JP2001312094A - Toner and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which decreases shaping or scratching of an organic photoreceptor, fixing roller, fixing film or the like, which extends the exchange life of the organic photoreceptor or the like, and which can form an image of high quality for a long time without causing any filming, melt sticking, white spots, black spots, contamination on the back face of an image. SOLUTION: In the toner containing at least toner particles and hydrophobic inorganic fine powder, the toner particles contain at least a binder resin, magnetic particles and wax and have the following properties. (a) The peak area of melting of the wax measured by DSC of the toner is >=5 J/g, and (b) by FE-SAM observation of the toner particle surface, the average number αof magnetic particles identified per unit area (μm2) of the toner particle surface at 1.0 kV acceleration voltage, and the average number β of the magnetic particles identified per unit area (μm2) of the toner particle surface at 2.0 kV acceleration voltage satisfy 1.1<=β/α<=50.0 when α≠0 and 0.1<=β<=20.0 when α=0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used for electrophotography, electrostatic recording, electrostatic printing, toner jet, and the like, and an image forming method.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
(U.S. Pat. No. 3,666,363) and Japanese Patent Publication No. 43-24748 (U.S. Pat.
Many methods are known, as described in US Pat. No. 1,361). Generally, using a photoconductive substance, an electric latent image is formed on a photoreceptor by various means, the latent image is developed using toner, and then a toner image is transferred to a transfer material. The image is fixed by heating, pressurizing, heating and pressurizing or solvent vapor to obtain a copy. The toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

As a developing system, there are a one-component developing system, a two-component developing system, and the like. Among them, many of them are excellent in suggesting a one-component developing system using magnetic toner particles.

However, since such a developing method uses a simple developing device, it is difficult to further improve the image quality without improving the developing performance of the magnetic toner. Therefore, it is required that the chargeability of the magnetic toner particles be more uniform and stable.

The chargeability of the magnetic toner largely depends not only on the type and presence (distribution, depth) of the external additive adhering to the toner surface, but also on the number of magnetic particles exposed on the toner surface.

[0006] Among the materials used for the magnetic toner, magnetic particles in particular affect the performance of the magnetic toner because they are contained in an amount of 20 to 70% by mass based on the magnetic toner. For example,
When the number of magnetic particles exposed on the toner surface increases, the abrasive force of the toner particles increases, and the surface of a member such as an organic photoreceptor, a developer carrier, a fixing roller or a fixing film is polished, It may also shorten the life. Further, since the surface of each member is damaged, the toner may be fused from the scratch as a starting point, thereby causing an image defect.

[0007] As a charging method, as a charging method that suppresses the generation of ozone as much as possible, a charging member such as a roller or a blade is brought into contact with the surface of the photoreceptor, and a narrow space is formed in the vicinity of the contact portion to discharge. Have become mainstream. For example, JP-A-57-178257, JP-A-56-104351, JP-A-58-40566, JP-A-58-139156, and JP-A-58-139156 −
It is reported in, for example, Japanese Patent Publication No. 150975.

However, if the toner or the free toner constituent material remains on the surface of the photoreceptor, it adheres to the contact charging member at the contact portion between the contact charging member and the photoreceptor and becomes contaminated.
Image defects such as poor charging, filming or fusion may occur.

In the transfer method, a transferable toner image formed on the surface of the latent image carrier / photoreceptor is statically transferred onto a sheet-like transfer material mainly made of paper, as a transfer method that minimizes ozone generation. In an image forming apparatus including a step of electrically transferring, a latent image carrier running endlessly such as a rotating cylinder or an endless belt is used, and a biased transfer device is pressed against the latent image carrier and pressed between them. A method of transferring the toner image on the latent image carrier side to the transfer material by passing the transfer material is used. For example, an apparatus as disclosed in Japanese Patent Application Laid-Open No. Sho 59-46664 has already been proposed.

However, when the above-mentioned contact charging means is used, there is a problem that insufficient charging occurs if sufficient contact with the member to be charged cannot be maintained. Further, in the contact portion, if residual toner is present on the surface of the photoconductor, the charging member has a predetermined contact pressure, so that the residual toner is fixed on the surface of the charging member and the surface of the photoconductor, which may affect the image. Also have.

In an apparatus for performing transfer by contact, as in the above-mentioned JP-A-59-46664, since a transfer current is supplied from a contact portion, it is necessary to apply a certain pressure to the transfer apparatus. is there. When the contact pressure is applied, pressure is applied to the toner image on the latent image carrier, and aggregation occurs.

Further, when the surface of the latent image carrier is made of a resin, adhesion occurs between the toner aggregate and the latent image carrier, and as a result, the toner is transferred to the surface of the latent image carrier or transferred. The phenomenon of sticking to the surface of the contact member of the device may occur.

When such a phenomenon occurs, the latent image formation of the latent image carrier may be lost, or the transfer may be omitted.
The result is a defective image copy.

Various studies have been made to solve the above problems.

For example, JP-A-6-110249 discloses a technique in which crystalline wax is used for a magnetic toner. Although the release effect caused by the wax is effective for filming and fusing, there is a case where the magnetic toner particle shape is non-uniform. I haven't.

For example, JP-A-49-42354 and JP-A-55-26518 disclose a technique of subjecting a powder such as silica to silicone treatment. Further, JP-A-58-60754 discloses a toner containing wet silica treated with silicone oil.

In the case where silica treated with silicone oil or the like by a wet method is used for a toner, in a system having a low copying speed,
The release property of oil is exhibited, and the effect of reducing omission during transfer and the adverse effect on the photoreceptor is recognized.However, in a system with a high copy speed or a system with a high pressure at the transfer contact part, the toner surface Hesica is buried and deteriorated, so that the mold releasability may not be exhibited.

Further, for example, attempts have been made to improve the releasability of the toner itself by improving the binder resin, but the above problem has not been completely solved.

As described above, the performance improvement of the toner is still insufficient, and there are many points to be improved at present.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner and an image forming method which solve the above-mentioned problems.

An object of the present invention is to provide a toner and an image forming method for extending the service life of an organic photoreceptor without deteriorating image quality.

It is a further object of the present invention to provide a toner and an image forming method for reducing scraping and flaws of an organic photoreceptor.

Still another object of the present invention is to provide a toner and an image forming method for suppressing the occurrence of filming and fusing.

Still another object of the present invention is to provide a toner free from image white spots and an image forming method.

It is a further object of the present invention to provide a toner and an image forming method free from black spots and image back stains.

It is a further object of the present invention to provide a toner and an image forming method for reducing abrasion / scratch of a fixing roller or a fixing film.

Further, an object of the present invention is to provide a high image density,
An object of the present invention is to provide a toner capable of obtaining a copy image without background fog and an image forming method.

[0028]

According to the present invention, there is provided a toner having at least toner particles and a hydrophobic inorganic fine powder, wherein the toner particles contain at least a binder resin, magnetic material particles and a wax; Has a wax melting peak area of 5 J / g or more in a DSC measurement of
(B) In the FE-SEM observation of the toner particle surface, the average value α of the number of magnetic particles that can be identified per unit area (μm ² ) of the toner particle surface at an acceleration voltage of 1.0 kV.
And the average value β of the number of magnetic particles that can be identified per unit area (μm ² ) of the toner particle surface at an acceleration voltage of 2.0 kV when the following condition α ≠ 0: 1.1 ≦ β / α ≦ 50. 0 When α = 0, the toner satisfies 0.1 ≦ β ≦ 20.0.

Further, according to the present invention, an electrostatic image is formed on an electrostatic image carrier, and the electrostatic image is developed by developing means having a toner to form a toner image. In an image forming method for transferring a toner image to a transfer material via an intermediate transfer member or without an intermediate transfer member, and fixing the toner image on the transfer material by a fixing unit, the toner comprises toner particles and hydrophobic inorganic fine powder. Wherein the toner particles contain at least a binder resin, magnetic particles and wax, and (a) the wax melting peak area of the toner measured by DSC is 5 J / g or more, and (b) the toner particle surface In the FE-SEM observation of the sample, the heating voltage was 1.0 kV.
The average value α of the number of magnetic particles that can be identified per unit area (μm ² ) of the toner particle surface at
The average value β of the number of magnetic particles that can be identified per unit area (μm ² ) of the toner particle surface at kV is as follows: α ≦ 0 1.1 ≦ β / α ≦ 50.0 α = 0 The present invention relates to an image forming method satisfying 0.1 ≦ β ≦ 20.0.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The inventor of the present invention considers the reason why the toner and the image forming method according to the present invention exhibit an original effect as follows.

In general, as a method for producing a magnetic toner, a so-called pulverization method, in which toner constituent materials are mixed and melt-kneaded, pulverized, classified, externally added, and sieved, is widely used. The addition amount of one wax as a toner constituent material was considered to be 2 to 4 parts by mass in terms of parts per 100 parts by mass of the binder resin. Addition of a further amount of wax causes a decrease in developability, so toners containing a large amount of wax have been avoided.

However, in general, wax has a low molecular weight and does not have charge holding power as much as a binder resin, and thus has a low charging order. Since the hydrophobic inorganic fine powder has a relatively high charge imparting power, it is high in charging order. In addition, wax is softer than binder resin. Then, it is the wax having a large difference in charging sequence that has a large electrostatic adhesion to the hydrophobic inorganic fine powder, and the sticking property of the hydrophobic inorganic fine powder as the toner particles (the electrostatic adhesion and the embedded Condition) will depend on how much wax is deposited on the surface.

Further, at the time of pulverization, the toner kneaded material is pulverized from a portion where the mutual force between the toner constituent materials is weak, depending on the pulverization method, and pulverized from the interface of the magnetic particles with a high probability. This is due to the fact that the inorganic magnetic particles hardly interact with the polymer chains in the binder resin.

The magnetic particles protruding from the toner surface are as follows:
Sharpness of toner leak points and photoreceptor members
It is known to work as a wound point.

On the other hand, when observing the surface of the toner particles,
The method using M and FE-SEM is simple and widely used. However, when observing the surface of the toner particles in a unit of μm at a high magnification, the electron beam concentrates near the surface of the object to be observed, the magnetic toner particles are charged up, and the image observation tends to be difficult. The detector that detects the electron beam reflected from the object to be observed is mainly arranged above, and the toner image projected on the monitor in a dark room is a fragmentary image due to electron beam scanning. Therefore, when observed at a high magnification, the toner image fluctuates during scanning, and it is difficult to distinguish irregularities on the toner surface and magnetic particles precipitated on the toner surface. If only the magnetic particles in the toner particles are identified, it can be confirmed by increasing the acceleration voltage in preparation for charge-up. It is necessary to identify the difference between the acceleration voltage changes. In order to avoid these problems, a system that can detect reflected electrons efficiently with lower acceleration is required.

The present inventor has conducted intensive studies in view of the above points and found the following.

First, in the pulverizing method, a large amount of wax is contained in the toner, so that a large amount of wax molecules enter the polymer chains of the binder resin during melt-kneading, and the intermolecular force between the polymer chains is reduced. As a result, the magnetic particles easily enter the location due to the shear from the stirring member (kneading shaft) of the kneading machine. As a result, the magnetic particles exert a filler effect in the binder resin, increasing the toughness as a kneaded product of the toner, and, when the toner is pulverized into fine particles, at the interface of the wax dispersed and present between the polymer chains. The toner kneaded material is disintegrated, and a wax-rich toner surface with little protrusion of magnetic particles is obtained.

This can be confirmed by, for example, a scanning electron microscope S-4700 system manufactured by Hitachi, Ltd. That is, it has secondary electron detectors above and below,
Efficiently supplements the reflected electron beam in the concave portion of the toner surface,
Since the image is converted into a digital signal, image-processed and an image is displayed on a CRT, the unevenness of the toner surface can be observed in more detail at a low acceleration and a high magnification, and the magnetic particles protruding from the toner surface can be identified. At 1 kV accelerating voltage, only the substance on the toner surface layer can be confirmed, but when the accelerating voltage is increased to 2 kV, the electron beam is irradiated to the inside of the toner surface layer, and the magnetic material protruding from the toner surface is separated from other toner constituent materials. Since it is excited first and emits reflected electrons, identification becomes possible. When a voltage of 3 kV or more is applied, even the magnetic particles inside the toner are excited, which hinders discrimination of the magnetic particles protruding from the toner surface layer. By observing the same toner particles at 1 kV and 2 kV, the number of magnetic particles protruding from the toner surface can be counted.

Second, by adding a large amount of wax to the toner, the kneaded product of the toner is easily crushed, and there are many crushing points on the surface of the toner particles during the crushing process. Since the toner particles are efficiently formed into fine particles, the obtained toner particles have a uniform shape. In addition, ultrafine particles (so-called fine powder) generated in the crushing process are mostly wax-rich and small in specific gravity, so that they are easily separated and removed in the classification process. As a result, the obtained toner particles have a small variation in the particle size distribution and have a uniform shape.

Third, the wax-rich toner surface is
Compared to the other toner surface, it has a soft surface property so that the hydrophobic inorganic fine powder can be captured on the toner surface at an appropriate depth during the external addition process. Therefore, the hydrophobic inorganic fine powder adheres to the surface of the toner particles, and the release of the hydrophobic inorganic fine particles hardly occurs due to the effects of durability and environment.

Fourth, since the number of protrusions of the magnetic particles on the toner surface is small, the detachment of the magnetic particles in the pulverizing, classifying and externally adding processes is small, and the number of concaves on the toner surface due to this is small. As a result, the number of hydrophobic inorganic fine powders that enter the recesses and are trapped is reduced, and the number of hydrophobic inorganic fine powder particles added as a toner total exists on the toner surface at face value. Functions are fully demonstrated. In addition, since the number of concave portions is reduced, the influence of water molecules due to humidity is reduced.

As described above, in the toner having the hydrophobic inorganic fine powder and the magnetic toner particles, the wax melting peak area in DSC measurement of the toner is 5 J / g or more (preferably 5 to 35 J / g); FE-SEM In the observation, the average value α of the number of magnetic particles that can be identified per unit area (μm ² ) of the toner particle surface at an acceleration voltage of 1.0 kV and the average value α per unit area (μm ² ) of the toner particle surface at an acceleration voltage of 2.0 kV 1.1 ≦ β / α ≦ 50.0 (preferably 1.1 ≦ β / α ≦ 30.0) when α = 0, and α = 0 when α = 0 If the magnetic toner satisfies the condition of 1 ≦ β ≦ 20.0, the effects of the present invention can be obtained.

If the wax melting peak area in the DSC measurement is less than 5 J / g, a wax-rich toner surface cannot be obtained, and reduction of drum abrasion / scratch, suppression of filming / fusion, and the like cannot be expected.

When α ≠ 0, if β / α is smaller than 1.1, no magnetic particles exist in the vicinity of the toner surface, and the charge leakage function as the toner particles is impaired. Charge-up continues, causing problems such as a decrease in image density. If β / α is more than 50.0, the number of magnetic particles protruding from the surface of the toner particles increases, the polishing power as toner increases, and the surface of the photoreceptor is flawed and scraped. Problems such as low image density due to a decrease in toner chargeability under wet conditions occur.

When α = 0, if β is larger than 20.0, there is a problem of damage to the surface of the photoreceptor. If it is less than 0.1, charge-up under low temperature and low humidity becomes remarkable, and fog suppression and the like deteriorate.

Further, when the magnetic toner particles of the present invention are combined with an inorganic fine powder that has not been subjected to a hydrophobic treatment, a toner is obtained.
Inorganic fine powder is easily released from the surface of toner particles due to durability, and problems such as poor cleaning, filming, and fusion occur.

Further, the present invention will be described in detail.

As the binder resin for the toner used in the present invention, polyester resin, vinyl resin, epoxy resin and the like can be used.
A vinyl resin or a mixed resin of both is more preferable in terms of fixing characteristics and developing characteristics.

In particular, in the present invention, a binder resin containing a vinyl resin, a polyester resin, and a hybrid resin component having a vinyl polymer unit and a polyester unit is preferably used for adding a large amount of wax.

The term “hybrid resin component” as used herein means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded.

Examples of the production method for preparing the binder resin used in the present invention include the following production methods (1) to (6).

(1) A method in which a vinyl resin, a polyester resin, and a hybrid resin component are blended after their production, respectively. The blend dissolves and swells in an organic solvent (eg, xylene) and then distills off the organic solvent. , Preferably in this blending step with the addition of wax. The hybrid resin component is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. Can be used. (2) A method of producing a polyester unit and a hybrid resin component in the presence of a vinyl-based polymer unit after the production. The hybrid resin component is produced by reacting a vinyl-based polymer unit (a vinyl-based monomer can be added if necessary) with a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used. Preferably, a wax is added in this step. (3) This is a method of producing a vinyl polymer unit and a hybrid resin component in the presence of a polyester unit after the production thereof. The hybrid resin component is produced by reacting a polyester unit (a polyester monomer can also be added if necessary) with a vinyl monomer and / or a vinyl polymer unit. Preferably,
In this step, wax is added. (4) After the production of the vinyl polymer unit and the polyester unit, the hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used. Preferably, a wax is added in this step. (5) After the production of the hybrid resin component, a vinyl-based monomer and / or a polyester monomer (alcohol, carboxylic acid) are added to carry out addition polymerization and / or polycondensation to produce a vinyl-based polymer unit and a polyester unit. Is done. In this case, as the hybrid resin component, one produced by the production method of the above (2) to (4) can be used, and if necessary, one produced by a known production method can be used. .
Further, an organic solvent can be appropriately used. Preferably, a wax is added in this step. (6) A vinyl-based polymer unit, a polyester unit, and a hybrid resin component are produced by mixing a vinyl-based monomer and a polyester monomer (such as alcohol and carboxylic acid) and continuously performing addition polymerization and polycondensation. Further, an organic solvent can be appropriately used. Preferably, a wax is added in this step.

In the production methods (1) to (6), a plurality of polymer units having different molecular weights and different degrees of crosslinking can be used as the vinyl polymer unit and / or the polyester unit.

Among the above-mentioned production methods (1) to (6), the production method (3) is particularly easy to control the molecular weight of the vinyl polymer unit and can control the production of the hybrid resin component. The addition of a wax is preferred in that the state of dispersion can be controlled.

The following are examples of the monomer of the polyester resin used in the present invention.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and (a)
A bisphenol derivative represented by the formula:

[0057]

Embedded image (Wherein R is an ethylene or propylene group, x, y
Is an integer of 1 or more, respectively, and the average value of x + y is 2 to 10. ) Diols represented by the formula (b);

[0058]

Embedded image And the like.

The divalent carboxylic acid containing 50 mol% or more of the total acid component includes phthalic acid, isophthalic acid,
Benzenedicarboxylic acids such as terephthalic acid and phthalic anhydride or anhydrides thereof; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof, and further substituted with alkyl groups having 6 to 18 carbon atoms Succinic acid or its anhydride; and dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid.

Also, polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of, for example, novolak phenolic resins; trimellitic acid, pyromellitic acid,
Examples include polyvalent carboxylic acids such as benzophenonetetracarboxylic acid and its anhydride.

The polyester unit of the binder resin is preferably cross-linked by a trivalent or higher polyhydric carboxylic acid or polyhydric alcohol. The cross-linking components include trimellitic anhydride, benzophenonetetracarboxylic acid, and pentaerythritol. And oxyalkylene ether of a novolak type phenol resin.

The polyester resin thus obtained has a glass transition temperature of 40 to 90 ° C., preferably 45 to 85 ° C., and a number average molecular weight (Mn) of 1,000 to 50,000.
000, preferably 1,500 to 20,000, and the weight average molecular weight (Mw) is 3,000 to 100,000, preferably 40,000 to 90,000.

The following are examples of the vinyl-based monomer for producing the vinyl-based resin.

For example, styrene, o-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
styrene and its derivatives such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene; ethylene; Ethylenically unsaturated monoolefins such as propylene, butylene and isobutylene; unsaturated polyenes such as butadiene;
Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate and vinyl benzoate;
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylamino methacrylate Α-methylene aliphatic monocarboxylic esters such as ethyl and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate , 2-ethylhexyl acrylate, stearyl acrylate,
Acrylic acid esters such as 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; -Vinyl pyrrole, N-vinyl carbazole,
N such as N-vinyl indole, N-vinyl pyrrolidone
-Vinyl compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; esters of the aforementioned α, β-unsaturated acids and diesters of dibasic acids.

Also, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydrides such as those; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl half mesaconic acid; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Acid, methacrylic acid, crotonic acid, such as cinnamic acid alpha, beta-unsaturated acid; crotonic acid anhydride, such as alpha of cinnamic acid anhydride, beta-unsaturated acid anhydride, the alpha, beta
-Anhydrides of unsaturated acids and lower fatty acids; and monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides and monoesters thereof. Furthermore, 2-
Acrylic acid or methacrylic acid esters such as hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4
-(1-hydroxy-1-methylbutyl) styrene, 4
And monomers having a hydroxy group such as-(1-hydroxy-1-methylhexyl) styrene.

Further, if necessary, the polymer may be crosslinked with a crosslinking monomer as exemplified below.

Aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; diacrylate compounds linked by an alkyl chain such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate and 1,4-butanediol Diacrylate,
1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond , Such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds instead of methacrylate Diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, polyoxyethylene (2) -2,2-bis ( - hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,
2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; further, polyester-type diacrylate compounds, for example, trade name MANDA (Nippon Kayaku) . As the multifunctional crosslinking agent, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds are replaced with methacrylate. That is triallyl cyanurate,
Triallyl trimellitate; and the like.

These cross-linking agents can be used in combination with other monomer components 10
It is preferable to use 0.01 to 10 parts by mass (more preferably 0.03 to 5 parts by mass) with respect to 0 parts by mass.

Among these crosslinkable monomers, those which are preferably used in the binder resin from the viewpoint of fixing properties and anti-offset properties include an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and an ether bond. And diacrylate compounds linked together.

In the present invention, the vinyl polymer component and / or the polyester resin component preferably contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer include, for example, phthalic acid, maleic acid,
Unsaturated dicarboxylic acids such as citraconic acid and itaconic acid and anhydrides thereof; Examples of the monomer constituting the vinyl copolymer component include those having a carboxyl group or a hydroxyl group, and acrylic acid or methacrylic acid esters.

As a method for obtaining a reaction product of a vinyl resin and a polyester resin, either a polymer containing a monomer component capable of reacting with each of the above-mentioned vinyl resins and polyester resins is used. Alternatively, a method obtained by polymerizing both resins is preferable.

Examples of the polymerization initiator used for producing the vinyl copolymer include, for example, 2,2'-azobisisobutyronitrile and 2,2'-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 ′
-Azobis (2-methylbutyronitrile), dimethyl-
2,2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethyl Ketone peroxides such as pentane), 2-phenylazo 2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, and cyclohexanone peroxide; , 2-bis (t-butylperoxy) butane, t-butyl hydroperoxide,
Cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide,
Di-cumyl peroxide, α, α-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5
-Trimethylhexanoyl peroxide, benzoyl peroxide, m-trioil peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethyl Peroxycarbonate, di-methoxyisopropylperoxydicarbonate, di- (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate ,
t-butyl peroxy neodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate,
t-butyl peroxyisopropyl carbonate, di-
t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-
Ethyl hexanoate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate and the like can be mentioned.

The glass transition temperature of the vinyl binder resin is 45 to 80 ° C., preferably 55 to 70 ° C., the number average molecular weight (Mn) is 2,500 to 50,000, and the weight average molecular weight (Mw) is It is preferably from 10,000 to 1,000,000.

In the present invention, a homopolymer or copolymer of a vinyl monomer, polyester, polyurethane, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, If necessary, aromatic petroleum resin
It can be used by mixing with the binder resin described above.

When two or more resins are mixed and used as a binder resin, as a more preferred form, those having different molecular weights are preferably mixed at an appropriate ratio.

In the present invention, a metal-containing compound which causes a crosslinking reaction with a resin binder may be contained.

The reactive metal compound usable in the present invention and
Examples include those containing the following metal ions. suitable
Na-valent metal ions include Na⁺, Li⁺, Cs⁺, Ag⁺,
Hg ⁺, Cu⁺And divalent metal ions include Be
²⁺, Mg²⁺, Ca²⁺, Hg²⁺, Sn²⁺, Pb²⁺, F
e²⁺, Co²⁺, Ni²⁺, Zn²⁺And so on. In addition, trivalent
Al ions³⁺, Sc³⁺, Fe³⁺, Co³⁺,
Ni³⁺, Cr³⁺and so on. Metal ions like above
The more decomposable the compounds, the better the results
give. This is due to the fact that the decomposable
The metal ions in the compound can be more easily
It is presumed that it is easily bonded to a sil group.

Among the reactive metal compounds, the organometallic compounds are excellent in compatibility and dispersibility with the polymer, and the crosslinking by the reaction with the metal compound proceeds more uniformly in the polymer, so that more excellent results are obtained. .

Among the reactive organometallic compounds as described above, those containing an organic compound which is particularly highly vaporizable and sublimable as a ligand and a counter ion are useful. Among the organic compounds forming a ligand or a counter ion with a metal ion, those having the above properties include, for example, salicylic acid, salicylamide, salicylamine, salicylaldehyde, salicylosalicylic acid, di-tert-butyl. Salicylic acid and its derivatives, such as salicylic acid;
Β-diketones such as acetylacetone and propionacetone; and low-molecular carboxylate salts such as acetate and propionic acid.

The amount of the metal compound used in the present invention is:
0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass is desirable per 100 parts by mass of the binder resin.

In the present invention, it is necessary that one or more waxes be contained in the toner as required.

For example, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax;
Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes mainly containing fatty acid esters such as carnauba wax, sasol wax, montanic acid ester wax; and deacidification Fatty acid esters such as carnauba wax are partially or entirely deoxidized. Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandinic acid, eleostearic acid, and vinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, and seryl alcohol And polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide;
Saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N'-dioxide Unsaturated fatty acid amides such as rail adipamide and N, N'-dioleyl sebacamide; aromatic bisamides such as m-xylene bisstearic acid amide and N, N'-distearyl isophthalic amide; Fatty acid metal salts such as calcium phosphate, calcium laurate, zinc stearate, and magnesium stearate (commonly referred to as metal soaps); grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid Tawa Box acids; behenic acid monoglyceride fatty acids with polyhydric alcohols partial esters of such, also like methyl ester compounds having hydroxyl groups obtained by and hydrogenated vegetable oils.

The wax particularly preferably used in the present invention comprises a hydrocarbon having a straight-chain alkyl group having a small number of branches. Specifically, a wax obtained by radical polymerization of alkylene under high pressure or polymerization of Zylene under low pressure with a Ziegler catalyst is used. Alkylene polymer having a high molecular weight, an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer,
A wax such as a synthetic hydrocarbon obtained from the distillation residue of hydrocarbons obtained from the synthesis gas composed of carbon monoxide and hydrogen by the Age method or by hydrogenation thereof is preferred. Further, those obtained by separating a hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation or a separation crystallization method are more preferably used. Hydrocarbons as a parent are
Synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide-based catalyst (often a multi-component system of two or more types),
For example, hydrocarbons having up to several hundred carbons, ethylene, etc., obtained by the Zintall method, the hydrochol method (using a fluidized catalyst bed), or the Aage method (using a fixed catalyst bed), which produces a large amount of waxy hydrocarbons Hydrocarbons obtained by polymerizing the above alkylene with a Ziegler catalyst are preferred because they are linear hydrocarbons having a small number of branches, a small number of branches and a long saturation. Particularly, a wax synthesized by a method not based on the polymerization of alkylene is preferable in view of its molecular weight distribution.

In the present invention, the molecular weight distribution of the wax is preferably in the range of 400 to 2400, more preferably 450 to 2400.
000, particularly preferably 500 to 1600. By providing such a molecular weight distribution, the toner can have favorable thermal characteristics.

In the present invention, the acid value of the wax is from 0 to 1 m.
gKOH / g, and a hydroxyl value of 0 to 1 mgKOH / g
It is preferred that If the acid value is larger than 1, the wax is finely dispersed in the binder resin, plasticization of the toner at the time of melting easily proceeds, and the high-temperature offset resistance deteriorates. on the other hand,
When the hydroxyl value is larger than 1, the wax domain diameter becomes small, and it becomes impossible to impart sufficient hydrophobicity to the toner particles.

The amount of the wax used in the present invention is desirably 0.1 to 30 parts by mass, preferably 5 to 20 parts by mass per 100 parts by mass of the binder resin.

As the colorant used in the present invention, one component,
Regardless of the two components, carbon black, titanium white,
Any pigment and / or dye can be used, and the magnetic material may also serve as the colorant.

Examples of the magnetic material include iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; metals such as Fe, Co, and Ni; or these metals and Al, Co, Cu, Pb, Mg, N
i, Sn, Zn, Sb, Be, Bi, Cd, Ca, M
Alloys with metals such as n, Se, Ti, W, and V, and mixtures thereof, and the like.

Conventionally, as a magnetic material, triiron tetroxide (F
e ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe
₅ O ₁₂ ), cadmium iron oxide (CdFe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe ₅ O ₁₂ ), copper iron oxide (CuFe
₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), iron neodymium oxide (NdFe ₂ O ₃ ),
Barium iron oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe
₂ O ₄ ), iron oxide lanthanum (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like are known. In the present invention, the above-mentioned magnetic materials can be used alone or in combination of two or more kinds. Particularly preferred magnetic materials are fine powders of iron tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
When the applied magnetic properties are about 袖 m and 796 kA / m (10 k Oe) is applied, the coercive force is 1.6 to 12 kA / m, the saturation magnetization is 50 to 200 Am ² / kg (preferably 50 to 100 Am ² / kg).
Am ² / kg), it is desirable for residual magnetization 2~20Am ² / kg.

The magnetic material is used in an amount of 10 to 200 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the binder resin.

When the toner of the present invention is used as a color toner, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I.
I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I.
Modant Blue 7, C.I. I. Direct Green 6,
C. I. Basic Green 4, C.I. I. Basic Green 6 and others. Examples of pigments include: graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red-mouthed graphite, molybdenum orange, permanent orange GT
R, pyrazolone orange, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt, eosin lake, brilliant carmine 3B, manganese purple, fast violet B, methyl violet lake, navy blue, cobalt blue, alkaline blue lake, Victoria Blue Lake, Phthalocyanine Blue, First Sky Blue, Indanthrene Blue BC, Chrome Green, Chromium Oxide, Pigment Green B, Malachite Green Lake, Final Yellow Green G and the like.

The amount of the colorant other than the magnetic substance used is 0.1 to 60 parts by mass, preferably 0.5 to 50 parts by mass, per 100 parts by mass of the binder resin.

For the toner of the present invention, it is necessary to use a hydrophobic inorganic fine powder. When an inorganic fine powder having no hydrophobicity is used, it becomes difficult to reduce scraping or damage of a member such as a photoreceptor and to simultaneously improve development characteristics.

Examples of the hydrophobic inorganic fine powder that can be used in the present invention include fine powders of inorganic oxides and hydrophobicized products such as inorganic carbonate compounds. In particular, hydrophobic silica fine powder, hydrophobic titanium oxide fine powder and the like are preferably used.

In the present invention, it is preferable to treat the inorganic fine powder with an organosilicon compound, for example, a silane coupling agent, in order to improve the hydrophobicity.

Examples of the silane coupling agent used in the hydrophobizing treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allyl Phenyldichlorosilane, benzyldimethylchlorosilane,
Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan,
Triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and For example, dimethylpolysiloxane having 2 to 12 siloxane units per molecule and having hydroxyl groups bonded to Si, each of which is located at one terminal unit, may be used. These are used alone or as a mixture of two or more.

The above-mentioned silica fine powder is treated with a silane coupling agent by a dry process in which a vaporized silane coupling agent is reacted with a ground silica fine powder by stirring or the like, or silica is dispersed in a solvent. The treatment can be performed by a generally known method such as a wet method in which a silane coupling agent is dropped and reacted.

In the present invention, treatment with an organosilicon compound, for example, silicone oil or the like is preferred for improving hydrophobicity. Preferred silicone oils include 2
Those having a viscosity at 5 ° C. of about 30 to 1000 centistokes are used.

In the case of the negatively chargeable silica fine powder, for example, dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, fluorine-modified silicone oil and the like are preferable.

In the case of positively chargeable silica fine powder, it is preferable to treat with a silicone oil having an organo group having at least one nitrogen atom in a side chain, or a nitrogen-containing silane coupling agent.

In the method of treating silicone oil, for example, an inorganic fine powder treated with a silane coupling agent and silicone oil may be directly mixed using a mixer such as a Henschel mixer. Alternatively, the silicone oil may be dissolved or dispersed in an appropriate solvent, mixed with a base silica fine powder, and the solvent may be removed.

In the present invention, the hydrophobizing treatment is applied by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs the inorganic fine powder. As a preferable method, a method of treating an inorganic fine powder with a silane coupling agent, or simultaneously with a treatment with a silane coupling agent, with an organosilicon compound such as silicone oil may be mentioned. Specifically, the method includes preparing an inorganic fine powder by treating it with dimethyldichlorosilane, then treating it with hexamethyldisilazane, and then treating it with silicone oil.

It is particularly preferable to treat the inorganic fine powder with two or more kinds of silane coupling agents as described above, and then treat the powder with oil since the degree of hydrophobicity can be effectively increased.

Of the hydrophobic inorganic fine powders, those having a specific surface area of 30 m ² / g or more (particularly 50 to 400 m ² / g) by nitrogen adsorption measured by the BET method are preferably used.

If necessary, an external additive other than inorganic fine powder such as silica fine powder and titanium oxide fine powder may be added to the toner of the present invention. For example, a lubricant such as Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride, among which polyvinylidene fluoride is preferable. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate, among which strontium titanate is preferable. Alternatively, for example, a fluidity-imparting agent such as titanium oxide and aluminum oxide, particularly a hydrophobic agent is preferable. Anti-caking agent, or a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, tin oxide,
Alternatively, white fine particles and black fine particles of opposite polarity can be used in small amounts as a developing property improver.

Further, if necessary, resin fine particles may be added internally or externally to such an extent that the fixability is not impaired. For example, vinyl-based resin fine particles are produced by an emulsion polymerization method, a spray drying method, or the like. Preferably, styrene, acrylic acid, 2-ethylhexyl acrylate, methyl methacrylate, dimethylaminoethyl methacrylate,
Diethylaminoethyl methacrylate, N-methyl-N
-Phenylethyl methacrylate, diethylaminoethyl methacrylamide, dimethylaminoethyl methacrylamide, 4-vinylpyridine, vinyl monomers such as 2-vinylpyridine, or resin particles obtained by copolymerizing a mixture of these monomers by an emulsion polymerization method. Is good.

The amount of the hydrophobic inorganic fine powder, resin fine particles or inorganic fine powder mixed with the toner is 0.1 to 5 parts by mass (preferably 0.1 to 3 parts by mass) with respect to 100 parts by mass of the toner.
Parts by mass)

Further, when the toner of the present invention is a magnetic toner using a carrier together,
For example, non-coated carriers such as iron powder, ferrite powder, magnetite powder, and glass beads, carriers coated with styrene-acrylic resin, silicone resin, fluorine-modified acrylic resin, and the like, or granulated carriers can be used.

In this case, 10 to 1000 parts by mass of the carrier (preferably 30 to 500 parts by mass) is added to 10 parts by mass of the toner.
Parts by mass). As the particle size of the carrier,
Those having a thickness of 4 to 100 μm (preferably 10 to 80 μm, more preferably 20 to 60 μm) are preferably used in matching with the toner of the present invention.

In the toner used in the present invention, it is preferable to use a charge control agent mixed (internally added) with toner particles or mixed (externally added) with toner particles. The charge control agent makes it possible to control the charge amount adapted to other systems such as a developing system. In particular, in the present invention, this makes it possible to optimize the charge amount of the toner on the transfer material. And good transferability is obtained.

When the toner of the present invention has a negative triboelectric charging property,
Examples of the charge control agent include organometallic complexes, metal salts, chelate compounds such as monoazo metal complexes, acetylacetone metal complexes, hydroxycarboxylic acids, metal complexes, polycarboxylic acid metal complexes, and polyol metal complexes. Also, metal complex salts of carboxylic acids, carboxylic anhydrides,
Condensates of carboxylic acid derivatives such as esters and aromatic compounds, phenol derivatives such as bisphenols and calixarenes, copolymers of styrene / acrylic monomers and sulfonic acid-containing acrylamide monomers, etc. No.

The negative charge control agent for the dye compound is represented by, for example, the following general formula.

[0114]

Embedded image [Wherein, M represents a coordination center metal, and Cr, C
o, Ni, Mn, Fe and the like. Ar is an aryl group, such as a phenyl group or a naphthyl group, which may have a substituent. In this case, as a substituent,
Examples include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms and an alkoxy group. X, X ', Y and Y' are -O-, -CO-, -NH
-Or -NR- (R is an alkyl group having 1 to 4 carbon atoms)
It is. A ⁺ represents a hydrogen ion, a sodium ion, a potassium ion, an ammonium ion, or an aliphatic ammonium ion. ]

As a more effective charge control agent usable in the present invention, a charge control resin such as a copolymer of a styrene / acrylic monomer and a sulfonic acid-containing acrylamide monomer is preferably used. Can be This copolymer is preferable in terms of compatibility and dispersibility in a toner to which a large amount of wax is added, and can improve toner performance.

The styrene / acrylic monomer used in the charge control agent is appropriately selected from the above-mentioned vinyl monomers for producing the vinyl polymer.

The sulfonic acid-containing acrylamide monomers include 2-acrylamidopropanesulfonic acid,
2-acrylamide-n-butanesulfonic acid, 2-acrylamide-n-hexanesulfonic acid, 2-acrylamide-n-octanesulfonic acid, 2-acrylamide-
n-dodecanesulfonic acid, 2-acrylamide-n-tetradecanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2-acrylamide-2-phenylpropanesulfonic acid, 2-acrylamide-2,
2,4-trimethylpentanesulfonic acid, 2-acrylamido-2-methylphenylethanesulfonic acid, 2-acrylamido-2- (4-chlorophenyl) propanesulfonic acid, 2-acrylamido-2-carboxymethylpropanesulfonic acid, 2- Acrylamide-2- (2-
Pyridyl) propanesulfonic acid, 2-acrylamide-
1-methylpropanesulfonic acid, 3-acrylamide-
3-methylbutanesulfonic acid, 2-methacrylamide-
Examples thereof include n-decanesulfonic acid and 2-methacrylamide-n-tetradecanesulfonic acid. Preferably, 2-acrylamido-2-methylpropanesulfonic acid is used.

The polymerization initiator used when synthesizing the charge control resin is appropriately selected from the initiators used when producing the above-mentioned vinyl copolymer. Preferably, a peroxide initiator is used.

Further, as a method for synthesizing the charge control resin,
There is no particular limitation, and any method such as solution polymerization, suspension polymerization, or bulk polymerization can be used. However, solution polymerization in which copolymerization is performed in an organic solvent containing a lower alcohol is preferable.

The copolymerization ratio between the styrene / acrylic monomer and the sulfonic acid-containing acrylamide monomer is 9
8: 2 to 80:20 and a weight average molecular weight of 2,000
It is preferably a polymer of 〜15,000. If the proportion of the sulfonic acid-containing acrylamide-based monomer is less than 2% by mass, the effect on the charging characteristics becomes insufficient. If the content exceeds 20% by mass, environmental stability such as moisture resistance deteriorates. When the weight average molecular weight is less than 2,000, the charge amount is reduced in a high humidity environment, and the offset resistance is also deteriorated. The weight average molecular weight is 15
If it exceeds 000, the compatibility with the resin is deteriorated, and a stable charging property cannot be obtained due to environmental fluctuations or aging due to a reduction in the particle size of the toner.

On the other hand, when the toner of the present invention has a positive triboelectric property, a modified product of nigrosine and a fatty acid metal salt, etc .;
Quaternary ammonium salts such as hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof, lake pigments thereof, triphenylmethane dyes and lake pigments thereof (As the lake agent, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanide, etc.), metal salts of higher fatty acids; dibutyltin oxide,
Diorganotin oxides such as dioctyltin oxide and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate; guanidine compounds and imidazole compounds; these can be used alone or in combination of two or more. Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used. Also, the general formula

[0122]

Embedded image [R ₁ represents H and CH ₃ , and R ₂ and R _{3 each} represent a substituted or unsubstituted alkyl group (preferably C _{1 to} C ₄ ). And a copolymer with a polymer monomer such as styrene, acrylate or methacrylate described above. The charge control agent in these cases also has an action as (all or part of) the binder resin.

One or more kinds of the above charge control agents can be contained. The content is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the binder resin of the toner.
3 parts by weight are preferred. If the proportion of the charge control agent is too large, the fluidity of the toner deteriorates and fogging is likely to occur, while if it is too small, it is difficult to obtain a sufficient charge amount.

The toner particles used in the present invention have a weight average particle size of 3.5 to 13 μm (more preferably 5 to 9 μm).
μm) is good. When the weight average particle size exceeds 13 μm, a high-definition image faithful to a latent image cannot be provided, or the image density is reduced under long-term durability or high humidity. On the other hand, when the thickness is less than 3.5 μm, the cleaning property of the transfer residual toner on the electrostatic image carrier becomes poor, or the productivity of the toner becomes extremely poor, which leads to an increase in cost.

The specific gravity of the toner is 1.3 to 2.0 g /
cm ³ is good. If it is less than 1.3 g / cm ³ , fogging will be worse, and if it is more than 2.0 g / cm ³ , damage to members will be worse.

The toner of the present invention has a temperature of 125 ° C. and a load of 9
8N (10 kgf) melt index value (M
Preferably, I) is from 1.0 to 15.0 g / 10 min. When the MI is smaller than 1.0, the adhesion of the hydrophobic inorganic fine powder to the toner particle surface during the external addition step becomes shallow,
Image defects such as white spots occur. On the other hand, if the MI is larger than 15.0, the toner tends to fuse to the drum.

To prepare the magnetic toner of the present invention, a binder resin, a magnetic substance (and a colorant), a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and the mixture is kneaded. Melting, kneading and kneading using a hot kneader such as an extruder to make the resins compatible with each other, cooling and solidifying the melt-kneaded product, pulverizing the solidified substance, classifying the pulverized substance, and classifying the magnetic material of the present invention A toner can be obtained. Other methods include dispersing the constituent materials in a binder resin solution and then spray drying to obtain a toner, or mixing a predetermined material with a monomer to form the binder resin and emulsifying the mixture. There is a method for producing a toner by a polymerization method in which a suspension is formed and then polymerized to obtain a toner. The toner according to the present invention may be a microcapsule toner composed of a core material and a shell material.

Further, the hydrophobic inorganic fine powder, other inorganic fine powder, and magnetic toner particles are sufficiently mixed by a mixer such as a Henschel mixer to obtain the toner of the present invention having an additive on the surface of the toner particles.

The following are generally used apparatuses for producing toner, but are not limited thereto.

(1) Example of crushing apparatus for toner production Apparatus name Manufacturer Maker Counter Jet Mill Hosokawa Micron Micron Jet Hosokawa Micron IDS Mill Nippon Pneumatic Industries PJM Jet Pulverizer Nippon Pneumatic Industries Cross Jet Mill Kurimoto Iron Works ur Max Date Cao engineering · SK jet-O-mill Seishin enterprise-Cryptron Kawasaki Heavy Industries, turbo mill turbo industrial and Inomizer Hosokawa Micron (2) toner manufacturing mixing device for example apparatus name manufacturer, Henschel mixer manufactured by Mitsui Mining Super mixer Kawata-Ribocone Okawara Works ・ Nauta Mixer Hosokawa Micron ・ Spiral Pin Mixer Taiheiyo Kiko ・ Redige Mixer Matsubo ・ Turbulizer Hosokawa Micron ・ Sa Black Mix Hosokawa Micron (3) for producing a toner classifier example device name manufacturer & classy Le Seishin Enterprise Micron crush fire Seishin Enterprise-spare Dick crush fire Seishin Enterprise Turbo crush Fire Nisshin Engineering micron separator by Hosokawa Micron-Turboplex (ATP ) Hosokawa Micron-TSP Separator Hosokawa Micron-Elbow Jet Nippon Steel Mining-Dispersion Separator-Nippon Pneumatic-YM Micro Cut Yasukawa Shoji (4) Example of kneading equipment for toner production Equipment name Manufacturer -KRC Kneader Kurimoto Iron Works-Bus Co. Kneader Buss ・ TEM extruder TOSHIBA MACHINE ・ TEX twin screw kneader Nippon Steel Works ・ PCM kneader Ikekai Iron Works ・ Three roll mill Inoue Manufacturing mixing roll mill Inoue Manufacturing & kneader Inoue Seisakusho, KNEADEX Mitsui Mining & MS-type pressure kneader Moriyama Seisakusho-Nida Ruder Moriyama Seisakusho, a Banbury mixer by Kobe Steel (5) Toner manufacturing sieving apparatus example device name manufacturer Ultra Sonic Koei Sangyo ・ Resonasive Tokuju Kogyo ・ Vibra Sonic System Dalton ・ Soniclean Shinto Kogyo ・ Gyro Shifter Tokuju Kogyo ・ Many manufacturers of circular vibrating sieves ・ Turbo Screener Turbo Kogyo ・ Micro Shifter Makino Sangyo

The physical properties of the toner in the present invention are measured by various measuring instruments according to the methods corresponding thereto. The measuring methods are described below.

(1) Measurement of wax melting peak area The amount of wax was measured by a differential thermal analyzer (DSC analyzer),
It is measured using DSC-7 (manufactured by PerkinElmer).

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

In the course of this temperature rise, a peak of the wax other than the glass transition point of the binder resin is obtained in the temperature range of 70 to 150 ° C.

The area between the baseline and the differential heat curve before and after the endothermic peak appears at this time is defined as the wax melting peak area in the present invention.

(2) Measurement of Number of Magnetic Materials on Toner Surface A carbon paste was applied or a double-sided tape containing a carbon paste was applied to a sample table for SEM (diameter 15 mm, thickness 5 mm), and the toner was placed on the tape to remove excess toner. Remove with dry air to obtain a sample.

Using a scanning electron microscope S-4700 manufactured by Hitachi, Ltd., the sample surface was WD 12 mm, acceleration voltage 1
Observe the toner particles corresponding to the average particle size at kV,
An image is photographed at 0000 × (a). Next, the acceleration voltage is changed from 1 kV to 2 kV while the sample is placed in the chamber, and an image is photographed (b) at the magnification of 10,000 times under the same sample and the same place. FIGS. 1A and 1B show an example thereof.

When comparing the photographs (a) and (b), 1 μm
The number of magnetic particles per m ² was counted, the observation field was changed, 10 points were measured, and the arithmetic average was taken as α.
(1 kV) and β (2 kV).

Since the S-4700 can handle an image as electronic information, after converting the data into a BMP file or the like, α (1 kV), β (2 k
kV).

(3) Measurement of Specific Gravity of Toner Using Accupyc 1330 manufactured by Shimadzu Corporation at room temperature and at room temperature.
The toner bulk density was determined under normal humidity.

The measuring method was in accordance with the instruction manual.

(4) Measurement of Melt Index Value (MI) The MI value is measured according to the method A of JIS K7210. However, the measurement conditions are a temperature of 125 ° C. and a load of 98 N (10 kgf).

(5) Measurement of Particle Size Particle size can be measured by various methods. In the present invention, Coulter Multisizer (manufactured by Coulter Co., Ltd.) is used. % NaCl aqueous solution is prepared. As the electrolytic solution, for example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and the measurement sample is further added to 0.002 to 0.002.
Add ~ 0.020 g. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the sample solution is added to a cell of the measuring device by a pipette or the like. In addition, using a 100 μm aperture as the aperture, 2 μm
The volume distribution and the number distribution were calculated by measuring the volume and the number of m or more toners.

The weight average diameter according to the present invention was determined from the weight standard average diameter (D4: the median value of each channel is a representative value for each channel) obtained from the volume distribution.

(6) Measurement of glass transition temperature Tg Tg was measured by a differential thermal analyzer (DSC analyzer), DSC
-7 (manufactured by PerkinElmer). The measurement sample is precisely weighed in an amount of 5 to 20 mg, preferably 10 mg.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

In this heating process, an endothermic peak of a main peak in a temperature range of 40 to 100 ° C. is obtained.

The intersection between the line of the midpoint of the base line before and after the endothermic peak appears and the differential heat curve is defined as the glass transition temperature Tg in the present invention.

(7) Measurement of Molecular Weight The molecular weight is measured by the following conditions under the following conditions: GPC (gel permeation chromatography).

That is, the column was stabilized in a heat chamber at 40 ° C., THF (tetrahydrofuran) as a solvent was flowed through the column at this temperature at a flow rate of 1 ml per minute, and the sample concentration was 0.05 to 0.6 mass. % Of the THF sample solution of the resin adjusted to 50% to 200 μl is measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical
Co. Or Toyo Soda Kogyo Co., Ltd. with a molecular weight of 6
× 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 1
0 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ ,
It is appropriate to use 8.6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

Incidentally, as the column, 10 ³ to 2 × 10 ⁶
In order to accurately measure the molecular weight region of the polystyrene gel column, it is preferable to combine a plurality of commercially available polystyrene gel columns.
μ-styragel 500, 10 manufactured by ters
3, 104, 105 combinations, and Sho Showa Denko
dex KA-801, 802, 803, 804, 80
A combination of 5,806,807 is preferred.

(8) Measurement of Melting Point (Tm) The melting point of resin or toner was measured using a flow tester C manufactured by Shimadzu Corporation.
Die 1mm, 98N (10k
gf) Determined by melt viscosity measurement obtained under measurement conditions of load and heating rate of 10 ° C./min. Handling is in accordance with the attached manual prepared by Shimadzu Corporation.

Next, the image forming method of the present invention will be described.

In the present invention, an electrostatic image is formed on an electrostatic image carrier, and the electrostatic image is developed by developing means having toner to form a toner image. It is preferable that the image forming method is such that the toner image is transferred to a transfer material via a transfer member or not, and the toner image on the transfer material is fixed by a fixing unit.

In the charging / transferring step which can be used in the present invention, (a) a method using a corona discharger and not in contact with an electrostatic image carrier (a) roller type, belt type, belt and electrode blade There are any types of contact types, such as combinations, and any type can be used.

As the electrostatic image carrier of the present invention, there are an amorphous silicon photoconductor and an organic photoconductor (OPC), but an organic photoconductor is preferably used.

The organic photoreceptor may be a so-called single layer type in which the photosensitive layer contains a charge generating substance and a substance having a charge transporting property in the same layer. It may be a type photoreceptor. A laminated photoreceptor having a structure in which a charge generation layer and a charge transport layer are laminated on a conductive substrate in this order is one of preferred examples.

That is, in the image forming method of the present invention, matching of the toner of the present invention to an organic photoconductor in which the surface of an electrostatic image carrier is an organic compound such as a resin is particularly effective. That is, the organic photoreceptor is shaved by a contact member such as a cleaning blade. When the organic photoreceptor is combined with the toner of the present invention, the shaving of the organic photoreceptor is reduced by the interposition of a particle layer deposited on the cleaning blade nip.
Further, since the release of the hydrophobic inorganic fine powder due to durability is small, it is possible to prevent the occurrence of fusion and filming caused by the release.

In the present invention, it is preferable to have a cleaning step for removing the toner remaining on the surface of the electrostatic image carrier after the transfer step.

As a cleaning method, a blade cleaning method, a mag brush cleaning method, a fur brush cleaning method, a roller cleaning method, and a combination thereof can be used. Particularly, blade cleaning is preferable.

In blade cleaning, urethane rubber, silicone rubber, or resin having elasticity is used as a blade, or a blade made of metal or the like with a tip-shaped resin held at the tip thereof is moved forward or backward with respect to the moving direction of the photoconductor. It is known as abutting or pressing in the opposite direction. Preferably, the blade is pressed against the moving direction of the photoreceptor in the opposite direction. At this time, the contact pressure of the blade against the photosensitive member was 19.6 N / m (20 g /
cm) or more, more preferably 29.4-7.
8.4 N / m (30 to 80 g / cm).

Since the toner of the present invention not only provides an appropriate friction but also has excellent releasability and lubricity, it not only shows good cleaning properties by blade cleaning, but also makes it possible to bring the blade into contact with the photoreceptor. It is hard to be scratched and hard to cut. On the other hand, fusion, filming, and the like hardly occur.

In the fixing step of the present invention, in addition to the heating / pressure roller fixing means, a fixedly supported heating element is pressed against the heating element, and the transfer material is brought into close contact with the heating element via a film. A fixing unit that heats and fixes the toner depending on the pressing member to be used.

The surface of the fixing roller or the fixing film comes into contact with the surface of the toner particles on the unfixed image, and receives a friction history through durability. The toner having abrasive power is magnetic material particles protruding from the toner surface, or external additive particles or free external additive particles having low adhesion on the toner surface. In combination with the toner of the present invention, abrasion on the surface of the fixing roller or the fixing film can be reduced, and image defects such as black spots due to surface roughness and scratches can be reduced.

The transfer material that can be used in the present invention may be an intermediate transfer belt or an intermediate transfer member such as the belt, in addition to commercially available paper and OHT.

FIGS. 2 and 3 show examples of an image forming apparatus which can be used in the present invention. However, the present invention is not limited to this. Among them, FIG.
An image forming apparatus in which the fixing device 13 is a fixing unit including a heating roller 13a and a pressure roller 13b is shown. FIG.
Fixing film 33a, pressure roller 33b and heating element 33
3 shows an image forming apparatus using a fixing device 33 made of C.

The electrostatic image carrier 1 is made of an organic photoreceptor, is uniformly charged by the charging roller 6, and is irradiated with a laser beam L modulated by an image signal by a laser scanner (not shown). A charge image is formed. The toner 5 accommodated in the developing device 7 is transported to the developing area by the toner carrier 2, and the electrostatic charge image is reversely developed by the toner 5 and is visualized as a toner image. On the other hand, the transfer material P fed by a sheet feeding means (not shown) is guided to a transfer portion by a pair of conveyance rollers 8a and 8b and transfer entrance guides 9a and 9b, and a voltage having a polarity opposite to that of the toner is applied. Transfer roller 3 for forming nip N with electrostatic image carrier
Thus, the toner image is transferred onto the transfer material P. Thereafter, the transfer material P is conveyed by the conveyance guide 11 (or the conveyance belt 31) after the excessive transfer current is removed by the negative needle 10, guided to the fixing device 13 (or 33), and The toner image is heat-fixed. After the transfer, the toner remaining on the surface of the electrostatic image carrier is transferred to the blade 1 of the cleaner 12.
Cleaning is performed by 2a, and the same image forming process is repeated again.

[0169]

The present invention will be described below with reference to production examples and examples. However, this does not limit the present invention in any way.

(Resin Production Examples 1 to 6) A polyester monomer shown in Table 1 was charged into an autoclave together with an esterification catalyst, and a pressure reducing device, a water separator, a nitrogen gas introducing device, a thermometer, and a stirrer were attached to the autoclave. At 130 ° C
A mixture of the vinyl copolymer monomers was dropped from the dropping funnel over 4 hours while stirring at a temperature of. 13
Aging was performed for 3 hours while maintaining the temperature at 0 ° C., and the temperature was raised to 230 ° C. to perform a reaction. After completion of the reaction, the mixture was taken out of the vessel, cooled and pulverized to obtain a binder resin B1 composed of a polyester resin, a vinyl polymer, and a hybrid resin component having a polyester unit and a vinyl polymer unit. B1
Melting point (Tm) was 133 ° C.

Hereinafter, by changing the kind and composition ratio of the monomer as shown in Table 1, the binder resin B2 shown in Table 1 was obtained.
To B5.

Example 1 100 parts by mass of binder resin B1 70 parts by mass of magnetic iron oxide (average particle size 0.2 μm, Hc 8 kA / m, σs 80 Am ² / kg, σr 11 Am ² / kg) Polyethylene 5 parts by mass Monoazo Iron compound 2 parts by mass-Aluminum salicylate metal compound 1 part by mass After premixing the above materials with a Henschel mixer, 130
Melt kneading was performed at 2 ° C. by a twin screw kneading extruder. After allowing the kneaded product to cool, it was coarsely pulverized by a cutter mill, pulverized by a fine pulverizer, and further classified by an air classifier to obtain magnetic toner particles having a weight average particle diameter of 6.5 μm.

Further, with respect to the magnetic toner particles, Table 2
Hydrophobic dry silica P1 (BET 300 m ² / g)
1.5% by mass and strontium titanate P5 (BET
3 m ² / g), and added externally using a Henschel mixer to prepare a toner T1 shown in Table 3. Table 4 shows measurement results of various physical properties of the magnetic toner measured by the methods described above.

Using this externally added toner, a digital copier GP405 manufactured by Canon Inc. can withstand 100,000 sheets under normal temperature and normal humidity environment (23 ° C., 60% RH), low temperature and low humidity environment (10 ° C.
15% RH) and high temperature and high humidity environment (30 ° C, 80% R)
H), and the image characteristics were evaluated. As a result, good results shown in Table 5 were obtained in any environment.

The evaluation method is as follows.

The "image density" was measured by measuring reflection density using a Macbeth densitometer (manufactured by Macbeth) using an SPI filter to measure the density of a 5 mm circle (5φ).

The “morning-one density change rate” refers to the change rate of the image density in the morning to the image density at the last time.

The “fog” is performed using a reflection densitometer (reflectometer model TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.). The worst value of the reflection density on a white background after image formation is Ds, and the reflection of the transfer material before image formation is performed. Fog was measured with the average density as Dr and Ds-Dr as fog amount. The smaller the value, the better the fog suppression.

The state of occurrence of flaws on the surface of the photosensitive drum and fusing of residual toner and the effect on printout images were visually evaluated. ：: not generated △: fusion observed on the photoreceptor less than 5 points, no effect on the image ×: fusion observed on the photoreceptor 10 points or more, causing image defects

The occurrence of white spots recognized in the solid black image and the effect on the printout image were visually evaluated. ：: not generated △: less than 5 white spots on the image, no effect on the image ×: 10 or more white spots on the image, causing image defects

The occurrence of black spots recognized in the solid white image and the effect on the printout image were visually evaluated. ：: Not generated Δ: Black spots observed on the image were less than 5 points, no effect on the image ×: Black spots observed on the image were 10 points or more, causing image defects

The state of occurrence of stains due to toner recognized on the back surface of the sample during durability and the effect on the printout image were visually evaluated. ：: not generated △: less than 5 stains on the back of the image, no effect on the image ×: 10 or more stains on the back of the image, causing image defects

The state of occurrence of toner adhesion / contamination on the surface of a member such as a fixing roller / film and the effect on printout images were visually evaluated. ：: not generated △: less than 5 points of toner adhesion on the member surface, no effect on the image ×: 10 points or more of toner adhesion on the member surface, causing image defects

The scraping amount of the organic photoreceptor used in GP405 was measured every 10,000 sheets, and the scraping amount of the photoreceptor was evaluated based on the average value of 100,000 sheet durability. ：: Photoreceptor scraping amount is 0.5 to 2.0 μm / 10,000 sheets. Δ: Photoreceptor scraping amount is 2.0 to 3.5 μm / 10,000 sheets. X: The shaving amount of the photoconductor is larger than 3.5 μm / 10,000 sheets.

The occurrence state of filming (black streaks) recognized in the solid white image and the effect on the printout image were visually evaluated. ：: not generated △: less than 5 black streaks observed on the image, no effect on the image ×: 10 or more black streaks observed on the image, causing image defects

Examples 2 to 9 Toners were prepared in the same manner as in Example 1 except that the types and amounts of the binder resin, the wax, the magnetic material and the external additive were changed, and toners T2 to T9 in Table 3 were obtained. Table 4 shows the measurement results of various physical properties of the toner measured by the methods described above. As for the image characteristics, good results as shown in Table 5 were obtained.

Comparative Examples 1 to 3 Toners were prepared in the same manner as in Example 1 except that the types and amounts of the binder resin, wax, magnetic substance and external additives were changed. Table 4 shows the measurement results of various physical properties of the toner measured by the methods described above. As for the image characteristics, the results shown in Table 5 were obtained.

[0188]

[Table 1]

[0189]

[Table 2]

[0190]

[Table 3]

[0191]

[Table 4]

[0192]

[Table 5]

[0193]

As described above, by using the toner and the image forming method of the present invention, scraping and scratching of an organic photoconductor, a fixing roller, a fixing film, and the like are reduced, and the replacement life of the organic photoconductor is reduced. It is possible to provide a toner and an image forming method capable of outputting a high-quality image free of filming, fusing, white spots, black spots, and stains on the back of an image for a long period of time while extending the image quality.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram based on an example of an SEM photograph of the surface of a toner of the present invention observed at acceleration voltages of 1 kV and 2 kV.

FIG. 2 is a schematic explanatory view of an image forming method used in an embodiment of the present invention.

FIG. 3 is a schematic explanatory view of another image forming method used in the embodiment of the present invention.

[Explanation of symbols]

 Reference Signs List 1 electrostatic image carrier (photoconductor) 2 toner carrier 3 transfer roller 5 toner 6 charging roller 7 developing container 13 fixing device 33 fixing device

Claims (13)

[Claims] 1. A toner having at least toner particles and a hydrophobic inorganic fine powder, wherein the toner particles contain at least a binder resin, magnetic particles and wax, and (a) the toner has a wax melting peak area of 5 J in a DSC measurement. / G or more, and (b) FE-SEM observation of the toner particle surface shows that the accelerating voltage is 1.
The average value α of the number of magnetic particles that can be identified per unit area (μm ² ) of the toner particle surface at 0 kV and the unit area (μm) of the toner particle surface at an acceleration voltage of 2.0 kV
When the average value β of the number of magnetic particles that can be identified per m ² ) is the following condition α ≠ 0: 1.1 ≦ β / α ≦ 50.0 When α = 0: 0.1 ≦ β ≦ 20.0 Satisfies the following. 2. In the FE-SEM observation of the surface of the toner particles, an average value α of the number of magnetic particles that can be identified per unit area (μm ² ) of the surface of the toner particles at an acceleration voltage of 1.0 kV, and an acceleration voltage of 2. When the average value β of the number of magnetic particles that can be identified per unit area (μm ² ) of the toner particle surface at 0 kV is the following condition α ≠ 0, 1.1 ≦ β / α ≦ 30.0 α = 0 The toner according to claim 1, wherein 0.1 ≦ β ≦ 20.0 is satisfied. 3. The toner has a specific gravity of 1.3 to 2.0 g / g.
^3. The toner according to claim 1, wherein the toner is cm ³ . 4. The toner according to claim 1, wherein the toner has a wax melting peak area of 5 to 35 J / g in DSC measurement. 5. The toner has a temperature of 125 ° C. and a load of 98N.
(10 kgf) melt index value is 1.0
The toner according to any one of claims 1 to 4, wherein the toner weight is from 1 to 15.0 g / 10 min. 6. The toner according to claim 1, wherein the hydrophobic inorganic fine powder is treated with an organosilicon compound. 7. An electrostatic image is formed on an electrostatic image carrier, and the electrostatic image is developed by developing means having toner to form a toner image, and the toner image on the electrostatic image carrier is intermediately formed. An image forming method in which a toner image on a transfer material is transferred to or from a transfer material via a transfer body or not by a fixing means, and the toner has at least toner particles and hydrophobic inorganic fine powder. The toner particles contain at least a binder resin, magnetic particles and wax, (a) a wax melting peak area of 5 J / g or more in DSC measurement of the toner, and (b) FE- In the SEM observation, the unit area (μm) of the toner particle surface at an acceleration voltage of 1.0 kV was
m ² ), the average value α of the number of magnetic particles that can be identified,
Average value β of the number of magnetic particles that can be identified per unit area (μm ² ) of the toner particle surface at an acceleration voltage of 2.0 kV
Is the following condition: α ≠ 0 1.1 ≦ β / α ≦ 50.0 When α = 0, the image forming method satisfies 0 ≦ β ≦ 20.0. 8. In the FE-SEM observation of the surface of the toner particles, an average value α of the number of magnetic particles that can be identified per unit area (μm ² ) of the surface of the toner particles at an acceleration voltage of 1.0 kV; When the average value β of the number of magnetic particles that can be identified per unit area (μm ² ) of the toner particle surface at 0 kV is the following condition α ≠ 0, 1.1 ≦ β / α ≦ 30.0 α = 0 The image forming method according to claim 7, wherein 0.1 ≦ β ≦ 20.0 is satisfied. 9. The toner has a specific gravity of 1.3 to 2.0 g / g.
The image forming method according to claim 7, wherein the image forming method is cm ³ . 10. The image forming method according to claim 7, wherein the toner has a wax melting peak area in a DSC measurement of 5 to 35 J / g. 11. The toner has a temperature of 125 ° C. and a load of 98.
The melt index value at N (10 kgf) is 1.
The image forming method according to claim 7, wherein the weight is 0 to 15.0 g / 10 min. 12. The method according to claim 7, wherein said hydrophobic inorganic fine powder is treated with an organosilicon compound.
2. The image forming method according to any one of 1. 13. The image forming method according to claim 7, wherein the electrostatic image carrier is an organic photoreceptor.