JP2016142758A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that satisfies demands for cleaning property, contamination prevention in a charging member, and followability to a solid image upon outputting a great number of images in a low temperature and low humidity environment, all in high levels in a capsule toner aiming to achieve both low-temperature fixability and heat-resistant storage property.SOLUTION: A toner includes: toner particles having a core-shell structure having a core comprising a binder resin and a shell comprising a polyester resin (A) formed on a surface of the core; and an external additive (A). The polyester resin (A) shows a dielectric loss tangent of 0.0070 or more and 0.0140 or less; and the toner contains the polyester resin (A) by 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin. The external additive (A) comprises organic inorganic composite fine particles in which inorganic fine particles (a) are exposed on a surface of resin particles so as to form projections derived from the inorganic fine particles (a) on the surface; and an abundance of the inorganic fine particles (a) on the surface of the organic inorganic composite fine particles is 20% or more and 70% or less.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic image forming method for developing an electrostatic image.

In recent years, printers and copiers have been required to have higher speed and lower power consumption, and toner fixing performance has been improved. On the other hand, the toner cartridge may be exposed to a high temperature during transportation, and it is required to simultaneously satisfy heat-resistant storage stability that does not cause a change such as toner solidification in such an environment. In order to satisfy these requirements, research and development of capsule toners in which a core having excellent fixing performance is covered with a shell having excellent heat resistance has been actively conducted. Among these, a polymerized toner produced by a polymerization method such as a suspension polymerization method, an emulsion polymerization aggregation method, or a dissolution suspension method has attracted attention because it can easily form a capsule structure.
These polymerized toners are easier to obtain smaller particle size, spherical shape, and sharper particle size distribution than conventional pulverized toners, and are excellent in transferability and fine line reproducibility, resulting in high quality image quality. Has characteristics.

On the other hand, since the toner becomes easier to pass through the cleaning blade as the spherical shape and the particle diameter become smaller, the residual toner after transfer on the electrophotographic photosensitive member (hereinafter also referred to simply as the photosensitive member) or on the intermediate transfer member is removed. Tend to be difficult. As described above, when the capsule toner is employed, it is a big problem to ensure the cleaning performance in any use environment.
As countermeasures for preventing poor cleaning of a small-sized and spherical capsule toner, for example, an attempt is made to prevent the toner from slipping by increasing the linear pressure applied to the edge portion of the cleaning blade. However, this measure by simply increasing the linear pressure promotes problems such as the chipping of the blade edge is promoted, abnormal noise is generated due to chatter vibration of the blade, and the wear of the photosensitive member is promoted by the contact of the blade. There is.
For this reason, a method has been proposed in which an external additive is retained in the blade edge portion to form a blocking layer, and toner particles are blocked to stabilize cleaning (see, for example, Patent Document 1). In this method, the external additive that forms the blocking layer slips through the blade and contaminates the charging member. Therefore, it is necessary to provide a mechanism for cleaning the charging member, which complicates the mechanism and increases the cost.

In addition, as a means for improving the cleaning performance, a method of adding an external additive having a large particle diameter of about several hundred nanometers has been proposed (see, for example, Patent Documents 2 and 3).
The addition of the external additive having a large particle size produces a so-called spacer effect, and the adhesion of toner to the photosensitive member and the intermediate transfer member is reduced, so that the cleaning performance is improved.
As a generally used large particle size external additive, for example, a large particle size external additive having a spherical shape and a sharp particle size distribution such as sol-gel silica and resin particles is used. However, when the surface of the external additive has a single composition of silica, the electrostatic adhesion to the photosensitive drum is high, and the effect on the cleaning property with the spherical toner is insufficient. In addition, a spherical external additive has a problem that it easily slips through the cleaning blade and contaminates the charging member. Furthermore, when used under harsh conditions such as printing multiple sheets with a single-component developing device in a low-temperature and low-humidity environment, the fluidity of the toner decreases due to embedding and releasing of external additives, resulting in poor solid followability. There was also a problem to do.

JP 2002-318467 A Japanese Patent No. 4390994 JP 2007-171666 A

The present invention has been made in view of the above problems and situations, and an object of the present invention is to provide a toner capable of solving the above problems.
In other words, in capsule toners that are compatible with both low-temperature fixing and heat-resistant storage stability, it provides a toner that satisfies a high level of cleanability, prevention of charging member contamination, and solid-state followability when outputting multiple images in a low-temperature, low-humidity environment. It is to be.

The present invention is a toner comprising a core containing a binder resin, core-shell structured toner particles having a shell containing a polyester resin A formed on the surface of the core, and an external additive A.
The dielectric loss tangent of the polyester resin A at 25 ° C. and 10,000 Hz is 0.0070 or more and 0.0140 or less,
The toner contains 1.0 to 20.0 parts by mass of the polyester resin A with respect to 100.0 parts by mass of the binder resin.
The external additive A is organic-inorganic composite fine particles,
The organic-inorganic composite fine particles are particles in which the inorganic fine particles a are exposed on the surface of the organic resin particles so that convex portions derived from the inorganic fine particles a are formed on the surface. Yes,
The present invention relates to a toner characterized in that the abundance of inorganic fine particles a on the surface of the organic-inorganic composite fine particles is 20% or more and 70% or less.

  According to the present invention, even in a capsule toner that is compatible with both low-temperature fixing and heat-resistant storage stability, the cleaning property, the prevention of contamination of the charging member, and the solid follow-up property when outputting a large number of images in a low-temperature and low-humidity environment at a high level. A satisfactory toner can be provided.

As a result of intensive studies, the present inventors have made the structure and physical properties described in detail below in the polyester resin and external additive forming the shell, so that cleaning property, prevention of contamination of the charging member, and low temperature and low humidity environment Has found that it is possible to provide a capsule toner that satisfies the solid followability when a large number of images are output.
The toner of the present invention is a toner in which an external additive A is externally added to toner particles having a core-shell structure in which a shell containing a polyester resin A is formed on a core containing a binder resin.

  The external additive A in the present invention is organic-inorganic composite fine particles in which the inorganic fine particles a are exposed on the surface of the organic resin particles so that convex portions derived from the inorganic fine particles a are formed on the surface. The organic-inorganic composite fine particles have a form like silica-polymer particles reported at the 109th Japan Imaging Society Research Meeting. As reported here, the silica-polymer particles have low specific gravity and many contact points due to surface irregularities while exhibiting chargeability and fluidity equivalent to colloidal silica. It is shown that it has the characteristic that there are few. As a result, it is reported that the spacer effect and the blocking resistance are more effectively exhibited with respect to the toner having a small particle diameter and a low melting point. The silica-polymer particles are also disclosed in International Publication No. 2013/063291 and JP2013-92748A.

In the present invention, the abundance of the inorganic fine particles a on the surface of the organic / inorganic composite fine particles needs to be 20% or more and 70% or less. If the abundance of the inorganic fine particles a on the surface of the organic / inorganic composite fine particles is less than 20%, the convex portions derived from the inorganic fine particles a are few, so that the cleaning blade passes through and contaminates the charging member. If it exceeds 70%, the electrostatic adhesion force to the photosensitive member becomes high and the cleaning property is deteriorated. More preferably, the abundance of the inorganic fine particles a is 30% or more and 60% or less.
The abundance of the inorganic fine particles a can be appropriately controlled by changing the particle size of the inorganic fine particles used in the production of the organic-inorganic composite fine particles, the amount ratio of the inorganic fine particles to the resin, and the production conditions.
The organic-inorganic composite fine particles of the present invention can be produced by the method described in International Publication No. 2013/063291.

The inorganic fine particles a used for the organic / inorganic composite fine particles or the organic / inorganic composite fine particles are preferably chemically hydrophobized with an organosilicon compound that physically adsorbs to them. As a preferred method, silica fine particles produced by vapor phase oxidation of a silicon halogen compound are treated with an organosilicon compound. Examples of such organosilicon compounds include the following.
Hexamethyldisilazane, methyltrimethoxysilane, octyltrimethoxysilane, isobutyltrimethoxysilane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane , Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, Dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1-hexamethyl Disiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and dimethylpolysiloxane. These are used by 1 type, or 2 or more types of mixtures.

The inorganic fine particles a used for the organic / inorganic composite fine particles or the organic / inorganic composite fine particles may be treated with silicone oil, or may be treated together with the hydrophobization treatment.
As a preferable silicone oil, one having a viscosity at 25 ° C. of 30 mm ² / s or more and 1000 mm ² / s or less is used. For example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil are particularly preferred.
Examples of the method for treating silicone oil include the following methods. A method in which silica fine particles treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer. A method of spraying silicone oil onto silica fine particles as a base. Alternatively, it is preferable to dissolve or disperse silicone oil in an appropriate solvent, and then add and mix silica fine particles to remove the solvent.

Examples of the inorganic fine particles a of the organic-inorganic composite fine particles of the present invention include silica, alumina, titania, zinc oxide, strontium titanate, cerium oxide, calcium carbonate and the like. In particular, when the inorganic fine particles are silica, it is preferable because the chargeability is excellent and an effect on the developability is obtained. Silica may be obtained by a dry method such as fumed silica, or may be obtained by a wet method such as sol-gel silica.
The content of the inorganic fine particles a in the organic / inorganic composite fine particles is preferably 30% by mass or more and 80% by mass or less based on the organic / inorganic composite fine particles from the viewpoint of production stability and particle size distribution control.

In order to improve the cleaning property and stably maintain the performance, it is preferable that the external additive is present in a state where it is difficult to roll. Therefore, the organic-inorganic composite fine particles have a shape factor SF-2 measured using an enlarged image (magnification of 200,000 times) of the organic-inorganic composite fine particles photographed using a scanning electron microscope of 103 to 120. preferable.
SF-2 is an index indicating the degree of unevenness of the surface. If SF-2 is smaller than 103, the organic-inorganic composite fine particles are likely to roll on the toner surface, and therefore, the electrostatic adhesion force to the photoreceptor tends to be high. . In addition, the organic / inorganic composite fine particles are less likely to be caught by the cleaning blade, and as a result, it is difficult to form a firm blocking layer, and a defective cleaning tends to occur. If SF-2 is greater than 120, the cleaning blade tends to be scratched, but the photosensitive drum is likely to be damaged. More preferably, SF-2 is 105 or more and 120 or less.
The shape factor SF-2 of the organic-inorganic composite particles can be appropriately controlled by changing the particle size of the inorganic fine particles used in the production of the organic-inorganic composite particles or the amount ratio of the inorganic fine particles to the resin.

The organic-inorganic composite fine particles preferably have a number average particle size (A) of 50 nm or more and 400 nm or less. If the number average particle size (A) of the organic-inorganic composite fine particles is smaller than 50 nm, the cleaning blade will pass through and the member will be easily contaminated. If it is larger than 400 nm, the organic-inorganic composite particles are easily released from the toner, and image defects such as streaks are likely to occur. More preferably, the number average particle diameter (A) is from 80 nm to 250 nm, and more preferably from 90 nm to 200 nm.
The number average particle size (A) of the organic / inorganic composite fine particles can be controlled by changing the particle size of the inorganic fine particles used for the production of the organic / inorganic composite particles and the quantitative ratio of the inorganic fine particles to the resin.

  The amount of the organic / inorganic composite fine particles added is preferably 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles. Within the above range, it is possible to satisfactorily form the blocking layer while suppressing the occurrence of scratches on the photosensitive drum, and to satisfactorily suppress poor cleaning. More preferably, it is 0.5 parts by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

The toner of the present invention preferably contains inorganic fine particles b as the second external additive. By containing the inorganic fine particles b, chargeability and fluidity can be imparted. As the inorganic fine particles b, wet-process silica, fine-powder silica such as dry-process silica, silica treated with a silane coupling agent, titanium coupling agent, or silicone oil, or titanium oxide, etc. Is mentioned. The inorganic fine particles b may be the same as or different from the inorganic fine particles a.
From the viewpoint of imparting electric charge and fluidity, dry process silica or fumed silica produced by vapor phase oxidation of a silicon halogen compound is preferred. For example, the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen is utilized, and the reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl
Further, in this production process, a composite fine powder of silica and another metal oxide obtained by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound may be used.

Furthermore, it is preferable to use a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of the silicon halogen compound. Among the treated silica fine powders, those obtained by treating the silica fine powder so that the degree of hydrophobicity titrated by a methanol titration test is in the range of 30 to 98 are particularly preferable.
As a hydrophobizing method, it is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound. Examples of such organosilicon compounds include the following.

  Hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloro Ethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1- Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyl Rudisiloxane and dimethylpolysiloxane. These are used by 1 type, or 2 or more types of mixtures.

The silica fine powder may be treated with silicone oil in order to improve the slipperiness of the photoreceptor. Moreover, you may process together with the said hydrophobic treatment.
As a preferable silicone oil, one having a viscosity at 25 ° C. of 30 mm ² / s or more and 1000 mm ² / s or less is used. For example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil are particularly preferred.
Examples of the method for treating silicone oil include the following methods. A method in which silica fine powder treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer. A method of spraying silicone oil onto silica fine powder as a base. Alternatively, after dissolving or dispersing silicone oil in a suitable solvent, silica fine powder is added and mixed to remove the solvent. More preferably, the silicone oil-treated silica is heated to 200 ° C. or higher (more preferably 250 ° C. or higher) in an inert gas to stabilize the surface coating after the silicone oil treatment.

A preferred silane coupling agent is hexamethyldisilazane (HMDS).
In the present invention, the silica is preferably treated by a method in which silica is treated with a coupling agent and then treated with silicone oil, or a method in which silica is treated with a coupling agent and silicone oil at the same time.
The inorganic fine particles b are preferably used in an amount of 0.01 parts by mass or more and 5.00 parts by mass or less, more preferably 0.10 parts by mass or more and 3.00 parts by mass or less with respect to 100.00 parts by mass of the toner particles. .

  The inorganic fine particles b as the second external additive have a ratio (A / B) where the number average particle size of the organic-inorganic composite fine particles is A (nm) and the number average particle size of the inorganic fine particles b is B (nm). ) Is preferably 1.5 or more and 10.0 or less, and more preferably 2.5 or more and 8.5 or less. When the ratio (A / B) of the number average particle diameter (A) to the number average particle diameter (B) is within the above range, it is possible to satisfactorily suppress toner fluidity reduction and fogging. The number average particle diameter B of the inorganic fine particles b is preferably 5 nm or more and 40 nm or less.

The toner particles of the present invention may be toner particles having a core-shell structure in which a shell layer containing polyester resin A is formed on a core containing a binder resin, and if necessary, a colorant and a wax. And a polymerization method. Among these, the production by a production method including a step of granulating in an aqueous medium such as a suspension polymerization method or a dissolution suspension polymerization method is preferable in terms of easy formation and control of the core-shell structure. In particular, toner particles produced by a suspension polymerization method that is easy to obtain a core-shell structured toner particle that can be easily reduced in particle size and has a close to spherical shape and less surface irregularities are preferable.
For example, in the suspension polymerization method, a colorant and a wax are added to the polymerizable monomer and the polar resin as necessary to produce toner particles, and the binder resin is added mainly as necessary. Thus, toner particles having a core-shell structure in which a core formed from the formed colorant and wax is coated with a shell layer formed from a polar resin can be obtained.

In the present invention, a polyester resin A described in detail below is added as a polar resin for forming a shell layer of toner particles.
The dielectric loss tangent of the polyester resin A of the present invention at 25 ° C. and 10000 Hz is 0.0070 or more and 0.0140 or less. When the dielectric loss tangent is 0.0070 or more, the shell layer on the toner surface has an appropriate charge leakage property, and good solid followability can be obtained without being charged up even under severe conditions. In addition, when the dielectric loss tangent is 0.0140 or less, charging failure due to excessive leakage of charges is suppressed, and good solid followability can be obtained without any adverse effects such as fogging. The dielectric loss tangent is more preferably 0.0080 or more and 0.0120 or less.

  The organic-inorganic composite fine particles described above exhibit excellent effects in improving cleaning properties and preventing contamination of the charging member. On the other hand, since organic-inorganic composite fine particles have a structure in which inorganic fine particles are embedded in resin particles, it is considered that charge-up due to resin tends to occur. For this reason, when used under severe conditions such as printing with a single component developing device in a low-temperature and low-humidity environment, there is a concern that the fluidity of the toner is reduced due to electrostatic aggregation and the solid followability is poor. On the other hand, in the present invention, the authors believe that by using the polyester resin A in which the dielectric loss tangent is appropriately controlled, charges are appropriately leaked, charge-up can be suppressed, and good solid followability can be obtained. Yes.

The dielectric loss tangent of the polyester resin A can be adjusted by appropriately adjusting the alcohol component and acid component used in preparing the polyester, and the content thereof. Specifically, by adding a component having an ether structure such as an isosorbide unit represented by the formula (1) or ethylene glycol, the dielectric loss tangent can be increased, and the dielectric loss tangent can be set to an arbitrary value depending on the content thereof. Can be adjusted.
In the present invention, it is particularly preferable to adjust the dielectric loss tangent within the above range by adjusting the content of the isosorbide unit.

The reason why it is preferable to adjust the content of the isosorbide unit is presumed to be due to the following effects.
Since the isosorbide unit has an ether bond in the cyclic structure, the influence on the dielectric loss tangent per unit is not so large as compared with a unit having an ether bond such as ethylene glycol, and is moderate. Therefore, it is presumed that the polyester resin does not partially increase the dielectric loss tangent and can impart an appropriate dielectric loss tangent to the polyester resin A.

The content of the isosorbide unit is preferably 0.10 mol% or more and 20.00 mol% or less based on all the monomer units of the polyester resin A.
When the content of the isosorbide unit is within the above range, it is easy to control the dielectric loss tangent of the polyester resin A within the range of the present invention. Further, since the glass transition temperature of the polyester resin A tends to increase as the isosorbide unit content increases, the above range is preferable also in terms of reducing fixing inhibition by the polyester resin A as a shell.
More preferably, it is 1.00 mol% or more and 15.00 mol% or less.

In the toner of the present invention, the polyester resin A is 1.0 parts by mass or more and 20.0 parts by mass or less, preferably 1.5 parts by mass or more and 10.10 parts by mass with respect to 100.0 parts by mass of the binder resin forming the core. Contains 0 parts by mass or less.
When the amount of the polyester resin A is less than 1.0 part by mass, the formation of the shell layer is insufficient, so that the effect of suppressing the charge-up by the polyester resin A cannot be sufficiently obtained.
When the amount of the polyester resin A is more than 20.0 parts by mass, it becomes difficult to dissolve in the polymerizable monomer, the formation of the shell becomes unstable, the heat resistant storage stability and the stress resistance are deteriorated, etc. Development properties such as fogging and image density stability may be deteriorated.

The acid value of the polyester resin A is preferably 0.5 mgKOH / g or more and 25.0 mgKOH / g or less, and more preferably 0.5 mgKOH / g or more and 15.0 mgKOH / g or less. Since the shell layer is more firmly formed when the acid value of the polyester resin A is 0.5 mgKOH / g or more, the effect of suppressing the charge-up by the polyester resin A can be more effectively obtained.
Further, when the acid value of the polyester resin A is 25.0 mgKOH / g or less, a sharper particle size distribution is obtained when toner particles are produced by suspension polymerization, and image defects such as fog are less likely to occur. .
This acid value can be made into the said range by adjusting the kind and compounding quantity of the monomer used for resin. Specifically, it can be controlled by adjusting the alcohol monomer component ratio / acid monomer component ratio and molecular weight during resin production.

In the polyester resin A of the present invention, it is desirable to use isosorbide as an alcohol component, but the following can also be used as other alcohol components.
Examples of the dihydric alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl). ) Propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4) -Alkylene oxide adducts of bisphenol A such as hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene Glycol, 1,3-propylene glycol, 1,4-butanediol, neope Fats such as til glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Group-based diols; bisphenol A such as bisphenol A and hydrogenated bisphenol A.

Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene Can be mentioned.

Moreover, the following are mentioned as an acid component used in order to form the polyester resin A. For example, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid; carbon numbers such as fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid Aliphatic polycarboxylic acids such as succinic acid substituted with 1-20 alkyl groups or alkenyl groups with 2-20 carbon atoms; anhydrides of these acids and alkyl (1-8 carbon atoms) esters of these acids Is mentioned. Among them, in particular, a polyester obtained by polycondensation using a bisphenol derivative as an alcohol component and a divalent or higher carboxylic acid or acid anhydride thereof or a lower alkyl (carbon number 1 to 8) ester thereof as an acid component. Resin A can be preferably used.
In the present invention, conventionally known polyester resins may be used in combination with the polyester resin A.

Next, the toner and the toner production method of the present invention will be described in detail.
The weight average particle diameter (D4) of the toner of the present invention is preferably 4.0 μm or more and 9.0 μm or less. More preferably, it is 5.0 μm or more and 7.5 μm or less.
When the weight average particle diameter of the toner is 4.0 μm or more, the fluidity of the toner is good, and it is difficult to cause adverse effects such as fogging, scattering, and low image density. Further, the cleaning property of the transfer residual toner remaining on the photosensitive member and the intermediate transfer member is improved, and the photosensitive member, the intermediate transfer member, and the charging member are hardly contaminated. Moreover, when it is 9.0 μm or less, it becomes difficult to cause deterioration of reproducibility of fine lines such as minute characters and image scattering, and a high-quality image desired recently can be provided.

Hereinafter, the toner particles produced by the suspension polymerization method, which is a preferred production method of the toner particles of the present invention, will be described in detail.
The toner particles produced by the suspension polymerization method of the present invention are produced, for example, as follows. A polymerizable monomer composition is prepared by mixing a polymerizable monomer, if necessary, a colorant composition, a wax and a polymerization initiator. Next, the polymerizable monomer composition is dispersed in an aqueous medium to form (granulate) particles of the polymerizable monomer composition. Then, the polymerizable monomer in the particles of the polymerizable monomer composition is polymerized in an aqueous medium to obtain toner particles.

The binder resin according to the present invention is preferably a styrene acrylic resin. As the polymerizable monomer for obtaining such a binder resin, a vinyl polymerizable monomer capable of radical polymerization is preferable. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.
Examples of the monofunctional polymerizable monomer include the following. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n- Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n -Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl Phosphate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as methacrylate; methylene aliphatic monocarboxylic acid ester; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl Vinyl ethers such as ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone;

  The following are mentioned as a polyfunctional polymerizable monomer. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2 '-Bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-bu Lenglycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxy-diethoxy) phenyl) propane, 2,2′-bis ( 4- (methacryloxy polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether.

A monofunctional polymerizable monomer is used individually or in combination of 2 or more types or in combination with a polyfunctional polymerizable monomer. The polyfunctional polymerizable monomer can also be used as a crosslinking agent.
The polymerizable monomer composition in the above step is prepared by mixing a dispersion in which a colorant is dispersed in the first polymerizable monomer with the second polymerizable monomer. Is preferred. That is, after sufficiently dispersing the colorant with the first polymerizable monomer, the colorant is mixed with the second polymerizable monomer together with the other toner materials, so that the colorant is in a better dispersed state. It can be present in the toner particles.

As a polymerization initiator used in the polymerization of the polymerizable monomer, an oil-soluble initiator and / or a water-soluble initiator is used. Examples of oil-soluble initiators include the following. 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4 -Pigment dispersants such as methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t- Butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide Peroxide initiators such as id, di-t-butyl peroxide and cumene hydroperoxide.
The following are mentioned as a water-soluble initiator. Ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) Hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

In order to control the degree of polymerization of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor or the like can be further added and used.
The concentration of the polymerization initiator is preferably in the range of 0.1 to 20 parts by mass, more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer. The kind of the polymerizable initiator is slightly different depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

Furthermore, in the present invention, a crosslinking agent can be used during the synthesis of the vinyl polymer in order to increase the stress resistance of the toner particles and to control the molecular weight of the particle constituent molecules.
As the crosslinking agent, a compound having two or more polymerizable double bonds is used. Specifically, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; two compounds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, and 1,3-butanediol dimethacrylate. Examples thereof include carboxylic acid esters having two heavy bonds; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.
These cross-linking agents are preferably in the range of 0.05 to 10 parts by mass, more preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer in terms of toner fixability and offset resistance. Used in the range of 5 parts by mass.

  The polymerizable monomer and the crosslinking agent are used alone or by appropriately mixing monomers so that the theoretical glass transition temperature (Tg) is in the range of 40 to 75 ° C. When the theoretical glass transition temperature is 40 ° C. or higher, there is little problem in terms of storage stability and stress resistance of the toner, while when it is 75 ° C. or lower, transparency and low-temperature fixability in the case of toner full-color image formation. Is preferable because it does not decrease.

The aqueous medium used in the suspension polymerization method preferably contains a dispersion stabilizer. As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used. Examples of inorganic dispersion stabilizers include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate. , Barium sulfate, bentonite, silica, alumina and the like.
Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. Nonionic, anionic and cationic surfactants can also be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like can be mentioned.

  Among the above dispersion stabilizers, in the present invention, it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in an acid. In the present invention, when preparing a water-based dispersion medium using a hardly water-soluble inorganic dispersion stabilizer, these dispersion stabilizers are added in an amount of 0.2 to 2 to 100 parts by mass of the polymerizable monomer. It is preferable to use it in a proportion that is in the range of 0.0 part by mass. This is because, when used in such a ratio, the droplet stability of the polymerizable monomer composition in the aqueous medium is improved. Moreover, in this invention, it is preferable to prepare an aqueous medium using the water of the range of 300-3000 mass parts with respect to 100 mass parts of polymerizable monomer compositions.

  In the present invention, when preparing an aqueous medium in which the poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is. However, in order to obtain dispersion stabilizer particles having a fine uniform particle size, it is preferable to prepare by preparing the above hardly water-soluble inorganic dispersion stabilizer under high speed stirring in water. For example, when calcium phosphate is used as a dispersion stabilizer, a preferable dispersion stabilizer can be obtained by mixing a sodium phosphate aqueous solution and a calcium chloride aqueous solution under high speed stirring to form calcium phosphate fine particles.

In the suspension polymerization method, a polar resin is added to the polymerizable monomer composition to produce toner particles, whereby a binder resin that mainly forms a core and a wax or the like that is added as necessary is polyester. A toner having a core-shell structure coated with a polar resin (shell) such as resin A can be obtained.
For this reason, these polymerized toners contain wax in a toner well, so that even if a relatively large amount of wax is contained, exposure to the surface of the toner is small and toner deterioration in continuous printing is suppressed. Can do.

As the colorant of the toner of the present invention, the following black, yellow, magenta and cyan pigments and, if necessary, dyes can be used.
A known black colorant can be used as the black colorant.
For example, the black colorant includes carbon black.
Moreover, the following yellow / magenta / cyan colorants are mixed and adjusted to black.
Although there is no restriction | limiting in particular as carbon black, For example, carbon black obtained by manufacturing methods, such as a thermal method, an acetylene method, a channel method, a furnace method, a lamp black method, can be used.

The average primary particle size of the carbon black used in the present invention is not particularly limited, but the average primary particle size is preferably 14 to 80 nm, more preferably 25 to 50 nm. When the average primary particle size is 14 nm or more, the toner does not exhibit a reddish color and is preferable as black for forming a full-color image. When the average primary particle size of carbon black is 80 nm or less, it is preferable that the carbon black is well dispersed and the coloring power is not too low.
The average primary particle size of carbon black can be measured by taking a photograph enlarged with a scanning electron microscope.
The carbon black may be used alone or in combination of two or more.
These may be crude pigments, and may be prepared pigment compositions as long as they do not significantly inhibit the effects of the present invention.

A known yellow colorant can be used as the yellow colorant.
As the pigment-based yellow colorant, compounds represented by condensed polycyclic pigments, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 155, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191: 1, 191, 192, 193 199.
Examples of the dye-based yellow colorant include C.I. I. solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. Disperse Yellow 42, 64, 201, 211 are listed.

A known magenta colorant can be used as the magenta colorant.
As the magenta colorant, condensed polycyclic pigments, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Violet 19 is exemplified.

As the cyan colorant, phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds are used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.
The colorants can be used alone or mixed and further used in the form of a solid solution. In the present invention, the colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHT transparency, and dispersibility in the toner. The addition amount of the colorant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin forming the core.

  The toner of the present invention preferably contains one or more waxes. The total amount of wax contained in the toner is preferably 2.5 to 25.0 parts by mass in 100 parts by mass of toner particles. Further, the total amount of wax contained in the toner is more preferably 4.0 parts by mass or more and 20 parts by mass or less, and further preferably 6.0 parts by mass or more and 18.0 parts by mass or less.

  Examples of the wax include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, Fischer-Tropsch wax, paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof ; Waxes mainly composed of fatty acid esters such as carnauba wax and montanic acid ester wax, and deoxidized part or all of fatty acid esters such as deoxidized carnauba wax; palmitic acid, stearic acid, montanic acid, etc. Saturated linear fatty acids; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, merisyl Saturated alcohols such as alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide; Saturated fatty acid bisamides such as hexamethylene bisstearic acid amide; unsaturated fatty acids such as ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N ′ dioleyl sebacic acid amide Amides; aromatic bisamides such as m-xylene bis-stearic acid amide and N, N ′ distearyl isophthalic acid amide; fats such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate Metal salts (generally referred to as metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides and polyhydric alcohols Partially esterified products: methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.

In the toner of the present invention, a charge control agent may be used in order to keep the toner chargeability stable regardless of the environment.
Examples of negatively charged charge control agents include the following. Monoazo metal compound, acetylacetone metal compound, aromatic oxycarboxylic acid, aromatic dicarboxylic acid, oxycarboxylic acid and dicarboxylic acid-based metal compound, aromatic oxycarboxylic acid, aromatic mono- and polycarboxylic acid and metal salt thereof, Examples include anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.
Examples of the positive charge control agent include the following. Nigrosine-modified products of nigrosine and fatty acid metal salts, etc .; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Phosphonium salts and other onium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid Acid, ferricyanide, ferrocyanide, etc.); metal salt of higher fatty acid; diorganotin oxide such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; DOO, dioctyl tin borate, diorgano tin borate such as dicyclohexyl tin borate; resin charge control agents.
These can be used alone or in combination of two or more.

Among them, as the charge control agent other than the resin charge control agent, a metal-containing salicylic acid compound is preferable, and in particular, the metal is aluminum or zirconium. A particularly preferred control agent is an aluminum salicylate compound.
As the resin charge control agent, a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group, a salicylic acid moiety, or a benzoic acid moiety is preferably used.
The blending amount of the charge control agent is preferably 0.01 parts by mass to 20.00 parts by mass, more preferably 0.05 parts by mass to 10.00 parts by mass with respect to 100.00 parts by mass of the polymerizable monomer. It is.

In addition to the polyester resin A, the toner of the present invention may use a polar resin that forms a shell layer. Examples of the polar resin are given below, but other resins may be used.
Examples of the polar resin used in the present invention include polyester resin, polycarbonate resin, phenol resin, epoxy resin, polyamide resin, and cellulose resin. More preferably, a polyester resin is desired because of the variety of materials. From the viewpoint of production stability, the polar resin is preferably 20.0 parts by mass or less, more preferably 10.0 parts by mass or less, per 100 parts by mass of the resin forming the core.

The toner of the present invention may contain a crystalline polyester in the core for the purpose of improving the low-temperature fixability.
Examples of the crystalline polyester include the followings composed of a polycondensation resin of an aliphatic dicarboxylic acid and an aliphatic diol.
Aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, peric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecane Dicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, cyclohexanedicarboxylic acid, anhydrides or lower alkyl esters of these acids, etc. Is mentioned.

In the present invention, the carboxylic acid monomer as described above is used as a main component, but a trivalent or higher polyvalent carboxylic acid may be used in addition to the above components.
Trivalent or higher polyvalent carboxylic acid components include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, Examples thereof include 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, and derivatives such as acid anhydrides or lower alkyl esters thereof.
These may be used alone or in combination of two or more.

Specific examples of the aliphatic diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, and pentamethylene. Examples include glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol, 1,4-butadiene glycol and the like. In the present invention, the above alcohol monomer is used as a main component. In addition to the above components, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A, 1,4-cyclohexanedimethanol, etc. Dihydric alcohol, aromatic alcohol such as 1,3,5-trihydroxymethylbenzene, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol Trivalent alcohols such as glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and the like may be used.
Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like.
These may be used alone or in combination of two or more.

The aliphatic dicarboxylic acid and the aliphatic diol are more preferably composed of a linear dealiphatic dicarboxylic acid represented by the following formula (2) and a linear aliphatic diol represented by the following formula (3).
HOOC- _{(CH 2)} m -COOH Formula (2)
[Wherein m represents an integer of 4 to 16]
HO— (CH ₂ ) _n —OH Formula (3)
[Wherein n represents an integer of 4 to 16]

  The linear type is excellent in the crystallinity of the polyester resin and has an appropriate crystal melting point, and thus is excellent in toner blocking resistance, image storage stability, and low-temperature fixability. Further, when the number of carbon atoms is 4 or more, the melting point (Tm) is appropriate, and therefore, toner blocking resistance, image storage stability, and low-temperature fixability are excellent. Further, when it is 16 or less, it is easy to obtain practical materials. The carbon number is more preferably 14 or less.

The melting point Tm (C) of the crystalline polyester is preferably 55 ° C. or higher and 90 ° C. or lower, and more preferably 60 ° C. or higher and 85 ° C. or lower. If it is lower than 55 ° C., toner blocking resistance of the toner tends to occur, and storage stability may be lowered. On the other hand, when the melting point is higher than 90 ° C., the solubility of the crystalline polyester in the polymerizable monomer tends to be deteriorated, and the dispersibility of the toner constituting material such as the pigment and the crystalline polyester is deteriorated. Sexuality may worsen.
Tm (C) can be adjusted by the kind of aliphatic dicarboxylic acid and aliphatic diol to be used, the degree of polymerization, and the like.

Below, the measuring method of each physical property concerning this invention is described. Each resin sample may be collected from the toner and analyzed.
<Measurement of dielectric loss tangent of polyester resin A>
The dielectric loss tangent of the polyester resin A in the present invention is determined by the following operation.
Using a 4284A Precision LCR meter (manufactured by Hewlett-Packard Company), the dielectric loss tangent (tan δ = ε ″ / ε ′) is calculated from the measured value of the complex dielectric constant at a frequency of 10,000 Hz.
A polyester resin coarsely pulverized in a mortar is weighed in an amount of 0.3 to 0.7 g, and 350 kgf / cm ^2.
Is molded for 2 minutes to obtain a disk-shaped measurement sample having a diameter of 25 mm and a thickness of 1 mm or less. Using this measurement sample, ARES (manufactured by Rheometric Scientific F.E.) equipped with a dielectric constant measuring jig (electrode) having a diameter of 25 mm, a load of 350 g was applied at 25 ° C. It is obtained by measuring three times in the frequency range of 100,000 Hz and calculating the average value of the measured values at 10,000 Hz of each measurement.

<Measurement of acid value of polyester A>
The acid value of the polyester resin A in the present invention is determined by the following operation.
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the polyester resin A was measured according to JIS K 0070-1992. Specifically, it measured according to the following procedures.
(1) Preparation of reagents
Phenolphthalein 1.0 g was dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchange water was added to make 100 ml to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide was dissolved in 5 ml of water, and ethyl alcohol (95 vol%) was added to make 1 l. In order to avoid contact with carbon dioxide, etc., it was placed in an alkali-resistant container and allowed to stand for 3 days, followed by filtration to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution was stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. It calculated | required from the quantity of the potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 was used.

(2) Operation
(A) Main test
2.0 g of the pulverized polyester resin A sample was precisely weighed in a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene: ethanol (2: 1) was added and dissolved over 5 hours. Next, several drops of the phenolphthalein solution were added as indicators and titrated with the potassium hydroxide solution. The end point of the titration was when the light red color of the indicator lasted for about 30 seconds.
(B) Blank test
Titration was performed in the same manner as described above, except that no sample was used (that is, only a mixed solution of toluene: ethanol (2: 1) was used).
(3) The acid value was calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Weight average molecular weight of polyester resin A>
The weight average molecular weight of the polyester resin A in this invention is calculated | required by the following operation.
After 0.03 g of polyester resin is dispersed and dissolved in 10 ml of o-dichlorobenzene, the mixture is shaken with a shaker at 135 ° C. for 24 hours, filtered through a 0.2 μm filter, and the filtrate is used as a sample. Perform analysis at
[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene mobile phase flow rate: 1.0 ml / min.
Sample concentration: about 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71
In calculating the molecular weight of the sample, standard polystyrene resin (TSO standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- manufactured by Tosoh Corporation) was used. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

<Method for measuring the abundance of inorganic fine particles a on the surface of organic / inorganic composite fine particles>
In the present invention, the abundance of the inorganic fine particles a on the surface of the organic / inorganic composite fine particles is measured by ESCA (X-ray photoelectron spectroscopy). When the inorganic fine particles a are silica particles, it is calculated from the atomic weight of silicon derived from silica (hereinafter abbreviated as Si). ESCA is an analysis method for detecting atoms in a region of several nm or less in the depth direction of the sample surface. Therefore, it is possible to detect atoms on the surface of the organic / inorganic composite fine particles.
As a sample holder, a 75 mm square platen (provided with a screw hole of about 1 mm diameter for fixing the sample) attached to the apparatus was used. Since the screw hole of the platen penetrates, the hole is closed with resin or the like, and a recess for measuring powder having a depth of about 0.5 mm is produced. A sample was prepared by filling the recess with a measurement sample with a spatula or the like and grinding it.
The ESCA apparatus and measurement conditions are as follows.
Equipment used: Quantum 2000 manufactured by ULVAC-PHI
Analysis method: Narrow analysis Measurement conditions:
X-ray source: Al-Kα
X-ray conditions: 100μ25W15kV
Photoelectron capture angle: 45 °
PassEnergy: 58.70eV
Measurement range: φ100μm
Measurement was performed under the above conditions.

The analysis method first corrects the peak derived from the C—C bond of the carbon 1s orbital to 285 eV. Then, from the peak area derived from the silicon 2p orbit where the peak top is detected at 100 eV or more and 105 eV or less, the relative sensitivity factor provided by ULVAC-PHI is used to calculate the amount of Si derived from silica relative to the total amount of constituent elements. To do.
First, organic-inorganic composite fine particles are measured. Moreover, the particle | grains of the inorganic component used when producing organic-inorganic composite fine particles by the same method are measured. When the inorganic component is silica, the ratio of the “Si amount when measuring the organic-inorganic composite fine particles” to the “Si amount when measuring the silica particles” is the ratio of the inorganic fine particles a on the surface of the organic-inorganic composite fine particles in the present invention. Presence rate. In this measurement, calculation was performed using sol-gel silica particles (number average particle diameter 110 nm) as silica particles.
In addition, although the case where the inorganic fine particle a is a silica particle was demonstrated, when the inorganic fine particle a is not a silica particle, the metal seed | species contained in the inorganic fine particle a is specified from the database attached to a measuring apparatus, The An analysis focusing on the metal species may be performed.
(When measuring from toner)
When measuring the abundance of the inorganic fine particles a from the toner, the organic inorganic composite fine particles may be separated from the toner by the method described later, and the above measurement may be performed.
First, using the separated organic-inorganic composite fine particles, “Si amount when measuring organic-inorganic composite fine particles” is measured. Then, the organic component is dissolved and removed from the organic-inorganic composite fine particles with an appropriate solvent, and the “amount of Si when the inorganic fine particles are measured” is measured using the obtained inorganic fine particles, whereby the abundance ratio can be calculated.

<Method for Measuring Toner Weight Average Particle Size (D4)>
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels. As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software was set as follows. On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked. In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Method for separating organic-inorganic composite fine particles from toner>
The method of separating the organic-inorganic composite fine particles from the toner is as follows:
(1) Put 5 g of toner into a sample bottle and add 200 mL of methanol.
(2) The sample is dispersed for 5 minutes with an ultrasonic cleaner to separate the external additive.
(3) Separating toner particles and external additives by suction filtration (10 μm membrane filter). (4) Perform the above (2) and (3) three times.
By the above operation, the externally added external additive is isolated from the toner particles. The collected aqueous solution is centrifuged to separate and collect the organic / inorganic composite fine particles and the inorganic fine particles. Next, the content of the organic-inorganic composite particles and the inorganic fine particles can be obtained by removing the solvent, sufficiently drying with a vacuum dryer, and measuring the weight. When a plurality of types of inorganic fine particles are added, they can be separated by adjusting the conditions for centrifugation.

<Method for measuring number average particle diameter of external additive>
The number average particle diameter of the external additive is measured using a scanning electron microscope “S-4800” (manufactured by Hitachi, Ltd.). The toner with the external additive added is observed, and the major axis of the primary particles of 100 external additives is randomly measured to obtain the number average particle size in a field of view that is magnified 100,000 to 200,000 times. . The observation magnification is appropriately adjusted according to the size of the external additive.

<Method for measuring SF-2 of external additive>
The external additive SF-2 was observed by observing the external additive on the toner with a scanning electron microscope “H-4800” (manufactured by Hitachi, Ltd.). Were calculated using image processing software Image-Pro Plus 5.1J (manufactured by Media Cybernetics).
Similarly, the area of the primary particles is also observed with the transmission electron microscope “H-4800” (manufactured by Hitachi, Ltd.), and in the enlarged field of view, the area of the entire primary particles including the organic component and the inorganic component is imaged. It calculated using processing software Image-Pro Plus5.1J (made by MediaCybernetics).
SF-2 was calculated by the following formula, and the average value was defined as SF-2.
SF-2 = (peripheral length of primary particles) ² / area of primary particles × 100 / 4π

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but this does not limit the present invention in any way. Unless otherwise specified, all parts and% in the examples and comparative examples are based on mass. Hereinafter, a method for producing a resin and a toner will be described.

<Example of production of polyester resin 1>
100 parts by mass of a mixture of raw material monomers mixed in the charge ratio shown in Table 1 and 0.55 parts by mass of di (2-ethylhexanoic acid) tin as a catalyst were equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. The mixture was placed in a 4-liter flask and allowed to react at 200 ° C. for 6 hours under a nitrogen atmosphere. Furthermore, trimellitic anhydride was added at 210 ° C., and the reaction was carried out under reduced pressure of 40 kPa, and the reaction was continued until the weight average molecular weight (Mw) became 12,000. The obtained polyester resin is designated as polyester resin 1. The composition analysis of the polyester resin 1 was conducted, and the results of the isosorbide monomer ratio are shown in Table 1. Moreover, the acid value of the obtained polyester resin 1 was as shown in Table 1.
The composition analysis of the polyester resin 1 was performed by 1-NMR. The specific measurement method is as follows.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times
Measurement temperature: 30 ° C
A sample of 50 mg is put into a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl 3) is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C. to prepare a measurement sample. It measured on the said conditions using the said measurement sample.

<Production example of polyester resins 2 to 13>
Polyester resins 2 to 13 were produced in the same manner as in the production example of polyester resin 1 except that the amounts of the acid component and alcohol component were changed as shown in Table 1. Table 1 shows the physical properties of polyester resins 2 to 13.

ＴＰＡ：テレフタル酸
ＴＭＡ：トリメリット酸
ＢＰＡ（ＰＯ２）：ビスフェノールＡのプロピレンオキサイド２ｍｏｌ付加物
ＥＧ：エチレングリコール

TPA: terephthalic acid TMA: trimellitic acid BPA (PO2): propylene oxide 2 mol adduct of bisphenol A EG: ethylene glycol

<Production example of charge control resin 1>
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts by mass of methanol, 150 parts by mass of 2-butanone and 100 parts by mass of 2-propanol were used. Then, 77 parts by mass of styrene, 15 parts by mass of 2-ethylhexyl acrylate, and 8 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added as monomers and heated to reflux temperature while stirring. A solution obtained by diluting 1 part by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours. Further, a solution prepared by diluting 1 part by mass of t-butylperoxy-2-ethylhexanoate with 20 parts by mass of 2-butanone was added dropwise over 30 minutes and stirred for 5 hours to complete the polymerization. While maintaining the temperature, 500 parts by mass of deionized water was added, and the mixture was stirred at 80 to 100 revolutions per minute for 2 hours so as not to disturb the interface between the organic layer and the aqueous layer. After standing for 30 minutes and separating the layers, the aqueous layer was discarded, and anhydrous sodium sulfate was added to the organic layer for dehydration. Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less using a cutter mill equipped with a 150 mesh screen. The obtained charge control resin 1 having a sulfur atom had Tg = 58 ° C., Mp = 13,000, and Mw = 30,000.

<Production Example of Toner Particle 1>
With respect to 100 parts by mass of the styrene monomer, C.I. I. 16.5 parts by mass of Pigment Blue 15: 3 and 3.0 parts by mass of an aluminum compound of di-tertiary butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Industries)] were prepared. These were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.), and zirconia beads having a radius of 1.25 mm (140 parts by mass) were used.
Stirring was performed at 25 ° C. for 180 minutes at 00 rpm to prepare a master batch dispersion 1.
On the other hand, after adding 450 parts by mass of 0.1 M Na ₃ PO ₄ aqueous solution to 710 parts by mass of ion-exchanged water and heating to 60 ° C., 67.7 parts by mass of 1.0 M CaCl ₂ aqueous solution was gradually added. An aqueous medium containing a calcium phosphate compound was obtained.
-Master batch dispersion 1 40 parts by mass-Styrene monomer 49.5 parts by mass-N-butyl acrylate monomer 16.5 parts by mass-Hydrocarbon wax 9 parts by mass (Fischer-Tropsch wax, peak of maximum endothermic peak Temperature = 78 ° C., Mw = 750)
-Charge control resin 1 0.3 parts by mass-Polyester resin 1 5.0 parts by weight The above materials are heated to 65 ° C and uniform at 5,000 rpm using a TK homomixer (manufactured by Special Machine Industries). Dissolved in and dispersed. In this, 7.1 mass part of 70% toluene solution of polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate was dissolved to prepare a polymerizable monomer composition.
The polymerizable monomer composition is put into the aqueous medium, and stirred at 12,000 rpm for 10 minutes with a TK homomixer in a N ₂ atmosphere at a temperature of 65 ° C. to obtain a polymerizable monomer composition. Granulated. Thereafter, the temperature was raised to 67 ° C. while stirring with a paddle stirring blade. When the polymerization conversion rate of the polymerizable vinyl monomer reached 90%, a 0.1 mol / liter sodium hydroxide aqueous solution was added. The pH of the aqueous dispersion medium was adjusted to 9. Furthermore, it heated up at 80 degreeC with the temperature increase rate of 40 degreeC / h, and was made to react for 4 hours. After completion of the polymerization reaction, the residual monomer in the toner particles was distilled off under reduced pressure. After cooling the aqueous medium, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 6 hours to dissolve the calcium phosphate salt. The toner particles were separated by filtration and washed with water, and then dried at a temperature of 40 ° C. for 48 hours. The obtained dried product was strictly classified and removed at the same time with a multi-division classifier (elbow jet classifier manufactured by Nittetsu Mining Co., Ltd.) to obtain a cyan color having a weight average particle diameter (D4) of 6.3 μm. Toner particles 1 were obtained.

<Production example of toner particles 2 to 18>
Toner particles 2 to 18 were obtained in the same manner as in the production example of toner particles 1 except that the type of polyester resin A used and the addition amount of polyester resin A were changed as shown in Table 2. Table 2 shows the weight average particle diameter D4 of the obtained toner particles.

<Production example of organic-inorganic composite fine particles>
The organic / inorganic composite fine particles can be produced according to the description in the examples of International Publication No. 2013/066291.
As organic-inorganic composite fine particles used in the examples described later, those prepared according to Example 1 of International Publication No. 2013/063291 using silica shown in Table 3 were prepared.
Table 3 shows the physical properties of the organic-inorganic composite fine particles 1 to 9.

<Production example of resin particle 1>
Instead of colloidal silica, 6 parts by mass of nonionic surfactant (Nonipol 400: manufactured by Sanyo Kasei Co., Ltd.) and 10 parts by mass of anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were added. Produced resin particles 1 in the same manner as in the organic-inorganic composite fine particles 1.

<Preparation of inorganic fine particles b>
As the inorganic fine particles b, inorganic fine particles described in Table 4 below were prepared.

<Manufacture of toner 1-30>
To the obtained toner particles (100 parts), the external additives listed in Table 5 were externally added with a power of 0.5 kW for 5 minutes using Nobilta (manufactured by Hosokawa Micron) to obtain toners 1 to 30.
Table 5 shows the physical properties of each toner.

<Example 1>
Image evaluation was performed using A1 color laser copier paper (manufactured by Canon, 80 g / m ² ) using toner 1 as a developer. As the image forming apparatus, a remodeled machine of LBP-7700C (manufactured by Canon), which is a commercially available laser printer, was used. The remodeling points of the evaluation machine (remodeled machine) are as follows.
The process speed was increased by 1.3 times by changing the gear and software of the main body of the evaluation machine. Further, the cleaning blade contact linear pressure was changed to 0.3 N / cm and the contact angle was changed to 23 degrees.
As the evaluation paper, A4 size plain paper was used. In the case of a conventional spherical toner, the contact linear pressure was set to 1.0 N / cm or more, and examination was performed under strict conditions for cleaning performance. The cartridge used for evaluation was a cyan cartridge. That is, the product toner was taken out from a commercially available cyan cartridge, the inside was cleaned by air blow, and 165 g of the toner according to the present invention was filled for evaluation. In addition, the product toner was extracted from each of the magenta, yellow, and black stations, and evaluation was performed by inserting magenta, yellow, and black cartridges in which the toner remaining amount detection mechanism was disabled.

≪Evaluation≫
<Toner cleaning property>
In a low-temperature and low-humidity environment (10 ° C./14% Rh), an endurance test for continuously outputting 3000 ruled line images with a printing ratio of 5% was performed to evaluate the cleaning performance.
A: No cleaning failure observed on paper, no contamination of charging roller with toner.
B: No cleaning failure observed on paper, and contamination of charging roller with toner.
C: After 50 sheets or more are printed out, vertical streaks due to poor cleaning are seen on the paper.
D: Longitudinal streaks due to poor cleaning can be seen on paper when printing out 49 sheets or less.

<Flat followability>
A durability test was performed in which 3000 images with a printing ratio of 1% were output in a low-temperature and low-humidity environment (10 ° C./14% Rh). At 100, 500, 1000, 2000, and 3000 sheets, a solid image is output, and an image density of a central portion of 4 cm from the top of the solid image and an image density of the central portion of 4 cm from the bottom of the solid image are represented by a color reflection densitometer (X -Rite 404A) and evaluated as follows from the image density difference.
A: The image density difference is 0.05 or less.
B: The image density difference is larger than 0.05 and not larger than 0.10.
C: The image density difference is larger than 0.10 and 0.15 or less.
D: The image density difference is larger than 0.15.

<Photoreceptor scratch>
In a low-temperature, low-humidity environment (10 ° C / 14% Rh), a durability test was performed to continuously output 3,000 ruled line images with a printing ratio of 5%. Evaluation was made based on the observation results of 10-point average roughness Rz and scratches measured with a total surf coder SE3500.
A: Rz change rate is less than 20% (there is no deep scratch and is not known in the output image).
B: Rz change rate is 20% or more, but there is no scratch of 1 μm or more (almost no influence on the image).
C: Deep scratches of 1 μm or more and less than 2 μm occur (effect on the image is slight).
D: Deep scratches of 2 μm or more occur (the effect of scratches can be seen in the output image).

<Contamination of charging member>
In a low-temperature and low-humidity environment (10 ° C./14% Rh), an endurance test for continuously outputting 1000 images with a printing ratio of 20% was performed. The charging roller contamination due to the external additive was visually confirmed at 100, 500, and 1000 sheets, a halftone image was output, and the charging member contamination was evaluated.
A: There is no problem of contamination of the charging roller up to 1000 sheets.
B: No charging roller contamination problem up to 500 sheets.
C: No charging roller contamination problem up to 100 sheets.
D: An image defect due to contamination of the charging roller occurred on 100 sheets.

<Image cover>
In a high temperature and high humidity environment (30 ° C., 80% RH), a durability test was performed to output 3000 images with a printing ratio of 1%. A solid white image was output at 100, 500, 1000, 2000, and 3000 sheets, and the following evaluation criteria were used.
Using “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), the reflectance of the white background portion of the standard paper and the printout image was measured, and the fog (reflectance:%) was calculated by the following formula. The filter was measured with a blue filter attached.
In addition, the evaluation criteria judged the worst value through durability with the following criteria.
Fog (reflectance;%) = (reflectance of standard paper;%) − (reflectance of sample;%)

A: The fog is less than 1.0%.
B: The fog is 1.0% or more and less than 2.0%.
C: The fog is 2.0% or more and less than 3.0%.
D: The fog is 3.0% or more.

<Examples 2 to 24>
In Example 1, the toner 1 was changed to the toner shown in Table 6 and evaluated. The evaluation results are shown in Table 6.

<Comparative Examples 1-6>
In Example 1, the toner 1 was changed to the toner shown in Table 6 and evaluated. The evaluation results are shown in Table 6.

Claims (8)

A toner having a core-shell structure toner particle having a core containing a binder resin and a shell containing a polyester resin A formed on the surface of the core, and an external additive A,
The dielectric loss tangent of the polyester resin A at 25 ° C. and 10,000 Hz is 0.0070 or more and 0.0140 or less,
The toner contains 1.0 to 20.0 parts by mass of the polyester resin A with respect to 100.0 parts by mass of the binder resin.
The external additive A is organic-inorganic composite fine particles,
The organic-inorganic composite fine particles are particles in which the inorganic fine particles a are exposed on the surface of the organic resin particles so that convex portions derived from the inorganic fine particles a are formed on the surface. Yes,
A toner characterized in that the abundance of inorganic fine particles a on the surface of the organic / inorganic composite fine particles is 20% or more and 70% or less. 2. The toner according to claim 1, wherein the polyester resin A contains 0.10 mol% or more and 20.00 mol% or less of an isosorbide unit represented by the formula (1) based on all monomer units.

  The toner according to claim 1, wherein the acid value of the polyester resin A is 0.5 mgKOH / g or more and 25.0 mgKOH / g or less.   The toner according to claim 1, wherein the binder resin is a styrene acrylic resin.   The toner according to claim 1, wherein the toner particles are toner particles produced by a production method including a step of granulating in an aqueous medium.   The toner particles form polymerizable monomer composition particles containing a polymerizable monomer and the polyester resin A in an aqueous medium, and the toner particles are contained in the particles of the polymerizable monomer composition. The toner according to claim 1, wherein the toner particles are obtained by polymerizing a polymerizable monomer. The shape factor SF-2 when the organic-inorganic composite particles are measured at a magnification of 200,000 times is 103 or more and 120 or less,
The toner according to claim 1, wherein the number average particle diameter (A) of the organic-inorganic composite particles is 50 nm or more and 400 nm or less. The toner further has inorganic fine particles b as an external additive,
The number average particle diameter (B) of the inorganic fine particles b is 5 nm or more and 40 nm or less,
The toner according to claim 7, wherein a ratio (A / B) of the number average particle diameter (A) to the number average particle diameter (B) is 1.5 or more and 10.0 or less.