JP2016142760A - Toner and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has high fluidity while suppressing contamination of members during a long-term use.SOLUTION: There is provided a toner containing toner particles having a core-shell structure that contains polyester resin A in a shell part, and inorganic fine particles A, where the polyester resin A contains an isosorbide unit represented by the formula (1) in an amount of 0.10 mol% or more and 20.00 mol% or less; the content of the polyester resin A is 1.0 part by mass or more and 20.0 parts by mass or less based on 100.0 parts by mass of a binder resin; the inorganic fine particles A has an average value of density measured with a scanning electron microscope (SEM) of 0.40 or more and 0.80 or less.SELECTED DRAWING: None

Description

  The present invention relates to a toner for developing an electrostatic image used for image formation by electrophotography.

  In recent years, copiers and printers have been reduced in size and extended in life, and the performance required for toner has become more severe. In order to reduce the size, there is a demand for a simpler developing device configuration, and there is a demand for a toner that can be circulated in the developing device with a simple stirring mechanism. Further, as the service life is extended, there is a tendency that the toner in the developing machine is subjected to stresses such as heat and impact. When the toner is subjected to a lot of stress such as heat and impact, the surface composition of the toner changes, the fluidity is deteriorated, and the chargeability may be uneven. In such a case, the adhesion force of the toner is increased, stress is concentrated on a part of the toner, and as a result, image quality such as uneven image density is likely to be deteriorated. In order to avoid the above adverse effects, it is necessary to improve the toner circulation in the developing machine. That is, from the viewpoints of miniaturization and long life of copying machines and printers, there is a demand for toner having high fluidity and good circulation in the developing machine.

Another problem that arises due to the extended life is contamination of the member with toner and external additives. In a conventional general image forming apparatus, a photosensitive member as an image carrier is uniformly charged by a charging means such as a charging roller, and image exposure is performed on the photosensitive member, for example, by irradiation with a laser beam. An electric latent image is obtained. This latent image is developed as a toner image by reversal development or normal development by the developing means to be visualized. The toner image is electrostatically transferred to a recording medium by a transfer unit such as a transfer roller, and then fixed on the recording medium by applying heat and pressure by a fixing unit such as a heat fixing device. The toner remaining on the surface of the photoconductor after the toner image is transferred to the recording medium is removed and cleaned by a cleaning device, and is prepared for the next image forming process.
During long-term use, it is difficult to remove all of the toner remaining in the cleaning process, and part of the toner and external additives may remain on the surface of the photoreceptor. By repeating the image forming process, the remaining toner and external additives adhere to a charging member such as a charging roller, and the charging on the photoconductor may become non-uniform during long-term use. In such a case, as a result, adverse effects such as image unevenness in halftone occur. In particular, it is known that toner with high fluidity is difficult to remove at the cleaning portion.

In order to solve the above problems, various attempts have been made conventionally.
In Patent Document 1, by using aggregated particles formed by aggregating two or more external additives having a primary particle size of 50 to 150 nm as external additives, burying of the external additives on the toner surface is suppressed, and durability is improved. We are trying to improve.
Further, in Patent Document 2, the toner cleaning property is improved by using a specific amount of colloidal silica fine particles containing a specific proportion or more of irregular shaped particles having a specific elliptical spherical shape as an external additive.
Attempts have been made to improve toner durability and suppress contamination of members by the measures described above.
However, the toners described in Patent Documents 1 and 2 both use irregularly shaped particles having a relatively large primary particle size as an external additive, and it is difficult to obtain a toner having high fluidity that satisfies the above-mentioned demand. . It was insufficient for the problem of maintaining high fluidity even during long-term use and suppressing adhesion of toner and external additives to the charging roller. Therefore, it can be said that there is still room for improvement from the viewpoint of further improving developability.

JP 2010-134220 A Japanese Patent No. 5353204

  The present invention aims to solve the above problems. That is, an object of the present invention is to provide a toner having high fluidity while suppressing contamination of members during long-term use.

稠密度＝無機微粒子の面積／包絡線により囲まれた無機微粒子の面積 …式（２） As a result of intensive studies, the present inventors have found that the above-described problems can be solved by the following toner.
That is, the present invention
A toner having a core-shell structure toner particle in which a core containing a polyester resin A is formed on a core containing a binder resin, and inorganic fine particles A;
The toner particles contain 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 polyester resin A contains 0.10 mol% or more and 20.00 mol% or less of the isosorbide unit represented by the formula (1) based on the total monomer units,
The inorganic fine particles A are toners characterized in that the average value of the dense density represented by the following formula (2) observed by a scanning electron microscope (SEM) is 0.40 or more and 0.80 or less. .

Density = area of inorganic fine particles / area of inorganic fine particles surrounded by an envelope (2)

  According to the present invention, it is possible to provide a toner having high fluidity while suppressing member contamination during long-term use.

Schematic showing polycarbonate thin film adhesion measurement method Example of binarized image used for quantification of external additive shape

Hereinafter, the present invention will be described in detail.
The toner of the present invention is a toner having 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, and inorganic fine particles A;
The toner particles contain 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, and the polyester resin A is represented by the formula (1). Containing 0.10 mol% or more and 20.00 mol% or less of isosorbide units based on all monomer units,
The inorganic fine particles A are toners characterized in that the average value of the dense density represented by the following formula (2) observed by a scanning electron microscope (SEM) is 0.40 or more and 0.80 or less.

稠密度＝無機微粒子の面積／包絡線により囲まれた無機微粒子の面積 …式（２）

Density = area of inorganic fine particles / area of inorganic fine particles surrounded by an envelope (2)

In the present invention, the specific polyester resin contained in the toner particles is also referred to as “polyester resin A”. In the present invention, it is essential to contain the polyester resin A in the shell portion of the core-shell structure. Further, the content of the polyester resin A in the toner particles is 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. Furthermore, the polyester resin A used for this invention contains 0.10 mol% or more and 20.00 mol% or less of isosorbide units shown by Formula (1) as above-mentioned.
In addition, as described above, the inorganic fine particles A used in the present invention have an average density of 0.40 or more and 0.80 or less represented by the formula (2) observed by a scanning electron microscope (SEM). It is characterized by that.

In the toner of the present invention, due to the synergistic effect of the polyester resin A and the inorganic fine particles A contained in the shell part of the toner particles, a toner having high fluidity can be obtained while suppressing member contamination during long-term use.
The reason is guessed as follows.

Concerning member contamination during long-term use, regarding charging member contamination which is a particular problem, it is conceivable that slipping of the external additive at the cleaning blade edge portion in the toner cleaning process causes member contamination. Therefore, as a result of intensive studies to suppress slipping of the external additive at the cleaning blade edge portion, the inventors have found that the shape of the external additive is particularly important. Therefore, we focused on an index called dense density. The dense density is an index represented by the formula (2), and is a value obtained by dividing the area of the inorganic fine particles by the convex area of the inorganic fine particles. The convex area is an area of a portion surrounded by an envelope created based on the contour of the target external additive. The density is an amount that takes a value between 0 and 1, and the smaller the value, the more complicated the concave portion. In order to effectively suppress slipping of the external additive, it contains inorganic fine particles having a shape with an average density of 0.40 or more and 0.80 or less as observed by a scanning electron microscope (SEM). It is necessary.
Density = area of inorganic fine particles / area of inorganic fine particles surrounded by an envelope (2)

  Although the details of the effect are not clear, they are considered as follows. If the shape has many concave portions, the inorganic fine particles are easily caught and hardly rolled. For this reason, even if inorganic fine particles are sandwiched in the cleaning nip portion, it does not rotate, so that it tends to stay in the nip portion, and a stable block layer is easily formed. Thereby, it is considered that not only the inorganic fine particles themselves are difficult to slip through, but also the other external additives are prevented from slipping through and the charging member is prevented from being contaminated. Incidentally, the aspect ratio conventionally used as an index of the shape of the external additive is insufficient to obtain the above effect. This is because the aspect ratio is simply an index indicating the length of the shape, and if the shape is elongated, the inorganic fine particles are not easily caught.

When the average value of the dense density is larger than 0.80, the inorganic fine particles hardly stay in the cleaning nip portion, so that it is difficult to obtain an effect of suppressing slip-through.
The average value of the dense density is preferably 0.50 or more and 0.80 or less, and more preferably 0.60 or more and 0.75 or less.
By using the inorganic fine particles A, it is possible to suppress member contamination.
In the present invention, the use of the polyester resin A for the shell portion of the toner particles can maximize the effect of the inorganic fine particles A during long-term use. The reason is considered as follows.
By imparting a certain rigidity to the toner by the cyclic skeleton of the isosorbide unit, embedding of the inorganic fine particles in the toner particles can be suppressed, and a toner having excellent durability can be obtained. Thereby, even during long-term use, the inorganic fine particles A easily migrate to the surface of the photoreceptor and are easily supplied to the cleaning nip portion. As a result, member contamination during long-term use can be suppressed.
Further, by controlling the polarity of the toner particle surface layer, it becomes possible to change the adhesion of the inorganic fine particles A to the toner and to control the migration of the inorganic fine particles A to the surface of the photoreceptor. By using the polyester resin A having an appropriate polarity, it is possible to appropriately control the supply amount of the inorganic fine particles A to the cleaning nip portion. Thereby, a high effect is acquired with respect to suppression of member contamination at the time of long-term use.
On the other hand, the inorganic fine particles A that are easily caught are unlikely to contribute to the improvement of toner fluidity. In particular, when the toner is used for a long time, the toner fluidity tends to decrease as the external additive is embedded in the toner particles.

In the present invention, by using the polyester resin A in the shell part of the toner particles, a toner having high fluidity can be obtained even when the inorganic fine particles A are used.
Although the details of the effect are not clear, they are considered as follows.
When the inorganic fine particles A are used, when the inorganic fine particles are partially embedded in the toner particles during long-term use of the toner, it is considered that the inorganic fine particles are caught between the toners and the toner fluidity is lowered. Further, it is considered that the inorganic fine particles are locally triboelectrically charged by rubbing in the developing machine, so that electrostatic aggregation between the inorganic fine particles is likely to occur and the catch is likely to occur. Therefore, it is considered that electrostatic aggregation can be suppressed if the charge leakage property on the surface of the toner particles can be increased to suppress the local charge on the inorganic fine particles.

In the present invention, it is considered that the isosorbide unit represented by the formula (1) contained in the polyester resin A exhibits the effect on the surface of the toner particles and suppresses the deterioration of the fluidity of the toner. Since the isosorbide unit has a cyclic structure having an ether group in the unit, it has an appropriate polarity. By incorporating this unit into the polyester resin, the charging characteristics of the polyester resin can be made appropriate. As a result, the charge leakage property on the surface of the toner particles becomes moderate, so that electrostatic aggregation of the inorganic fine particles is suppressed and deterioration of the toner fluidity is suppressed.
In addition, it is considered that due to the above-described rigidity effect, the embedding of inorganic fine particles in the toner particles can be suppressed, and a toner having excellent durability can be obtained.
Based on the above effects, it is considered that a toner having high fluidity can be obtained while suppressing contamination of members during long-term use.

The toner particles of the present invention may be toner particles having a core-shell structure in which a core containing a binder resin is formed on a core containing a polyester resin A, and can be produced using a known pulverization method and polymerization method. . Among them, the toner particles are preferably produced through a granulation step in an aqueous medium, and can be produced by a suspension polymerization method, a solution suspension polymerization method, or an emulsion aggregation method that can easily form and control the core-shell structure. More preferred. 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 polar resin and, if necessary, a colorant and a wax are added to the polymerizable monomer composition to produce toner particles, which are mainly formed from a binder resin. Toner particles having a core-shell structure in which the core is covered with a shell layer formed of a polar resin can be obtained.

The polyester resin A described in detail below is added as a polar resin for forming the shell layer of the toner particles of the present invention.
The polyester resin A of the present invention contains the isosorbide unit represented by the formula (1) in a range of 0.10 mol% to 20.00 mol%, preferably 1.00 mol% to 15.00 mol% based on the total monomer units. .

In the polyester resin A, when the content of the isosorbide unit is within the above range, the interaction with the inorganic fine particles A works most effectively, and the fluidity of the toner during durability is remarkably improved. As a result, adverse effects such as image density unevenness in the second half of durability are unlikely to occur.
When the content of the isosorbide unit is less than 0.10 mol%, the presence ratio of the isosorbide unit in the polymer chain of the polyester resin A is too small, so when combined with the inorganic fine particles A, it contributes to the fluidity of the polyester resin A. The properties to be lost are impaired.
On the other hand, when the content of the isosorbide unit exceeds 20.00 mol%, the moisture absorption characteristic of the polyester resin A becomes strong, and there is a concern that the charge amount of the toner in a high humidity environment is reduced.

The polyester resin A of the present invention is 1.0 part by mass or more and 20.0 parts by mass or less, preferably 1.5 parts by mass or more and 10.0 parts by mass with respect to 100.0 parts by mass of the binder resin forming the core. Add up to parts.
Within the above range, the polyester resin A forms a sufficient shell on the surface of the toner particles and effectively exhibits the interaction with the inorganic fine particles A described above.
When the content of the polyester resin A is less than 1.0 part by mass, the interaction between the polyester resin A and the inorganic fine particles A does not work sufficiently, and it is difficult to obtain the effect of improving the toner fluidity.
Moreover, when content of the polyester resin A exceeds 20.0 mass parts, the polyester resin A becomes difficult to melt | dissolve in a polymerizable monomer composition, and formation of a shell becomes unstable. As a result, developability may deteriorate when used for a long time.

The polyester resin A of the present invention uses 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; carbons 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 an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms; anhydrides of these acids and alkyls of these acids (1 to 8 carbon atoms) Examples include esters. Among them, in particular, a polyester resin A obtained by polycondensation of a bisphenol derivative as an alcohol component and a divalent or higher carboxylic acid or acid anhydride thereof or a lower alkyl ester thereof as an acid component is preferably used. it can.

The dielectric loss tangent of the polyester resin A of the present invention at 25 ° C. and 10000 Hz is preferably 0.0070 or more and 0.0140 or less, and more preferably 0.0080 or more and 0.0120 or less. By controlling the dielectric loss tangent within the above range, good toner charging characteristics can be obtained, and the amount of transfer of the inorganic fine particles A to the photoconductor is optimized. As a result, charging member contamination and fogging are improved.
Examples of the method for adjusting the dielectric loss tangent to the above preferred range include a method of adjusting the content of the isosorbide unit and the alcohol component and acid component exemplified above. In the present invention, for example, in addition to the isosorbide unit, a component having an ether structure such as ethylene glycol can be added and the content can be adjusted to adjust the dielectric loss tangent. Especially, it is preferable to adjust a dielectric loss tangent in the said range by adjusting content of an 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. For this reason, it is presumed that the polyester resin A can be imparted with appropriate charging characteristics without partially increasing the dielectric loss tangent as the polyester resin.

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.
When the acid value of the polyester resin A is less than 0.5 mgKOH / g, the compatibility with the binder resin forming the core is improved, the formation of the shell layer is insufficient, and the heat resistant storage stability and developability are deteriorated. There is.
In addition, when the acid value of the polyester resin A is less than 0.5 mgKOH / g or more than 25.0 mgKOH / g, the particle size distribution when the toner particles are produced by the suspension polymerization method is deteriorated and the developability is deteriorated. There is a case.
The acid value of the polyester resin A can be adjusted to the above range by adjusting the type and blending amount of monomers used for the resin. Specifically, it can be controlled by adjusting the alcohol monomer component ratio / acid monomer component ratio and molecular weight during resin production.

The weight average molecular weight (Mw) of the polyester resin A is preferably 5000 or more and 30000 or less, and more preferably 7000 or more and 20000 or less.
Within the above range, the compatibility between low-temperature fixability, heat-resistant storage stability, and developability is improved.
When the weight average molecular weight (Mw) is less than 5000, the strength of the shell layer becomes weak and developability may deteriorate. On the other hand, if the weight average molecular weight (Mw) is larger than 30000, the low-temperature fixability may be deteriorated.
In the present invention, a conventionally known polyester resin may be used in combination with the binder resin and the polyester resin A.

The inorganic fine particles A used in the present invention are not particularly limited as long as they are inorganic fine particles, but silica is preferable and dry silica is preferable because of easy shape control with many concave portions, which is one of the features of the present invention. Is more preferable.
Dry silica is made from a silicon halogen compound or the like.
Silicon tetrachloride is used as the silicon halogen compound, but silanes such as methyltrichlorosilane and trichlorosilane can be used alone or in a mixed state of silicon tetrachloride and silanes.
After the raw material is vaporized, the target silica is obtained by a so-called flame hydrolysis reaction that reacts with water generated as an intermediate in an oxyhydrogen flame.
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

Below, the manufacturing method of dry non-spherical silica is demonstrated.
After supplying oxygen gas to the burner and igniting the ignition burner, hydrogen gas is supplied to the burner to form a flame, and silicon tetrachloride as a raw material is charged into this to gasify it. A flame hydrolysis reaction is performed, and the produced silica powder is recovered.
The average particle size and shape can be arbitrarily adjusted to create the shape of inorganic fine particles with many recesses by appropriately changing the flow rate of silicon tetrachloride, the flow rate of oxygen gas, the flow rate of hydrogen gas, and the residence time of silica in the flame. It is.
As a means for controlling the shape having many concave portions, the obtained silica powder may be transferred to an electric furnace and spread in a thin layer, and then heat-treated and sintered. By sintering, the coalescence strength of the inorganic fine particles is increased, and the catching effect at the cleaning portion is more easily improved.

Furthermore, the inorganic fine particles A used in the present invention may be subjected to a surface treatment such as a hydrophobic treatment or a silicone oil treatment.
As a hydrophobizing method, it is given by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica. As a preferred method, silica 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.
Further examples include bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, and triorganosilyl acrylate.
Furthermore, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, and 1-hexamethyldisiloxane are exemplified.
Furthermore, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane can be exemplified.

These are used by 1 type, or 2 or more types of mixtures.
In the silicone oil-treated silica, a preferable silicone oil having a viscosity at 25 ° C. of 30 mm ² / s to 1000 mm ² / s is used.
Examples include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil.

Examples of the method for treating silicone oil include the following methods.
A method in which silica treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer.
A method in which silicone oil is sprayed onto the base silica. Alternatively, after dissolving or dispersing silicone oil in an appropriate solvent, silica 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).

The amount of the inorganic fine particles A added is not particularly limited as long as desired characteristics can be obtained, but is 0.1 parts by mass or more and 3.0 parts by mass or less with respect to 100.00 parts by mass of the toner particles. It is more preferable.
Moreover, it is preferable that the minimum ferret diameter observed with a scanning electron microscope (SEM) of the inorganic fine particles A is 50 nm or more and 300 nm or less.
In order to obtain the effect of catching the inorganic fine particles in the cleaning nip portion, it is also important that the inorganic fine particles having a large number of concave portions migrate from the toner to the surface of the photosensitive drum. Therefore, as a result of intensive studies by the present inventors, the toner was deposited and contacted on the surface of the polycarbonate thin film in which the conductive paste and the polycarbonate thin film were laminated on the aluminum sheet, and the toner was sucked and removed. It was found that the area ratio of the amount of inorganic fine particles A adhering to the removed polycarbonate thin film surface can be measured by a technique of observing with a scanning electron microscope (SEM). Specific measurement methods are shown below.

<Polycarbonate thin film adhesion measurement method>
In the polycarbonate thin film adhesion measurement method, the amount of inorganic fine particles A deposited is measured by analyzing the surface of the polycarbonate thin film taken with Hitachi Ultra High Resolution Field Emission Scanning Electron Microscope S-4800 (Hitachi High-Technologies Corporation). Software image processing software ImageJ (
It is calculated by analyzing using the developer Wayne Randhand. The measurement procedure is shown below.

(1) Sample preparation The sample preparation process of the polycarbonate thin film adhesion measurement method is shown in FIG. In FIG. 1, a stainless mesh screen 11 having a mesh opening of 75 μm is used as a method for disposing the toner T on the substrate 12. In order to simulate the surface layer of the photoreceptor as the substrate, a conductive paste (TED PELLA, Inc, Product No. 16053, PELC) is applied to an aluminum sheet.
O Colloidal Graphite, Isopropanol base) is thinly coated in a square shape of 1 mm square, and a polycarbonate thin film (bisphenol Z type, trade name: Iupilon Z200, manufactured by Mitsubishi Gas Chemical Co., Ltd., square shape 1.0 mm × 1.0 mm) The thin film was attached to the substrate holder 13. The substrate was a square with a side of about 3 mm.
About 10 mg of toner was added to the sieve, and the substrate was placed at a distance of 20 mm immediately below the sieve. The opening of the sieve has a diameter of 10 mm so that the toner dropped from the sieve can be efficiently deposited on the substrate.
A sawtooth waveform vibration having an amplitude of 1 mm and a duty ratio of 33%, which corresponds to an acceleration of 5 G, was applied to the frame holding the sieve at 5 Hz for 30 seconds in the in-plane direction of the sieve to deposit toner on the substrate.
Next, sawtooth waveform vibration with an amplitude of 1 mm and a duty ratio of 33%, which corresponds to an acceleration of 0.5 G, was applied to the substrate on which the toner was deposited for 20 seconds in the in-plane direction of the substrate to promote contact between the substrate and the toner. .
As the suction means 14 to the substrate after applying the vibration, an elastomer suction port having an inner diameter of about 5 mm connected to the tip of the nozzle of the toner cleaner is brought close to the toner placement surface to remove the toner adhering to the substrate. . The toner was sucked and removed at a distance between the suction port end and the substrate of about 1 mm and the suction time of about 3 seconds (suction force 6 kPa) to obtain an observation sample.

(2) SEM observation The amount of inorganic fine particles A attached in the polycarbonate thin film adhesion measurement method is measured using an image obtained by S-4800 reflected electron image observation. Since the reflected electron image is easy to obtain a high-contrast inorganic fine particle image as compared with the secondary electron image, it is possible to accurately measure the amount of inorganic fine particles A deposited in the polycarbonate thin film adhesion measurement method. The observation conditions are shown below.
Acceleration voltage: 0.8 kV
Emission current: 20μA
Detector: [on SE (U)], [+ BSE (LA.100)]
Probe current: [Normal]
Focus mode: [UHR]
WD: [3.0mm]

(3) Image storage Brightness adjustment is performed in the ABC mode, and a photograph is taken with a size of 640 × 480 pixels and stored. The following analysis is performed using this image file. At this time, the observation magnification was set to 20k, and 100 views were observed to obtain 100 images.

(4) Image analysis Since the image obtained by observation shows the inorganic fine particles with high luminance and the substrate with low luminance, the amount of inorganic fine particles in the visual field can be quantified by binarization. In the present invention, the adhesion amount of the inorganic fine particles A is calculated by binarizing the observation image obtained by the above-described method using image processing software ImageJ (developer Wayne Rhandand). The analysis conditions are as follows. The background luminance distribution was removed from the Subtract Background menu with a flattening radius of 40 pixels and then binarized with a luminance threshold value of 50. An example of the obtained binarized image is shown in FIG. The adhesion area of the inorganic fine particles A was calculated from the obtained binarized image by performing particle analysis using image analysis software ImageJ. Two areas of particles of the digitized image is 0.005 .mu.m ² or 0.100 .mu.m ² or less, compactness of 0.40 or more, and extract particles of 0.80 shape by image analysis software, the adhesion of the inorganic fine particles A The area was calculated. Incidentally, the density is a value expressed by the following formula (2) by calculating the area of the inorganic fine particles and the area of the inorganic fine particles surrounded by the envelope, and the density is determined by the image analysis software ImageJ.
It is possible to define a numerical range with the name “dity”.
Density = area of inorganic fine particles / area of inorganic fine particles surrounded by envelope equation (2)
The adhesion area of the inorganic fine particles A was divided by the total area of the binarized image used for the analysis to determine the amount (area%) of the inorganic fine particles A in the polycarbonate thin film adhesion measurement method.
The above measurement was performed on 100 binarized images, and the median value was defined as the amount of inorganic fine particles A (area%).
Further, this polycarbonate thin film adhesion measurement can be performed in the same manner for a toner containing other than the inorganic fine particles A. When the reflected electron image is observed in S-4800, the element of each fine particle can be specified using elemental analysis such as EDAX. At this time, fine particles other than the inorganic fine particles A are recorded and excluded during the image analysis, so that they can be excluded from the target of the adhesion amount of the inorganic fine particles A.

In the toner of the present invention, the amount of inorganic fine particles A having a density of 0.40 or more and 0.80 or less, which adheres when the area of the polycarbonate thin film is 100% in the polycarbonate thin film adhesion measurement method, is 0.1. The area% is preferably 5.0 area% or less, and more preferably 0.3 area% or more and 1.5 area% or less. In the present invention, a stable block layer of inorganic fine particles can be obtained by controlling the amount of inorganic fine particles A having a specific density that migrates to the surface of the photosensitive drum within the above range, and other external additives can be prevented from slipping through. It is easy to obtain the suppressing effect.
The amount of the inorganic fine particles A having a density of 0.40 or more and 0.80 or less is adjusted to the above range by adjusting the addition amount of the inorganic fine particles A, the external addition conditions, and the value of the dielectric loss tangent of the polyester resin A. Can be controlled. In the present invention, from the viewpoint of maintaining high fluidity while suppressing contamination of the member during long-term use, the value of the dielectric loss tangent of the polyester resin A is optimized after the addition amount of the inorganic fine particles A and the external addition conditions are optimized. It is preferable to control by.

It is preferable to add an external additive other than the inorganic fine particles A to the toner of the present invention. As an external additive other than the inorganic fine particles A, inorganic fine particles selected from silica, alumina, titania, or composite oxides thereof can be used. Examples of the composite oxide include silica alumina composite oxide, silica titania composite oxide, strontium titanate fine powder, and the like. As these external additives, it is preferable to use the surface after hydrophobizing. Examples of the hydrophobizing treatment include treatment with an organosilicon compound, silicone oil, long chain fatty acid and the like.
Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylethoxysilane, isobutyltrimethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, and hexamethyl. Examples thereof include disiloxane. These are used in one kind or a mixture of two or more kinds.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil.

In the toner of the present invention, as an external additive other than the inorganic fine particles A, an inorganic fine powder having a high fluidity-imparting ability on the toner particle surface and an average primary particle size in a particle size distribution on a number basis of 5 nm to 30 nm. It is preferable to use it.
For example, as commercially available silica, AEROSIL (Nippon Aerosil Co., Ltd.) 130, 200, 300, 380, TT600, MOX170, MOX80, COK84, Ca—O—SiL (CABOT Co.) M-5, MS-7, MS -75, HS-5, EH-5, W
acker HDK N 20 (WACKER-CHEMIE GMBH) V15, N20E, T30, T40, DC Fine Silica (Dow Corning Co.), and Fransol (Fransil) are commercially available. In the invention, these can also be suitably used.
The amount of these external additives added is preferably 0.1 parts by weight or more and 3.0 parts by weight or less, and 0.5 parts by weight or more and 2.0 parts by weight or less with respect to 100 parts by weight of the toner particles. More preferably.

  Further, the toner used in the present invention may further contain other additives, for example, a lubricant powder such as Teflon (registered trademark) powder, zinc stearate powder, and polyvinylidene fluoride powder within a range that does not substantially adversely affect the toner. Abrasives such as cerium oxide powder and silicon carbide powder, anti-caking agents, and organic and / or inorganic fine particles having reverse polarity can also be used in small amounts as developability improvers. These additives can also be used after hydrophobizing the surface.

As a mixer for externally adding external additives to toner base particles, Henschel mixer (manufactured by Nippon Coke Industries Co., Ltd.), super mixer (manufactured by Kawata Corp.), nobilta (manufactured by Hosokawa Micron Corp.), hybridizer (Nara Machinery Co., Ltd.) Manufactured). Among these, Nobilta is preferable in order to control the liberation rate of the external additive and to coat the external additive uniformly.
Examples of the sieving device used for sieving coarse particles after external addition include the following. Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokuju Kosakusha Co., Ltd.); Vibrasonic System (manufactured by Dalton Co.); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); This is performed using a micro shifter (manufactured by Hadano Sangyo Co., Ltd.).

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, and more preferably 5.0 μm or more and 7.5 μm or less.
When the weight average particle size of the toner is smaller than 4.0 μm, the fluidity of the toner is easily deteriorated, the charge rising property and the charge distribution are easily deteriorated, and it is difficult to cause problems such as fogging, scattering, and low image density. Tend to be. In addition, the cleaning property of the transfer residual toner remaining on the photosensitive member or the intermediate transfer member is deteriorated, and the photosensitive member, the intermediate transfer member, or the charge imparting member may be contaminated to cause an image defect. When it is larger than 9.0 μm, it tends to cause deterioration of fine line reproducibility of minute characters and the like and deterioration of image scattering.
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.

  Toner particles produced by the suspension polymerization method are produced, for example, as follows. A polymerizable monomer composition is prepared by mixing a polymerizable monomer, polyester resin A, and, if necessary, a colorant composition, a wax, a polymerization initiator, and the like. 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.

The monofunctional polymerizable monomer can be used alone or in combination of two or more kinds 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 was prepared by mixing a dispersion obtained by dispersing the colorant composition in the first polymerizable monomer with the second polymerizable monomer. It is preferable that That is, after the colorant composition is sufficiently dispersed by the first polymerizable monomer, the colorant is made better by mixing with the second polymerizable monomer together with other toner materials. It can be present in the toner particles in a dispersed state.

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. is there. 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 may be used during the polymerization of the polymerizable monomer in order to increase the stress resistance of the toner particles and to control the molecular weight of the components constituting the toner particles.
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 5 parts with respect to 100 parts by mass of the polymerizable monomer in terms of toner fixing property and offset resistance. Used in the range of parts by mass.

  The polymerizable monomer and the crosslinking agent are preferably used alone or by appropriately mixing the 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. Does not drop.

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, so that a binder resin that mainly forms a core and a wax that is added as necessary are 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, or may be prepared pigment compositions as long as they do not significantly inhibit the effect of the pigment dispersant 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 amount of the colorant added is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the 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 straight chain fatty acids; Unsaturated fatty acids such as brandic acid, eleostearic acid, parinalic 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; aliphatic gold such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate Salts (generally called 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 alcohol moieties 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 these, as the charge control agent other than the resin-based charge control agent, a metal-containing salicylic acid-based compound is preferable, and the metal is particularly preferably 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.
A preferable blending amount of the charge control agent is 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. .

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. The amount of the polar resin added 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 in order to obtain the above-described effect of the polyester resin A. It is.

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 (4) and a linear aliphatic diol represented by the following formula (5).
HOOC- _{(CH 2)} m -COOH (4)
[Wherein m represents an integer of 4 to 16]
HO— (CH ₂ ) _n —OH Formula (5)
[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 a pigment or the crystalline polyester tends to be deteriorated. Image uniformity may deteriorate.
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.

  In the present invention, a magnetic toner can be obtained by containing a magnetic material. In this case, the magnetic material can also serve as a colorant. Examples of magnetic materials that can be used in the present invention include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and these metals and aluminum, cobalt, copper, lead, magnesium, tin, Examples thereof include alloys with metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

Further, as these magnetic materials used in the present invention, a surface-modified magnetic material is more preferably used. In particular, when a toner is produced by a polymerization method, it is preferable to use a toner that has been subjected to a hydrophobic treatment with a surface modifier that does not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.
Further, as these magnetic materials, those having an average particle diameter of 1 μm or less, preferably 0.1 to 1 μm may be used. As magnetic materials, coercive force (HC) is 1.6 to 24 kA / m (20 to 300 oersted), and saturation magnetization (σS) is 50 to 200 Am as magnetic characteristics when 795.8 kA / m (10 k ested) is applied. ² / kg, residual magnetization (.sigma.r) it is preferable to use those 2~20Am ² / kg.

  The toner of the present invention can be used in any developing system as a one-component or two-component developer. For example, in the case of a magnetic toner in which a magnetic material is contained in the toner as the one-component developer, there is a method of transporting and charging the magnetic toner using a magnet built in the developing sleeve. In addition, when using a non-magnetic toner that does not contain a magnetic material, there is a method in which a blade or a fur brush is used to frictionally charge the toner to adhere it onto the developing roller.

  When used as a two-component developer, for example, the magnetic carrier to be mixed with the toner is composed of an element selected from iron, copper, zinc, nickel, cobalt, manganese, chromium and the like alone or in a composite ferrite state. The shape of the magnetic carrier used at this time may be spherical, flat, irregular, or the like, and a magnetic carrier whose surface state fine structure (for example, surface irregularity) is appropriately controlled may be used. it can. A resin-coated carrier whose surface is coated with a resin can also be suitably used. The average particle diameter of the carrier to be used is preferably 10 to 100 μm, more preferably 20 to 50 μm. Further, when the two-component developer is prepared by mixing these carrier and toner, the toner concentration in the developer is preferably about 2 to 15% by mass.

  The toner according to the present invention can be used, for example, for image formation by electrophotography. A charging step for charging the photosensitive member; an exposure step for exposing the charged photosensitive member to form an electrostatic latent image; and a developing step for developing the electrostatic latent image with toner to form a toner image; It is preferable to use in an image forming method including a transfer step of transferring the toner image to a transfer material and a cleaning step of removing residual toner remaining on the surface of the photoreceptor after transfer.

Hereinafter, methods for measuring physical properties related to the present invention will be described. Each resin sample may be collected from the toner and analyzed.
<Measurement method of dielectric loss tangent of polyester resin A>
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.

<Method for Measuring Acid Value of Polyester Resin A>
The acid value of the polyester resin A in the present invention is determined by the following operation. The basic operation is JIS K0070. The acid value of the genus polar resin was measured by the following method.
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 polar resin 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-exchanged 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. As the factor of the potassium hydroxide solution, take 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, add a few drops of the phenolphthalein solution, titrate with the potassium hydroxide solution, and the hydroxylation 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
A sample of 2.0 g of the pulverized polyester resin was precisely weighed into 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 potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in final test, f: potassium hydroxide Solution factor, S: sample (g).

<Molecular weight measurement of resin>
The molecular weight and molecular weight distribution of the polyester resin A and other resins used in the present invention are calculated in terms of polystyrene by gel permeation chromatography (GPC). When measuring the molecular weight of a resin having an acid group, the column elution rate also depends on the amount of the acid group. Therefore, it is necessary to prepare a sample in which the acid group is capped in advance. Methyl esterification is preferable for capping, and a commercially available methyl esterifying agent can be used. Specifically, a method of treating with trimethylsilyldiazomethane can be mentioned.
The molecular weight is measured by GPC as follows. The resin was added to THF (tetrahydrofuran) and allowed to stand at room temperature for 24 hours. The solution was filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. Measure under the following conditions. In addition, sample solution preparation adjusts the quantity of THF so that the density | concentration of resin may be 0.8 mass%. If the resin is difficult to dissolve in THF, a basic solvent such as DMF can be used.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin column listed below is used. Specifically, trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F manufactured by Tosoh Corporation -4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ".

<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 an aperture tube of 100 μm 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, 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 Measuring Toner Circularity>
The circularity of the toner in the present invention is measured using a flow type particle image measuring device “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement / analysis conditions during calibration.
A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. 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 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
For the measurement, the above-mentioned flow type particle image analyzer equipped with “UPlanApro” (magnification 10 times, numerical aperture 0.40) as an objective lens is used, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. It was used. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the equivalent circle diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity is obtained.
In the measurement, before starting the measurement, standard latex particles (for example, Duke Science)
Automatic focusing is performed using “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by tific. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In this embodiment, a flow type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle size was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

<Measuring method of dense density and minimum ferret diameter of inorganic fine particles A>
To measure the density and minimum ferret diameter of the inorganic fine particles A, a toner surface observation image taken with Hitachi Ultra High Resolution Field Emission Scanning Electron Microscope S-4800 (Hitachi High-Technologies Corporation) is used for image analysis software image processing. Calculation is performed by using software ImageJ (developed by Wayne Rashhand). The measurement procedure is shown below.
(1) Sample preparation Conductive paste (TED PELLA, Inc, Product No. 16053, PELCO Colloida on a sample table (aluminum sample table 15 mm × 6 mm))
l Graphite, Isopropanol base) is applied thinly, and the toner is deposited thereon. Using a blower, the excess toner is air blown and then dried sufficiently. Set the sample stage on the sample holder.
(2) S-4800 Observation Conditions Under the same conditions as the polycarbonate thin film adhesion measurement method described above, the toner surface is observed with an observation magnification of 20k. With respect to the weight-based equivalent weight average diameter D4 (μm) of the toner measured by the particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.), 0.9 ≦ R / 100 toners having a long diameter R (μm) satisfying the relationship of D4 ≦ 1.1 are selected, a relatively flat portion of the toner surface (a visual field in which the entire observation surface is in focus) is selected, and one visual field per toner is selected. Observation is performed to obtain 100 images.

(3) Image analysis From the obtained SEM observation image, an average density and a minimum ferret diameter are calculated using image processing software ImageJ (developer Wayne Randhand). The calculation procedure is shown below.
1) Set the scale with [Analyze]-[Set Scale].
2) Set a threshold value with [Image]-[Adjust]-[Threshold].
(Set to a value that does not leave noise, but leaves inorganic fine particles A to be measured)
3) Select the image portion of the measured inorganic fine particles A with [Image]-[Crop].
4) The superposed inorganic fine particles are erased by image editing.
5) Invert the monochrome image with [Edit]-[Invert].
6) Check [Area], [Shape Descriptors], [Perimeter], [Fit Ellipse], [Ferets Diameter] in [Analyze]-[Set Measurements]. In addition, [Redirect to] is set to [None], and [Decimal Place (0-9)] is set to 3.
7) In [Analyze]-[Analyze Particle], specify the area of the particles to be 0.005 μm ² or more, and execute.
8) Obtain the solidity and minimum ferret diameter values of each particle specified in 7) above.
9) Measurement is performed on 100 observed images, and an arithmetic average value of the obtained Solidity is calculated to obtain an average density. Similarly, an arithmetic average value of the obtained minimum ferret diameter is calculated and set as a value of the minimum ferret diameter.

<Measurement of BET specific surface area of inorganic fine particles>
The BET specific surface area of the inorganic fine particles is measured according to JIS Z8830 (2001). A specific measurement method is as follows.
As a measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method is used. Setting of measurement conditions and analysis of measurement data are performed using dedicated software “TriStar3000 Version 4.00” attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe are connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas is defined as the BET specific surface area in the present invention.

The BET specific surface area is calculated as follows.
First, nitrogen gas is adsorbed onto the inorganic fine particles, and the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g ⁻¹ ) of the inorganic fine particles at that time are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g ⁻¹ ) is plotted on the vertical axis. The adsorption isotherm is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g ⁻¹ ), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the inorganic fine particles, is obtained by applying the following BET equation.
Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)
The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 1 / (Vm × C)
When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept value of the straight line can be calculated. Vm and C can be calculated by solving the above slope and intercept simultaneous equations using these values.

Furthermore, the BET specific surface area S (m ² · g ⁻¹ ) of the inorganic fine particles is calculated from the calculated Vm and the molecular occupation cross-sectional area of the nitrogen molecule (0.162 nm ² ) based on the following formula.
S = Vm × N × 0.162 × 10 ⁻¹⁸
(N is Avogadro's number (mol- ¹ ).)
The measurement using this apparatus follows the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus, and specifically, the measurement is performed according to the following procedure.
Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 ml) that has been thoroughly cleaned and dried. Then, about 0.1 g of inorganic fine particles are put into this sample cell using a funnel.

The sample cell containing the inorganic fine particles is set in a “pretreatment device Bacrepprep 061 (manufactured by Shimadzu Corporation)” connected with a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. In vacuum degassing, the inorganic fine particles are gradually degassed while adjusting the valve so as not to be sucked into the vacuum pump. The pressure in the cell gradually decreases with deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the accurate mass of the inorganic fine particles is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber plug during weighing so that the inorganic fine particles in the sample cell are not contaminated by moisture in the atmosphere.
Next, a dedicated “isothermal jacket” is attached to the stem portion of the sample cell containing the inorganic fine particles. Then, a dedicated filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member having an inner surface made of a porous material and an outer surface made of an impervious material capable of sucking liquid nitrogen to a certain level by capillary action.

Subsequently, the free space of the sample cell including the connection tool is measured. Free space is measured by measuring the volume of the sample cell with helium gas at 23 ° C., and then measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen in the same manner using helium gas. Calculated from the difference in volume. Further, the saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.
Next, after performing vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum deaeration. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules on the inorganic fine particles. At this time, the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, and the adsorption isotherm is converted into a BET plot. Note that the points of relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Further, using the value of Vm, the BET specific surface area of the inorganic fine particles is calculated as described above.

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.
In addition, isosorbide in the table is a compound having a structure of the following formula (3).

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 Examples 2 to 16 of polyester resin>
Polyester resins 2 to 16 were produced in the same manner as in Production Example of Polyester Resin 1 except that the charged amounts of the acid component and alcohol component were changed as shown in Table 1. Table 1 shows the physical properties of polyester resins 2-16.

<Production Examples 17-22 of polyester resin>
In the manufacture example of the polyester resin 1, it reacted similarly except having adjusted the reaction time and changing the weight average molecular weight (Mw), and manufactured the polyester resins 17-22. Table 1 shows the physical properties of the polyester resins 17-22.

ＴＰＡ：テレフタル酸
ＴＭＡ：トリメリット酸
ＢＰＡ（ＰＯ）：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 (PO): 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 stirred at 200 rpm at 25 ° C. for 180 minutes using zirconia beads (140 parts by mass) with a radius of 1.25 mm 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 4 parts by mass The above materials are heated to 65 ° C and uniformly dissolved at 5,000 rpm using a TK homomixer (manufactured by Special Machine Industries). 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 of the replenishing 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 classified and removed at the same time by a multi-division classifier (elbow jet classifier manufactured by Nippon Steel Mining Co., Ltd.) to obtain cyan toner particles 1.

<Production example of toner particles 2 to 22>
Toner particles 1 to 22 were obtained in the same manner as in the production example of toner particles 1 except that the polyester resin 1 was changed to polyester resins 2 to 22 and the addition amount of the polyester resin was changed to the values shown in Table 3. .

<Example of production of inorganic fine particles 1>
After supplying oxygen gas to the burner and igniting the ignition burner, hydrogen gas was supplied to the burner to form a flame, and silicon tetrachloride as a raw material was charged into this to gasify to obtain silica fine particles. . As a specific method, it was produced with reference to the description in JP-A-2002-3213.
Hydrophobization treatment was performed by adding 10 parts by mass of hexamethyldisilazane as a surface treatment agent to 100 parts by mass of the obtained silica fine particles. Table 2 shows the physical properties of the inorganic fine particles 1.

<Example of production of inorganic fine particles 2>
After recovering the silica powder with the inorganic fine particles 1, the obtained silica powder was transferred to an electric furnace and spread in a thin layer, and then subjected to heat treatment at 900 ° C. to sinter and aggregate. Thereafter, the same surface treatment as that of the inorganic fine particles 1 was performed to obtain inorganic fine particles 2. Table 2 shows the physical properties of the inorganic fine particles 2.

<Production example of inorganic fine particles 3 to 6>
With reference to the description in JP-A-2002-3213, the amount of silicon tetrachloride, the amount of oxygen gas, the amount of hydrogen gas, the silica concentration and the residence time were adjusted to obtain inorganic fine particles 3 to 6.
Table 2 shows the physical properties of the inorganic fine particles 3 to 6.

<Example of production of inorganic fine particles 7>
In accordance with the method described in JP-A-60-255602, silica powder was prepared by deflagration using metal silicon as a raw material. The obtained silica powder was transferred to an electric furnace and spread in a thin layer, and then subjected to heat treatment at 900 ° C. to sinter and aggregate. Thereafter, a surface treatment was performed in the same manner as the inorganic fine particles 1 to obtain inorganic fine particles 7. Table 2 shows the physical properties of the inorganic fine particles 7.
<Example of inorganic fine particles 8>
JR-405 (manufactured by Teika Co., Ltd.), which is rutile titanium oxide, was used as inorganic fine particles 8. Table 2 shows the physical properties of the inorganic fine particles 8.
In addition, regarding the measurement of the minimum ferret diameter and the average density of the inorganic fine particles 1, a sample was prepared by the following method. To 100 parts by mass of toner particles 1, 0.5 parts by mass of inorganic fine particles 1 were dry-mixed with a Henschel mixer FM10C (manufactured by Mitsui Mining) for 10 minutes at 3400 rpm. The minimum ferret diameter and average density of the inorganic fine particles 1 were measured on the surface of the obtained toner according to the above-described measurement method. Moreover, the minimum ferret diameter and average density of the inorganic fine particles 2 to 8 were measured under the same conditions.

<Production Example of Toner 1>
For 100 parts by mass of toner particles 1, 0.5 parts by mass of inorganic fine particles 1, 1.0 parts by mass of hydrophobic silica particles RY300 (manufactured by Nippon Aerosil Co., Ltd.) and 0.2 parts by mass of titanium oxide fine powder JMT −150 AO (manufactured by Teika Co., Ltd.) was dry mixed with a Henschel mixer FM10C (manufactured by Mitsui Mining Co., Ltd.) at 3400 rpm for 10 minutes to obtain toner 1. Table 3 shows the physical properties of Toner 1 thus obtained.

<Production Example of Toners 2 to 36>
Toners 1 to 36 were obtained in the same manner as in Production Example of Toner 1 except that the toner particles and inorganic fine particles A were changed to the combinations shown in Table 3. In the toner 35, no additional inorganic fine particles A are added to 1.0 part by mass of RY300 and 0.2 part by mass of JMT-150AO. Table 3 shows the physical properties of Toner 2 to 36 obtained.

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

The evaluation method and evaluation criteria of the present invention will be specifically described below.
As the image forming apparatus, LBP-7700C (manufactured by Canon) which is a commercially available laser printer and a modified cartridge of a toner cartridge 323 (cyan) (manufactured by Canon) which is a process cartridge were used.
This modified cartridge was modified so that the toner supply roller moved in the same direction at the contact portion with the toner carrying roller by changing / adding the gear inside the cartridge. The peripheral speed of the toner supply roller on the basis of the toner carrying roller was adjusted to 160%. The amount of penetration of the cleaning blade into the photosensitive drum was adjusted to 0.8 mm. The product toner was extracted from the inside of the cartridge, cleaned by air blow, and then charged with 100 g of the toner of the present invention.
The toner was evaluated by performing a durability test using the modified cartridge.

(1) Contamination of parts during durability (contamination of charging parts)
In order to evaluate the member contamination property of the toner, the charging member contamination was evaluated by the following method.
Canon color laser copier paper (A4: 81.4 g / m ^{2 in} the low temperature and low humidity environment (15 ° C / 10% RH), this paper will be used unless otherwise specified)
In addition, an image with a printing rate of 0.2% was output 20000 sheets every 2 sheets with an interval of 2 seconds. Thereafter, the charging roller was removed from the toner cartridge. The charging roller was removed from a new process cartridge (commercially available), the durable charging roller was attached, and a halftone image was output. The uniformity of the halftone image was visually evaluated to evaluate the charging member contamination.
It is known that when the charging member is contaminated, uneven charging occurs on the photosensitive member, resulting in uneven density of the halftone image.
(Charging member contamination)
Evaluation criteria A: Image density is uniform and uniform B: Image density is slightly uneven C: Image density is uneven but level of use is not problematic Level D: Image density is uneven and uniform Level that is not a halftone image

(2) Fluidity during durability (solid follow-up)
In order to evaluate the durability and fluidity of the toner, the solid followability was evaluated by the following method.
In a low-temperature and low-humidity environment (15 ° C./10% RH), all solid images were output in succession as three sample images. Thereafter, 20000 sheets of an image with a printing rate of 0.5% were output every two sheets with an intermittent time of 2 seconds. In order to separate from the evaluation of the contamination of the member, the drum unit was replaced with a new one, and all the solid images similar to the initial one were output in succession. The solid followability was evaluated by visual evaluation on the third sheet of all the solid images obtained.
In addition, it is known that the above evaluation items give better results as the toner fluidity is higher.
(Flat followability)
Evaluation criteria A: Image density is uniform with no unevenness B: Image density is slightly uneven C: Image density is uneven but there is no problem in use Level D: Image density is uneven and uniform Levels that are not solid images

(3) Chargeability under high temperature and high humidity environment (image fogging)
From the viewpoint of charging stability, image fog was evaluated by the following method.
Letter B HP Bro in a high temperature and high humidity environment (30 ° C, 80% RH)
A solid white image having a printing rate of 0% was output as a sample image on the Chue Paper, Glossy (200 g / m ² ). After outputting the sample image, 5000 images with a printing rate of 0.5% were output. Then, after storing for 7 days in the same environment, the same solid white image was output. The fog was evaluated on the obtained solid white image. In addition, as for the said evaluation item, it is known that a favorable result will be obtained, so that it is excellent in the charging property at the time of high temperature, high humidity storage.
The fog density (%) was measured using “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), and the fog density ( %). An amber filter was used as the filter.
(Fog)
Evaluation criteria A: fog density of less than 0.5% B: fog density of 0.5% to less than 1.0% C: fog density of 1.0% to less than 2.0% D: fog density of 2.0% or more

<Examples 2 to 30>
The same evaluation as in Example 1 was performed on the toners 2 to 30. The obtained evaluation results are shown in Table 4.

<Comparative Examples 1-6>
The toner 31 to 36 were evaluated in the same manner as in Example 1. The obtained evaluation results are shown in Table 4.

In Examples 1 to 30, good results were obtained for any of the evaluation items. On the other hand, in Comparative Examples 1-6, it was a result inferior to an Example about either of the said evaluation items.
From the above results, according to the present invention, it is possible to provide a toner having high fluidity while suppressing contamination of members during long-term use.

T: toner, A: external additive, 11: sieve, 12: substrate, 13: substrate holder, 14: suction means

Claims (8)

A toner having a core-shell structure toner particle in which a core containing a polyester resin A is formed on a core containing a binder resin, and inorganic fine particles A;
The toner particles contain 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 polyester resin A contains 0.10 mol% or more and 20.00 mol% or less of the isosorbide unit represented by the formula (1) based on the total monomer units,
The inorganic fine particle A is a toner characterized in that an average value of a dense density represented by the following formula (2) observed by a scanning electron microscope (SEM) is 0.40 or more and 0.80 or less.

Dense density = area of inorganic fine particles / area of inorganic fine particles surrounded by envelope (2)   The toner according to claim 1, wherein a 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 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 inorganic fine particle A has a minimum ferret diameter of 50 nm to 300 nm.   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 through a granulating step 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. A charging step for charging the photosensitive member; an exposure step for exposing the charged photosensitive member to form an electrostatic latent image; and a developing step for developing the electrostatic latent image with toner to form a toner image; A transfer step of transferring the toner image to a transfer material, and a cleaning step of removing residual toner remaining on the surface of the photoconductor after transfer;
An image forming method comprising:
An image forming method, wherein the toner is the toner according to claim 1.

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