional group that is converted to a hydroxy group after a hydrolysis reaction. The type of hydrolyzable group includes at least one substituent selected from the group consisting of halogen functional groups (fluoro, chloro, bromo, and iodine groups), alkoxy groups, and acyloxy groups. Among the above, alkoxy groups and acetoxy groups are preferred, and at least one substituent selected from the group consisting of methoxy groups, ethoxy groups, propoxy groups, and acetoxy groups is more preferred. When these hydrolyzable groups are hydrolyzed, they are converted to a silyl alcohol structure, which is preferable because it is believed that it is easy to form a polysiloxane skeleton or a crosslinked structure by polycondensation from there.

The monomer raw material may contain, for example, the following compounds.
A compound in which R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ in formula (4) are each independently a hydrolyzable group (hereinafter, referred to as a tetrafunctional silane),
An organosilicon compound in which R ⁷ and R ⁸ in the formula (4) are each independently an alkyl group or a phenyl group having from 1 to 6 carbon atoms, and R ⁹ and R ¹⁰ are each independently a hydrolyzable group (hereinafter, bifunctional silane);
An organosilicon compound represented by the formula (4) in which R ⁷ , R ⁸ , and R ⁹ are each independently an alkyl group or a phenyl group having 1 to 6 carbon atoms, and R ¹⁰ is a hydrolyzable group (hereinafter, monofunctional silane).

Examples of the tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, and tetraisocyanate silane.

The above trifunctional silanes include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, ethoxymethoxysilane, ethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxy ... Examples of the silane include ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltrihydroxysilane, and pentyltrimethoxysilane.

The above bifunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethyldimethoxysilane, diethoxydimethylsilane, diethyldimethoxysilane, etc.

Examples of the monofunctional silanes include t-butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t-butyldiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, trimethylmethoxysilane, ethoxytrimethylsilane, triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, tripentylmethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, and triphenylethoxysilane.

<Binder resin>
The toner particles preferably contain a binder resin. Examples of the binder resin include vinyl resin, polyester, and epoxy resin, and one type may be used alone or two or more types may be used in combination. Among them, from the viewpoint of electrostatic chargeability and fixability, vinyl resin and/or polyester are preferable, and polyester is more preferable.

If necessary, polyurethane, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, etc. can also be mixed with the binder resin.

<Polyester>
The polyesters preferable as the binder resin are described below.

Based on the total monomer units constituting the polyester, it is preferable that 45 mol% to 55 mol% is an alcohol component, and 45 mol% to 55 mol% is a carboxylic acid component.

The acid value of the polyester is preferably 0 mgKOH/g or more and 90 mgKOH/g or less, more preferably 5 mgKOH/g or more and 50 mgKOH/g or less. The hydroxyl value of the polyester is preferably 0 mgKOH/g or more and 50 mgKOH/g or less, more preferably 5 mgKOH/g or more and 30 mgKOH/g or less. When the acid value and hydroxyl value of the polyester are within the above ranges, it is believed that the charging characteristics of the toner are less environmentally dependent.

The glass transition temperature (Tg) of the polyester is preferably 50°C or more and 75°C or less, more preferably 55°C or more and 65°C or less. The number average molecular weight (Mn) of the polyester is preferably 1500 or more and 50,000 or less, more preferably 2000 or more and 20,000 or less. The weight average molecular weight (Mw) of the polyester is preferably 6000 or more and 150,000 or less, more preferably 10,000 or more and 100,000 or less.

The content of polyester in the binder resin is preferably 50% by mass or more and 100% by mass or less, and more preferably 80% by mass or more and 100% by mass or less.

A crystalline polyester may be added to the toner particles in order to promote the plasticizing effect of the toner particles and improve the low-temperature fixability of the toner. An example of the crystalline polyester is a polycondensate of a monomer composition containing, as main components, an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms.

The aliphatic diol having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms) is not particularly limited, but is preferably a chain (more preferably a straight-chain) aliphatic diol. Among these, particularly preferred examples include straight-chain aliphatic α,ω-diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol.

Of the alcohol components, preferably 50% by mass or more, more preferably 70% by mass or more, is an alcohol selected from aliphatic diols having 2 to 22 carbon atoms.

Polyhydric alcohol monomers other than aliphatic diols can also be used. Dihydric alcohol monomers include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol, etc.

Examples of trihydric or higher polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; and aliphatic alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

Monohydric alcohol may also be used to the extent that it does not impair the properties of the crystalline polyester.

On the other hand, the aliphatic dicarboxylic acid having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms) is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. Also included are those obtained by hydrolyzing the acid anhydrides or lower alkyl esters of these.

Of the carboxylic acid components, preferably 50% by mass or more, more preferably 70% by mass or more, is a carboxylic acid selected from aliphatic dicarboxylic acids having 2 to 22 carbon atoms.

Polyvalent carboxylic acids other than the above aliphatic dicarboxylic acids having 2 to 22 carbon atoms can also be used. Examples of divalent carboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecylsuccinic acid and n-dodecenylsuccinic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, as well as their acid anhydrides and lower alkyl esters.

Examples of trivalent or higher polyvalent carboxylic acids include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic acid, and aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, as well as their acid anhydrides and derivatives such as lower alkyl esters.

It may also contain a monovalent carboxylic acid to the extent that it does not impair the properties of the crystalline polyester.

Crystalline polyesters can be produced according to conventional polyester synthesis methods. For example, a carboxylic acid monomer and an alcohol monomer can be subjected to an esterification reaction or an ester exchange reaction, followed by a conventional polycondensation reaction under reduced pressure or by introducing nitrogen gas, to obtain the desired crystalline polyester.

The amount of crystalline polyester used is preferably 0.1 parts by weight or more and 30 parts by weight or less, more preferably 0.5 parts by weight or more and 20 parts by weight or less, and even more preferably 3 parts by weight or more and 15 parts by weight or less, per 100 parts by weight of binder resin.

<Various additives>
If necessary, the toner may contain one or more additives selected from a colorant, a release agent, inorganic fine particles, etc. Various additives used in the toner will be specifically described.

<Coloring Agent>
Examples of the colorant include the following: As the colorant, a pigment may be used alone, or a dye and a pigment may be used in combination.

Carbon black is used as a black colorant; yellow, magenta, and cyan colorants are used to adjust the black color.

Examples of color pigments for magenta toner include:

Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds.

Specifically, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57 : 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, 269; C.I. Pigment Violet 19, C.I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

Dyes for magenta toner include the following:

C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. Disperse Red 9, C.I. Solvent Violet 8, 13, 14, 21, 27, C.I. Disperse Violet 1 and other oil-soluble dyes, C.I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28 and other basic dyes.

Color pigments for cyan toner include the following:

C.I. Pigment Blue 1, 2, 3, 7, 15:2, 15:3, 15:4, 16, 17, 60, 62, 66; C.I. Bat Blue 6, C.I. Acid Blue 45, copper phthalocyanine pigments with 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

Yellow color pigments include the following:
Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal compounds, methine compounds, and allylamide compounds.

Specific examples include C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 155, 168, 174, 180, 181, 185, 191; C.I. Bat Yellow 1, 3, 20. In addition, dyes such as C.I. Direct Green 6, C.I. Basic Green 4, C.I. Basic Green 6, and Solvent Yellow 162 can also be used.

The content of the colorant is preferably 0.1 parts by mass or more and 30.0 parts by mass or less, more preferably 0.5 parts by mass or more and 20.0 parts by mass or less, and even more preferably 3.0 parts by mass or more and 15.0 parts by mass or less, relative to 100 parts by mass of the binder resin.

<Release Agent>
Examples of the release agent include the following. One type may be used alone, or two or more types may be used in combination.

Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax are preferably used. Also usable are oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes whose main component is fatty acid esters such as carnauba wax, sazol wax, and montan acid ester wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

The content of the release agent is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the binder resin.

The release agent preferably has a melting point, as determined by the maximum endothermic peak temperature during heating measured with a differential scanning calorimeter (DSC), of 65°C or higher and 130°C or lower. More preferably, it is 80°C or higher and 125°C or lower. If the melting point is 65°C or higher, the toner has a suitable viscosity, which makes it possible to suppress toner adhesion to the photoreceptor. On the other hand, if the melting point is 130°C or lower, low-temperature fixability is good.

<Inorganic fine particles>
As the inorganic fine particles, silica fine particles, titanium oxide fine particles, and aluminum oxide fine particles are preferable. The inorganic fine particles may be added internally to the toner particles, or may be mixed with the toner particles as an external additive. In addition, one type of inorganic fine particles may be used alone, or two or more types may be used in combination.

The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof. When the inorganic fine particles are contained as an external additive, the amount of the inorganic fine particles is preferably 0.1 parts by mass or more and 10.0 parts by mass or less per 100.0 parts by mass of the toner particles. When adding inorganic fine particles to the toner particles, it is recommended to use a mixer such as a Henschel mixer.

<Method of producing toner and toner particles>
The method for producing the toner particles is not particularly limited, and examples thereof include a melt kneading method, a suspension polymerization method, a dissolution suspension method, and an emulsion aggregation method.

In addition, the method for producing toner particles preferably uses a mixture in which a colorant is mixed with a binder resin in advance to form a master batch. Then, by melting and kneading this mixture with other raw materials (binder resin, wax, etc.), the colorant can be well dispersed in the toner particles.

The melt-kneading method will be described. The melt-kneading method is a toner manufacturing method that includes a process of melting and kneading a mixture containing toner raw materials such as a binder resin, wax, and colorant to obtain a melt-kneaded product (hereinafter, also simply referred to as the melt-kneading process). It is also preferable to include a process of cooling the melt-kneaded product obtained in the melt-kneading process, pulverizing and classifying the resulting toner particles, and then heat-treating the toner particles (hereinafter, also simply referred to as the heat treatment process). This makes it possible to obtain toner particles with resin fine particles embedded in them.

The procedure for producing toner particles using the melt-kneading method is described below.

First, in the raw material mixing process, predetermined amounts of binder resin, wax, colorant, etc. are weighed out and mixed as toner raw materials.

The equipment used for the mixing includes Henschel mixer (manufactured by Nippon Coke Co.); Super mixer (manufactured by Kawata Co.); Ribocone (manufactured by Okawara Manufacturing Co.); Nauta mixer, Turbulizer, Cyclomix (manufactured by Hosokawa Micron Co.); Spiral pin mixer (manufactured by Pacific Machinery Works Co.); and Lödige mixer (manufactured by Matsubo Co.).

Next, the resulting mixture is melted and kneaded to melt the resins and disperse the wax, colorants, etc. into it (melt-kneading process).

The equipment used for melt kneading includes a TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); a TEX twin screw kneader (manufactured by Japan Steel Works, Ltd.); a PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.); and a Kneadex (manufactured by Mitsui Mining Co., Ltd.). Continuous kneaders such as single screw or twin screw extruders are preferred over batch kneaders because of their advantage of being capable of continuous production.

Next, the resulting molten kneaded product is rolled using a twin roll or the like, and cooled with water or the like.
The cooled material is then crushed to a desired particle size by first coarsely crushing it using a crusher, hammer mill, feather mill, or the like, and then finely crushing it using a Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.) or a Super Rotor (manufactured by Nisshin Engineering, Inc.), or the like.

The powder may then be classified to the desired particle size. Devices used for classification include Turboplex, Faculty, TSP, TTSP (manufactured by Hosokawa Micron Corporation); Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), etc.

The obtained toner base particles are subjected to a heat treatment to embed the resin particles. The heat treatment device shown in FIG. 2 performs surface treatment using hot air and can be preferably used for the treatment in the present invention.

The mixture (toner base particles and resin particles) supplied in a fixed amount by the material supplying means 1 is introduced into the inlet pipe 3, which is installed on the vertical line of the material supplying means, by compressed gas adjusted by the compressed gas adjusting means 2. The mixture that passes through the inlet pipe is uniformly dispersed by the conical protruding member 4 installed in the center of the material supplying means, and is introduced into the eight-way supply pipes 5 that radiate outward, and into the processing chamber 6 where heat treatment is carried out.

At this time, the flow of the mixture supplied to the treatment chamber is regulated by a regulating means 9 for regulating the flow of the mixture provided in the treatment chamber. Therefore, the mixture supplied to the treatment chamber is heat-treated while swirling within the treatment chamber, and then cooled.

Hot air for heat-treating the supplied mixture is supplied from the hot air supplying means 7, and is introduced into the treatment chamber by spirally swirling the hot air using the swirling member 13 for swirling the hot air. The configuration is such that the swirling member 13 for swirling the hot air has multiple blades, and the swirling of the hot air can be controlled by the number and angle of the blades. The hot air supplied into the treatment chamber preferably has a temperature of 100°C to 300°C at the outlet of the hot air supplying means 7. If the temperature at the outlet of the hot air supplying means is within the above range, it is possible to uniformly embed the resin fine particles in the toner base particles while preventing the toner particles from fusing or coalescing due to excessive heating of the mixture.

The heat-treated toner particles are further cooled by cold air supplied from cold air supply means 8, and the temperature supplied from the cold air supply means 8 is preferably -20°C to 30°C. If the temperature of the cold air is within the above range, the heat-treated toner particles can be efficiently cooled, and the fusion and coalescence of the heat-treated toner particles can be prevented without impeding the uniform heat treatment of the mixture. The absolute moisture content of the cold air is preferably 0.5 g/m3 or ^more and 15.0 g/m3 or ^less .

Next, the cooled heat-treated toner particles are collected by the collection means 10 at the bottom of the processing chamber. A blower (not shown) is provided beyond the collection means, which is used to suction and transport the particles.

The powder particle supply port 14 is provided so that the swirling direction of the supplied mixture and the swirling direction of the hot air are the same, and the recovery means 10 of the surface treatment device is provided on the outer periphery of the treatment chamber so as to maintain the swirling direction of the swirled powder particles. Furthermore, the cold air supplied from the cold air supply means 8 is configured to be supplied horizontally and tangentially from the outer periphery of the device to the circumferential surface inside the treatment chamber. The swirling directions of the toner supplied from the powder supply port, the swirling direction of the cold air supplied from the cold air supply means, and the swirling direction of the hot air supplied from the hot air supply means are all the same. Therefore, no turbulence occurs in the treatment chamber, the swirling flow in the device is strengthened, a strong centrifugal force is applied to the toner, and the dispersibility of the toner is further improved, so that a toner with a uniform shape and few coalesced particles can be obtained.

If coarse particles are present after the above heat treatment, they may be removed by classification or sieving, as necessary. Apparatuses used for classification include those mentioned above. Apparatuses used for sieving include Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resonaseave, Gyroshifter (Tokuju Kogyo Co., Ltd.); Turbo Screener (manufactured by Turbo Kogyo Co., Ltd.); and Hi-Volter (manufactured by Toyo Hitec Co., Ltd.).

Before or after the heat treatment step, inorganic fine particles, organosilicon polymers, etc. may be added as necessary.

<Developer>
The toner of the present invention can be used as a one-component developer, but in order to suppress localization of charge on the toner surface, it can also be mixed with a magnetic carrier and used as a two-component developer.

As magnetic carriers, generally known ones can be used, such as iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, and oxide particles thereof; magnetic materials such as ferrite; magnetic material-dispersed resin carriers (so-called resin carriers) that contain magnetic materials and binder resins that hold the magnetic materials in a dispersed state; etc.

When the toner is mixed with a magnetic carrier to be used as a two-component developer, the mixing ratio of the magnetic carrier is preferably 2% by mass or more and 15% by mass or less, and more preferably 4.0% by mass or more and 13.0% by mass or less, in terms of the toner concentration in the two-component developer.

<Various measurement methods, etc.>
Various measurement methods are described below.

Identification of Organosilicon Polymer Particles
The composition and ratio of the constituent compounds of the organosilicon polymer particles contained in the toner are identified using a pyrolysis gas chromatography mass spectrometer (hereinafter also referred to as "pyrolysis GC/MS") and NMR. If the organosilicon polymer particles are available separately, they can also be measured separately.

Pyrolysis GC/MS is used to analyze the types of constituent compounds in organosilicon polymer particles.

The types of constituent compounds of the organosilicon polymer particles are identified by analyzing the mass spectrum of the components of the decomposition products derived from the organosilicon polymer particles that are produced when the toner is thermally decomposed at 550°C to 700°C. The specific measurement conditions are as follows:

(Measurement conditions for pyrolysis GC/MS)
・Pyrolysis device: JPS-700 (Japan Analysis Industry)
Decomposition temperature: 590°C
GC/MS equipment: Focus GC/ISQ (Thermo Fisher)
Column: HP-5MS, length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm
Inlet temperature: 200℃
Flow pressure: 100 kPa
Split: 50 mL/min MS ionization: EI
Ion source temperature: 200°C Mass Range 45-650

Next, the abundance ratios of the identified constituent compounds of the organosilicon polymer particles are measured and calculated by solid-state ^29Si -NMR. In solid-state ^29Si -NMR, peaks are detected in different shift regions depending on the number of functional groups bonded to the Si of the constituent compounds of the organosilicon polymer particles. The number of functional groups of each peak is identified using a standard sample. The abundance ratios of each constituent compound are calculated from the peak areas obtained.

The measurement conditions for solid-state ²⁹ Si-NMR are as follows:
・Device: JNM-ECX5002 (JEOL RESONANCE)
Temperature: Room temperature Measurement method: DDMAS method 29Si 45°
Sample tube: Zirconia 3.2 mm diameter
Sample: Powdered and filled into test tube Sample rotation speed: 10 kHz
relaxation delay: 180s
Scan: 2000

If the toner contains silicon-containing materials other than the organosilicon polymer particles, the toner is dispersed in a solvent such as chloroform, and then the silicon-containing materials other than the organosilicon polymer particles are removed by the difference in specific gravity using centrifugation or other methods. One example of this method is shown below.

First, 1 g of toner is added to 31 g of chloroform in a vial and dispersed, and silicon-containing materials other than the organosilicon polymer particles are separated from the toner. The dispersion is processed for 30 minutes using an ultrasonic homogenizer to produce a dispersion liquid. The processing conditions are as follows:
・Ultrasonic processing device: Ultrasonic homogenizer VP-050 (manufactured by Taitec Co., Ltd.)
Microchip: Step type microchip, tip diameter φ2mm
Position of the tip of the microchip: at the center of the glass vial and at a height of 5 mm from the bottom of the vial. Ultrasonic conditions: intensity 30%, 30 minutes (ultrasonics was applied while cooling the vial with ice water to prevent the temperature of the dispersion from increasing).

The dispersion is transferred to a glass tube (50 mL) for a swing rotor, and centrifuged in a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) at 58.33 S ^-1 for 30 minutes. After centrifugation, silicon-containing materials other than the organosilicon polymer particles and a residue from which silicon-containing materials other than the organosilicon polymer particles have been removed from the toner are separated in the glass tube. The residue from which silicon-containing materials other than the organosilicon polymer particles have been removed from the toner is extracted and dried under vacuum conditions (40°C/24 hours) to obtain a sample from which silicon-containing materials other than the organosilicon polymer particles have been removed from the toner. The composition and ratio of the constituent compounds of the organosilicon polymer particles contained in the toner can be identified by the same procedure as above.

<Method for quantifying organosilicon polymer particles contained in toner>
The content of organosilicon polymer particles in the toner is measured using fluorescent X-rays.

The measurement of fluorescent X-rays conforms to JIS K 0119-1969, but is specifically as follows. The measurement equipment is a wavelength dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and the accompanying dedicated software "SuperQ ver. 5.0L" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, and the measurement diameter (collimator mask diameter) is 27 mm. The measurement is performed using the Omnian method to measure the range of elements F to U, and detection is performed with a proportional counter (PC) when measuring light elements and a scintillation counter (SC) when measuring heavy elements. The acceleration voltage and current value of the X-ray generator are set to an output of 2.4 kW. The measurement sample was prepared by placing 4 g of toner in a special aluminum ring for pressing, flattening it, and pressing it at 20 MPa for 60 seconds using a tablet press "BRE-32" (Maekawa Test Machinery Manufacturing Co., Ltd.) to form a pellet with a thickness of 2 mm and a diameter of 39 mm.

The pellets formed under the above conditions are irradiated with X-rays, and the characteristic X-rays (fluorescent X-rays) that are generated are dispersed using a spectroscopic element. Next, the intensity of the fluorescent X-rays dispersed at angles corresponding to the wavelengths specific to each element contained in the sample is analyzed using the fundamental parameter method (FP method), and the content ratio of each element contained in the toner is obtained as the analysis result, and the silicon atom content in the toner is calculated.

The content of organosilicon polymer particles in a toner can be calculated from the relationship between the silicon content in the toner determined by fluorescent X-rays and the silicon content ratio in the constituent compounds of the organosilicon polymer particles whose structure has been identified using solid ^- state 29Si NMR and pyrolysis GC/MS.

If the toner contains silicon-containing materials other than the organosilicon polymer particles, the amount of organosilicon polymer particles in the toner can be quantified by removing the silicon-containing materials other than the organosilicon polymer particles from the toner using the same method as above.

<Method of Measuring Charge Amount Q of Organosilicon Polymer Particles>
The charge amount (mC/kg) of the organosilicon polymer particles is calculated as follows.
The measurement is performed under an environment with a temperature of 23°C and a relative humidity of 50%. A mixture of 9.8 g of a standard carrier for negatively charged toner (manufactured by Nippon Imaging Co., Ltd.) and 0.2 g of a sample to be measured for chargeability is placed in a 50 ml polyethylene bottle and left to stand for 12 hours. Next, the mixture is shaken at 200 rpm for 5 minutes using a Model-YS-LD shaker (manufactured by Yayoi Co., Ltd.). Next, in the friction charge amount measuring device shown in FIG. 1, 0.15 g of the mixture is placed in a metal measuring container 2A with a 635 mesh screen 3A at the bottom, and a metal lid 4A is placed on it. The total mass of the measuring container 2A at this time is weighed and is designated as W1 (g). Next, in the suction machine 1A (the part in contact with the measuring container 2A is at least an insulator), suction is performed from the suction port 7A, and the air flow control valve 6A is adjusted to set the pressure of the vacuum gauge 5A to 1.5 kPa. In this state, suction is performed for 2 minutes, and the developer is removed by suction. The potential of the electrometer 9A at this time is designated as V (volts). Here, 8A is a capacitor with a capacity of C (μF). The mass of the entire measuring device after suction is weighed and is set to W2 (g). The amount of triboelectric charge Q (mC/kg) of the sample is calculated using the following formula:
Q=CV/(W1-W2)

<Method for measuring number average particle size of primary particles of organosilicon polymer particles and resin fine particles>
The number average particle size of the primary particles of the organosilicon polymer particles is measured using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). The toner particles to which the organosilicon polymer particles have been added are observed, and the number average particle size is determined by measuring the major axis of the primary particles of 100 randomly selected organosilicon polymer particles in a field of view magnified up to 50,000 times. The observation magnification is appropriately adjusted depending on the size of the organosilicon polymer. In addition, when the organosilicon polymer can be obtained alone, the organosilicon polymer can also be measured alone.

In the same manner as above, the number average particle size of the primary particles of the resin microparticles can also be determined.

When the toner contains silicon-containing substances other than organosilicon polymer particles, EDS analysis (energy dispersive X-ray analysis) is performed on each particle of the external additive in observing the toner particles, and it can be determined whether the analyzed particle is an organosilicon polymer particle or not from the presence or absence of an Si element peak. In addition, when the toner contains both organosilicon polymer particles and silica fine particles, the organosilicon polymer particle is identified by comparing the ratio of the elemental contents (atomic%) of Si and O (Si/O ratio) with a standard. EDS analysis is performed on the standard of each organosilicon polymer particle and silica fine particle under the same conditions to obtain the elemental contents (atomic%) of Si and O. The Si/O ratio of the organosilicon polymer particle is defined as A, and the Si/O ratio of the silica fine particle is defined as B. Measurement conditions are selected under which A is significantly larger than B. Specifically, 10 measurements are performed on the standard under the same conditions, and the arithmetic mean values of A and B are obtained. Measurement conditions are selected under which the obtained average value A/B>1.1.

If the Si/O ratio of the microparticles to be identified is on the A side of [(A+B)/2], the microparticles are judged to be organosilicon polymer particles. Tospearl 120A (Momentive Performance Materials Japan LLC) is used as a standard for organosilicon polymer particles, and HDK V15 (Asahi Kasei) is used as a standard for silica microparticles.

<Method for Measuring Water Adsorption Amount of Organosilicon Polymer Particles>
The amount of water adsorption by the organosilicon polymer particles is measured using an adsorption equilibrium measuring device (BELSORP-aqua3, manufactured by BEL Japan Inc.). This device measures the amount of adsorption of the target gas (water vapor in this case). The specific measurement method is described below.

(Degassing)
Before measurement, degas the moisture adsorbed in the sample. Attach the cell, filler rod, and cap, and weigh the empty sample. Weigh out approximately 0.3 g of sample and place it in the cell. Place the filler rod in the cell, attach the cap, and attach it to the degassing port. Once all the cells to be measured are attached to the degassing port, open the helium valve. Turn on the button for the port to be degassed, and press the "VAC" button. Degas in this manner for at least one day.

(measurement)
Turn on the power of the main unit and start the vacuum pump. Turn on the power of the main unit and the operation panel for the circulating water, and start "BELaqua3.exe (measurement software)" in the center of the PC screen. Temperature control of the high-temperature air chamber: Double-click "SV" in the "TIC1" frame on the "Flow path diagram" window to open the "Temperature setting" window. Enter the temperature (80°C) and click "Set". Adsorption temperature control: Double-click "SV" in "Adsorption temperature" on the "Flow path diagram" window to enter the "SV value" (adsorption temperature). Click "Start circulation" and "External temperature control", then click "Set". Press the "PURGE" button to stop degassing, turn off the port button, remove the sample, attach the cap, weigh the sample, and then attach the sample to the main unit measurement unit. On the PC, click "Measurement conditions" to open the "Measurement condition setting" window. The measurement conditions are as follows.
Air thermostatic chamber temperature: 80.0°C
・Adsorption temperature: 30.0℃
・Adsorbate name: H ₂ O
・Equilibrium time: 500sec
・Temperature waiting time: 60 minutes ・Saturated vapor pressure: 4.245 kPa
Sample tube pumping speed: normal; Chemical adsorption measurement: not performed; Initial introduction amount: 0.20 cm ³ (STP)·g ^-1
・Number of measurement relative pressure ranges: 4
Select the number of samples to be measured, enter the "measurement data file name" and "sample weight." Start the measurement.

(analysis)
The analytical software is started and the water adsorption amount (cm ³ g ^-1 ) at a temperature of 30° C. and a relative humidity of 80% is calculated.

<Method of measuring average surface roughness (Ra) and ten-point average roughness (Rzjis) of toner particle surface>
The average surface roughness (Ra) and ten-point average roughness (Rz) of the toner particle surface were measured using the following measuring device and under the following measuring conditions.
Scanning probe microscope: Hitachi High-Tech Science Corporation Measurement unit: E-sweep
Measurement mode: DFM (resonance mode) Shape image resolution: X data number 256, Y data number 128
Measurement area: 1 μm square. For toner particles containing external additives, the external additives must be removed in advance, and the specific method used was a water washing method described below.

The toner particles selected for measurement were those with a particle size equal to the weight average particle size (D4) measured by the Coulter Counter method described below. The measured data was obtained by measuring 10 or more different toner particles, and the average value of the obtained data was calculated to obtain the average surface roughness (Ra) and ten-point average roughness (Rzjis) of the toner particles.

The average surface roughness (Ra) is the centerline average roughness Ra defined in JIS B0601 (1994) extended three-dimensionally so that it can be applied to the measurement surface. It is the average absolute value of the deviation from the reference surface to the specified surface, and is expressed by the following formula.

Ｆ（Ｘ，Ｙ）：全測定データの示す面
Ｓ０：指定面が理想的にフラットであると仮定したときの面積
Ｚ０：指定面内のＺデータ（粗さデータ）の平均値

F(X, Y): Surface indicated by all measured data S0: Area when the specified surface is assumed to be ideally flat Z0: Average value of Z data (roughness data) within the specified surface

In this invention, the designated surface means a measurement area of 1 μm square.

Meanwhile, the ten-point average roughness (Rzjis) was measured according to the definition in JIS B0601 (1994). That is, as shown in Figure 4, a reference length was extracted from the roughness curve in the direction of the average line, and the sum (see the following formula) of the average of the absolute values of the elevations (Yp) from the highest peak to the fifth peak, and the average of the absolute values of the elevations (Yv) from the lowest valley bottom to the fifth valley bottom, measured in a direction perpendicular to the average line of this extracted portion, was calculated.

<Water washing treatment method>
In the present invention, the water washing treatment was carried out as follows. 6 mL of a surfactant, Contaminon N (a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.), was added to an aqueous sucrose solution prepared by dissolving 20.7 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) in 10.3 g of ion-exchanged water, and mixed thoroughly to prepare a dispersion. 1.0 g of toner was added to this vial, and the toner was allowed to stand until it naturally settled to prepare a pre-treatment dispersion. This dispersion was shaken for 5 minutes with a shaker (YS-8D type: manufactured by Yayoi Co., Ltd.) at a shaking speed of 200 rpm to remove the external additive from the surface of the toner particles. A centrifuge was used to separate the toner with the remaining external additive from the removed external additive. The centrifugation step was carried out at 3700 rpm for 30 minutes. The remaining toner particles were collected by suction filtration and dried to obtain toner particles.

<Method of Measuring Weight Average Particle Size (D4) of Toner>
The weight average particle diameter (D4) of the toner was measured with an effective measurement channel number of 25,000 channels using a precision particle size distribution measuring device using a pore electrical resistance method equipped with a 100 μm aperture tube, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), and the attached dedicated software for setting measurement conditions and analyzing measurement data, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.), and the measurement data was analyzed and calculated. The electrolyte solution used for the measurement is one in which special grade sodium chloride is dissolved in ion-exchanged water to a concentration of about 1 mass %, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used.

Before performing measurements and analysis, the dedicated software was configured as follows:

In the "Change Standard Measurement Method (SOM) screen" of the dedicated software, the total count number in the control mode was set to 50,000 particles, the number of measurements was set to 1, and the Kd value was set to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). The threshold and noise level were automatically set by pressing the threshold/noise level measurement button. In addition, the current was set to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and the aperture tube flush after measurement was checked. In the "Pulse to particle size conversion setting screen" of the dedicated software, the bin interval was set to logarithmic particle size, the particle size bin to 256 particle size bin, and the particle size range from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Approximately 200 ml of the electrolyte solution was placed in a 250 ml round-bottom glass beaker for use with the Multisizer 3, which was then set on a sample stand. The stirring rod was then rotated counterclockwise at 24 revolutions per second. Dirt and air bubbles were removed from inside the aperture tube using the "aperture flush" function of the analysis software.
(2) About 30 ml of the aqueous electrolyte solution was placed in a 100 ml flat-bottom glass beaker, and about 0.3 ml of a solution prepared by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, having a pH of 7, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water was added as a dispersant.
(3) A predetermined amount of ion-exchanged water was placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) having two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees and an electrical output of 120 W, and about 2 ml of the Contaminon N was added to this water tank.
(4) The beaker of (2) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was operated. Then, the height position of the beaker was adjusted so that the resonance state of the liquid surface of the electrolytic solution in the beaker was maximized.
(5) In a state where the electrolyte solution in the beaker in (4) was irradiated with ultrasonic waves, about 10 mg of toner was added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment was continued for another 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank was appropriately adjusted to be 10°C or higher and 40°C or lower.
(6) The electrolyte aqueous solution (5) in which the toner was dispersed was dropped using a pipette into the round-bottom beaker (1) placed in the sample stand, and the measurement concentration was adjusted to about 5%. Then, the measurement was continued until the number of particles measured reached 50,000.
(7) The measurement data was analyzed using the dedicated software included with the device to calculate the weight-average particle diameter (D4). Note that the "average diameter" on the analysis/volume statistics (arithmetic mean) screen when the dedicated software is set to graph/volume % is the weight-average particle diameter (D4).

<Method for Measuring Adhesion Rate A (%) of Organosilicon Polymer Particles>
The adhesion rate A (%) of the organosilicon polymer particles was measured as follows.

A mixture of 98 g of standard carrier for negatively charged toner (manufactured by Nippon Imaging Co., Ltd.) and 2 g of the sample for which the adhesion rate is to be measured was placed in a 500 ml polyethylene bottle and left to stand for 12 hours. Next, this mixture was shaken for 10 minutes using a Model-YS-LD shaker (manufactured by Yayoi Co., Ltd.) at a shaking speed of 14.5 cm/sec and a shaking width of 3.0 cm. The toner after shaking was then dispersed in ion-exchanged water containing a surfactant, and the resulting dispersion was shaken for 5 minutes at a shaking speed of 46.7 cm/sec and a shaking width of 4.0 cm.

5 g of the shaken sample was then mixed with 50 ml of distilled water and 1 ml of Contaminon N (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.), and while stirring, a magnet was placed on the outside bottom of the beaker to separate the toner and carrier. The supernatant liquid containing the toner was filtered with a vacuum filter, then dried in a dryer for at least 1 hour, and after shaking, the toner was obtained. This was repeated until 1 g of toner was obtained.

The adhesion rate (%) is calculated from the ratio of the measured elements between the resulting shaken toner and the initial toner.

The adhesion rate was measured as follows:

160 g of sucrose (Kishida Chemical) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a concentrated sucrose solution. 31 g of the concentrated sucrose solution and 6 mL of Contaminon N (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a centrifuge tube (volume 50 ml) to prepare a dispersion. 1.0 g of toner is added to this dispersion, and the toner clumps are loosened with a spatula or the like.

The centrifuge tube is shaken in a shaker at 350 strokes per minute (spm) for 20 minutes. After shaking, the solution is transferred to a glass tube for a swing rotor (50 mL capacity) and separated in a centrifuge (H-9R, manufactured by Kokusan Co., Ltd.) at 3,500 rpm for 30 minutes. Visually check that the toner and the aqueous solution are sufficiently separated, and collect the toner separated in the top layer with a spatula or the like. The collected aqueous solution containing the toner is filtered with a vacuum filter, and then dried in a dryer for at least 1 hour. The dried product is crushed with a spatula, and the amount of silicon is measured by fluorescent X-rays. The adhesion rate (%) is calculated from the ratio of the amount of the measured element between the toner after shaking and the initial toner.

Measurements of X-ray fluorescence for each element are in accordance with JIS K 0119-1969, specifically as follows:

The measurement equipment used is a wavelength-dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and the accompanying dedicated software "SuperQ ver. 4.0F" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 10 seconds. In addition, detection is performed using a proportional counter (PC) when measuring light elements, and a scintillation counter (SC) when measuring heavy elements.

Measurements are performed under the above conditions, and the elements are identified based on the peak positions of the obtained X-rays, and their concentrations are calculated from the counting rate (unit: cps), which is the number of X-ray photons per unit time.

To quantify the amount of silicon in a toner, for example, add 0.5 parts by weight of organosilicon polymer fine powder to 100 parts by weight of toner particles, and mix thoroughly using a coffee mill. In the same way, mix 2.0 and 5.0 parts by weight of organosilicon polymer fine powder with the toner particles, respectively, and use these as samples for the calibration curve.

For each sample, a pellet of the calibration curve sample is prepared as described above using a tablet molding compression machine, and the count rate (unit: cps) of Si-Kα rays observed at a diffraction angle (2θ) = 109.08° when PET is used as the analyzing crystal is measured. At this time, the acceleration voltage and current value of the X-ray generator are 24 kV and 100 mA, respectively. A linear function calibration curve is obtained by taking the obtained X-ray count rate as the vertical axis and the amount of _SiO2 added in each calibration curve sample as the horizontal axis.

Next, the toner to be analyzed is pelletized as described above using a tablet molding compressor, and the count rate of the Si-Kα radiation is measured. The content of the organosilicon polymer in the toner is then calculated from the calibration curve. The ratio of the element amount of the toner after washing with water to the element amount of the initial toner calculated by the above method is calculated and used as the adhesion rate (%).

<Method of measuring the coverage of resin fine particles>
The coverage rate (unit: area %) of the resin fine particles on the toner particles from which the external additives had been removed using the above-mentioned water washing method was measured as follows.

The coverage rate of the resin microparticles was measured using observation and image measurement with a scanning electron microscope. In the observation with a scanning electron microscope, a magnification of 50,000 times was used to observe the resin microparticles. The above-mentioned Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (product name) was used as the scanning electron microscope.

The image capture conditions were as follows:

Sample preparation: Apply a thin layer of conductive paste to a sample stage (aluminum sample stage 15 mm x 6 mm) and spray toner onto it. Then, use air to remove excess toner from the sample stage and dry thoroughly. Set the sample stage in the sample holder and adjust the sample stage height to 36 mm using the sample height gauge.

Setting observation conditions for the S-4800 The coverage of resin particles is calculated using an image obtained by observing a backscattered electron image with the S-4800. Backscattered electron images have less charge-up than secondary electron images, so the coverage of resin particles can be measured with high accuracy.

Pour liquid nitrogen into the anti-contamination trap attached to the S-4800 housing until it overflows, and leave it for 30 minutes. Start the S-4800's "PC-SEM" and perform flushing (cleaning the FE chip, which is the electron source). Click the accelerating voltage display area on the control panel on the screen, and press the [Flushing] button to open the flushing execution dialog. Check that the flushing intensity is 2, and then execute. Check that the emission current due to flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.

Click the acceleration voltage display to open the HV setting dialog, and set the acceleration voltage to [0.8 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [Top (U)] and [+BSE] for the SE detector, and select [L.A. 100] in the selection box to the right of [+BSE] to set the mode to observation using backscattered electron images.

Also on the [Basic] tab of the operation panel, set the probe current in the electron optical system condition block to [Normal], the focus mode to [UHR], and the WD to [3.0 mm]. Press the [ON] button on the acceleration voltage display section of the control panel to apply the acceleration voltage.

(3) Focus adjustment Drag within the magnification display area on the control panel to set the magnification to 5000 (5k). Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the entire field of view is in focus to a certain extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. Rotate the STIGMA/ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and rotate the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop the image movement or adjust it so that it moves as little as possible. Close the aperture dialog and adjust the focus using autofocus. Repeat this operation two more times to adjust the focus.

Next, for the target toner, align the midpoint of the maximum diameter with the center of the measurement screen, and drag within the magnification display on the control panel to set the magnification to 10,000 (10k). Rotate the focus knob [COARSE] on the operation panel, and once the image is in focus to a certain extent, adjust the aperture alignment. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA/ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles.

Next, select [Aperture] and turn the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop the image movement or adjust it so that it moves as little as possible. Close the Aperture dialog and use autofocus to adjust the focus. After that, set the magnification to 50,000 (50k)x and use the focus knob and STIGMA/ALIGNMENT knob to adjust the focus as above, then use autofocus to adjust the focus again. Repeat this operation to adjust the focus. Here, if the tilt angle of the observation surface is large, the accuracy of the coverage measurement is likely to be low, so when adjusting the focus, select one that brings the entire observation surface into focus at the same time, and select one with as little surface tilt as possible for analysis.

Image storage Adjust the brightness in ABC mode, take a photo with a size of 640 x 480 pixels, and save it. Use this image file to perform the following analysis. Take one photo for each toner, and obtain images for at least 30 toner particles.

The observed image is binarized using image analysis software Image J (available from https://imagej.nih.gov/ij/). After binarization, only the resin particles corresponding to the diameter of the resin particles used are extracted, and the coverage rate (unit: area %) of the resin particles on the toner particles is calculated.

The above measurement is performed on 100 binarized images, and the average value of the resin microparticle coverage (unit: area %) is taken as the resin microparticle coverage.

<Method for measuring embedment rate of resin microparticles>
The embedding ratio (unit: %) of the resin fine particles in the toner particles from which the external additives were removed using the above-mentioned water washing method was calculated from the image obtained by S-4800, similarly to the above-mentioned coverage ratio.

The images used to calculate the embedding rate were different from the above-mentioned coverage rate. Images were selected where the observation surface had a large inclination angle, and the embedding rate was calculated as the ratio of the part b where the resin microparticles were embedded to the diameter a of the resin microparticles (see Figure 3).
Buried rate (%) = buried part of resin microparticle b / diameter of resin microparticle a

The above embedding rate was calculated for at least 100 resin microparticles, and the average value was taken as the embedding rate of the resin microparticles.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Parts in the following formulations are by weight unless otherwise specified.

<Production Example of Organosilicon Polymer Particles 1>
(First process)
A reaction vessel equipped with a thermometer and a stirrer was charged with 360.0 parts of water, and 15.0 parts of hydrochloric acid (concentration: 5.0% by mass) was added to obtain a homogeneous solution. 135.0 parts of methyltrimethoxysilane (a silane compound) was added to the homogeneous solution while stirring at a temperature of 25° C., and the mixture was stirred for 5 hours and then filtered to obtain a transparent reaction liquid.

(Second step)
In a reaction vessel equipped with a thermometer, a stirrer, and a dropping device, 440.0 parts of water was placed, and 17.0 parts of ammonia water with a concentration of 10.0 mass% was added to obtain a homogeneous solution. While stirring the homogeneous solution at a reaction initiation temperature of 35°C, 100 parts of the reaction liquid obtained in the first step was dropped over 1.2 hours (dropping time), and the mixture was stirred for 6 hours to obtain a suspension.

(Hydrophobizing process)
To the resulting suspension was added 30.0 parts of hexamethyldisilazane as a hydrophobizing agent, and the mixture was stirred for 2.5 hours at 60° C. After standing for 5 minutes, the powder that had precipitated at the bottom of the solution was recovered by suction filtration and dried under reduced pressure at 120° C. for 24 hours, yielding Organosilicon Polymer 1.

<Production Examples of Organosilicon Polymer Particles 2 to 14>
Organosilicon polymer particles 2 to 14 were obtained in the same manner as in the preparation example of organosilicon polymer particles 1, except that in the above-mentioned method for preparing organosilicon polymer particles, the amounts of various materials in the second step, the reaction initiation temperature, and the dropping time, and the type and amount of hydrophobizing agent in the hydrophobization step were changed as shown in Table 1. The physical properties of the resulting organosilicon polymer particles 2 to 14 are shown in Table 1.

表１中の略号は以下の通り。
ＨＭＤＳ：ヘキサメチルジシラザン
ＡＳ：アミノシランカップリング剤

The abbreviations in Table 1 are as follows.
HMDS: Hexamethyldisilazane AS: Aminosilane coupling agent

The measurement results in Table 1 were measured using the method described above.

<Production Example of Toner Particle 1>
The following materials were mixed using a Henschel mixer (FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 1500 rpm for a rotation time of 5 minutes, and then kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 135° C. to obtain a kneaded product.
Binder resin: 100 parts of the following polyester (Tg: 58°C, acid value: 15 mgKOH/g, hydroxyl value: 15 mgKOH/g, Mn: 3600, Mw: 96000); Fischer-Tropsch wax (peak temperature (melting point) of maximum endothermic peak: 90°C); 5.0 parts of C.I. Pigment Blue 15:3; 5.5 parts. The kneaded product obtained was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The coarsely pulverized product obtained was finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.) to obtain a finely pulverized product. The finely pulverized product obtained was further classified using a Faculty (F-300, manufactured by Hosokawa Micron Corporation) to obtain toner base particles 1 having a weight average particle size of 4.8 μm. The operating conditions of the above faculty were a classifying rotor rotation speed of 11,000 rpm and a dispersing rotor rotation speed of 7,200 rpm.

The polyester used as the binder resin was a polycondensate of 40 parts of polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane, 10 parts of polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane, 40 parts of terephthalic acid, 2 parts of trimellitic anhydride, and 8 parts of fumaric acid.

Toner base particles 1 100 parts Resin fine particles (acrylic resin; number average particle size R = 110 nm) 5 parts The above materials were mixed in a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 1900 rpm for a rotation time of 3 minutes, and then heat-treated by the heat treatment device shown in Fig. 2 to obtain toner particles 1. The operating conditions were a feed rate of 5 kg/hr, a hot air temperature of 150°C, a hot air flow rate of 6 ^m3 /min, a cold air temperature of -5°C, a cold air flow rate of 4 ^m3 /min, a blower air flow rate of 20 ^m3 /min, and an injection air flow rate of 1 ^m3 /min.

<Production Examples of Toner Particles 2 to 33>
In the above toner particle production example, the type and number average particle size of the resin fine particles, the number of parts, and the conditions of the Henschel mixer were changed as shown in Table 2, and the same procedure as in the toner particle production example 1 was carried out to obtain toner particles 2 to 33.

The physical properties of the resulting toner particles 1 to 33 are shown in Table 2.

<Toner Production Example>
Toner particles 1 100 parts Small particle size inorganic fine particles: titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (median diameter (D50) on a number basis of 10 nm) 0.5 parts Organosilicon polymer particles 1 (number average particle size S=130 nm) 1.0 part The above materials were mixed in a Henschel mixer (FM-75 model, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 1900 rpm for a rotation time of 10 minutes to obtain toner 1.

<Production Examples of Toners 2 to 42>
Toners 2 to 42 were obtained by carrying out the same operations as in Production Example of Toner 1, except that the type of organosilicon polymer particles and the adhesion rate A (%) of the organosilicon polymer particles to the toner particles after shaking the toner for 10 minutes under conditions of a shaking speed of 14.5 cm/sec and a shaking width of 3.0 cm were changed as shown in Table 3.

The physical properties of the obtained toners 1 to 42 are shown in Table 3. In Table 3, those that satisfy the relationship of formula (1) are marked with "○", and those that do not are marked with "×".

<Production Example of Magnetic Core Particle 1>
Step 1 (weighing and mixing step):
The ferrite raw materials were weighed so as to obtain the above composition ratio _, and then crushed and _mixed for 5 hours in a _dry vibration mill _using stainless steel beads having a diameter _of 1/8 inch.

Step 2 (pre-firing step):
The obtained pulverized material was made into pellets of about 1 mm square using a roller compactor. The pellets were passed through a vibrating sieve with 3 mm openings to remove coarse powder, and then through a vibrating sieve with 0.5 mm openings to remove fine powder. The pellets were then fired in a burner-type firing furnace at 1000° C. for 4 hours in a nitrogen atmosphere (oxygen concentration 0.01% by volume) to produce calcined ferrite. The composition of the calcined ferrite obtained was as follows:
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393

Step 3 (grinding step):
After crushing to about 0.3 mm with a crusher, 30 parts of water was added to 100 parts of the calcined ferrite and crushed in a wet ball mill using zirconia beads with a diameter of 1/8 inch for 1 hour. The slurry was crushed in a wet ball mill using alumina beads with a diameter of 1/16 inch for 4 hours to obtain a ferrite slurry (finely crushed calcined ferrite).

・Process 4 (granulation process):
To the ferrite slurry, 1.0 part of ammonium polycarboxylate as a dispersant and 2.0 parts of polyvinyl alcohol as a binder were added per 100 parts of calcined ferrite, and the mixture was dried in a spray dryer (manufacturer: Okawara Kakoki) to form spherical particles. The resulting particles were granulated, and the particle size was adjusted, and then the particles were heated at 650° C. for 2 hours in a rotary kiln to remove the organic components of the dispersant and binder.

Step 5 (firing step):
In order to control the firing atmosphere, the material was heated from room temperature to 1300° C. in a nitrogen atmosphere (oxygen concentration 1.00% by volume) in an electric furnace over a period of 2 hours, and then fired at a temperature of 1150° C. for 4 hours. The temperature was then lowered to 60° C. over a period of 4 hours, and the material was returned from the nitrogen atmosphere to the air and taken out at a temperature of 40° C. or less.

Step 6 (sorting step):
After the aggregated particles were crushed, low magnetic particles were removed by magnetic separation, and coarse particles were removed by sieving through a sieve with 250 μm openings, to obtain magnetic core particles 1 having a volume distribution-based 50% particle size (D50) of 37.0 μm.

<Preparation of Coating Resin 1>
Cyclohexyl methacrylate monomer 26.8% by mass
Methyl methacrylate monomer 0.2% by weight
Methyl methacrylate macromonomer 8.4% by mass
(Macromonomer having a weight average molecular weight of 5000 and a methacryloyl group at one end)
Toluene 31.3% by mass
Methyl ethyl ketone 31.3% by mass
Azobisisobutyronitrile 2.0% by mass
Among the above materials, cyclohexyl methacrylate monomer, methyl methacrylate monomer, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were placed in a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer, and nitrogen gas was introduced to create a sufficient nitrogen atmosphere, and the mixture was heated to 80° C. Then, azobisisobutyronitrile was added and the mixture was refluxed for 5 hours to polymerize. Hexane was poured into the resulting reaction product to precipitate a copolymer, and the precipitate was filtered and then vacuum dried to obtain coating resin 1.

30 parts of the obtained coating resin 1 were dissolved in 40 parts of toluene and 30 parts of methyl ethyl ketone to obtain polymer solution 1 (solid content 30% by mass).

<Preparation of Coating Resin Solution 1>
Polymer solution 1 (resin solid content concentration 30%) 33.3% by mass
Toluene 66.4% by mass
Carbon black (Regal 330; manufactured by Cabot Corporation) 0.3% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² /g, DBP oil absorption 75 ml/100 g)
The mixture was dispersed for 1 hour using a paint shaker with zirconia beads having a diameter of 0.5 mm. The resulting dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Production Example of Magnetic Carrier 1>
(Resin coating process):
The coating resin solution 1 was added to a vacuum degassing kneader maintained at room temperature so that the resin component was 2.5 parts per 100 parts of the magnetic core particles 1. After addition, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes, and after a certain amount (80 mass%) of the solvent had evaporated, the mixture was heated to 80° C. while mixing under reduced pressure, and the toluene was distilled off over 2 hours, followed by cooling.

The obtained magnetic carrier was separated into low magnetic particles by magnetic separation, passed through a sieve with an opening of 70 μm, and then classified using an air classifier to obtain magnetic carrier 1 with a 50% particle size (D50) based on volume distribution of 38.2 μm.

Toners 1 to 42 were added to magnetic carrier 1 so that the toner concentration was 8.0% by mass, and mixed using a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) under conditions of 0.5 s ^-1 and a rotation time of 5 min to obtain two-component developers 1 to 42, which are shown in Table 4.

Example 1
The obtained two-component developer and replenishment developer were used for the following evaluations.

A modified Canon color copier, ImagePRESS C850, was used as the image forming device.

A two-component developer was placed in the developing unit, a replenishment developer container containing replenishment developer was set, an image was formed, and various evaluations were performed before and after the durability test.

For durability testing, a FFH output chart with an image ratio of 1% was used in a printing environment of 23°C temperature and 5% RH (hereafter referred to as "N/L").

In addition, in a printing environment of 30°C temperature/80% RH (hereinafter referred to as "H/H"), a chart with FFH output at an image ratio of 1% and a chart with FFH output at an image ratio of 40% were used. FFH is a value that expresses 256 gradations in hexadecimal, with 00h being the first gradation of the 256 gradations (white background) and FFH being the 256th gradation of the 256 gradations (solid area).

The number of images output was 50,000 in each environment.

(conditions)
Paper: Laser beam printer paper CS-814 (81.4 g/ ^m2 )
(Canon Marketing Japan Inc.)
Image forming speed: A4 size, 85 sheets/min
Development conditions: The development contrast was made adjustable to any value, and the automatic correction by the main body was not activated. The peak-to-peak voltage (Vpp) of the alternating electric field was modified to a frequency of 2.0 kHz, and Vpp was modified to be variable in 0.1 kV increments from 0.7 kV to 1.8 kV. Each color was modified so that a monochrome image could be output.

[Evaluation of thin line reproducibility]
After carrying out the durability test described above using a chart with FFH output and an image ratio of 1% in an H/H environment, five FFH images with an image ratio of 100% were output. In addition, three evaluation images were output in which ten 0.25 pt thin lines were arranged at equal intervals parallel to the printing direction. The number of scattered and broken thin lines in the obtained evaluation images was evaluated according to the following criteria. The evaluation results are shown in Table 5.

(Evaluation Criteria)
A: 0 B: 1 or more, 3 or less C: 4 or more, 6 or less D: 7 or more, 8 or less E: 9 or more

[Image Density Change under H/H Environment]
Under H/H environment, FFH images of 15 mm x 15 mm size (toner amount on paper: 0.35 mg/ ^cm2 ) were printed on A4 size paper (CS-814) at nine locations in total, including the center and edges of the paper, and the density of the center of each image was measured using an X-Rite color reflection densitometer (X-Rite 404A). The average value of the obtained image densities was taken as Ds.

Furthermore, after a durability test was performed using a FFH output chart with an image ratio of 1% in an H/H environment, evaluation images were output in the same manner as before the durability test, and the average value of the obtained image density was taken as _Dl1 .

In addition, after a durability test was performed in an H/H environment using a FFH output chart with an image ratio of 40%, an evaluation image was output in the same manner as before the durability test, and the average value of the obtained image density was taken as _Dl2 .

_D1 and _D2 were calculated from the average image density obtained by the following calculation formula, and the image was evaluated according to the following criteria. The evaluation results are shown in Table 5.
_D1 = Dl1 - _Ds
D2 = Dl2 - _Ds

(Evaluation Criteria)
A: 0.00≦|Dx|<0.03
B: 0.03≦|Dx|<0.06
C: 0.06≦|Dx|<0.09
D: 0.09≦|Dx|<0.12
E: 0.12≦|Dx| (x is 1 or 2)

[Evaluation of post-durability developability (electric field followability)]
In an N/L environment, the initial Vpp was fixed at 1.3 kV, and the contrast potential was set at which the density of a cyan monochrome solid image reached 1.50 (reflection density).

With this setting, a chart with an FFH output and an image ratio of 5% was used, and after the durability test described above, the contrast potential at which the image density became 1.50 was determined with a Vpp of 1.3 kV, and the difference from the initial value was compared. The evaluation was performed in monochromatic cyan.

The reflection density was measured using a spectrodensitometer 500 series (manufactured by X-Rite). The evaluation results are shown in Table 5.

(Evaluation Criteria)
A: The difference from the initial state is less than 40V. B: The difference from the initial state is 40V or more and less than 60V. C: The difference from the initial state is 60V or more and less than 80V. D: The difference from the initial state is 80V or more and less than 100V. E: The difference from the initial state is 100V or more.

[Evaluation of component contamination prevention]
As the image forming apparatus, a modified Canon digital commercial printing printer imageRUNNER ADVANCE C5560 was used, and two-component developer 1 was placed in the developing device at the black position. The apparatus was modified so that the fixing temperature, process speed, direct current voltage VDC of the developer carrier, charging voltage VD of the electrostatic latent image carrier, and laser power could be freely set. The image output evaluation was performed by outputting an FFh image (solid image) with a desired image ratio, and adjusting VDC, VD, and laser power so that the toner loading amount of the FFh image was desired, and then performing the evaluation described below.

After the durability test, the product was evaluated according to the following evaluation method, and the results are shown in Table 5.

(1) Durability test paper: GFC-081 (81.0 g/ ^m2 )
(Canon Marketing Japan Inc.)
Evaluation image: 00h image Test environment: High temperature and high humidity environment (temperature 30°C/humidity 80% RH (hereinafter H/H))
Fixing temperature: 160°C
Process speed: 377 mm/sec
The above evaluation images were output on 100,000 sheets and a durability test was carried out.

(2) Evaluation paper for suppressing contamination of components: GFC-081 (81.0 g/m ² )
(Canon Marketing Japan Inc.)
Vcontrast: 350V
(Adjusted by DC voltage VDC of developer carrier, charging voltage VD of electrostatic latent image carrier, and laser power)
Evaluation image: 80-hour image printed on the entire surface of the A3 paper Test environment: Normal temperature and humidity environment: Temperature 23°C / Humidity 50% RH (hereinafter referred to as "N/N")
Fixing temperature: 170°C
Process speed: 377 mm/sec

The above evaluation image was output, and the member contamination suppression was evaluated. Before the durability evaluation, a solid image was output on the entire surface of A3 paper for 80 hours, and the average density of six points of the output image was set as ds. The DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, the laser power, and the transfer current were set in the same manner as before the durability evaluation, and the average density de of six points of the output image after the durability evaluation was measured, and the density change was calculated using the following formula. Since the charging ability and the like are reduced by the member contamination and appear as a density change of the image, the density change before and after the durability evaluation was used as an index of the member contamination suppression. It was judged that the effect of the present invention was obtained when it was C or higher.
Density change = de - ds

(Evaluation Criteria)
A: Density change is less than 0.10 B: Density change is 0.10 or more and less than 0.15 C: Density change is 0.15 or more and less than 0.25 D: Density change is 0.25 or more and less than 0.35 E: Density change is 0.35 or more

[Examples 2 to 35 and Comparative Examples 1 to 6]
Except for using two-component developers 2 to 42, the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 5.

1A. Aspirator, 2A. Measuring container, 3A. Screen, 4A. Lid, 5A. Vacuum gauge, 6A. Air flow control valve, 7A. Suction port, 8A. Condenser, 9A. Electrometer, 1. Raw material fixed amount supply means, 2. Compressed gas flow rate adjustment means, 3. Inlet tube, 4. Projection member, 5. Supply tube, 6. Treatment chamber, 7. Hot air supply means, 8. Cold air supply means, 9. Regulating means, 10. Recovery means, 11. Hot air supply means outlet, 12. Distribution member, 13. Swirling member, 14. Powder particle supply port

Claims (7)

A toner having toner particles and an external additive,
The external additive contains organosilicon polymer particles,
the organosilicon polymer particles have an absolute charge quantity Q (mC/kg) of 200 (mC/kg) or less;
the organosilicon polymer particles have a number average particle size S (nm) of 25 nm or more and 250 nm or less;
the toner particles have an arithmetic average roughness Ra (nm) measured by a scanning probe microscope of 15 nm or more and 200 nm or less;
The toner is characterized in that the relationship between the number average particle size S (nm) of the organosilicon polymer particles and the arithmetic mean roughness Ra of the toner particles satisfies the following formula (1):
Ra≦S (1) The toner according to claim 1, wherein the arithmetic mean roughness Ra (nm) of the toner particles measured by a scanning probe microscope is 70 nm or more and 150 nm or less. The toner according to claim 1 or 2, wherein the ten-point average roughness Rzjis (nm) of the toner particles measured by a scanning probe microscope is 70 nm or more and 250 nm or less. The toner according to any one of claims 1 to 3, wherein the toner is shaken for 10 minutes at a shaking speed of 14.5 cm/sec and a shaking width of 3.0 cm, the toner after shaking is dispersed in ion-exchanged water containing a surfactant, and the resulting dispersion is shaken for 5 minutes at a shaking speed of 46.7 cm/sec and a shaking width of 4.0 cm, and the adhesion rate A of the organosilicon polymer particles to the toner particles is measured using a sample obtained by the above-mentioned method, and is 75% or more. The toner particles have protrusions that form the roughness of the toner particles,
The convex portions are formed by embedding the resin fine particles in the toner base particles,
The embedding rate of the resin microparticles is 15% or more and less than 50%;
a coverage rate of the resin fine particles in the toner particles is 20% or more and 50% or less;
5. The toner according to claim 1, wherein the number average particle diameter R (nm) of said fine resin particles is equal to or less than the number average particle diameter S (nm) of said organosilicon polymer particles. The toner according to claim 5, wherein the resin particles have a carbonyl group. The toner according to any one of claims 1 to 6, wherein the organosilicon polymer particles contain silanol groups, and the amount of moisture adsorbed at a relative humidity of 80% in a moisture adsorption isotherm at 30°C is 5 mg/g or more and 35 mg/g or less.

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