JP2003270838A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner giving a high image density even at a high temperature and a high humidity and at a low temperature and a low humidity, not causing a fogging and having high durability. <P>SOLUTION: The toner is obtained by adding a colorant and a charge controlling agent having an acid value of 2.0-50.0 mgKOH/g to a polyester-base bonding resin and further adding inorganic fine particles in such a way that the rate of isolating charge controlling agent particles by number from toner particles is adjusted to 0.01-10.0%. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic charge image such as electrophotography, electrostatic recording and electrostatic printing, or a toner used for image formation by a toner jet method.

[0002]

It is well known in the art to form an electrostatic latent image on the surface of a photoconductive material by electrostatic means and develop it with toner.

That is, US Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-43.
Although a number of methods are known, such as Japanese Patent No. 24748, a photoconductive substance is generally used to form an electric latent image on a photoconductor by various means, and then the toner is called toner on the latent image. A toner image corresponding to an electrostatic latent image is formed by adhering an extremely finely ground electrophotographic material.

Then, if necessary, the toner is transferred onto the surface of an image support (transfer material) such as paper and then fixed by heating, pressurizing or solvent vapor to obtain a copy.
In addition, when there is a step of transferring the toner image, a step for removing the residual toner is usually provided.

A developing method for visualizing an electric latent image by using a toner is, for example, a powder cloud method described in US Pat. No. 2,221,776 and 2,618,55.
No. 2 specification, cascade development method, No. 2,874,063 specification, magnetic brush method, and No. 3,909,258 specification, conductivity. A method using a magnetic toner is known.

As the toner applied to these developing methods, generally, colorant-containing resin particles which are finely pulverized after mixing and dispersing a colorant in a thermoplastic resin are used. Polystyrene resin is the most common thermoplastic resin,
Polyester resin, epoxy resin, acrylic resin, urethane resin, etc. are also used. Carbon black is most widely used as the colorant, and iron oxide-based black magnetic powder is often used in the case of magnetic toner. In the case of a system using a so-called two-component developer, the toner is usually used by being mixed with carrier particles such as glass beads, iron powder and ferrite powder.

The toner image on the final copy image forming member such as paper is permanently fixed on the support by heat, pressure or the like. Conventionally, this fixing process has been often adopted by heat.

When the method has a step of transferring a toner image, a step for removing the residual toner on the photosensitive member is usually provided.

In recent years, the development from mono-color copying to full-color copying has been rapidly progressing in copying machines and the like, and two-color copying machines and full-color copying machines have been studied and put to practical use. For example, “Journal of the Electrophotographic Society”, Vol.
22, No. 1 (1983) and "Electronic Photography Society" Vo
l. 25, No. 1, P52 (1986), there are reports of color reproducibility and gradation reproducibility.

However, it is not immediately compared with the real thing like a television, a photograph, and a color printed matter, and
The full-color electrophotographic images currently in practical use are not always satisfactory to those who are conceived of more beautifully processed color images.

Color image formation by full-color electrophotography generally reproduces all colors using color toners of three primary colors of yellow, magenta, and cyan.

In this method, light from the original is first radiated onto the photoconductive layer through a color separation light transmission filter having a complementary color relationship with the color of the toner to form an electrostatic latent image, and then the development and transfer steps are performed. Then, the toner is held on the support. This step is sequentially carried out a plurality of times, the toners are superposed on the same support while matching the registration, and then the final full-color image is obtained by fixing once.

Generally, a so-called two-component developing method in which a developer is composed of a toner and a carrier causes the toner to be charged to a required charge amount and charge polarity by friction with the carrier, and electrostatic latent force is used by utilizing electrostatic attraction. The image is developed. Therefore, in order to obtain a good visible image, it is necessary that the triboelectric chargeability of the toner, which is mainly determined by the relationship with the carrier, is good.

To solve the above problems, a search for a carrier core material or a carrier coating material or optimization of the coating amount, or a study of a charge control agent or a fluidity imparting agent added to a toner,
Further, much research has been conducted to achieve excellent triboelectric chargeability in all materials constituting the developer, including improvement of the base binder.

For example, as disclosed in JP-A-57-167033, a metallizable azo compound is treated with a metal-imparting agent by a known method, and then diluted with water containing an acidic or mineral acid to precipitate. It was made possible to obtain a negatively chargeable toner having stable charging characteristics by using the azo metal complex obtained by filtration.

However, even in a toner using a charge control agent such as an azo metal complex as described in the above publication,
It has been found that good results cannot always be obtained in the case of a sharp melt binder resin used for full-color toners and the like. Specifically, the charging becomes excessive, and it becomes difficult for the toner to be transferred from the photoconductor to the transfer material in the process of development to transfer, and the amount of residual toner on the photoconductor increases and the cleaning mechanism is used. The toner that cannot be collected may cause filming or defective cleaning. Further, it becomes difficult to uniformly charge the toner, and the toner that is not sufficiently charged or the toner that is charged in the opposite polarity is generated, and the fog is generated in the background portion of the obtained visible image.

On the other hand, in Japanese Patent Laid-Open No. 4-21862, the amount ratio of the charge control agent present in the surface layer of the toner particles and the amount ratio of the charge control agent present in the entire toner particles are specified. Achieved stabilization of the triboelectric chargeability of the toner. However, since the charge control agent present in the surface layer takes a means of being fixed from the outside of the toner particles by electrostatic force or mechanical impact force, when subjected to a durability test or the like in a long-term range, the charge control agent is Deterioration of the toner particle surface due to mixing (detachment of adhered matter due to toner spent, impact, etc.) is conceivable. Even after triboelectrification within a suitable range after preparation of the developer, the charge gradually becomes unstable, resulting in image deterioration. This will cause a sharp change in density and adverse effects on electrophotographic characteristics such as fog.

Further, Japanese Patent Application Laid-Open No. 8-160670 proposes a technique in which the amount of charge control agent in the toner surface layer is regulated. However, the releasing property of the charge control agent is not taken into consideration, and there is a point that the environmental stability, the charging uniformity, and the durability stability of the toner should be improved.

Further, Japanese Patent Laid-Open No. 2000-298375 proposes an invention which defines the liberation rate of elements due to pigments, magnetic materials and charge control agents. However,
Dispersibility of charge control agent, dispersing means, environmental stability of toner,
No consideration was given to the freeness of the external additive and its adverse effects, and there was a point to be improved in order to obtain good toner characteristics.

Further, Japanese Patent Application Laid-Open No. 11-258847 proposes an invention which defines the liberation rate of Si and Ti. However, the release property of the charge control agent is not taken into consideration, and the environmental stability of the toner, charge uniformity,
There were points to be improved in durability stability.

Further, as a technique for adding a charging auxiliary agent such as charging fine particles to a toner, Japanese Patent Publication No. 52-32256 and Japanese Patent Laid-Open No. 56-64352 disclose a resin fine powder having a polarity opposite to that of the toner. Further, in JP-A-61-160760, a fluorine-containing compound is added to each developer,
A technique for obtaining a stable triboelectric charging property has been proposed, and many charging aids have been developed even today.

Further, various methods have been devised as a method of adding the charging auxiliary agent as described above. For example, a method of adhering the toner particles to the surface of the toner particles by an electrostatic force between the toner particles and the charging auxiliary agent, a Van der Waals force, or the like is common, and a stirring device, a mixer, or the like is used. However, in this method, it is not easy to uniformly disperse the additive on the surface of the toner particle, and the additive does not adhere to the toner particle and the additives become aggregates, so that there is an additive in a so-called free state. Is difficult to avoid. This tendency becomes more remarkable as the specific electric resistance of the charging aid increases and the particle size decreases. In such a case, the performance of the toner is affected. For example, the amount of triboelectric charge becomes unstable, the image density is not constant, and the image has a lot of fog.

Further, when continuous copying or the like is performed, the content of the charging aid changes, and there is a problem that the initial image quality cannot be maintained.

As another addition method, there is a method in which a charging auxiliary agent is added in advance together with the binder resin and the colorant at the time of manufacturing the toner. However, it is not easy to make the charge control agent uniform, and it is substantially contributed to the charging property.
It is not near the surface of the toner particles, and the charging aid and charge control agent present inside the particles do not contribute to the charging property, so that it is not easy to control the addition amount of the charging aid and the dispersion amount on the surface. Further, even in the toner obtained by such a method, the triboelectric charge amount of the toner is unstable, and it is not possible to easily obtain a toner that satisfies the developer characteristics as described above. In reality, the quality is not sufficiently satisfactory.

Further, in recent years, demands for high definition and high image quality of copying machines have been increasing in the market, and in this technical field, an attempt has been made to achieve high image quality color by making toner particle size fine. However, as the particle size becomes finer, the surface area per unit mass increases, and the charge amount of the toner tends to increase, and there is a concern that the image density will be low and the durability will deteriorate. In addition, since the charge amount of the toner is large, the adhesion between the toners is strong, the fluidity is lowered, and problems arise in stability of toner replenishment and tribo imparting to the replenished toner.

Further, since the color toner does not contain a conductive substance such as a magnetic material or carbon black, there is no portion for leaking the charge, and the charge amount generally tends to increase. This tendency is more remarkable when a polyester binder having high charging performance is used.

Further, it is known that the charge of the toner greatly changes depending on the releasing property and the dispersibility of the charge control agent in the toner particles. After discharging, the charge control agent released or desorbed adheres and adheres to the surface of the carrier, significantly lowering the charge imparting ability of the carrier, and the toner charge amount distribution becomes extremely wide, causing fogging, toner scattering, and extreme This causes problems such as high image density and toner filming on the drum. Therefore, it is an important technical subject to suppress the release property of the charge control agent.

[0028]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which solves the above problems.

That is, the object of the present invention is to (1) exhibit good environmental stability, (2) have sufficient and uniform triboelectrification and its durability stability, and (3) have good image quality. , (4) Excellent long-term storage stability, (5) Good fixability and color mixture, (6) High temperature offset is sufficiently prevented, and a wide fixable temperature range is provided. (7) Repeated fixing Offset resistance is maintained even when the paper is passed, no winding around the fixing roller occurs, and (8) inside the developing device, that is, the developing sleeve,
The present invention provides a toner that does not fuse toner to parts such as a blade and a coating roller, (9) does not film on the surface of the photoconductor, and (10) exhibits good transparency.

[0030]

The present invention contains at least a binder resin, a colorant, a charge control agent and inorganic fine particles, and the binder resin contains a polyester resin as a main component,
Acid value of the binder resin is 2.0 to 50.0 mgKOH / g
And the number release rate of the charge control agent with respect to the toner particles is 0.01% to 10.0%.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the binder resin is composed mainly of a polyester resin, and the acid value of the binder resin is 2.
It is more preferably from 0 to 50.0 mgKOH / g, preferably from 3.0 to 40.0 mgKOH / g because excellent charging stability can be obtained in each environment.

When the acid value of the binder resin is less than 2.0 mgKOH / g, the toner shows a charge-up tendency, and the image density tends to be low in a low temperature and low humidity environment. Furthermore, the dispersibility of the charge control agent is lowered, and the amount of charge between the toner particles is likely to be different from each other, and fogging is likely to occur due to long-term durability.

The acid value of the binder resin is 50.0 mg KO.
If it is larger than H / g, the stability of the charging of the toner with time deteriorates, and the charge amount is likely to decrease with the endurance. Particularly in a high temperature and high humidity environment, image defects such as toner scattering and fog are likely to occur. Furthermore, the acid value of the binder resin is 50.0.
If it is more than mgKOH / g, even if the charge control agent is blended in the toner, water adsorption is likely to occur and a sufficient charge amount cannot be obtained.

The polyester resin used in the present invention is not particularly limited, and any polyester resin conventionally used as a binder resin for a toner is preferably used.

The polyester resin is preferably contained in the binder resin in an amount of at least 70% by mass.

Next, the charge control agent and the inorganic fine particles according to the present invention will be described.

In the toner of the present invention, the charge control agent is internally added to the toner particles and the inorganic fine particles are externally added. Further, the charge control agent has a number liberation rate of 0.01% to 10.00%, preferably 0.01% to toner particles.
The number free ratio of the inorganic fine particles to the toner particles is preferably 0.01 to 20.0%, more preferably 0.01 to 15.00%.

The number release rate of the charge control agent and the inorganic fine particles according to the present invention can be measured by a particle analyzer (PT10).
00: Yokogawa Electric Co., Ltd.)
It can be obtained by measuring the number release rate of a specific metal element possessed by each. The particle analyzer is the 6th collection of Japan Hardcopy 97,
The measurement is performed according to the principle described on pages 5 to 68. Specifically, the apparatus uses an electron density of 5 × 10 5 for each fine particle such as toner.
^It was introduced into a high-temperature non-thermal equilibrium plasma having a high electron temperature of ¹³ cm ^-3 , an excitation temperature of 3,300 K, and 20,000 K, and the emission spectrum of the fine particles accompanying this excitation was used to determine the element, number of particles, and You can know the particle size.

Among them, the liberation rate is defined as a value obtained by the following formula from the simultaneity of the luminescence of the carbon atom which is a constituent element of the binder resin and the luminescence of the element to be measured.

Release rate (%) of element to be measured = [A / (A
+ B)] × 100 A: Number of times of light emission of only the measurement target element B: Number of times of light emission of the measurement target element that emitted light simultaneously with the carbon atom

Here, the simultaneous emission of the carbon atom and the element to be measured means the emission of the element to be measured emitted within 2.6 msec from the emission of the carbon atom, and the emission of the element to be measured thereafter is measured. Only the target element emits light. In the present invention, since the charge control agent is internally added, the fact that the carbon atom and the specific element possessed by the charge control agent emit light at the same time means that the charge control agent exists in the toner particle surface layer or inside the toner particle. means. Further, in the present invention, since the inorganic fine particles are externally attached to the surface of the toner particles, the fact that the carbon atom and the specific metal element of the inorganic fine particles emit light at the same time means that the inorganic fine particles adhere to the surface of the toner particles. This means that the emission of only a specific metal element contained in the inorganic fine particles means that the inorganic fine particles are released from the surface of the toner particles.

As a specific measuring method, helium gas containing 0.1% oxygen was used, and measurement was carried out in an environment of 23 ° C. and a humidity of 60%, and carbon atoms (measurement wavelength: 247.860 nm, channel 4) were measured. (K factor is the recommended value for the main unit)
To measure channel 1, channel 2, channel 3
(K factor is the recommended value for the main unit) and the charge control agent and the inorganic fine particles are measured. The element to be measured in each channel is selected according to the conditions recommended by the main body. In addition, the number of emission of carbon atoms is 1000 ± 20 in one scan of the main body.
Sampling is performed so that the number becomes 0, and scanning is repeated until the total number of emission of carbon atoms reaches 10000 or more, and the number of emission is integrated. Based on this data, the release rates of the charge control agent and the inorganic fine particles are calculated using the above formula.

In measuring the liberation rate of the charge control agent and the inorganic fine particles, the toner of the present invention is a color toner containing a colorant, and therefore any channel for measuring carbon atoms (4 channels in the present invention is used). Use) and lower the cube root voltage value.

The reason for this is that the particle analyzer (PT1000: Yokogawa Electric Co., Ltd.) used for measurement is used.
In (made by), a signal proportional to the number of atoms (mass) of the element is detected, but the equivalent particle size display (when light emission of a certain element is obtained, assuming a true spherical particle made of only that element) ) Is taken as the cube root of the detected voltage. This is defined as the cube root voltage, but the cube root of the number of atoms is proportional to the particle size, so the cube root voltage is proportional to the particle size.

Therefore, when the color toner particles according to the present invention are compared with the one-component toner particles using a magnetic material at the same cube root voltage portion, the emission intensity of carbon atoms in the base toner particles is the binder resin component, Due to the influence of the colorant component, etc., the color toner particles become larger, and at the same cube root voltage value as the one-component toner particles, it is not possible to show the particle size distribution up to the part where the particle size is small. This is because the cube root voltage value must be set low in order to measure the release rate for various particle size distributions.

From the above, when the toner of the present invention is measured, the cube root voltage of the carbon atom is Low Volta.
The release rate of the charge control agent and the inorganic fine particles is measured by setting ge (1.8 V).

In calculating the liberation rate according to the present invention, the noise level is set to 1.5 V for channels 1 to 4,
The channel was set at 1.3V.

As a result of earnest studies by the present inventors, when the liberation rate of the charge control agent is less than 0.01%, the amount of the charge control agent present in the surface layer of the toner particles is remarkably reduced, so that sufficient charge stability is obtained. Insufficient charge quantity under high humidity environment. Therefore, problems such as fogging, toner scattering, and extremely high image density occur.

The release rate of the charge control agent is 10.00%.
When it is larger, the amount of the charge control agent liberated and desorbed from the surface of the toner particles is significantly increased. Since the charge control agent released and released has a remarkably high charge amount, charge-up occurs in a low humidity environment. In addition, after printing a large number of sheets, the charge control agent released or desorbed adheres to the carrier surface.
Adhesion is caused, the charge imparting ability of the carrier is remarkably reduced, the toner charge amount distribution is extremely widened, and there are problems such as fog, toner scattering, extremely high image density, and toner filming on the drum.

Furthermore, the release rate of the inorganic fine particles is 0.01%.
If it is less than the above range, the fog increases and the image becomes rough in the latter half of the multi-image printing test, especially under high temperature and high humidity. Generally, in a high temperature environment, embedding of the external additive easily occurs due to stress of the regulating member, etc., and after printing a large number of sheets, the fluidity of the toner particles becomes inferior to that at the initial stage, and the above problems occur. Conceivable.

On the other hand, the release rate of inorganic fine particles is 20.00%.
When it exceeds, such a problem is unlikely to occur, and the released inorganic fine particles are present between the toner particles, so that an appropriate spacer effect is generated and high transfer efficiency is obtained. However, due to the high liberation rate, the effect of reducing the charging gap between environments greatly related to humidity dependency cannot be obtained, and the inorganic fine particles that are difficult to be retained on the toner particle surface are transferred from the developer carrier to the photosensitive member during development. Image does not fly to the bottom of the developing device, causing fluttering to the area below the developing device, causing contamination of other process steps (charging, transfer, fixing, etc.), and free-floating inorganic fine particles adhering to the unfixed image. There arises a problem that a white image defect occurs in a part. Further, since the inorganic fine particles do not adhere to the toner surface, they do not function effectively for long-term storage stability. For this reason, particularly when stored for a long period of time in a high temperature environment, the toner particles coalesce with each other, and in an extreme case, a block-like lump is formed, which is not preferable.

In the present invention, the elements contained in the charge control agent are Al, Zn, Fe and Cr in terms of charge stability.
Is preferable, and Al is more preferable in terms of high charge amount and environmental stability. Further, when the black toner is formed by using the black colorant, good chargeability can be obtained even when the element contained in the charge control agent is Fe.

When the charge control agent and the inorganic fine particles have the same content element, when the release rate is measured as the toner, the charge control agent and the inorganic fine particles are sufficiently separated to determine the release rate. It cannot be observed. However, the lower the liberation rate is, the more various harmful effects tend to occur, which is preferable. Therefore, when the charge control agent and the inorganic fine particles have the same contained element, the total number liberation rate of the both is preferably 0.01% to 10.00%.

Further, the BET specific surface area of the inorganic fine particles is a physical property showing the influence on the toner fluidity imparting ability and the environmental stability. The BET specific surface area of the inorganic fine particles of the present invention is 100.
˜350 m ² / g, preferably 150 to 300 m ² / g.

When the BET specific surface area is smaller than 100 m ² / g, the particle size of the inorganic fine particles is large, and there is the presence of aggregates or coalesced particles. However, there are problems such as scratching the surface, damage and deformation of the cleaning means such as the cleaning blade, and these are undesirable because they appear as image defects.

When the BET specific surface area is larger than 350 m ² / g, the humidity adversely affects the charging characteristics, and the toner charge amount is remarkably reduced especially in a high humidity environment. It is not preferable because it causes problems such as rising, toner scattering, and fog.

Further, the inventors of the present invention examined the addition of the inorganic fine particles to the toner for imparting fluidity, charging property and polishing property. As a result, the reactivity with the surface treatment agent is high, the average particle size is small, and by treating the inorganic fine particles having a high polishing effect with a surface treatment agent such as an organic silane compound,
It has been found that it is possible to impart high fluidity, high chargeability, and high abrasiveness to the toner. In the present invention, known inorganic fine particles can be used, but alumina, titanium oxide, and silica are particularly preferable from the viewpoint of imparting high fluidity, high chargeability, and high abrasiveness to the toner.

The raw material of titanium oxide fine particles used in the present invention and the production method are not particularly limited, but titanium oxide fine particles obtained by subjecting titanium oxide particles produced by the sulfuric acid method to a hydrophobic treatment are preferable.

The raw material of the silica fine particles used in the present invention, the production method, etc. are not particularly limited, but silica fine particles obtained by hydrophobizing silica particles obtained by firing silicon tetrachloride at a high temperature are preferable.

The raw material for the alumina fine particles used in the present invention, the manufacturing method and the like are not particularly limited, but in order to maximize the effects of the present invention, 300 to 120 aluminum ammonium carbonate hydroxide is used.
Amorphous, γ crystal, or θ crystal alumina fine particles obtained by thermal decomposition at a temperature of 0 ° C.
The present invention is a desirable material for obtaining specific physical properties.

Since conventionally known α-crystal alumina fine particles have a large average particle diameter and a small BET specific surface area, they have a very low fluidity imparting ability to the toner and cause a large scratch on the surface of the photoreceptor. . Further, since the reactivity with the surface treatment agent is low, a sufficient degree of hydrophobicity cannot be obtained, so that there is a problem in that the charge amount is lowered particularly in a high humidity environment. Further, since the charge imparting ability to the toner is low, fog and toner scattering become problems, which is not preferable.

In the present invention, the average particle size of the inorganic fine particles is from 1 to 100 from the viewpoint of imparting toner fluidity and polishing property.
nm is desirable. The average particle size of the inorganic particles is 1
If it is less than nm, the toner is likely to be embedded on the surface of the toner, so that the toner is deteriorated at an early stage and durability is deteriorated, which causes a problem, and sufficient abradability cannot be obtained, which is not preferable.

On the other hand, the average particle size of the inorganic fine particles is 100 nm.
If it is larger, not only the fluidity of the toner is significantly lowered, but also the charging becomes non-uniform, resulting in deterioration of image quality, toner scattering, and fog, which are problems. In addition, there are problems such as a large scratch on the surface of the photoconductor, the scratched portion appears as an image defect, or a cleaning member such as a cleaning blade is deformed or damaged. It is not preferable because it appears as a defect.

Furthermore, in the present invention, the degree of hydrophobicity of the inorganic fine particles is preferably in the range of 40 to 90%.

When the degree of hydrophobicity is less than 40%, the hydrophobic treatment is insufficient and the charge amount is lowered, particularly in a high humidity environment, the charge amount is remarkably reduced, and toner scattering, fog, image quality deterioration, etc. Is a problem. If the degree of hydrophobicity is more than 90%, it becomes difficult to control the charge of the inorganic fine particles themselves, and as a result, the charge amount of the toner is increased especially in a low humidity environment. In addition, particle coalescence occurs after the hydrophobic treatment and the toner fluidity is significantly reduced, which is not preferable.

In the present invention, the surface treatment of the inorganic fine particles with a surface treatment agent such as a silane compound includes the following methods, but the present invention is not particularly limited to these methods.

As the surface treatment method by the wet method, for example, while mixing and stirring the inorganic fine particles in the solution, a predetermined amount of the surface treatment agent or its diluting solution or a mixture thereof is added, and the mixture is sufficiently stirred. After that, dry and disintegrate.

As the surface treatment method by the dry method, for example, a predetermined amount of the surface treatment agent or its diluting solution, or a mixed solution thereof may be dropped or sprayed while stirring the inorganic fine particles with a device such as a blender. Add and stir thoroughly. The mixture obtained is then heated and dried. Then, it is crushed by a device such as a pin mill.

The surface treatment agent used in the present invention includes
Silane-based organic compounds are preferred. The silane-based organic compound may be appropriately selected according to the purpose of surface modification (for example, control of charging characteristics, and further stabilization of charging under high humidity) and the reactivity of the silane-based organic compound. For example, silane-based organic compounds such as alkoxysilane, alkylalkoxysilane, siloxane, silane, and silicone oil, which do not themselves thermally decompose at the reaction treatment temperature, are preferable.

Particularly preferred is an alkoxysilane which is volatile and has both a hydrophobic group and a highly reactive bonding group, such as a coupling agent.

Specifically, for example, as a silane coupling agent, a general formula R _m SiY _n R: an alkoxy group m: an integer of 1 to 3 Y: an alkyl group, a vinyl group, a phenyl group, a methacryl group, an amino group , An epoxy group, a mercapto group or a derivative thereof represented by an integer of n: 1 to 3 is preferable, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, Methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, etc. It can gel.

The treatment amount is preferably 1 to 60 parts by mass, and more preferably 3 parts by mass with respect to 100 parts by mass of the inorganic fine particles.
˜50 parts by mass.

[0073] Particularly preferred in the present invention is a general formula _{C n H 2n + 1 -Si- (} OC m H 2m + 1) coupling agent represented by ₃ n = _4~12 m = _1~3. Here, when n in the general formula is smaller than 4, the treatment becomes easy, but the degree of hydrophobicity cannot be sufficiently achieved. If n is greater than 12,
Although the hydrophobicity becomes sufficient, the coalescence of the inorganic fine particles increases and the fluidity-imparting ability decreases. On the other hand, when m is larger than 3, the reactivity is lowered and the hydrophobization is not sufficiently performed. Therefore, in the present invention, n is 4 to 1
2, preferably 4-8, m is 1-3, preferably 1-2
Is good.

The amount of treatment is preferably 1 to 50 parts by mass, more preferably 3 parts by mass with respect to 100 parts by mass of the inorganic fine particles.
-40 parts by mass is preferable.

The hydrophobizing treatment may be carried out with a hydrophobizing agent alone, or two or more kinds of hydrophobizing agents may be used. For example, one type of coupling agent may be used alone for the hydrophobic treatment, or two types of coupling agents may be used at the same time, or after the coupling agent is used for the hydrophobic treatment, another coupling agent may be used for further hydrophobic treatment. You may perform a conversion process. There are no particular restrictions on the method of using the hydrophobizing agent and the method of adding the hydrophobizing agent.

In the present invention, the amount of the inorganic fine particles added to the toner is 0.1 to 100 parts by weight of the toner particles.
3 parts by mass is preferable, and 0.1 to 2 parts by mass is preferable. When the content is less than 0.1 part by mass, it is difficult to obtain high fluidity and sufficient abrasivity of the toner, and when the content exceeds 3 parts by mass, release of the inorganic fine particles can be suppressed. In addition to being difficult, the fluidity of the toner is too high, which in turn hinders uniform charging, not only has poor mixability with the replenished toner, but also increases abrasivity and reduces the durability of the drum. To do.

Further, the present inventors have found that the stability of the image density,
As a result of earnestly examining highlight reproducibility, fine line reproducibility, and environmental stability, the toner of the present invention has a weight average particle diameter of 4
It has been found that when the thickness is -10 μm, the latent image on the photoconductor can be faithfully developed.

When the weight average particle diameter of the toner is larger than 10 μm, it basically means that there are few fine particles which can contribute to the improvement of image quality, and it is easy to obtain a high image density and the fluidity of the toner is excellent. However, it is difficult to faithfully adhere to the minute latent image on the drum, the highlight reproducibility is poor, and sufficient resolution cannot be obtained.
Further, there is also a tendency that excessive development, that is, excessive toner overload occurs, resulting in an increase in toner consumption.

On the contrary, when the weight average particle diameter of the toner is smaller than 4 μm, it means that the charge amount per unit weight of the toner becomes extremely high, and the density is low, particularly the image density is low at low temperature and low humidity. . This is not suitable for applications with a high image area ratio such as graphic images.

When the particle size is less than 4 μm, the contact charging with the carrier is not smoothly performed, the amount of toner that cannot be sufficiently charged increases, and scattering to the non-image area, that is, fog becomes conspicuous. In order to deal with this, it is conceivable to reduce the particle size of the carrier in order to increase the specific surface area of the carrier. However, with toner having a weight average diameter of less than 3 μm, toner self-aggregation easily occurs, and uniform mixing with the carrier is achieved in a short time. However, in continuous toner replenishment durability, fog toner tends to occur.

Therefore, in the present invention, the weight average particle diameter of the toner is preferably 4 to 10 μm.

In order to make full use of the toner having a weight average particle diameter of 4 to 10 μm, high flowability, charge stability and environmental stability of the toner are important points, and even if any one of them is missing, a good image is obtained. Can't hope

Therefore, in order to maximize the potential of the toner having the above-mentioned weight average particle diameter and achieve high resolution and high gradation, a binder resin which is not easily affected by humidity as in the present invention is used. It is essential to use and have a specific charge control agent release rate, preferably high fluidity,
By adding the inorganic fine particles that impart high chargeability and abrasivity, an image having high environmental stability and high definition can be obtained for a long period of time.

Further, in the present invention, the cohesion degree of the toner is preferably 2 to 25%, more preferably 2 to 20%.
It is preferably 2 to 15%.

If the degree of cohesion exceeds 25%, problems such as deterioration of toner transportability from the toner hopper to the developing device, poor mixing of toner and carrier, and poor charging of toner are likely to occur. Therefore, even if the toner is made fine and the coloring power of the toner is optimized, it is difficult to obtain a high-quality image.

Examples of the colorant used in the present invention include dyes and pigments known as non-magnetic toner, such as phthalocyanine blue, indanthrene blue, peacock blue, permanent red, lake red, rhodamine lake, Hansa yellow, permanent yellow, Benzidine yellow or the like can be used. As for its content,
In order to sensitively reflect the transparency of the OHP film, the amount is 12 parts by mass or less, preferably 0.5 to 9 parts by mass, relative to 100 parts by mass of the binder resin.

In the toner of the present invention, a yellow colorant, a magenta colorant, a cyan colorant and a black colorant are used as colorants, and the yellow colorant, the magenta toner, the cyan toner and the black toner are formed by using them. It is possible to form a full-color image by using a combination of these four color toners.

Further, the toner of the present invention is not limited to the negative charging property and the positive charging property, but when the toner of the negative charging property is formed, the toner of the present invention is used for the purpose of stabilizing the negative charge characteristic. It is preferable to add such a charge control agent. Examples of the negative charge control agent include metal complexes of alkyl-substituted salicylic acid (for example, chromium complex, zinc complex or aluminum complex of di-tert-butylsalicylic acid) and organometallic complexes such as azo iron compounds.

When a positively chargeable toner is formed, nigrosine, a triphenylmethane compound, a rhodamine dye, polyvinyl pyridine or the like may be used as the charge control agent exhibiting the positive chargeability. In this case, it is desirable to use a colorless or light-colored positive charge control agent that does not affect the color tone of the toner.

The charge control agent used in the present invention is
In order to achieve the number release rate specified in the present invention,
The particle size is preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm. Further, in order to achieve the number liberation rate according to the present invention and obtain the charge stability, the addition amount of the charge control agent is 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Preferably 0.1
More preferably, it is from 8 to 8 parts by mass.

In the production of the toner of the present invention, a method in which the constituent materials are well kneaded by a heat kneader such as a heat roll, a kneader or an extruder, and then mechanically pulverized and the pulverized powder is classified to obtain a toner; A method in which a material such as a colorant is dispersed in a binder resin solution and then spray-dried; a polymerizable monomer that constitutes the binder resin is mixed with a predetermined material to obtain a monomer composition. A toner manufacturing method by suspension polymerization can be applied in which a toner is obtained by polymerizing an emulsion suspension of this composition.

When the toner of the present invention is used as a two-component developer in combination with a carrier, examples of the carrier used include surface-oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths. Metals such as and their alloys or oxides and ferrites can be used. In addition, there is no particular limitation on the manufacturing method.

As a method for coating the surface of the carrier with a resin or the like, a method in which a coating material such as a resin is dissolved or suspended in a solvent and applied to the carrier to adhere it to the carrier,
Any conventionally known method such as a method of simply mixing with powder can be applied.

The coating material for the surface of the carrier varies depending on the toner material. For example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, metal complex of di-tert-butylsalicylic acid, Styrene resin, acrylic resin, polyamide, polyvinyl butyral, nigrosine, amino acrylate resin, basic dye and its lake, fine silica powder, fine alumina powder and the like are suitable to be used alone or in plural, but it is not always necessary. Not restricted.

The treatment amount with the above-mentioned coating material may be appropriately determined so that the carrier satisfies the above conditions, but generally, the total amount is 0.1 to 30% by mass (preferably 0.5 to 20% by mass) based on the carrier. ) Is preferred.

The average particle size of these carriers is 10 to 100.
It is preferable to have a thickness of μm, preferably 20 to 70 μm.

Preferred embodiments of the carrier to which the toner of the present invention is combined are Cu-Zn-Fe and Mn-Mg.
-Fe is a three-element ferrite of which the surface is a combination of resins such as silicone resin or fluorine resin and styrene resin, for example, polyvinylidene fluoride and styrene / methyl methacrylate resin; polytetrafluoroethylene and styrene / methyl meta resin. Acrylate resin, fluorine-based copolymer and styrene-based copolymer; silicone resin and the like 90:10 to 20:80, preferably 70:30
~ 30: 70 in a mixture with a ratio of 0.01 ~
An example is a coated ferrite carrier coated with 5% by mass, preferably 0.1 to 1% by mass, having a mesh particle size of 250 mesh and a particle size of 400 mesh on of 70% by mass or more of the above-mentioned average particle size. Examples of the fluorine-based copolymer include vinylidene fluoride / tetrafluoroethylene copolymer (10:90 to 90:10), and examples of the styrene-based copolymer include styrene / 2-ethylhexyl acrylate (20:80 to 80:20), styrene / 2-ethylhexyl acrylate / methyl methacrylate (20 to 60: 5 to 30:10 to 50).

When the above-mentioned coated ferrite carrier has a sharp particle size distribution, a preferable triboelectrification property for the toner of the present invention can be obtained, and the electrophotographic properties can be further improved.

When a two-component developer is prepared by mixing the toner of the present invention with a carrier, the mixing ratio is 2% by mass to 15% by mass, preferably 3% by mass to the toner concentration in the developer. 13% by mass, more preferably 4% by mass to 1
When the content is 0% by mass, good results are usually obtained. If the toner density is less than 2% by mass, the image density will be low and it will be difficult to practically use.
If it exceeds 15% by mass, fog and scattering in the machine are increased, and the useful life of the developer tends to be shortened.

Next, an example of a developing device for developing a non-magnetic one-component toner using the toner of the present invention will be described, but the developing device is not limited to this. In Figure 1,
An example of an apparatus for developing an electrostatic image formed on a latent image carrier is shown. In the latent image carrier 1, the latent image is formed by electrophotographic process means or electrostatic recording means (not shown). The developer carrying member 2 is a non-magnetic sleeve made of aluminum, stainless steel or the like. The non-magnetic one-component color toner T is stored in the hopper 3 and is supplied onto the developer carrier 2 by the supply roller 4. The supply roller 4 also removes the toner on the developer carrying member 2 after development. The toner supplied onto the developer carrier 2 is uniformly and thinly applied by the developer applying blade 5. The contact pressure between the developer coating blade 5 and the developer carrying member 2 is 3 to 250 g / in linear pressure in the sleeve generatrix direction.
cm, preferably 10 to 120 g / cm is effective.
When the contact pressure is less than 3 g / cm, it becomes difficult to apply the toner uniformly, and the charge amount distribution of the toner becomes broad, which easily causes fog and scattering. Contact pressure is 25
If it exceeds 0 g / cm, a large pressure is applied to the toner, so that the toner particles tend to agglomerate or are crushed, which is not preferable. By adjusting the contact pressure to 3 to 250 g / cm, it becomes possible to satisfactorily loosen the agglomeration of the toner having a small particle diameter, and it is possible to instantly increase the triboelectric charge amount of the toner. As the developer coating blade 5, it is preferable to use a material of triboelectric charging series suitable for charging the toner to a desired polarity.

In the present invention, silicone rubber, urethane rubber, styrene-butadiene rubber and the like are preferable.
The use of conductive rubber is preferable because it can prevent the toner from being triboelectrically charged excessively. If necessary,
The surface of the blade 5 may be coated. In particular, when used as a negative toner, it is preferable to coat a positively chargeable resin such as polyamide resin.

In a system in which a thin layer of toner is coated on the developer carrying member 2 by the blade 5, the thickness of the toner layer on the developer carrying member 2 is adjusted to obtain a sufficient image density. It is preferable that the length is smaller than the opposing gap length between the latent image carrier 1 and the latent image carrier 1 and an alternating electric field is applied to this gap. By applying a developing bias in which a DC electric field is superimposed on the alternating electric field or the alternating electric field between the developer carrying member 2 and the latent image holding member 1 by the bias power source 6 shown in FIG. It is possible to facilitate the movement of the toner on the body 1 and obtain a higher quality image.

The method of measuring each characteristic value according to the present invention will be described below.

[Measurement Method of BET Specific Surface Area of Inorganic Fine Particles] The BET specific surface area is a fully automatic gas adsorption measuring device manufactured by Yuasa Ionics Co., Ltd .: Autosorb 1 is used, nitrogen is used as an adsorption gas, and BET multipoints are used. Find by law. As a pretreatment of the sample, deaeration is performed at 50 ° C. for 10 hours.

[Measurement Method of Average Particle Size of Inorganic Fine Particles] The inorganic fine particles are observed with a transmission electron microscope, and the average particle size is obtained by measuring the particle size of 300 particles in the visual field. Observe with a microscope and measure the particle size of 300 particles in the visual field to determine the average particle size.

[Measurement Method of Hydrophobicity of Inorganic Fine Particles] The methanol titration test is an experimental test for confirming the hydrophobicity of inorganic fine particles having a hydrophobized surface.

The hydrophobicity measurement using methanol for evaluating the hydrophobicity of the inorganic fine particles is performed as follows.
0.2 g of the inorganic fine particles to be tested is added to 50 ml of water in an Erlenmeyer flask having a volume of 250 ml. Titrate the methanol from the burette. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. When the sedimentation of the inorganic fine particles ends,
The total amount is confirmed by suspension in the liquid and the degree of hydrophobicity is expressed as the percentage of methanol in the liquid mixture of methanol and water at the end of the settling.

[Measurement Method of Particle Size Distribution of Toner and Charge Control Agent] As a measuring device, Coulter counter TA-
II or Coulter Multisizer II (manufactured by Coulter) is used. As the electrolytic solution, about 1% NaCl aqueous solution is prepared using first-grade sodium chloride. For example, ISO
TON-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, a surfactant (preferably an alkylbenzene sulfonate) as a dispersant was added to 100 to 150 ml of the electrolytic aqueous solution as described above.
Add 1 to 5 ml, and further add 2 to 20 mg of the measurement sample. The electrolytic solution in which the sample is suspended is about 1 to 3 with an ultrasonic disperser.
Dispersion treatment is performed for minutes, and the volume and number of particles are measured for each channel using the measuring device with an aperture of 100 μm as an aperture to calculate the volume distribution and number distribution of particles. Then, the weight average particle diameter (D4) of the weight-based particles obtained from the volume distribution of the particles
(The median value of each channel is used as a representative value for each channel).

The channels are 2.00 to 2.52.
μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm
m; 4.00 to 5.04 μm; 5.04 to 6.35 μ
m; 6.35 to 8.00 μm; 8.00 to 10.08 μm
m; 10.08-12.70 μm; 12.70-16.
00 μm; 16.0-20.20 μm; 20.20
25.40 μm; 25.40-32.00 μm; 32.
13 channels of 00-40.30 μm are used.

[Aggregation Degree Measuring Method] The aggregation degree is used as one means for measuring the flow characteristics of a sample (a toner having an external additive, etc.). The larger the value of this aggregation degree, the poorer the fluidity of the sample. To judge.

As the measuring device, a powder tester (manufactured by Hosokawa Micron Co.) having a digital vibrometer (Digivibro MODEL 1332) is used.

As a measuring method, 200 mesh, 100 mesh, and 60 mesh screens were placed on the vibrating table in the order of narrow openings, that is, in order of the 200 mesh, 100 mesh, and 60 mesh screens so that the 60 mesh screen was at the top. Set on top of each other.

5 g of an accurately weighed sample was added onto the set 60-mesh sieve, and the input voltage to the shaking table was set to 21.
The value of the displacement of the digital vibrometer is set to 0.
130, and the amplitude of the vibrating table at that time was adjusted to fall within the range of 60 to 90 μm (rheostat scale of about 2.
5), shake for about 15 seconds. Then, the mass of the sample remaining on each sieve is measured to obtain the cohesion degree according to the following formula.

[0114]

[Equation 1]

The sample used was left for 12 hours in an environment of 23 ° C./60% RH, and the measurement environment was 23 ° C./6.
It is 0% RH.

[Method of crystal structure analysis of alumina fine particles]
The X-ray crystal structure analysis is performed by an X-ray diffraction spectrum using Kα rays of Cu characteristic X-rays as a radiation source. As a measuring machine, for example, a powerful automatic X-ray diffractometer MXP18
(Manufactured by Mac Science) can be used.

When the alumina has a well-defined crystal structure,
That is, in the case of α type alumina, 2θ is 20 to 7
A sharp peak is observed in the range of 0 deg.

[Molecular Weight Distribution by GPC Measurement] The molecular weight of the resin according to the present invention is measured by a chromatogram by gel permeation chromatography (GPC) under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min to adjust the sample concentration to 0.05 to 0.6 mass%. About 50 to 200 μl of a THF sample solution of the resin is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value and the number of counts (retention time) of a calibration curve prepared using several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, manufactured by Tosoh Corporation or Pres
Sure Chemical Co. Made of 6 × molecular weight
10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ ,
5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.
It is suitable to use 6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As a column, a plurality of commercially available polystyrene gel columns may be combined in order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ⁶ , and for example, Shodex GPC KF-801 manufactured by Showa Denko KK 80
2, 803, 804, 805, 806, 807 combinations and Waters μ-styragel 50
A combination of 0, 103, 104 and 105 can be mentioned.

[0121]

EXAMPLES Examples of the present invention will be described below.

(Production Example 1 of fine alumina particles) 2 liters of 0.2 M ammonium-aluminum alum solution was added to 3 liters of 2 M ammonium bicarbonate solution at a rate of 0.8 liter / hour while keeping the liquid temperature at 30 ° C. Was added dropwise, and the mixture was sufficiently reacted with stirring to produce aluminum ammonium carbonate hydroxide fine powder, which was filtered and dried. The fine powder was heat-treated at 800 ° C. for 24 hours to produce an alumina calcined product. This fired alumina product was crushed with a speed mill to obtain fine alumina powder. This alumina fine powder has a BET specific surface area of 230 m ² / g,
The average particle size is 6 nm, and the crystal form is γ by X-ray diffraction.
It was confirmed to be a system.

Next, the above alumina fine powder was sufficiently wet pulverized in toluene with a ball mill using alumina balls having a diameter of 5 mm. Remove the alumina balls,
After sufficiently dispersing the alumina fine powder, isoC ₄ H ₉ was added as a surface treatment agent to 100 parts by mass of the alumina fine powder.
-Si- (OCH _{3) 3} was added in an amount of 30 parts by solid content based on the alumina fine powder 100 parts by weight. Then, the liquid temperature was maintained at 50 ° C., and the mixture was added dropwise with sufficient stirring to cause hydrolysis. Then, after filtering and drying, 18
It was baked at 0 ° C. for 3 hours and crushed. The crushing was performed with a speed mill to obtain alumina fine particles (inorganic fine particles 1) having a BET specific surface area of 170 m ² / g.

(Production Example 1 of titanium oxide fine particles) A surface treatment was carried out in the same manner as the method of the alumina fine particles 1 except that titanium oxide powder of anatase type crystal having a BET specific surface area of 131 m ² / g was used. BET specific surface area = 10
Titanium oxide fine particles (inorganic fine particles 2) of 1 m ² / g were obtained.

(Production Example 2 of titanium oxide fine particles) A surface treatment was carried out in the same manner as the method of the alumina fine particles 1 except that titanium oxide powder of anatase type crystal having a BET specific surface area of 200 m ² / g was used. BET specific surface area = 19
Titanium oxide fine particles (inorganic fine particles 3) of 0 m ² / g were obtained.

(Production Example 1 of Silica Fine Particles) Silica fine particles (inorganic fine particles) having a BET specific surface area of 280 m ² / g were subjected to hydrophobization treatment with hexamethyldisilazane in a gas phase after firing silicon tetrachloride at a high temperature. 4) was obtained.

(Production Example 2 of Silica Fine Particles) Silica fine particles having a BET specific surface area of 80 m ² / g were treated by hydrophobizing hexamethyldisilazane in a gas phase after firing silicon tetrachloride at a high temperature (inorganic fine particles). 5) was obtained.

Table 1 shows the physical properties of the above-mentioned inorganic fine particles.

[0129]

[Table 1]

Example 1 Polyester Resin 1 100 parts by mass Quinacridone pigment 4 parts by mass Di-tert-butylsalicylic acid aluminum complex 4 parts by mass (average particle size = 4.5 μm) were sufficiently premixed with a Henschel mixer, The mixture was melt-kneaded by a twin-screw extruder kneader, cooled, coarsely pulverized to about 1 to 2 mm using a hammer mill, and then finely pulverized by an air jet type fine pulverizer. Further, the finely pulverized product obtained was classified to obtain a negative triboelectrically charged magenta colored powder (toner particles).

100 parts by weight of the colored powder and 1.2 parts by weight of the inorganic fine particles 1 (alumina fine particles) were mixed with a Henschel mixer for 4 minutes to obtain a magenta toner 1. The weight average particle diameter of the magenta toner 1 is 6.2 μm (20.1% for 4.0 μm or less, 43.5% for 5.04 μm or less, 8.
6.0% for 0 μm or more, 0.6 for 10.08 μm or more
%)Met. Table 2 shows the physical properties of the resin used for producing the toner, and Table 3 shows the physical properties of the toner.

A magenta toner 1 and a silicone resin coated carrier having an average particle size of 40 μm are mixed at a toner concentration of 6% by mass to prepare a developer, and a color copying machine CLC-800 is prepared.
(Manufactured by Canon) using an original document with an image area ratio of 25% in a high temperature and high humidity environment (32.5 ° C / 90%),
Under low temperature and low humidity environment (10 ° C / 3%), 20,000 images were printed. The evaluation methods and results are shown in Table 4.

The above-mentioned developers had very small variations in image density, fog and toner charge amount in the printing durability test, and there was no problem of toner scattering after 20,000 sheets, and very excellent results were obtained. The surface of the photoconductor after 20,000 sheets of durability was observed with a scanning electron microscope. As a result, it was found to be in good condition with no deposits or scratches.

Further, 15 g of magenta toner 1 was sampled, placed in a beaker, and allowed to stand in a constant temperature bath at 50 ° C. for 10 days, and a storability test was conducted. The toner after standing was also highly fluid, and no toner aggregate was found. Magenta toner 1
Can be said to be a toner excellent in storage stability in a high temperature environment.

Each evaluation method will be described below.

[Fog] Evaluation of fog was performed by REFRECTOMER MODEL TC-6D manufactured by Tokyo Denshoku Co., Ltd.
S is used to measure, and for magenta toner images,
It was calculated from the following formula using an n filter. The smaller the value, the less the fog.

Fog (reflectance) (%) = reflectance (%) of standard paper-reflectance (%) of non-image area of sample A: Fog is less than 1.0%, which is a good level. B: 0.1% or more and less than 2.0%, which is a level with no practical problems. C: 2.0% or more and less than 4.0%, which is a practically problematic level. D: 4.0% or more, which is a practically problematic level.

[Toner scattering] Developing device after 10,000 sheets of durability,
Observe the degree of toner contamination around the in-body developing device. A: No contamination by toner around the developing device and the developing device in the main body is observed at all. B: Contamination due to a slight amount of toner is observed in the developing device. C: Contamination due to toner around the developing device and the developing device in the main body is observed. D: The developing device and the inside of the developing device in the main body are significantly soiled by the toner, and the function of the main body is adversely affected.

[Surface Condition of Photoreceptor] 30 places on the surface of the photoconductor after 20,000 sheets of durability are observed with a scanning electron microscope. A: No deposits such as toner and scratches are observed. B: Adhered substances such as toner and scratches are observed at several places, but they do not appear as image defects. C: Adhered substances such as toner and scratches are observed at ten or more places and appear as image defects. D: Many adherents such as toner and scratches are observed, and appear as remarkable image defects.

In the same manner as in Example 1 above, toners having the physical properties shown in Table 3 were manufactured and evaluated in the same manner. The results are shown in Table 4.
Shown in.

[0141]

[Table 2]

[0142]

[Table 3]

[0143]

[Table 4]

[0144]

The toner of the present invention has extremely stable environmental characteristics, uniform triboelectrification and its durability stability, long-term storage stability, high fluidity and transferability, and at the same time,
No fused substance is generated on the surface of the photoconductor even after long-term use, and it is possible to provide a very stable, high-definition and high-quality image in any environment.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an example of a developing device when toner development is performed using the toner of the present invention.

[Explanation of symbols]

1 Latent image holder 2 Developer support 3 hopper 4 supply roller 5 Developer coating blade 6 Bias power supply

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/09 G03G 9/08 346 9/097 361 (72) Inventor Katsumi Kondo 3-chome Shimomaruko, Ota-ku, Tokyo No. 30-2 Canon Inc. (72) Inventor Takaaki Kaji 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2H005 AA01 AA06 AA08 AA21 CA08 CA25 CA26 CB07 CB13 DA02 EA05 EA10 FA01

Claims (11)

[Claims] 1. A binder resin, a colorant, a charge control agent, and inorganic fine particles are contained at least, the binder resin comprises a polyester resin as a main component, and the binder resin has an acid value of 2.0 to 5.
A toner characterized in that it is 0.0 mgKOH / g, and the number release rate of the charge control agent with respect to the toner particles is 0.01% to 10.00%. 2. The charge control agent is Al, Zn, Fe, C
2. The toner according to claim 1, containing any one of r. 3. The toner according to claim 1, wherein the charge control agent contains Al. 4. The toner according to claim 1, wherein the charge control agent contains Fe and the colorant is a black colorant. 5. The toner according to claim 1, wherein the number liberation ratio of the inorganic fine particles to the toner particles is 0.01% to 20.00%. 6. The number liberation rate of the charge control agent and the inorganic fine particles combined with respect to the toner particles is 0.01 to 10.00%.
The toner according to any one of claims 1 to 5, wherein 7. The inorganic fine particles have a primary particle size of 1 to 10.
7. The toner according to claim 1, which is titanium oxide, silica, or alumina that has been subjected to a hydrophobic treatment of 0 nm. 8. The BET specific surface area of the inorganic fine particles is 10
8. Hydrophobized titanium oxide, silica, or alumina of 0 to 350 m ² / g.
The toner according to any one of 1. 9. The toner has a weight average particle diameter of 4 to 10 μm.
9. The color toner according to claim 1, wherein the color toner is 10. The toner according to claim 1, wherein the colorant is selected from the group consisting of a yellow colorant, a magenta colorant, a cyan colorant and a black colorant. 11. A full-color image obtained by using a combination of a yellow toner, a magenta toner, a cyan toner and a black toner, wherein the toner contains a yellow colorant, a magenta colorant, a cyan colorant and a black colorant as colorants. The toner according to claim 10, wherein the toner is formed.