JP2002296829A - Image forming method and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method in which a cleaning blade is less liable to wear, the service life of a photoreceptor is prolonged because of suppressed wear of the photoreceptor and prevented toner filming, image fog and image blurring are not caused even in printing at high temperature and high humidity and a fine dot image uniform in halftone and having little scattered toner is obtained and to provide a toner. SOLUTION: In the image forming method having a step for cleaning a residual image on an image forming body after a latent image on the image forming body is developed with a toner to form an image and this image is transferred to a transfer material, the crossed axes angle ϕ between the holder of a cleaning blade and the image forming body is <90 deg. and the toner contains 1.0-7.0 number % particles of <=3.17 μm based on the whole toner and contains a metallic salt of a fatty acid whose number average particle diameter is 0.5-4.0 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method for developing a latent image on an image forming body provided with an organic photosensitive layer using a toner to form an image, and a toner.

[0002]

2. Description of the Related Art At present, an organic photoconductor containing an organic photoconductive substance is most widely used as an image forming body used in an electrophotographic image forming apparatus. Conventionally, the toner developed on the organic photoreceptor and remaining on the photoreceptor through the transfer process has been collected and discarded by a cleaning blade, but in recent years, the toner collected from a viewpoint of economy and environmental safety has been transported by a conveying screw. For example, an image forming method using a so-called toner recycling system, which returns the toner to the developing device and reuses the toner as a developing toner, has attracted attention.

However, since the collected toner collected by the cleaning blade and conveyed to the developing unit by the conveyance member is deteriorated by stress, various problems occur in cleaning in a toner recycling system in which the toner is repeatedly used. It is easy to be.

[0004] In the electrophotographic image forming method, digital image formation has become mainstream due to recent advances in digital technology. Digital image forming method is 1200
It is based on visualizing small dot images of pixels such as dpi (however, dpi represents the number of dots per 2.54 cm), and a high image quality technology that faithfully reproduces these small dot images. Is required.

One of the most important technologies for realizing this high image quality technology is a technology relating to toner. Heretofore, for forming an electrophotographic image, a toner obtained by classifying a toner powder obtained by mixing and kneading a binder resin and a pigment and kneading them has been mainly used. The toner obtained through such a manufacturing process has a limit in making the particle size distribution of the toner particles uniform, and the particle size distribution and shape of the toner particles are insufficiently uniform. With an electrophotographic image using such a toner, it has been difficult to achieve sufficiently high image quality.

On the other hand, as means for achieving a uniform particle size distribution and shape of toner particles, an electrophotographic developer using a polymerized toner or an image forming method has been proposed. In the polymerized toner, since the raw material monomers are uniformly dispersed in an aqueous system and then polymerized to produce the toner, the particle size distribution and shape of the toner become uniform.

Here, when the polymerized toner is employed in an image forming apparatus using an organic photoreceptor, a new technical problem has arisen. That is, the polymerized toner is formed in a substantially spherical shape because the toner is formed after the monomer is dispersed in an aqueous system and polymerized.

[0008] The spherical transfer residual toner has a high adhesion to the organic photoreceptor, promotes wear of the cleaning blade and the photoreceptor, and has a problem of shortening the life of the cleaning blade and the photoreceptor. Further, there is a problem that cleaning failure easily occurs, image stains are generated, and a charging member is stained.

[0009] A technique of adding a fatty acid metal salt as a cleaning aid for preventing the occurrence of defective cleaning is known. Japanese Patent Application Laid-Open No. H11-323396 proposes metal soap particles having an average particle size of 4 μm or less and a ratio of particles larger than 10 μm is 4% by mass or less, that is, fatty acid metal salt particles.

Generally, when the particle size of the fatty acid metal salt particles is reduced, the fatty acid metal salt protects the surface of the photoreceptor and improves the cleaning property. However, when the fatty acid metal salt having high water absorption coats (films) the toner surface, the chargeability or charge retention ability of the toner is reduced. In particular, when printing is performed at high temperature and high humidity, fogging occurs, and when the image forming apparatus is stopped for a long period of time, when printing is performed, there is a problem that the gradation varies and the image image looks dark.

[0011]

DISCLOSURE OF THE INVENTION The present invention has been proposed in view of the above problems.
The wear of the cleaning blade is reduced, the toner does not slip through for a long period of time, the wear of the photoconductor is reduced, and the toner filming is not generated, thereby extending the life of the photoconductor. An object of the present invention is to provide an image forming method and a toner capable of obtaining an image which is free from image blurring, has a uniform halftone, and has little toner scattering of fine dots.

[0012]

The object of the present invention is achieved by adopting the following constitution.

1. The latent image on the image forming body having the organic photosensitive layer is developed using toner to form a toner image, and after transferring the toner image to a transfer material, the residual toner on the image forming body image is cleaned. In the image forming method having a step, the cleaning is performed by bringing the tip of an elastic cleaning blade, whose base is supported by a holder, into contact with the image forming body, and the intersection angle φ between the holder of the elastic cleaning blade and the image forming body is 90 °. The toner contains a toner component having a number average particle size of 4 to 9 μm and a number standard particle size of 3.17 μm or less in an amount of 1.0 to 7.0% by number of the whole toner, and has a number average particle size of 0. An image forming method, comprising using a toner containing a fatty acid metal salt having a particle size of 0.5 to 4.0 μm.

2. 2. The image forming method according to claim 1, wherein the toner contains an abrasive external additive and an external additive.

3. 3. The image forming method according to claim 1, wherein the cleaned toner is returned to a developing step and reused.

4. A toner containing 1 to 4.5% of toner particles having a number-based particle size of 3.17 μm or less and a fatty acid metal salt having a number-average particle size of 0.5 to 3.0 μm is used. 4. The image forming method according to any one of the above items 1 to 3.

5. 0.02 to 2.0 of the fatty acid metal salt
(1) The toner according to (1), wherein the toner contains parts by mass.
Item 5. The image forming method according to any one of Items 4 to 4.

6. 0.04 to 1.0 of the fatty acid metal salt
(1) The toner according to (1), wherein the toner contains parts by mass.
6. The image forming method according to any one of items 5 to 5.

[7] The circularity coefficient is 0.750 to 0.96
7. The image forming method according to any one of the above items 1 to 6, wherein the toner further comprises 0 of the abrasive external additive.

8. 8. The image forming method according to any one of items 1 to 7, wherein a toner in which the abrasive external additive is strontium titanate is used.

9. The toner, on the surface of the organic fine particles,
9. The image forming method according to any one of the above items 1 to 8, comprising inorganic / organic composite fine particles in which inorganic fine particles having a number average primary particle diameter of 5 to 100 nm are fixed to a fixing degree of 20 to 75%. Method.

10. When the external additive present on the surface of the toner particles is 0.005 to 0.025 μm,
5% by number, 4 to 3 with 0.025 to 0.080 μm
4% by number, 0.080 to 0.500 μm 0.3
10. The toner according to any one of 1 to 9 above, wherein a toner containing an abrasive external additive having a number average particle size of 0.5 to 5.0 μm is used for toner particles adhering to 10 to 10% by number.
Item.

11. Number average particle size is 0.005 to 0.0
15 μm silica a having a number average particle size of 0.020 to 0.2 μm.
080 μm silica b, number average particle size 0.015
0.070 μm titanium oxide c having a number average particle size of 0.0
The toner is characterized in that a toner containing an abrasive external additive having a number average particle diameter of 0.5 to 5.0 μm is used for toner particles having an external additive of titanium oxide d of 8 to 0.2 μm. The image forming method according to any one of the above items 1 to 10.

12. The coefficient of variation of the shape factor is 16% or less, the number variation coefficient in the number particle size distribution is 27% or less, and the proportion of toner particles having a shape coefficient in the range of 1.0 to 1.6 is 65% by number or more. 12. The image forming method according to any one of the above items 1 to 11, wherein a toner is used.

13. The percentage of toner particles without corners is 50
A toner having a number% or more, a number variation coefficient in the number particle size distribution of 27% or less, and a toner having a shape coefficient in a range of 1.0 to 1.6 and a percentage of toner particles of 65% by number or more. 13. The image forming method according to any one of the above items 1 to 12, wherein

14. Wherein the proportion of toner particles having a shape coefficient in the range of 1.2 to 1.6 is 65% by number or more, and a toner comprising toner particles having a shape coefficient variation coefficient of 16% or less is used. 14. The image forming method according to any one of items 1 to 13.

15. Assuming that the particle size of the toner particles is D (μm), the natural logarithm lnD is plotted on the horizontal axis, and the horizontal axis is defined as 0.
The relative frequency (m1) of the toner particles included in the most frequent class in the histogram showing the number-based particle size distribution divided into a plurality of classes at 23 intervals, and the toner particles included in the class having the second highest frequency after the most frequent class 15. The image forming method according to any one of items 1 to 14, wherein a toner having a sum (M) of 70% or more with respect to the relative frequency (m2) is used.

16. 16. The image forming method according to any one of items 1 to 15, wherein a toner obtained by forming particles in an aqueous medium is used.

17. (1) The toner according to (1), wherein a toner obtained by aggregating and fusing the resin particles in an aqueous medium is used.
Item 17. The image forming method according to any one of Items 16 to 16.

18. A latent image on an image forming body having an organic photosensitive layer is developed using toner to form a toner image,
After transferring the toner image to a transfer material, the toner used in the image forming method includes a step of cleaning residual toner on the image forming body image, wherein the cleaning is performed by removing the tip of an elastic cleaning blade having a base supported by a holder. The elastic cleaning blade and the image forming body have an intersection angle φ of less than 90 °, a toner number average particle diameter of 4 to 9 μm, and a number-based particle diameter of 3.17 μm or less. The toner component is set to 1.0% of the entire toner.
% To 7.0% by number, and the number average particle size is 0.5 to 4.0.
A toner comprising a fatty acid metal salt of μm.

19. The toner according to claim 18, wherein the toner contains an abrasive external additive and an external additive.
The toner according to Item.

20. The above-mentioned item 18 or 19, comprising 1 to 4.5% of toner particles having a number-based particle size of 3.17 μm or less and containing a fatty acid metal salt having a number-average particle size of 0.5 to 3.0 μm. The toner according to Item.

21. 0.02 to 2.
21. The toner according to any one of items 18 to 20, wherein the toner is contained in an amount of 0 parts by mass.

22. 0.04 to 1.
22. The toner according to any one of the items 18 to 21, wherein the toner is contained in an amount of 0 parts by mass.

23. The circularity coefficient is 0.750 to 0.9
23. The toner according to any one of the items 18 to 22, wherein the toner further comprises 60 of the abrasive external additive.

24. The above-mentioned 18 to 23, wherein the abrasive external additive is strontium titanate.
Item 10. The toner according to any one of items 1. to 4.

25. Inorganic fine particles having a number average primary particle diameter of 5 to 100 nm are fixed on the surface of the organic fine particles.
25. The toner according to any one of the above items 18 to 24, comprising inorganic / organic composite fine particles fixed to 5%.

26. When the external additive present on the surface of the toner particles is 0.005 to 0.025 μm,
5% by number, 4 to 3 with 0.025 to 0.080 μm
4% by number, 0.080 to 0.500 μm 0.3
26. The toner according to any one of the above items 18 to 25, wherein the toner particles adhered by 10 to 10% by number contain an abrasive external additive having a number average particle size of 0.5 to 5.0 μm. .

27. Number average particle size is 0.005 to 0.0
15 μm silica a having a number average particle size of 0.020 to 0.2 μm.
080 μm silica b, number average particle size 0.015
0.070 μm titanium oxide c having a number average particle size of 0.0
The number average particle size of the toner particles to which the external additive of titanium oxide d of 8 to 0.2 μm is externally added is 0.5 to 5.0 μm.
27. The toner according to any one of the above items 18 to 26, wherein m is added.

28. The coefficient of variation of the shape factor is 16% or less, the number variation coefficient in the number particle size distribution is 27% or less, and the proportion of toner particles having a shape coefficient in the range of 1.0 to 1.6 is 65% by number or more. 28. The toner according to any one of the items 18 to 27, wherein:

29. The proportion of toner particles having no corners is 50% by number or more, the number variation coefficient in the number particle size distribution is 27% or less, and the proportion of toner particles having a shape coefficient in the range of 1.0 to 1.6 is 65%. 29. The toner according to any one of the items 18 to 28, wherein the amount is not less than a number%.

30. Wherein the ratio of the toner particles having a shape factor in the range of 1.2 to 1.6 is 65% by number or more, and the toner particles have a shape coefficient variation coefficient of 16% or less. Item 10. The toner according to any one of items 1. to 4.

31. Assuming that the particle size of the toner particles is D (μm), the natural logarithm lnD is plotted on the horizontal axis, and the horizontal axis is defined as 0.
The relative frequency (m1) of the toner particles included in the most frequent class in the histogram showing the number-based particle size distribution divided into a plurality of classes at 23 intervals, and the toner particles included in the class having the second highest frequency after the most frequent class The sum (M) of the relative frequency (m2) of the above-mentioned is not less than 70%;
Item 30. The toner according to any one of items 30 to 30.

32. 32. The toner according to any one of items 18 to 31, wherein the toner is obtained by forming particles in an aqueous medium.

33. 33. The toner according to any one of the above items 18 to 32, wherein the toner is obtained by coagulating and fusing resin particles in an aqueous medium.

That is, when the present inventors cut the toner fine particles having a particle size distribution of 3.17 μm or less based on the number-based particle size distribution, voids are formed in the region of the particle size distribution occupied by the toner fine particles. It has been found that adding fatty acid metal salt particles of 0.5 to 4.0 μm and filling the voids can prevent the fatty acid metal salt from filming the toner surface. At the same time, the present inventors have also found that the wear of the photoreceptor is reduced by cutting the toner fine particles of 3.17 μm or less. That is, toner particles having strong adhesion to the photoreceptor accumulate in the cleaning blade pressing portion and entrain external additives liberated from the toner to reduce the photoreceptor. 4.
It is presumed that this is because the fatty acid metal salt selectively functions to concentrate on the cleaning blade pressing portion of 0 μm, so that the fatty acid metal salt functions effectively.

For a toner containing a toner component having a number-based particle size of 3.17 μm or less in an amount of 1.0 to 7.0% by number of the total toner, resin particles are aggregated and fused in an aqueous medium to produce toner particles. In the process, it can be produced by a method of controlling the size, aggregation, fusion conditions and the like of the resin particles.

Hereinafter, the present invention will be described in more detail. "Number-Based Particle Size Distribution of Toner" The toner of the present invention contains a toner component having a number-based particle size of 3.17 μm or less in an amount of 1.0 to 7.0% by number of the whole toner, and preferably 1.0%. ４4.5% by number. If the amount exceeds 7.0% by number, the wear of the cleaning blade and the photoconductor increases. If the amount is less than 1.0% by number, the vibration of the cleaning blade increases, and
So-called toner slippage tends to occur.

The particle diameter of the toner of the present invention is preferably 4 to 9 μm, more preferably 5 to 8 μm in number average particle diameter. The particle size of the toner can be controlled by changing the concentration of the coagulant (salting agent), the amount of the organic solvent added, the fusing time, and the composition of the polymer in the method for producing the polymerized toner.

When the number average particle size is 4.5 to 9 μm,
The transfer efficiency is improved, the halftone image quality is improved, and the image quality of fine lines, dots, and the like is improved.

The measurement of the particle size distribution based on the number of toners and the measurement of the number average particle size are performed by using a Coulter Counter TA-2, a Coulter Multisizer (manufactured by Coulter), a SLAD.
It can be measured using a 1000-type laser diffraction particle size analyzer (manufactured by Shimadzu Corporation) or the like.

In the present invention, a Coulter Multisizer was used, and an interface for outputting a particle size distribution (manufactured by Nikkaki Co., Ltd.) and a personal computer were connected.

In the present invention, the number-based particle size is 3.
A toner component having a particle size of 17 μm or less is used in an amount of 1.0 to 7.
As a specific means for obtaining a toner containing 0% by number, a polymerizable monomer is polymerized in an aqueous medium, and more specifically, resin particles are aggregated and fused in an aqueous medium to polymerize. This is achieved by using a method.

"Fatty acid metal salt" The number average particle diameter of the fatty acid metal salt according to the present invention is 0.5 to 4.0 µm. 0.5
If it is less than μm, the fatty acid metal salt tends to film the toner surface, and if it exceeds 4.0 μm, the cleaning blade and the photoreceptor are liable to be worn.

In the fatty acid metal salt according to the present invention, the content of particles exceeding 10 μm is preferably 4% by mass or less, more preferably not contained. Particles exceeding 10 μm damage the surface of the photoconductor, thereby shortening the life of the photoconductor.

In the toner of the present invention, the fatty acid metal salt is added in an amount of 0.0
It is preferably contained in an amount of 2 to 2.0 parts by mass,
More preferably, the content is 1.0 part by mass. If the amount exceeds 2.0 parts by mass, the amount of wear of the cleaning blade increases, and the cleaning performance decreases. On the other hand, if the amount is less than 0.02 parts by mass, the effect of preventing toner filming on the photoconductor is reduced.

The circularity coefficient of the fatty acid metal salt according to the present invention is preferably from 0.750 to 0.960, and more preferably from 0.820 to 0.960.
~ 0.950 is more preferable.

When the circularity coefficient is within this range, the slidability between the cleaning blade and the photosensitive member is improved, and fine vibration of the cleaning blade is reduced, so that the toner can be prevented from slipping through. If it exceeds 0.960, the amount of the fatty acid metal salt applied to the surface of the photoreceptor is too small and the function of preventing the depletion of the photoreceptor becomes low. If it is less than 0.750, the amount applied to the surface of the photoreceptor becomes excessive and the temperature becomes high. Image blur (also referred to as image deletion) is likely to occur under high humidity.
The measurement of the circularity coefficient is performed using a flow-type particle image analyzer “FPI
A-2000 "(manufactured by Toa Medical Electronics Co., Ltd.).

The fatty acid metal salt used in the present invention includes a higher fatty acid metal salt. Specific examples of the higher fatty acid metal salt include metal stearate such as zinc stearate, aluminum stearate, copper stearate, and magnesium stearate, zinc oleate, manganese oleate, iron oleate, copper oleate, and olein. Metal oleate such as magnesium oxalate, zinc palmitate, copper palmitate, metal palmitate such as magnesium palmitate, zinc linoleate, metal linoleate such as zinc linoleate, zinc ricinoleate,
And ricinoleic acid metal salts such as lithium ricinoleate.

From the viewpoint of preventing the wear of the cleaning blade and the photoconductor, the fatty acid calcium salt is particularly preferable.

Next, a preferred method for producing the fatty acid metal salt particles according to the present invention will be described. As raw materials for the production, aqueous solutions or dispersions of an aqueous solution of a fatty acid salt (hereinafter also referred to as component (a)) and an inorganic metal salt (hereinafter also referred to as component (b)) are used.

The fatty acid salt used for preparing the aqueous solution of the fatty acid salt includes an alkali metal salt or an ammonium salt of a fatty acid having 4 to 30 carbon atoms. The fatty acid may be saturated or unsaturated, and may be linear or branched. Examples of such fatty acids include caprylic, capric, lauric, myristic, myristoleic, palmitic, isopalmitic, palmitoleic, stearic, behenic, lignoceric, serotinic, montanic, Alkali metal salts or ammonium salts such as sodium and potassium of simple fatty acids such as isostearic acid, oleic acid, arachinic acid, ricinoleic acid, linoleic acid, behenic acid and erucic acid, or bovine fatty acids, soybean oil fatty acids, and coconut oil fatty acids And alkali metal salts or ammonium salts such as sodium and potassium of fatty acids derived from animal and vegetable fats such as palm oil fatty acids.

Among them, preferred are alkali metal salts or ammonium salts of fatty acids having 10 to 24 carbon atoms, particularly 12 to 22 carbon atoms, such as sodium and potassium.
These fatty acids may be used alone or in combination of two or more.

When an alkali metal salt or ammonium salt of a fatty acid having less than 4 carbon atoms is used, the resulting fatty acid metal salt has a high solubility in water, so that the yield decreases. On the other hand, when an alkali metal salt or an ammonium salt of a fatty acid having more than 30 carbon atoms is used, the solubility in water is too low, the concentration of the aqueous solution becomes low, and the production efficiency decreases.

The content of the alkali metal salt or ammonium salt of the fatty acid in the aqueous solution of the fatty acid salt is 0.001.
２2% by mass. This content is 0.00
If the amount is less than 1% by mass, the amount of the fatty acid metal salt obtained is remarkably low with respect to the amount of the reaction solution, resulting in poor production efficiency, which is not practical. If it exceeds 2% by mass, the average particle size of the obtained fatty acid metal salt particles may increase. Considering the amount of the obtained fatty acid metal salt and its particle size, the preferable content of the alkali metal salt or ammonium salt of the fatty acid in the aqueous solution is in the range of 0.5 to 1.5% by mass.

Examples of the inorganic metal salt used for preparing the aqueous solution or dispersion of the inorganic metal salt used in the present invention include:
Chlorides, sulfates, carbonates, nitrates or phosphates of alkaline earth metals such as calcium, barium and magnesium, or titanium, zinc, copper, manganese, cadmium, mercury, zirconium, lead, iron, aluminum, Examples include chlorides, sulfates, carbonates, nitrates and phosphates of metals such as cobalt, nickel, lithium and silver. These substances may be used alone or in combination of two or more.

The content of the inorganic metal salt in the aqueous solution or dispersion of the inorganic metal salt is selected in the range of 0.001 to 2% by mass. If the content is less than 0.001% by mass, the amount of the fatty acid metal salt obtained is extremely low with respect to the amount of the reaction solution, so that the production efficiency is poor and not practical. 2% by mass
If the average particle diameter exceeds the above range, the average particle diameter of the obtained fatty acid metal salt particles may increase. Considering the amount of the obtained fatty acid metal salt and the particle size thereof, the preferable content of the inorganic metal salt in the aqueous solution or dispersion is in the range of 0.01 to 1% by mass.

The water used for preparing the components (a) and (b) is not particularly limited, and water generally used may be used, but may be ion-exchanged water, purified water or distilled water. And the like, such as those having few impurities such as metal ions are preferable. In the present invention, the mixing ratio of the component (a) and the component (b) is not particularly limited and may be appropriately selected depending on the situation. Usually, the mixing ratio with respect to the inorganic metal salt in the component (b) is not limited. It is preferable to select the equivalent ratio of the fatty acid salt in the component (a) to be in the range of 0.9 to 11.1. If the equivalent ratio deviates from the above range, a large amount of unreacted raw materials will be present, and a removal step may be required. To reduce residual impurities, the corresponding amount ratio should be 0.95
A range of 1.05 is more preferred.

The apparatus for producing the amount of fatty acid metal salt is preferably one capable of separately supplying the components (a) and (b) into a mixer and mixing them. In particular, it is preferable that the component (a) and the component (b) can be separately supplied and mixed into the mixer at as high a speed as possible. For example, it is advantageous to inject each raw material solution (or dispersion) into the mixer from a different direction to mix each solution (or dispersion), and at the same time, discharge the mixture from the mixer to the outside of the system. As these apparatuses, it is preferable to use a flow jet mixer, a line homogenizer, a sand mill, or the like. or,
When the unreacted alkali metal salt or ammonium salt of the fatty acid remains after the reaction of the components (a) and (b), after the components (a) and (b) are discharged from the mixer, By mixing an aqueous solution or dispersion containing 0.001 to 1.5% by mass of an inorganic metal salt, an alkali metal salt or ammonium salt of a fatty acid which has not completely reacted can be reacted with the fatty acid metal salt.

The components (a) and (b) are preferably mixed at a temperature lower than the onset of crystal transition of the fatty acid metal salt to be formed, preferably at a temperature lower than the crystal transition temperature by 5 ° C. or higher.

The fatty acid metal salt slurry thus obtained is separated into a fatty acid metal salt cake and a filtrate by using a generally used filtration device. The fatty acid metal cake is sufficiently washed with warm water or the like to remove impurities, and then dried to obtain fatty acid metal salt fine particles. In the drying treatment of the fatty acid metal cake, the temperature of the obtained fatty acid metal salt is preferably equal to or lower than the crystal transition start temperature, and more preferably 5 ° C. or lower than the crystal transition start temperature. The specific drying temperature varies depending on the type of the obtained fatty acid metal salt. For example, in the case of zinc stearate, the drying temperature is 100 ° C. or less. If the drying treatment is performed at a temperature higher than the crystal transition start temperature of the fatty acid metal salt, aggregation of fine particles may occur, and the average particle diameter may increase. The drying process of the fatty acid metal salt cake may be performed at normal pressure, but may be performed under reduced pressure or vacuum in order to dry efficiently, or the fatty acid metal salt cake may be dried with a low boiling point solvent or the like. After the washing treatment, the obtained fatty acid metal salt cake may be dried. As the low boiling point solvent used at this time, a solvent capable of efficiently removing water from the fatty acid metal salt is preferable, and examples thereof include methanol, ethanol, acetone, and methylene chloride.

The amount of water in the fatty acid metal salt is preferably from 0.1 to 2.5% by mass, more preferably from 0.3 to 1.2% by mass, from the viewpoint of improving the humidity stability of charging. If the water content exceeds 2.5% by mass, image blurring tends to occur under high temperature and high humidity.

The amount of free fatty acid in the fatty acid metal salt is 0.0
1 to 0.7% by mass is preferable, and 0.05 to 0.5% by mass.
Is more preferred. If it exceeds 0.7% by mass, the charging member such as the carrier and the developing roll is contaminated. If the amount is less than 0.01% by mass, the wear of the cleaning blade tends to increase, which may shorten the life of the cleaning blade.

[Abrasive External Additive] In the present invention, an abrasive external additive is preferably used in order to prevent toner filming of the photoreceptor.

The abrasive external additive is added to the toner for the purpose of effectively polishing the surface of the image forming body and effectively preventing the occurrence of toner filming on the surface of the image forming body.

The abrasive external additive refers to inorganic / organic composite fine particles having a number average particle diameter of 0.5 to 5.0 μm, metal oxides, or inorganic particles composed of a metal. The number average particle diameter is determined from the average diameter of 200 particles measured using a scanning electron microscope.

The toner according to the present invention preferably contains 0.02 to 2.0 parts by mass of the abrasive external additive with respect to 10 parts by mass of the toner particles without the external additive.
More preferably, the content is 0.04 to 1.0 part by mass.
If the amount exceeds 2.0 parts by mass, the amount of wear of the cleaning blade increases, and the cleaning property decreases. On the other hand, 0.0
If the amount is less than 2 parts by mass, the effect of preventing toner filming on the photoconductor is reduced.

The circularity coefficient of the external abrasive additive according to the present invention is preferably 0.750 to 0.960. When the circularity coefficient is within this range, the slidability between the cleaning blade and the photoconductor is improved, and fine vibration of the cleaning blade is reduced, so that the toner can be prevented from slipping through. If it exceeds 0.960, the abrasive external additive may slip through without accumulating in the cleaning portion, and if it is less than 0.750, the amount of wear of the photoconductor increases. The measurement of the circularity coefficient is performed using a flow-type particle image analyzer “FPIA”.
-2000 "(manufactured by Toa Medical Electronics Co., Ltd.).

<Inorganic / Organic Composite Fine Particles> In the present invention, inorganic / organic composite fine particles are preferably used as an abrasive external additive. The inorganic / organic composite fine particles have a spherical shape,
The surface is made of inorganic fine particles with a high hardness, and the core is made of organic fine particles with relatively elasticity, so it does not accelerate the wear of the photoreceptor and does not damage the photoreceptor or the cleaning blade. Demonstrates cleaning properties.

The primary average particle diameter of the inorganic fine particles constituting the inorganic / organic composite fine particles is preferably from 5 to 100 nm from the viewpoint of improving the cleaning property, the polishing property and the filming resistance. In addition, the primary average particle diameter of the inorganic fine particles refers to the number-based average particle diameter measured by image analysis under observation with a scanning electron microscope.

As a constituent material of the inorganic fine particles, for example,
Silicon oxide, titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, cerium oxide, tungsten oxide, antimony oxide, copper oxide, tellurium oxide, manganese oxide, barium titanate, strontium titanate, magnesium titanate, silicon nitride, carbon nitride Are used.

The organic fine particles constituting the inorganic / organic composite fine particles include, for example, acrylic polymers, styrene polymers,
The resin particles are preferably made of a styrene-acrylic polymer or the like.

The acrylic polymer is, for example, a homopolymer or a copolymer obtained by polymerizing a monomer selected from acrylic acid or acrylic acid ester, methacrylic acid or methacrylic acid ester. Examples of the acrylic monomer used to obtain such an acrylic polymer include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, and n-acrylic acid. Octyl, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-chloromethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid Propyl, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid Methylaminoethyl and diethylaminoethyl methacrylate, and the like.

Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene and p-methylstyrene.
Methyl styrene, α-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, p- Examples thereof include n-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene.

A styrene polymer can be obtained from one or more of the above-mentioned styrene monomers. In the present invention, one or more other monomers may be copolymerized as necessary. May be used. In this case, it is preferable to use a styrene-based monomer in a proportion of 50% by mass or more in the monomer composition.

The styrene-acrylic copolymer is obtained from one or more of the above-mentioned acrylic monomers and one or more of the above-mentioned styrene monomers. May be copolymerized by one kind or two or more kinds. In this case, in the monomer composition, it is preferable to use the acrylic monomer and the styrene monomer in a ratio of 50% by mass or more. As the other monomer, for example, acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide, vinyl acetate, vinyl butyrate, vinyl esters such as vinyl benzoate, vinyl methyl ether, vinyl ethyl ether and the like Vinyl ethers, vinyl ketones such as vinyl methyl ketone, dienes such as butadiene and isoprene, unsaturated carboxylic acids such as maleic acid and fumaric acid, and the like.

The average particle size of the organic fine particles constituting the inorganic / organic composite fine particles is preferably from 0.1 to 4.5 μm from the viewpoints of improvement in cleaning properties and stability of triboelectric charging.
2-3.0 μm is more preferred. The average particle size of the organic fine particles refers to a laser diffraction particle size distribution analyzer “HELOS” equipped with a wet disperser (Sympatech (S
YMPATEC Co., Ltd.). However, before measurement, the number of organic fine particles is 10 m.
g was dispersed in 50 mL of water together with a surfactant, and then a pretreatment was performed by an ultrasonic homogenizer for 1 to 10 minutes while paying attention to reaggregation due to heat generation.

The inorganic / organic composite fine particles are constituted by fixing the above-mentioned inorganic fine particles on the surface of the organic fine particles. Here, the term “fixed” refers to a state in which the inorganic fine particles are not simply attached to the organic fine particles by electrostatic force, but the length of the inorganic fine particles embedded in the organic fine particles is 5 to 95%. Such a state can be confirmed by observing the surface of the inorganic / organic composite fine particles with a transmission electron microscope or a normal electron microscope. In fixing the inorganic fine particles to the surface of the organic fine particles, it is preferable to first make the organic fine particles spherical, and then to fix the inorganic fine particles to the surface of the organic fine particles. This is because when the organic fine particles are spherical, the inorganic fine particles are uniformly fixed, and the release of the inorganic fine particles is effectively prevented. Means for spheroidizing the organic fine particles include, for example, a method in which the organic fine particles are once melted by heat and then spray granulation, a method in which the hot-melted organic fine particles are jetted into water to form a sphere, and a suspension weight. A method of synthesizing spherical organic fine particles by a synthetic method or an emulsion polymerization method is exemplified.

As a means for fixing the inorganic fine particles on the surface of the organic fine particles, for example, a method of mixing the organic fine particles and the inorganic fine particles and then applying heat, a so-called method of mechanically fixing the inorganic fine particles on the surface of the organic fine particles. A mechanochemical method or the like is used. Specifically, the organic fine particles and the inorganic fine particles are mixed, and the mixture is stirred and mixed by a Henschel mixer, a V-type mixer or a turbular mixer, and the inorganic fine particles are attached to the surface of the organic fine particles by electrostatic force, and then atomized, sprayed. A method in which heat is applied to a heat treatment apparatus such as a dryer to apply heat to soften the surface of the organic fine particles to fix the inorganic fine particles to the surface. After the inorganic fine particles are attached to the surface of the organic fine particles by electrostatic force, mechanical energy is applied. The method of fixing inorganic fine particles to the surface of the organic fine particles using a device capable of imparting the fine particles, for example, a device such as an ong mill, a free mill, and a hybridizer is used.

The fixing rate of the inorganic fine particles to the organic fine particles is determined as follows. (BET specific surface area of inorganic / organic composite fine particles) / {(BET specific surface area of inorganic particles to be used) + (BET specific surface area of organic particles to be used)} × 100 The BET specific surface area is measured by an automatic specific surface area measuring device “GEMINI”.
2375 "(manufactured by Shimadzu Corporation) using the BET one-point method.

In obtaining the inorganic / organic composite fine particles, the blending amount of the inorganic fine particles with respect to the organic fine particles may be an amount capable of uniformly covering the surface of the organic fine particles. Specifically, although it depends on the specific gravity of the inorganic fine particles, it is usually 5 to 100% by mass, preferably 5 to 80% by mass based on the organic fine particles.
Inorganic fine particles are used in a ratio of mass%. When the proportion of the inorganic fine particles is less than 5 parts by mass, the cleaning property tends to decrease, and when the proportion of the inorganic fine particles exceeds 100 parts by mass, the inorganic fine particles are easily released.

<Abrasive External Additives Other than Inorganic / Organic Composite Fine Particles> In the present invention, examples of the abrasive external additives other than the inorganic / organic composite fine particles include calcium titanate powder, barium titanate powder, and magnesium titanate. Powder, strontium titanate powder, cerium oxide powder,
It is preferable to use zirconium oxide powder, titanium oxide powder, aluminum oxide powder, boron carbide powder, silicon carbide powder, silicon oxide powder, diamond powder, or the like, alone or in combination. Of these, strontium titanate powder is more preferred.

[External Additive] As the external additive present on the toner surface, it is preferable that silica particles and titanium oxide particles are present in addition to the above-mentioned abrasive external additive.
Further, if necessary, alumina, tin oxide, iron oxide or the like may be used in combination.

In order to obtain particularly good cleaning properties,
It is preferable to externally add two kinds of silica particles having different number average particle diameters and two kinds of titanium oxide particles having different number average particle diameters.

The two kinds of silica particles having different number average particle diameters and the two kinds of titanium oxide particles having different number average particle diameters are:
Small particle size silica having a number average particle size of 0.005 to 0.015 μm, large particle size silica having a number average particle size of 0.020 to 0.080 μm, and a number average particle size of 0.015 to 0.070 μm
m having a small particle size of titanium oxide and a number average particle size of 0.08 to
It is a large particle size titanium oxide of 0.2 μm.

The silica particles used in the present invention are generally
Although it is produced by a wet method or a dry method, a so-called fumed silica produced by a dry method (vapor phase oxidation of a silicon halide compound) is particularly preferred from the viewpoint of fluidity. This is manufactured by a conventionally known technique. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl In this manufacturing process, for example, by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide, a composite of silica and another metal oxide can be obtained. It is also possible to obtain a fine powder, and the silica core in the present invention also includes them.

The number average particle size is 0.005 to 0.015 μm
It is preferable to add 0.1 to 0.8 parts by mass of the small-particle-size silica particles of m with respect to 100 parts by mass of the toner (without adding external additives).

Examples of the silica particles include those commercially available under the following trade names.

AEROSIL 130, 200, 200
V, 200CF, 200FAD, 300, 300CF,
80 (manufactured by Nippon Aerosil Co., Ltd.), Cab-O-SilM-
5, MS-7D, MS-75D, H-5, HS-5, E
H-5 (manufactured by CABOT), Wacker HDK N
20, S13, V15, T30, T40 (WACKER
-CHFMIEGMBH) and the like.

Further, examples of the silica particles subjected to the hydrophobic treatment include those commercially available under the following trade names, for example.

HDK H2000, 2000/4, 30
04, 2050EP, HVK21 (manufactured by Clariant), R972, R974, RX200, RY200,
R202, R805, R812 (Nippon Aerosil Co., Ltd.)
etc.

The number average particle size is 0.020 to 0.080 μm
The addition amount of the large-diameter silica particles m is preferably 0.2 to 1.2 parts by mass, and more preferably 0.3 to 0.8 parts by mass with respect to 100 parts by mass of the toner (without adding external additives). More preferred.

Examples of the silica particles include those commercially available under the following trade names.

AEROSIL OX50, AEROSI
L50, TT600, MOX80, MOX170 (manufactured by Nippon Aerosil Co., Ltd.) and the like.

Further, examples of the silica particles subjected to the hydrophobic treatment include those commercially available under the following trade names, for example.

TS630 (manufactured by Cabot), NA-5
0H (manufactured by Kao Corporation), RY-50, NY-50, NAX-
50, RX-50, RM-50 (manufactured by Nippon Aerosil Co., Ltd.)
etc.

The titanium oxide particles used in the present invention are produced by a sulfuric acid method and a chlorine method.

The titanium oxide particles have a rutile type, an anatase type, a mixed crystal type of rutile and anatase, an amorphous type and a mixed type thereof, and all of them can be used. However, from the viewpoint of ensuring fluidity and reducing the environmental dependence of charging, titanium oxide particles in which the ratio between rutile-type titanium oxide and anatase-type titanium oxide is in the range of 2:98 to 45:55 by mass is preferable. Used. Further, it is preferable that the particle surface of the rutile-containing / anatase mixed titanium oxide is coated with a layer containing one or more elements of aluminum, silicon, titanium, zirconium and tin. That is, it is preferable that the surface of the particles before the treatment with the silane coupling agent is coated with a layer containing the predetermined element.

The reason why the layer is coated before the silane coupling agent treatment is performed is to adjust the charging property and the resistance. The treatment amount of the element is preferably 3 to 20% by mass. 3
If the amount is less than 20% by mass, it is difficult to obtain the effect of adjusting the charge.
If it exceeds 0% by mass, coalescence of the particles occurs, which may not be preferable.

The number average particle size is 0.015 to 0.070 μm
The addition amount of the titanium oxide particles having a small particle size of m is preferably 0.1 to 0.8 parts by mass, more preferably 0.2 to 0.8 parts by mass, per 100 parts by mass of the toner (without adding any external additives). Is more preferred.

As the above-mentioned titanium oxide particles, there are, for example, those commercially available under the following trade names.

P-25 (manufactured by Degussa), IT-S, I
T-PA, IT-PB (made by Idemitsu Kosan Co., Ltd.), R-820,
R-830, R-680, CR-50, CR-60, A
-100, A-220 (manufactured by Ishihara Sangyo), MT-100
SA, MT-150W, MT-500B, MT-600
B (manufactured by Teica).

Examples of commercially available titanium oxide particles subjected to a hydrophobic treatment include those commercially available under the following trade names, for example.

STT-30A, STT-30AS, ST
T-30S (manufactured by Titanium Industries), T-805 (manufactured by Nippon Aerosil), TTO-51 (manufactured by Ishihara Sangyo), TAF
-1500S (manufactured by Fuji Titanium Industry Co., Ltd.), MT-100
S, MT-100T (manufactured by Teica) and the like.

The number of added parts of the large-diameter titanium oxide particles having a number average particle diameter of 0.08 to 0.2 μm is 0.2 to 1.2 parts by mass based on 100 parts by mass of the toner (without adding external additives). And more preferably 0.3 to 1.0 part by mass.

As the above-mentioned titanium oxide particles, there are, for example, those commercially available under the following trade names.

TTO-51 (A), TTO-51 (B)
(Manufactured by Ishihara Sangyo), TAF-620 (manufactured by Fuji Titanium), and the like.

[0119] Commercially available hydrophobic titanium oxide particles include, for example, those commercially available under the following trade names.

STT-60J (manufactured by Titanium Industry Co., Ltd.), JA
-1, JA-3, JA-4, JA-5 (manufactured by Teica),
TAF-520, TAF-520AS, TAF-520
K (Fuji Titanium Industry Co., Ltd.) and the like.

<Preferably Used Coupling Agent> Hydrophilic fine particles can be obtained by treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane or octyltrimethoxysilane. . Hereinafter, specific examples of the coupling agent will be described.

CH ₃ (CH ₂ ) ₂ SiCl ₃ CH ₃ (CH ₂ ) ₅ SiCl ₃ CH ₃ (CH ₂ ) ₇ SiCl ₃ CH ₃ (CH ₂ ) ₉ SiCl ₃ CH ₃ (CH ₂ ) ₉ Si (OCH ₃ ) ₃ CH ₃ (CH ₂ ) ₉ Si (CH ₃ ) Cl ₂ CH ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ CH ₃ (CH _{2) 5 Si (OCH 3)} 3 CH 3 (CH 2) 5 CONH (CH 2) 2 Si (OC 2 H 5) 3 CH 3 (CH 2) 4 COO (CH 2) 2 Si (OCH 3) 3 CH _{3 (CH 2) 9 Si (} OCH 3) 3 CH 3 (CH 2) 9 Si (CH 3) (OCH 3) 2 CH 3 (CH 2) 7 SO 2 NH (CH 2) 3 Si (OC 2 H 5 )
_{3 CH 3 (CH 2) 8} (CH 2) 2 Si (OCH 3) 3 CF 3 (CH 2) 2 SiCl 3 CF 3 (CF 2) 5 SiCl 3 CF 3 (CF 2) 5 (CH 2) 2 SiCl _{3 CF 3 (CF 2) 7} (CH 2) 2 SiCl 3 CF 3 (CF 2) 7 CH 2 CH 2 Si (OCH 3) 3 CF 3 (CF 2) 7 (CH 2) 2 Si (CH 3) Cl _{2 CF 3 (CH 2) 2} Si (OCH 3) 3 CF 3 (CH 2) 2 Si (CH 3) (OCH 3) 2 CF 3 (CF 2) 3 (CH 2) 2 Si (OCH 3) 3 CF _{3 (CF 2) 5 CONH (} CH 2) 2 Si (OC 2 H 5) 3 CF 3 (CF 2) 4 COO (CH 2) 2 Si (OCH 3) 3 CF 3 (CF 2) 7 (CH 2) _{2 Si (OCH 3) 3 CF} 3 (CF 2) 7 (CH 2) 2 Si (CH 3) (OCH 3) 2 CF 3 (CF 2) 7 SO 2 NH (CH 2 ) ₃ Si (OC ₂ H ₅ )
₃ CF ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) _{3 and the} like.

Further, hydrophobic fine particles can be obtained by polysiloxane treatment. The treatment amount is preferably from 10 to 100% by mass, more preferably from 20 to 70% by mass, based on the silica particles or titanium oxide particles. When the treatment amount is less than 10% by mass, not only those having low hydrophobicity can be obtained, but also the solid fixation occurs during drying, resulting in poor dispersion. When the treatment amount exceeds 100% by mass, the specific surface area decreases. Is not preferred.

From the viewpoint of enhancing the fluidity and the dependence of charging on the environment, the hydrophobicity of the silica particles is preferably from 30 to 100, more preferably from 60 to 95. Moreover, the hydrophobicity of the titanium oxide particles is preferably from 20 to 90, and more preferably from 30 to 70.

<Various measuring methods> (1) Specific surface area The specific surface area was measured by an automatic specific surface area measuring apparatus "GEMINI 2375" (manufactured by Shimadzu Corporation) by the BET one-point method.

(2) Degree of hydrophobicity 0.1 g of hydrophobic titanium oxide fine powder was added to 50 mL of water, and methanol was poured into the water at a rate of 2 mL / min with stirring using a microtube pump to start sedimentation of the fine powder. The methanol concentration at the time of drying and the methanol concentration at the time of complete wetting were determined.

(3) Particle Size of External Additive The particle size of the external additive on the surface of the toner was measured using a field effect scanning electron microscope “JSM6400F” (acceleration voltage: 5 kV, magnification: 4).
) And analyzed with an image analyzer to determine.

(4) Abundance of Elements The abundances of the silica element, titanium element, and carbon element were determined by the ES
Using CA-1000 (manufactured by Shimadzu Corporation), the area ratio occupied by each element was determined from the relative intensity ratio of carbon, oxygen, silica, and titanium atoms.

<Amount of External Additive> The amount of the external additive to be added is preferably 0.1 to 5% by mass based on the toner particles without the external additive.

When the external additive present on the toner surface is 0.0
The number of external additives is 65 to 0.025 μm.
% To 95%, 0.025 to 0.080 μm is 4 to 35% of the total number of additives, 0.080 to 0.500
It is preferred that the particle size of μm is 0.3 to 10% by number of the total number of additives.

The external additive adhering with a particle size of 0.005 to 0.025 μm is preferably 65 to 95% by number from the viewpoint of obtaining high fluidity and making the charge amount distribution uniform. 65
If it is less than a few percent, fluidity is insufficient, cleaning is poor,
This tends to cause problems such as generation of toner granules. Here, the term “adhesion” does not refer to a state in which the external additive is buried in the toner particles, but refers to a state in which the external additives are simply attached to the surface of the toner particles by electrostatic force or the like. On the other hand, if it exceeds 95% by number, the external additive is easily buried when the toner is used for a long period of time in the developing device or when the toner recycling system is employed, which is liable to cause fogging and poor cleaning due to a decrease in the charge amount.

The external additive adhering with a particle size of 0.025 to 0.080 μm is a region having both a burying prevention function and a fluidity imparting function, and is adhering at a ratio of 4 to 35% by number. Is preferable, and 5 to 20% by number is more preferable. If it is less than 4% by number, the burying prevention function is insufficient, and if it exceeds 35% by weight, some external additives are detached from the toner, and a problem such as contamination of a triboelectric charging member such as a carrier or a member such as a photoreceptor easily occurs. .

The external additive adhering at a particle size of 0.080 to 0.500 μm is a region having an effect of improving transferability in addition to a function of preventing burial, and 0.3 to 10% by number.
Is preferable, and 0.8 to 5% by number is more preferable. When the amount is less than 0.3% by number, the above-mentioned effects are not exhibited. When the amount exceeds 10% by weight, some external additives are detached, and there is a problem that a frictional charging member such as a carrier or a member such as a photoreceptor is contaminated. Cheap.

In the present invention, the fatty acid metal salt and the abrasive external additive only need to be contained in the toner, and the external additive is preferably attached to the toner particles in a certain amount.

[Cleaning Blade] The cleaning mechanism of the present invention will be described.

FIG. 1 is a block diagram showing an example of the cleaning mechanism according to the present invention. In FIG. 1, 1 is an elastic cleaning blade, 2 is an image forming body, 3 is a holder, and 4 is a member for applying a contact pressure to the cleaning blade. The cleaning blade is in contact with the image forming body 2 while applying a certain amount of contact pressure while the base of the cleaning blade 1 is held by the holder 3. At the time of cleaning, the contact pressure is applied by the cleaning blade 4.

The image forming member 2 is a photosensitive member in the electrophotographic system, and is most often formed on a drum-shaped support. In FIG. 1, the arrow is the traveling direction. Reference numeral 6 denotes a guide plate for guiding the toner on the image forming body 2 scraped off by the elastic cleaning blade to the waste toner transport unit 5. Since the guide plate 6 is thin and soft, the toner adhering to the image forming body once passes under the image forming body,
It is scraped off with an elastic cleaning blade. Reference numeral 7 denotes an outer wall of the cleaning mechanism.

FIG. 2 is a diagram showing a situation in which the toner on the image forming body 2 is scraped off by the elastic cleaning blade 1.

FIG. 3 is a view for explaining an intersection angle φ between the holder 3 of the elastic cleaning blade 1 and the image forming body 2.

That is, when the intersection angle φ is less than 90 °,
When the extension line is extended in the direction (Y-Y) in which the elastic cleaning blade of the holder is supported, and a tangent line (XX) is drawn on the surface of the image forming body at a position reaching the surface of the image forming body, the tangent line and the extension This means that the angle between the lines is less than 90 °. P indicates the intersection of XX and YY.

If this angle is 90 ° or more and sufficient cleaning performance is to be ensured, toner having no corners,
That is, there is a problem that the toner produced by the polymerization method slips through the cleaning blade and contaminates the image. Although there is no particular lower limit angle, it is preferably 15 ° or more in terms of cleaning power. A preferable angle range is 20 to 90 °, more preferably 25 to 80 °.

As the material of the elastic cleaning blade used in the present invention, for example, urethane rubber, silicone rubber, fluorine rubber, chloroprene rubber, butadiene rubber and the like can be used. In particular, urethane rubber-based materials are preferable, and in particular, JP-A-59-3057.
No. 4, containing 30% by mass or more of a caprolactone ester component, and having an average molecular weight of 1,000 to 4,000.
A urethane rubber obtained by reacting and curing the polycaprolactone ester and polyisocyanate is preferred.

The average molecular weight is defined as the amount of potassium hydroxide that neutralizes acetic acid generated when an acetylation reaction is performed on polycaprolactone ester using an acetylation reagent consisting of acetic anhydride and pyridine to determine the amount of terminal OH. The group was quantified and the number average molecular weight was calculated.

The general formula of the polycaprolactone ester preferably used in the present invention can be shown below.

HO-[-X _1- ] _m -R-[-X _2- ] _n -OH Here, X ₁ and X ₂ are cleavage residues of a caprolactone ring, and are the same or different from each other. Alternatively, the sum of m and n is in the range of 2 to 35, and m: n = 3: 1 to 1: 3. R is a linking group of X ₁ and X ₂ having 300 carbon atoms.
These are the following divalent organic groups.

The compound represented by the above general formula has an average molecular weight of 1,000 to 4,000, and the content of the caprolactone ester component is 30% by mass or more.

In order to produce this polycaprolactone ester, the same or different caprolactone compounds 2
One mole of the polymerization initiator is added to 35 moles,
The polycaprolactone ester having an average molecular weight of 1,000 to 4,000 is obtained by ring-opening addition polymerization at 0 to 300 ° C. Examples of the polymerization initiator include -OH group, -N
An organic compound having two or more active hydrogens such as an H ₂ group or a —SH group can be given.

The caprolactone compound for forming the caprolactone ring-cleaving residue represented by the above general formula is a compound having a 3- to 7-membered ring and having 6 carbon atoms. Those to which a lower alkyl group such as a methyl group or an ethyl group is bonded are also included.

Specific examples are shown below.

[0150]

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[0151]

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Examples of the polymerization initiator for forming the linking group R in the above general formula include the following compound examples.

[0153]

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[0154]

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[0155]

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[0156] Commercially available polycaprolactone esters suitably used for the cleaning blade according to the present invention include, for example, those having the following trade names.

"NIAXPCP 0240" (manufactured by Union Carbide) "CATA 220" (manufactured by Rapolde) "ODX 640" (manufactured by Dainippon Ink and Chemicals) It reacts to form urethane rubber, which is the material of the cleaning blade according to the present invention. Here, as the polyisocyanate, for example, the following can be mentioned as preferable ones.

[0158]

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[0159]

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[0160]

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[0161]

Embedded image

[0162]

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The following are specific examples of the curing agent.

[0164]

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[0165]

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As a method for producing a cleaning blade composed of the above polycaprolactone ester, etc.,
Although not particularly limited, for example, the following methods can be mentioned.

That is, the dehydrated polycaprolactone ester and polyisocyanate are mixed and reacted at a temperature of 70 to 150 ° C. for 10 to 120 minutes to produce a urethane prepolymer. And a liquid rubber composition by adding a curing agent in such a ratio that the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups and / or amino groups by the polyester and the curing agent becomes 1.00 to 1.30. Making,
This rubber composition is poured into a centrifugal casting machine kept at a temperature of 140 ° C., for example. Next, the film is stretched to a uniform thickness on the inner surface of the rotor by the centrifugal force rotated at a high speed to form a cylindrical film. Thereafter, a cross-linking reaction by the curing agent proceeds and is solidified to form a urethane rubber.

In the present invention, the elastic cleaning blade has a pressing force of 150 to 250 mN / cm during use.
The hardness is 60-90 ° measured according to JIS K 6301, and the tensile strength is 2500 N / c.
m ² or more and rebound resilience of 200 N / cm ² or more are preferable. Preferably, the tensile strength is 2500-8000
N / cm ² , more preferably 3000-6000 N / c
m ^2, the rebound resilience 200~1000N / cm ^2, more preferably from 300~900N / cm ^2.

Next, the image forming body having the organic photosensitive layer used in the present invention will be described. "Image forming body (photoreceptor)" An image forming body having an organic photosensitive layer (hereinafter, also simply referred to as a photoreceptor) is at least one of a charge generation function and a charge transport function indispensable for the constitution of an electrophotographic photoreceptor. Means an electrophotographic photoreceptor composed of an organic compound having a function, a photoreceptor composed of a known organic charge generating substance or an organic charge transporting substance, composed of a polymer complex for the charge generating function and the charge transporting function. All known organic electrophotographic photoreceptors such as the photoreceptor thus obtained are contained.

The structure of the photoreceptor used in the present invention will be described below. <Conductive support> The conductive support used for the photoreceptor may be in the form of a sheet or a cylinder. However, in order to design an image forming apparatus compactly, the conductive support is preferably a cylindrical support. Is preferred.

The cylindrical conductive support means a cylindrical support necessary for forming an image endlessly by rotating, and has a straightness of 0.1 mm or less and a run-out of 0.1 mm.
Conductive supports in the following ranges are preferred. Exceeding the ranges of the roundness and the shake make it difficult to form a good image.

As the conductive material, a metal drum of aluminum, nickel, or the like, a plastic drum on which aluminum, tin oxide, indium oxide, or the like is deposited, or a paper / plastic drum coated with a conductive substance can be used. The conductive support has a specific resistance of 10 at room temperature.
^It is preferably ³ Ωcm or less.

The conductive support may have a surface on which a sealed alumite film is formed. Alumite treatment is usually performed, for example, chromic acid, sulfuric acid, oxalic acid,
Although the treatment is performed in an acidic bath such as phosphoric acid, boric acid, and sulfamic acid, anodizing treatment in sulfuric acid gives the most preferable results. In the case of anodizing treatment in sulfuric acid, the sulfuric acid concentration is 100
~ 200g / L, aluminum ion concentration is 1 ~ 10g
/ L, the liquid temperature is preferably about 20 ° C., and the applied voltage is preferably about 20 V, but is not limited thereto. The average thickness of the anodic oxide coating is usually 20 μm or less, especially 10 μm.
μm or less is preferred.

<Intermediate Layer> In order to improve the adhesion between the conductive support and the photosensitive layer or to prevent charge injection from the support, an intermediate layer (undercoat) is provided between the support and the photosensitive layer. (Including a layer). Examples of the material for the intermediate layer include polyamide resins, vinyl chloride resins, vinyl acetate resins, and copolymer resins containing two or more of the repeating units of these resins. Among these undercoating resins, polyamide resin is preferable as a resin capable of reducing an increase in residual potential due to repeated use. The thickness of the intermediate layer using these resins is preferably 0.01 to 0.5 μm.

As the material for the intermediate layer, a curable metal resin obtained by thermally curing an organic metal compound such as a silane coupling agent and a titanium coupling agent may also be used. The thickness of the intermediate layer using a curable metal resin is preferably 0.1 to 2 μm.

<Photosensitive Layer> The structure of the organic photosensitive layer may be a single-layered photosensitive layer having a charge generation function and a charge transport function on the intermediate layer in one layer. Functions include charge generation layer (CGL) and charge transport layer (CT
It is preferable to adopt a configuration separated into L). By adopting a configuration in which functions are separated, the increase in residual potential due to repeated use can be controlled to be small, and other electrophotographic characteristics can be easily controlled according to the purpose. It is preferable that the photoreceptor for negative charging has a configuration in which a charge generation layer (CGL) is provided on the intermediate layer and a charge transport layer (CTL) is provided thereon. In the case of a positively charged photoreceptor, the order of the layer configuration is opposite to that of the negatively charged photoreceptor. The most preferred photosensitive layer configuration of the present invention is a negatively charged photosensitive layer configuration having the function separation structure.

The structure of the photosensitive layer of the function-separated negatively charged photosensitive member will be described below. <Charge generation layer> The charge generation layer has a charge generation material (CGM)
It contains. As other substances, a binder resin and other additives may be contained as necessary.

As the charge generating substance (CGM), a known charge generating substance (CGM) can be used. For example,
Phthalocyanine pigments, azo pigments, perylene pigments, azurenium pigments and the like can be used. Among them, CGM that can minimize the increase in residual potential due to repeated use
Has a steric and potential structure capable of forming a stable aggregation structure among a plurality of molecules, and specifically includes CGM of a phthalocyanine pigment and a perylene pigment having a specific crystal structure. For example, Bragg angle 2θ for Cu-Kα ray
CGM such as titanyl phthalocyanine having a maximum peak at 27.2 °, and benzimidazole perylene having a maximum peak at 2θ of 12.4 have almost no deterioration due to repeated use and can reduce the increase in residual potential.

In the case where a binder is used as a CGM dispersion medium in the charge generation layer, a known resin can be used as the binder. Preferred resins are formal resin, butyral resin, silicone resin, silicone-modified butyral resin, and phenoxy resin. And the like. The ratio between the binder resin and the charge generating substance is preferably from 20 to 600 parts by mass per 100 parts by mass of the binder resin.
By using these resins, an increase in residual potential due to repeated use can be minimized. The thickness of the charge generation layer is preferably from 0.01 to 2 μm.

<Charge Transport Layer> The charge transport layer contains a charge transport material (CTM) and a binder resin for dispersing the CTM and forming a film. As other substances, additives such as antioxidants may be contained as necessary.

As the charge transport material (CTM), a known charge transport material (CTM) can be used. For example,
Triphenylamine derivatives, hydrazone compounds, styryl compounds, benzidine compounds, butadiene compounds and the like can be used. These charge transport materials are usually dissolved in a suitable binder resin to form a layer. Among these, the CTM that can reduce the increase in residual potential due to repeated use has a high mobility and an ionization potential difference from the combined CGM of 0.5 (eV) or less. 25 (eV) or less.

The ionization potential of CGM and CTM is measured with a surface analyzer AC-1 (manufactured by Riken Keiki Co., Ltd.).

Examples of the resin used for the charge transport layer (CTL) include polystyrene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin,
Phenolic resin, polyester resin, alkyd resin,
Polycarbonate resins, silicone resins, melamine resins, and copolymer resins containing two or more of the repeating units of these resins, as well as these insulating resins, and high-molecular organic compounds such as poly-N-vinylcarbazole Semiconductors.

Preferred as a binder for these CTLs are polycarbonate resins. Polycarbonate resins are most preferred for improving the dispersibility and electrophotographic properties of CTM. The ratio of the binder resin and the charge transporting material is 10 to 2 with respect to 100 parts by mass of the binder resin.
00 parts by mass is preferred. The charge transport layer has a thickness of 10 to 10.
40 μm is preferred.

<Protective Layer> Various resin layers can be provided as a protective layer of the photoreceptor. In particular, by providing a crosslinked resin layer, the organic photoreceptor of the present invention having high mechanical strength can be obtained.

Examples of the solvent or dispersion medium used for forming the intermediate layer, photosensitive layer, protective layer and the like include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethyl. Formamide, acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloromethane, 1,2-dichloroethane, 1,
2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane, tetrahydrofuran, dioxolan, dioxane, methanol, ethanol, butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl Cellosolve and the like. Although the present invention is not limited to these, dichloromethane, 1,2-dichloroethane, methyl ethyl ketone and the like are preferably used. These solvents can be used alone or as a mixture of two or more.

As a coating method for manufacturing the photoreceptor, a coating method such as dip coating, spray coating, circular amount control type coating and the like is used. It is preferable to use an application processing method such as spray application or circular amount control type (a typical example is a circular slide hopper type) application so as not to dissolve as much as possible and to achieve uniform application processing. It is most preferable that the protective layer according to the present invention uses the above-mentioned circular amount control type coating processing method. The circular amount control type coating is described in, for example, JP-A-58-18.
No. 9061 discloses this in detail.

Next, a method for producing the toner used in the present invention will be described. "Production Method of Toner" The toner of the present invention can be prepared by a suspension polymerization method or a liquid containing an emulsion of necessary additives (in an aqueous medium).
Emulsion polymerization or mini-emulsion polymerization of monomers to produce fine resin particles, add charge controllable resin particles, and then add an organic solvent, a coagulant such as salts, etc. It can be produced by a method of aggregating and fusing particles.

<Suspension polymerization method> One example of a method for producing the toner of the present invention is as follows. A charge control resin is dissolved in a polymerizable monomer, and a colorant and, if necessary, a release agent. Various constituent materials such as a polymerization initiator are added, and the various constituent materials are dissolved or dispersed in the polymerizable monomer using a homogenizer, a sand mill, a sand grinder, an ultrasonic disperser, or the like.
The polymerizable monomer in which the various constituent materials are dissolved or dispersed is dispersed in an aqueous medium containing a dispersion stabilizer into oil droplets having a desired size as a toner by using a homomixer, a homogenizer, or the like. Thereafter, the stirring mechanism is moved to a reaction device (stirring device), which is a stirring blade described later, and heated to cause the polymerization reaction to proceed. After the reaction, remove the dispersion stabilizer,
The toner of the present invention is produced by filtration, washing, and drying. In addition, the aqueous medium is at least 5% water.
It shows a content of 0% by mass or more.

<Emulsion Polymerization> Another method for producing the toner of the present invention is to salt out resin particles in an aqueous medium,
A method of producing by agglomeration and fusion can also be mentioned.
Although this method is not particularly limited, for example, JP-A-5-265252 and JP-A-6-32
No. 9947 and Japanese Patent Application Laid-Open No. 9-15904.

That is, a method of salting out, aggregating, and fusing a plurality of fine particles composed of a resin, a colorant, and the like, or a dispersion of resin particles and constituent materials such as a colorant, etc. After dispersing by using, a coagulant having a critical coagulation concentration or more is added and salting out.At the same time, the formed polymer itself is heat-fused at a temperature equal to or higher than the glass transition temperature to form a fused particle. When the target particle size is reached, a large amount of water is added to stop the particle size growth, and the particle surface is smoothed while heating and stirring to control the shape. By heating and drying in the state, the toner of the present invention can be formed. Here, a solvent that is infinitely soluble in water such as alcohol may be added together with the coagulant.

<Composite Resin Particles Obtained by Multi-Stage Polymerization> As typical examples of the method for producing a toner by an emulsion polymerization method, examples of composite resin particles obtained by a multi-stage polymerization are shown. It is preferable that a region other than the outermost layer of the composite resin particles contains a release agent.

The toner manufacturing process mainly includes the following steps. 1: Multi-stage polymerization step for obtaining composite resin particles in which the release agent is contained in a region other than the outermost layer (center or intermediate layer) 2: Salting out / fusing the composite resin particles and the colorant particles 3: Salting out / fusing step of obtaining toner particles by filtration: filtering the toner particles from the dispersion system of the toner particles,
A filtration / washing step of removing a surfactant or the like from the toner particles; a drying step of drying the washed toner particles; and a step of adding an additive to the dried toner particles.

Hereinafter, each step will be described in detail. << 1: Multi-stage polymerization step >> The multi-stage polymerization step is a step of producing composite resin particles by a multi-stage polymerization method in which a coating layer made of a monomer polymer is formed on the surface of the resin particles.

From the viewpoints of production stability and the crushing strength of the obtained toner, it is preferable to employ a multi-stage polymerization method of three-stage polymerization or more.

The two-stage polymerization method and the three-stage polymerization method, which are typical examples of the multi-stage polymerization method, will be described below.

(Two-Stage Polymerization Method) The two-stage polymerization method comprises a central portion (nucleus) formed of a high molecular weight resin containing a release agent and an outer layer (shell) formed of a low molecular weight resin. This is a method for producing composite resin particles.

More specifically, this method is described below. First, a release agent is dissolved in a monomer to prepare a monomer solution, and this monomer solution is dissolved in an aqueous medium (for example, an aqueous surfactant solution). After the oil droplets are dispersed, the system is subjected to a polymerization treatment (first-stage polymerization) to prepare a dispersion of high-molecular-weight resin particles containing a release agent.

Next, a polymerization initiator and a monomer L for obtaining a low molecular weight resin were added to the dispersion of the resin particles.
Polymerization treatment of monomer L in the presence of resin particles (second stage polymerization)
Is performed to form a coating layer made of a low molecular weight resin (monomer polymer) on the surface of the resin particles.

(Three-stage polymerization method) In the three-stage polymerization method, a central portion (nucleus) formed of a high molecular weight resin, an intermediate layer containing a release agent, and an outer layer (shell) formed of a low molecular weight resin are used. This is a method for producing composite resin particles.

The method will be described in detail. First, a dispersion of resin particles obtained by a polymerization treatment (first stage polymerization) according to a conventional method is added to an aqueous medium (for example, an aqueous solution of a surfactant). Along with the addition, the monomer solution obtained by dissolving the release agent in the monomer M in the aqueous medium is dispersed in oil droplets, and then the system is subjected to a polymerization treatment (second stage polymerization).
A coating layer (intermediate layer) made of a resin (polymer of monomer M) containing a release agent is formed on the surface of the resin particles (core particles) to form a composite resin particle (high molecular weight resin-intermediate molecular weight resin). )
To prepare a dispersion.

Next, a polymerization initiator and a monomer L for obtaining a low molecular weight resin are added to the obtained dispersion of the composite resin particles, and the monomer L is subjected to a polymerization treatment in the presence of the composite resin particles. By performing (third stage polymerization), a coating layer made of a low molecular weight resin (polymer of monomer L) is formed on the surfaces of the composite resin particles. In the above method, by incorporating the second-stage polymerization, the release agent can be finely and uniformly dispersed, which is preferable.

One feature of the method for producing a toner according to the present invention is to polymerize a polymerizable monomer in an aqueous medium. That is, when forming the resin particles (core particles) or the coating layer (intermediate layer) containing the release agent, the release agent is dissolved in the monomer, and the resulting monomer solution is oiled in an aqueous medium. In this method, latex particles are obtained by dispersing droplets, adding a polymerization initiator to the system, and performing a polymerization treatment.

The aqueous medium referred to in the present invention is water 50 to 10
A medium comprising 0% by mass and 0 to 50% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include, for example, methanol, ethanol, isopropanol, butanol,
Acetone, methyl ethyl ketone, tetrahydrofuran and the like can be exemplified, and an alcohol-based organic solvent which does not dissolve the obtained resin is preferable.

As a polymerization method suitable for forming a resin particle or a coating layer containing a release agent, a release agent is added to an aqueous medium in which a surfactant having a concentration equal to or lower than the critical micelle concentration is dissolved. The monomer solution dissolved in the monomer is dispersed in oil droplets using mechanical energy to prepare a dispersion, and a water-soluble polymerization initiator is added to the obtained dispersion, and the oil is dispersed in the oil droplets. A method of radical polymerization (hereinafter, referred to as “mini-emulsion method” in the present invention) can be exemplified. In the above method, an oil-soluble polymerization initiator may be used instead of or together with the water-soluble polymerization initiator.

According to the miniemulsion method in which oil droplets are formed mechanically, unlike a normal emulsion polymerization method, the release agent dissolved in the oil phase does not detach, and the resin particles or A sufficient amount of release agent can be introduced into the coating layer.

Here, the disperser for dispersing oil droplets by mechanical energy is not particularly limited. For example, a stirrer “CLEARMIX” (M) equipped with a high-speed rotating rotor -Technic), ultrasonic disperser, mechanical homogenizer,
Menton-Gaulin and a pressure type homogenizer can be exemplified. Further, the dispersed particle diameter is 10 to 10
00 nm, preferably 50 to 1000 nm, more preferably 30 to 300 nm.

As other polymerization methods for forming the resin particles or the coating layer containing the release agent, known methods such as an emulsion polymerization method, a suspension polymerization method, and a seed polymerization method can be employed. . Further, these polymerization methods can also be employed to obtain resin particles (core particles) or coating layers constituting the composite resin particles, which do not contain a release agent.

The particle diameter of the composite resin particles obtained in the polymerization step (I) was determined by using an electrophoretic light scattering photometer “ELS-80”.
It is preferable that the mass average particle diameter measured using “0” (manufactured by Otsuka Electronics Co., Ltd.) is in the range of 10 to 1000 nm.

Further, the glass transition temperature (T
g) is preferably in the range of 48 to 74 ° C,
~ 64 ° C is more preferred.

The softening point of the composite resin particles is 95 to 140.
It is preferably in the range of ° C. << 2: Salting-out / fusion step >> In the salting-out / fusion step, the composite resin particles obtained by the multi-stage polymerization step and the colorant particles are subjected to salting-out / fusion. At the same time) to obtain irregular (non-spherical) toner particles.

The salting out / fusion in the present invention means that salting out (aggregation of particles) and fusion (loss of interface between particles) occur simultaneously, or salting out and fusion occur simultaneously. Act. In order to simultaneously carry out the salting-out and the fusion, it is necessary to aggregate the particles (composite resin particles, colorant particles) under a temperature condition equal to or higher than the glass transition temperature (Tg) of the resin constituting the composite resin particles. .

In this salting-out / fusion step, together with the composite resin particles and the colorant particles, internal additive particles (fine particles having a number average primary particle diameter of about 10 to 1000 nm) such as a charge controlling agent are salted out / fused. May be. The colorant particles may be surface-modified, and any conventionally known surface-modifying agent can be used.

The colorant particles are subjected to salting out / fusion treatment in a state of being dispersed in an aqueous medium. The aqueous medium in which the colorant particles are dispersed is preferably an aqueous solution in which a surfactant is dissolved at a concentration equal to or higher than the critical micelle concentration (CMC).

The disperser used for the dispersion treatment of the colorant particles is not particularly limited, but is preferably a stirrer “CLEARMIX (CLEARM) equipped with a high-speed rotating rotor.
MIX) "(manufactured by M-Technic), ultrasonic disperser,
Examples include a pressure disperser such as a mechanical homogenizer, a Manton-Gaulin, a pressure homogenizer, and a medium disperser such as a Getzman mill or a diamond fine mill.

In order to carry out salting out / fusion of the composite resin particles and the colorant particles, a salting-out agent having a critical coagulation concentration or more (aggregating agent) is added to the dispersion in which the composite resin particles and the colorant particles are dispersed. ) And heating the dispersion above the glass transition temperature (Tg) of the composite resin particles.

The preferable temperature range for salting out / fusing is (Tg + 10 ° C.) to (Tg + 50 ° C.)
A more preferred temperature range is (Tg + 15 ° C.) to (Tg + 40
° C). In addition, in order to perform fusion effectively,
An organic solvent that is infinitely soluble in water may be added.

<< 3: Filtration / Washing Step >> In this filtration / washing step, a filtration treatment for filtering the toner particles from the dispersion system of the toner particles obtained in the above-described step and a filtration treatment for the toner particles (cake) Washing treatment for removing adhering substances such as a surfactant and a salting-out agent from the aggregate in the form of a liquid.

[0219] Here, the filtration method is not particularly limited, such as a centrifugal separation method, a vacuum filtration method using a Nutsche method, a filtration method using a filter press or the like.

<< 4: Drying Step >> This drying step is a step of drying the washed toner particles.

Examples of the drier used in this step include a spray drier, a vacuum freeze drier, a reduced pressure drier, etc., and a stationary shelf drier, a mobile shelf drier, a fluidized bed drier, a rotary drier It is preferable to use a type dryer, a stirring type dryer and the like.

The water content of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less.

Incidentally, the dried toner particles are
In the case where the aggregates are aggregated by a weak attraction between particles, the aggregates may be crushed. As the crushing device, a mechanical crushing device such as a jet mill, a Henschel mixer, a coffee mill, and a food processor can be used.

<< 5: Step of Adding Additive >> The step of adding the additive is a step of adding a fatty acid metal salt, an abrasive external additive and an external additive to the dried toner particles to produce a toner. It is. As a manufacturing apparatus used in this step, it is preferable to use a Henschel mixer, a Nauta mixer or the like.

The toner of the present invention forms composite resin particles in the absence of a colorant, adds a dispersion of colorant particles to a dispersion of the composite resin particles, and combines the composite resin particles with the colorant particles. It is preferably produced by salting out / fusing.

As described above, the production of the composite resin particles is performed in a system in which no colorant is present, so that the polymerization reaction for obtaining the composite resin particles is not hindered. Therefore, according to the toner of the present invention, the excellent offset resistance is not impaired, and the fixing device is not stained or the image is not stained due to the accumulation of the toner.

Further, as a result of the reliable polymerization reaction for obtaining the composite resin particles, no monomer or oligomer remains in the obtained toner particles. No unpleasant odor is generated in the heat fixing step.

Further, since the surface characteristics of the obtained toner particles are uniform and the charge amount distribution becomes sharp, an image having excellent sharpness can be formed for a long period of time. According to such a toner having a uniform composition, molecular weight, and surface characteristics among toner particles, good adhesion (high fixing strength) to an image support is maintained in an image forming method including a fixing step by a contact heating method. Meanwhile, the offset resistance and the anti-winding property can be improved, and an image having an appropriate gloss can be obtained.

Next, each component used in the toner manufacturing process will be described in detail. <Polymerizable monomer> As the polymerizable monomer for producing the resin (binder) used in the present invention, a hydrophobic monomer is an essential component, and a crosslinkable monomer is optionally used. Used. As described below, it is desirable to contain at least one monomer having an acidic polar group or a monomer having a basic polar group.

<< Hydrophobic Monomer >> The hydrophobic monomer constituting the monomer component is not particularly limited, and a conventionally known monomer can be used. Further, one kind or a combination of two or more kinds can be used so as to satisfy required characteristics.

Specifically, monovinyl aromatic monomers,
Acrylic ester monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers, halogenated olefin monomers and the like can be used.

As the vinyl aromatic monomer, for example,
Styrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n- Styrene-based monomers such as octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, 2,4-dimethylstyrene, and 3,4-dichlorostyrene, and derivatives thereof. .

Examples of the acrylic monomer include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, Ethyl methacrylate, butyl methacrylate, hexyl methacrylate, methacrylic acid
2-ethylhexyl, β-hydroxyethyl acrylate, γ-aminopropyl acrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like can be mentioned.

Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl benzoate and the like.

Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like.

Examples of the monoolefin-based monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like.

Examples of the diolefin monomer include butadiene, isoprene, chloroprene and the like.

<< Crosslinkable Monomer >> A crosslinkable monomer may be added to improve the properties of the resin particles. Examples of the crosslinkable monomer include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.

<< Monomer Having an Acidic Polar Group >> As the monomer having an acidic polar group, (a) a carboxyl group (—C
Α, β-ethylenically unsaturated compounds having OOH) and (b) α, β-ethylenically unsaturated compounds having a sulfone group (—SO ₃ H).

Examples of the (a) α, β-ethylenically unsaturated compound having a —COO group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, and monobutyl maleate. Examples thereof include esters, monooctyl maleate, and metal salts thereof such as Na and Zn.

Examples of the (b) α, β-ethylenically unsaturated compound having an —SO ₃ H group include sulfonated styrene, its Na salt, allyl sulfosuccinic acid, allyl sulfosuccinate octyl, its Na salt and the like. I can do it.

<< Monomer Having a Basic Polar Group >> As the monomer having a basic polar group, (1) an amine group or a quaternary ammonium group having 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and particularly preferably (Meth) acrylic acid esters of aliphatic alcohols of (2), (2) (meth) acrylic acid amides or (meth) acrylic acid amides optionally mono- or di-substituted with an alkyl group having 1 to 18 carbon atoms on N; (3) Vinyl compounds substituted with a heterocyclic group having N as a ring member, and (4) N, N-diallyl-alkylamine or a quaternary ammonium salt thereof. Among them, (1) a (meth) acrylic acid ester of an aliphatic alcohol having an amine group or a quaternary ammonium group is preferable as a monomer having a basic polar group.

Examples of the (meth) acrylate of the aliphatic alcohol having an amine group or a quaternary ammonium group (1) include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, Quaternary ammonium salts of four compounds, 3-dimethylaminophenyl acrylate, 2-hydroxy-
Examples thereof include 3-methacryloxypropyltrimethylammonium salt.

Examples of (2) (meth) acrylamide or (meth) acrylamide optionally mono- or dialkyl-substituted on N include acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, Methacrylamide, N-butyl methacrylamide, N, N-dimethylacrylamide,
N-octadecylacrylamide and the like can be mentioned.

Examples of the vinyl compound (3) substituted with a heterocyclic group having N as a ring member include vinylpyridine, vinylpyrrolidone, vinyl-N-methylpyridinium chloride, vinyl-N-ethylpyridinium chloride and the like. Can be done.

Examples of (4) N, N-diallyl-alkylamine include N, N-diallylmethylammonium chloride, N, N-diallylethylammonium chloride and the like.

<Polymerization Initiator> The radical polymerization initiator used in the present invention can be appropriately used as long as it is water-soluble. For example, persulfates (eg, potassium persulfate, ammonium persulfate, etc.), azo compounds (eg, 4,4 ′)
-Azobis-4-cyanovaleric acid and salts thereof, 2,2'-azobis (2-amidinopropane) salts and the like), peroxide compounds and the like. Further, the above radical polymerization initiator can be used as a redox initiator in combination with a reducing agent, if necessary. The use of a redox initiator is preferable because the polymerization activity is increased, the polymerization temperature can be reduced, and the polymerization time can be further shortened.

As the polymerization temperature, any temperature may be selected as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator. For example, a temperature in the range of 50 to 90 ° C. is used. However, by using a polymerization initiator started at room temperature, for example, a combination of hydrogen peroxide and a reducing agent (such as ascorbic acid), polymerization can be performed at room temperature or higher.

<Chain transfer agent> For the purpose of adjusting the molecular weight, a known chain transfer agent can be used. The chain transfer agent is not particularly limited, for example, octyl mercaptan, dodecyl mercaptan,
A compound having a mercapto group such as tert-dodecyl mercaptan is used. In particular, a compound having a mercapto group is preferably used because it suppresses odor at the time of heating and fixing, and a toner having a sharp molecular weight distribution is obtained, and has excellent storage stability, fixing strength, and offset resistance. For example, ethyl thioglycolate, propyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate And compounds having a mercapto group of ethylene glycol, compounds having a mercapto group of neopentyl glycol, and compounds having a mercapto group of pentaerythritol. Among them, n-octyl-3-mercaptopropionate is particularly preferable from the viewpoint of suppressing odor during toner heat fixing.

<Surfactant> In order to carry out miniemulsion polymerization using the above-mentioned polymerizable monomer, it is preferable to disperse oil droplets in an aqueous medium using a surfactant. The surfactant that can be used at this time is not particularly limited, but the following ionic surfactants can be mentioned as examples of suitable compounds.

Examples of the ionic surfactant include sulfonates (sodium dodecylbenzenesulfonate,
Sodium arylalkyl polyether sulfonate,
3,3-disulfonediphenylurea-4,4-diazo-
Sodium bis-amino-8-naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol -6
Sodium sulfonate), sulfate salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.),
Fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, etc.) are exemplified.

Also, a nonionic surfactant can be used. Specifically, for example, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, esters of higher fatty acids and polypropylene oxide, And sorbitan esters. These surfactants are mainly used as emulsifiers at the time of emulsion polymerization, but may be used for other steps or other purposes.

The molecular weight of the resin particles is from 100,000 to
A resin containing at least a high molecular weight component having a peak or shoulder in the region of 1,000,000 and a low molecular weight component having a peak or shoulder in the region of 1,000 to less than 50,000 is preferred. More preferably, it is preferable to use an intermediate molecular weight resin having a peak or shoulder at a peak molecular weight of 15,000 to 100,000.

The method for measuring the molecular weight of toner or resin is as follows:
The measurement is preferably performed by GPC (gel permeation chromatography) using HF (tetrahydrofuran) as a solvent. That is, 1.0 mL of THF is added to 0.5 to 5 mg, more specifically, 1 mg of the measurement sample, and the mixture is stirred at room temperature using a magnetic stirrer or the like to be sufficiently dissolved. Then, pore size 0.45 to 0.50 μm
After the treatment with the membrane filter described above, the mixture is injected into GPC. The GPC measurement conditions were as follows: the column was stabilized at 40 ° C., THF was flowed at a flow rate of 1.0 mL / min, and 1 mg /
Inject approximately 100 μL of the sample at a concentration of mL and measure. The column is preferably used in combination with a commercially available polystyrene gel column.

For example, Shodex G manufactured by Showa Denko KK
PC KF-801, 802, 803, 804, 80
5, 806, 807, and Tosoh TSKg
elG1000H, G2000H, G3000H, G4
000H, G5000H, G6000H, G7000
H, a combination of TSK guard column and the like. As the detector, a refractive index detector (IR detector) or a UV detector may be used. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve created using monodispersed polystyrene standard particles. 10 as polystyrene for making calibration curve
It is good to use about dots.

<Aggregating agent> The aggregating agent used in the present invention includes:
Those selected from metal salts are preferred.

Examples of the metal salt include monovalent metals such as salts of alkali metals such as sodium, potassium and lithium, divalent metals such as salts of alkaline earth metals such as calcium and magnesium, and salts of manganese and copper. Valent metal salts, iron,
Examples thereof include trivalent metal salts such as aluminum.

Specific examples of these metal salts are shown below.
Specific examples of metal salts of monovalent metals include sodium chloride,
Potassium chloride, lithium chloride, and metal salts of divalent metals include calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Examples of the trivalent metal salt include aluminum chloride and iron chloride. These are appropriately selected according to the purpose. In general, the divalent metal salt has a smaller critical aggregation concentration (coagulation value or coagulation point) than the monovalent metal salt, and the trivalent metal salt has a smaller critical aggregation concentration.

The critical aggregation concentration is an index relating to the stability of the dispersion in the aqueous dispersion, and indicates the concentration at which aggregation occurs when a coagulant is added. This critical aggregation concentration varies greatly depending on the latex itself and the dispersant. For example, Seizo Okamura et al., Polymer Chemistry 17,601 (196
0), etc., and according to these descriptions, the value can be known. As another method, a desired salt is added at a different concentration to the target particle dispersion, and the ζ potential of the dispersion is measured, and the salt concentration at the point where the ζ potential changes is defined as the critical aggregation concentration. It is also possible.

In the present invention, the polymer fine particle dispersion is treated with a metal salt so as to have a concentration higher than the critical aggregation concentration. At this time, of course, add the metal salt directly,
The addition as an aqueous solution is arbitrarily selected depending on the purpose. In the case of adding as an aqueous solution, the added metal salt needs to be at or above the critical aggregation concentration of the polymer particles with respect to the volume of the polymer particle dispersion and the total volume of the metal salt aqueous solution.

The concentration of the metal salt as the coagulant in the present invention may be at least the critical coagulation concentration, but is preferably added at least 1.2 times, more preferably at least 1.5 times the critical coagulation concentration.

<Other Manufacturing Method of Toner> Next, as another preferable manufacturing method of the toner of the present invention, the raw materials of resin, colorant and release agent are dissolved or dispersed in an organic solvent to remove the oil phase component. A forming step and a method of granulating the oil phase component in an aqueous solvent may be mentioned.

A step of dissolving or dispersing a resin, a charge control resin, a colorant, and a release agent in an organic solvent for dissolving a binder resin (binder resin) to prepare an oily component; And granulating the toner from a state in which the toner is dispersed in a medium.

The step of dissolving and dispersing a binder resin, a colorant, and a release agent in an organic solvent for solubilizing the binder resin to produce an oily component includes the steps of: binder resin, charge control resin, coloring This is a step of mixing and dispersing the agent and the release agent in an organic solvent for solubilizing the binder resin.

As an organic solvent for solubilizing the binder resin, a general organic solvent is used. For example, toluene,
Hydrocarbons such as xylene and hexane; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; esters such as methyl acetate, ethyl acetate and butyl acetate; acetone and methyl ethyl ketone ,
Ketones such as cyclohexanone are mentioned, and among these, ethyl acetate, methyl ethyl ketone and the like are preferable in view of the solubility of the resin and the solvent removing property. These may be used alone or as a mixture.

The step of granulating the toner from a state in which the oily component is dispersed in the aqueous medium means that the oily component produced in the above step is solidified from the state in which the oily component is dispersed in the aqueous medium to produce particles. This is a step of drying to obtain a toner.

As the method for producing particles, the binder resin,
A method in which a charge control resin, a coloring agent, a release agent, and a solution obtained by dissolving and dispersing other materials in a solvent are suspended and dispersed in an aqueous medium, and then the solvent is removed. The method of precipitating particles by adding, the binder resin, the charge control resin, a coloring agent, a release agent, a hot melt containing other materials is melted and dispersed in an aqueous medium, and then cooled to form particles. Examples of the method include a method of forming, a method of suspending and dispersing a mixed solution containing a polymerizable monomer, a colorant, a release agent, and other materials in an aqueous medium, and then polymerizing the monomer.

As the aqueous medium, water is mainly used, but a water-soluble solvent may be mixed. Further, it is preferable to add a dispersant in terms of particle size distribution. Examples of the dispersant include tricalcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, silica, cellulose, hydroxypropylmethylcellulose, methylcellulose, carboxymethylcellulose, starch,
Examples include polyvinyl alcohol and polyacrylic acid. The amount of the dispersant is 0 to 2 with respect to 100 parts by mass of the mother liquor.
0 parts by mass is preferred.

As a stirring method for producing particles, it is desirable to apply shearing, and a homogenizer, a colloid mill, a dissolver, or the like is used.

For drying, a through-air drying device, a spray drying device,
A rotary drying apparatus, a flash drying apparatus, a fluidized bed drying apparatus, a heat transfer heating type drying apparatus, a freeze drying apparatus and the like are known, and any of them can be used.

<Colorant> The toner of the present invention is not particularly limited, including a method obtained by salting out / fusing the composite resin particles and the colorant particles, and known colorants are widely used. .

As the colorant (colorant particles subjected to salting out / fusion with the composite resin particles) constituting the toner according to the present invention, various inorganic pigments, organic pigments and dyes can be mentioned. Conventionally known inorganic pigments can be used. Specific inorganic pigments are exemplified below.

Examples of black pigments include furnace black, channel black, acetylene black,
Carbon black such as thermal black and lamp black, and magnetic powder such as magnetite and ferrite are also used.

These inorganic pigments can be used alone or in combination of two or more as desired. The amount of the pigment added is 2 to 20% by mass relative to the polymer, preferably 3 to 20% by mass.
15% by weight is selected.

When used as a magnetic toner, the above-mentioned magnetite can be added. In this case, from the viewpoint of imparting predetermined magnetic characteristics, 20 to 6
It is preferable to add 0% by mass.

Known organic pigments and dyes can be used. Specific examples of organic pigments and dyes are shown below.

Examples of magenta or red pigments include C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I.
I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 5
7: 1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 13
9, C.I. I. Pigment red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166,
C. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 222 and the like.

The pigments for orange or yellow include:
For example, C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43, C.I. I. Pigment Yellow 1
2, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15,
C. I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I.
I. Pigment yellow 138, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 185,
C. I. Pigment yellow 155, C.I. I. Pigment Yellow 156 and the like.

Examples of green or cyan pigments include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15:
3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.

Examples of the dye include C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, C.I. I. Solvent Yellow 19,
44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, C.I.
I. Solvent Blue 25, 36, 60, 70
93 and 95 can be used, and a mixture thereof can also be used.

These organic pigments and dyes can be used alone or in combination of two or more as desired.
The amount of the pigment to be added is 2 to 20% by mass, preferably 3 to 15% by mass, based on the polymer.

The colorant (colorant particles) constituting the toner according to the present invention may be surface-modified. As the surface modifier, a conventionally known one can be used, and specifically, a silane coupling agent, a titanium coupling agent,
An aluminum coupling agent or the like can be preferably used.

As the silane coupling agent, for example,
Alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, siloxanes such as hexamethyldisiloxane, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltrimethoxysilane Examples include ethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, and the like. As the titanium coupling agent, for example,
TTS, 9S, 38S, 41B, 46B, 5B, which are commercially available under the trade name "Plenact" manufactured by Ajinomoto Co.
5, 138S, 238S, etc., commercial products A-
1, B-1, TOT, TST, TAA, TAT, TL
A, TOG, TBSTA, A-10, TBT, B-2,
B-4, B-7, B-10, TBSTA-400, TT
S, TOA-30, TSDMA, TTAB, TTOP and the like. As the aluminum coupling agent,
For example, (Plenact AL-M) manufactured by Ajinomoto Co. and the like can be mentioned.

The addition amount of these surface modifiers is preferably from 0.01 to 20% by mass, more preferably from 0.1 to 5% by mass, based on the colorant.

Examples of the method for modifying the surface of the colorant particles include a method in which a surface modifier is added to a dispersion of the colorant particles, and the system is heated and reacted.

The colorant particles having been subjected to the surface modification are collected by filtration, and are subjected to drying treatment after repeated washing and filtration with the same solvent.

<Releasing Agent> The toner of the present invention is preferably a toner obtained by fusing resin particles containing a releasing agent in an aqueous medium. In this manner, the resin particles having the release agent encapsulated in the resin particles are salted out with the colorant particles in an aqueous medium.
By fusing, a toner in which a release agent is finely dispersed can be obtained.

In the toner of the present invention, a low molecular weight polypropylene (number average molecular weight = 1500 to 900) is used as a releasing agent.
0), low molecular weight polyethylene, and the like are preferable, and an ester compound represented by the following formula is particularly preferable.

R ^1- (OCO-R ² ) n In the formula, n is an integer of 1 to 4, preferably 2 to 4, more preferably 3 to 4, and particularly preferably 4. R ^1, R
² represents a hydrocarbon group which may have a substituent. R ¹
Has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 2 to 5 carbon atoms. R ² has 1 to 40 carbon atoms, preferably 16 to 30 carbon atoms, and more preferably 18 to 26 carbon atoms.

Next, examples of typical compounds are shown below.

[0291]

Embedded image

[0292]

Embedded image

The addition amount of the above compound is 1 to 30% by mass, preferably 2 to 20% by mass, and more preferably 3 to 15% by mass based on the whole toner.

The toner of the present invention is preferably produced by encapsulating the above-mentioned release agent in resin particles by miniemulsion polymerization and salting out and fusing with the colored particles.

<Preferred Shape Range of Toner> The shape factor of the toner of the present invention is represented by the following equation, and indicates the degree of roundness of toner particles.

Shape coefficient = ((maximum diameter / 2) ² × π) / projected area Here, the maximum diameter is defined as a parallel line when a projected image of a toner particle on a plane is sandwiched between two parallel lines. Means the width of the particle at which the distance between the particles becomes maximum. The projection area refers to the area of a projected image of a toner particle on a plane. In the present invention, the shape factor can be determined by taking a photograph in which the toner particles are magnified 2,000 times with a scanning electron microscope, and then referring to the “SCCANNING IMAGE ANALYZE” based on the photograph.
R "(manufactured by JEOL Ltd.) was used to analyze photographic images. At this time, the shape factor according to the present invention was measured by the above calculation formula using 100 toner particles.

In the toner of the present invention, when the particle diameter of the toner particles is D (μm), the natural logarithm InD is plotted on the horizontal axis, and the horizontal axis is divided into a plurality of classes at intervals of 0.23. In the histogram showing the particle size distribution, the sum (M1) of the relative frequency (m1) of the toner particles included in the most frequent class and the relative frequency (m2) of the toner particles included in the class having the second highest frequency after the most frequent class. ) Is preferably 70% or more.

When the sum (M) of the relative frequency (m1) and the relative frequency (m2) is 70% or more, the dispersion of the particle size distribution of the toner particles becomes narrower. Thus, the occurrence of selective development can be reliably suppressed.

In the present invention, the histogram showing the number-based particle size distribution is obtained by plotting a natural logarithm lnD (D: particle size of individual toner particles) in a plurality of classes (0 to 0) at intervals of 0.23.
0.23: 0.23 to 0.46: 0.46 to 0.69:
0.69 to 0.92: 0.92 to 1.15: 1.15
1.38: 1.38 to 1.61: 1.61 to 1.84:
1.84 to 2.07: 2.07 to 2.30: 2.30 to
2.53: a histogram showing the number-based particle size distribution divided into 2.53 to 2.76..., Which is a particle size data of a sample measured by a Coulter Multisizer according to the following conditions. Is transferred to a computer via an I / O unit, and the computer creates the program using a particle size distribution analysis program.

<< Conditions for Measurement of Particle Size Distribution >> 1: Aperture: 100 μm 2: Sample preparation method: Electrolyte “ISOTON R-2”
(Coulter Scientific Japan) 50
To 100 mL, add an appropriate amount of a surfactant (neutral detergent), stir, and add 10 to 20 mg of a measurement sample to this. This system is prepared by subjecting it to a dispersion treatment with an ultrasonic disperser for 1 minute.

By using a toner having the following shape and configuration, the presence of the external additive on the toner surface becomes uniform, the charge amount distribution becomes sharp, and high fluidity is obtained. As a result, excellent developability and fine line reproducibility and stable cleaning properties can be formed for a longer period.

Further, the inventors of the present invention have conducted a study focusing on the minute shape of each toner particle. As a result, the shape of the corner portion of the toner particle changes inside the developing device and becomes round, and the portion becomes round. It was found that the burying of the external additive was promoted, and the change in the charge amount, the fluidity, and the cleaning property were reduced. In addition, when a charge is applied to the toner particles by triboelectric charging, it is presumed that the external additives are easily buried especially in the corner portions, and the charging of the toner particles is likely to be uneven, but this is also effectively prevented I can do it.

That is, the toner of the present invention has a shape coefficient variation coefficient of 16% or less, a number variation coefficient in the number particle size distribution of 27% or less, and a shape coefficient of 1.0 to 1.0.
It is preferable to use a toner in which the ratio of the toner particles in the range of 6 is 65% by number or more.

Further, in the toner of the present invention, the ratio of toner particles having no corners is 50% by number or more, the number variation coefficient in the number particle size distribution is 27% or less, and the shape factor is 1.
The ratio of toner particles in the range of 0 to 1.6 is 65% by number
It is preferable that it is above.

The toner of the present invention has a shape factor of 1.2 to 1.2.
It is preferable that the ratio of the toner particles in the range of 1.6 is 65% by number or more and the variation coefficient of the shape coefficient is 16% or less.

When the particle diameter of the toner particles according to the present invention is D (μm), the natural logarithm lnD is plotted on the horizontal axis, and
The relative frequency (m1) of the toner particles included in the most frequent class in the histogram showing the number-based particle size distribution in which the horizontal axis is divided into a plurality of classes at intervals of 0.23, and the next highest frequency after the most frequent class It is preferable to use a toner whose sum (M) with the relative frequency (m2) of the toner particles included in the class is 70% or more.

[Developer] The toner of the present invention may be used as a one-component developer or a two-component developer.

When used as a one-component developer, a non-magnetic one-component developer or a magnetic one-component developer containing magnetic particles of about 0.1 to 0.5 μm in toner can be used. Can also be used.

When used as a two-component developer by mixing with a carrier, magnetic particles of the carrier include, for example,
Conventionally known materials such as metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead can be used. Among these magnetic particles, ferrite particles are preferred. The volume average particle diameter of the magnetic particles is preferably from 15 to 100 μm, more preferably from 25 to 80 μm.

The volume average particle size of the carrier is typically measured by a laser diffraction type particle size distribution analyzer “HELOS” equipped with a wet disperser (SYMPATIC (SYMPIC)
(ATEC)).

The carrier is preferably a carrier in which magnetic particles are further coated with a resin, or a so-called resin-dispersed carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, for example,
An olefin resin, a styrene resin, a styrene-acrylic resin, a silicone resin, an ester resin, a fluorine-containing polymer resin, or the like is used. The resin for forming the resin dispersion type carrier is not particularly limited and may be a known resin. For example, a styrene-acrylic resin, a polyester resin, a fluororesin,
A phenol resin or the like can be used.

[Image Forming Method] Next, an image forming apparatus used in the image forming method of the present invention will be described.

FIG. 4 is a sectional view showing an example of an image forming apparatus used in the image forming method of the present invention.

In the drawing, reference numeral 2 denotes a photosensitive drum as an image forming body, which is formed by forming an organic photoconductor (OPC) as a photosensitive layer on the outer peripheral surface of a drum base made of aluminum and is arranged in the direction of an arrow. It rotates at a predetermined speed.

In FIG. 4, based on information read by a document reading device (not shown), the semiconductor laser light source 21
Exposure light is emitted from. This is distributed by the polygon mirror 22 in the direction perpendicular to the paper surface of FIG. 4, and is radiated on the photoreceptor surface via the fθ lens 13 for correcting image distortion to form an electrostatic latent image. The photosensitive drum 2, which is an image forming body,
It is uniformly charged in advance by the charger 15 and starts rotating clockwise in accordance with the timing of image exposure.

The electrostatic latent image on the surface of the photosensitive drum is
The developed image formed by the developing unit 6 is transferred to the transfer paper 18 which has been conveyed at a proper timing by the operation of the transfer unit 17. Further, the photosensitive drum 2 and the transfer paper 18 are separated by a separator (separation pole) 9, and the toner image is transferred and carried on the transfer paper 18, guided to the fixing device 10 and fixed.

The untransferred toner and the like remaining on the photosensitive member surface are
It is cleaned by the cleaning blade 1 of the cleaning device 11, and the residual charge is removed by the pre-charging exposure (PCL) 12,
It is uniformly charged again by the charger 15 for the next image formation.

[Toner Recycling System] The method for recycling the toner is not particularly limited. For example, the toner collected by the cleaning unit may be replenished with a toner hopper, a developing device, A method of mixing the replenishing toner with the intermediate chamber and supplying the mixed toner to the developing device can be used. Preferably, a method of directly returning the toner to the developing device or a method of mixing and supplying the replenishment toner and the recycled toner in the intermediate chamber can be exemplified.

FIG. 5 is a perspective view of a member showing an example of a toner recycling apparatus. In this method, the recycled toner is directly returned to the developing device. Cleaning blade 1
The untransferred toner collected by the
Recycle pipe 2 by conveying screw inside
4 and further into the receiving port 25 of this recycled pipe
Is returned to the developing device 16 and used again as a developer.

FIG. 5 is also a perspective view of a process cartridge detachable from the image forming apparatus according to the present invention. In FIG. 5, the photoconductor unit and the developer unit are separated so that the perspective structure can be easily understood, but they can be removably mounted on the image forming apparatus as an integrated unit. In this case, the photosensitive drum, the developing device, the cleaning device, and the recycling member are integrated to form a process cartridge.

[0321] The image forming apparatus may be configured to mount a process cartridge including a photosensitive drum and at least one of a charger, a developing device, a cleaning device, and a recycling member.

Next, the transfer paper is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and of course includes a PET base for OHP.

Further, as described above, the cleaning blade 1 uses a rubber-like elastic body having a thickness of about 1 to 30 mm, and urethane rubber is most often used as a material. Since this is used by being pressed against the photoconductor, it is easy to conduct heat. In the present invention, it is desirable to provide a release mechanism and keep the photoconductor away from the photoconductor when the image forming operation is not performed.

The present invention can also be used in an image forming apparatus by electrophotography, particularly in an apparatus for forming an electrostatic latent image on a photoreceptor by a modulated beam modulated with digital image data from a computer or the like.

In recent years, in the field of electrophotography and the like in which an electrostatic latent image is formed on a photosensitive drum and this latent image is developed to obtain a visible image, it is easy to improve image quality, convert, edit, etc. Research and development of an image forming method employing a digital method capable of forming an image have been actively conducted.

As a scanning optical system that modulates light with a digital image signal from a computer or a copy original used in the image forming method and apparatus, an acousto-optic modulator is interposed in a laser optical system, and the light is modulated by the acousto-optic modulator. There is a device for modulating the light and a device for directly modulating the laser intensity using a semiconductor laser. These scanning optical systems form a dot-like image by spot exposure on a uniformly charged photoconductor.

The beam emitted from the above-mentioned scanning optical system has a round or elliptical luminance distribution approximating a normal distribution with a skirt spreading left and right. One or both of the scanning direction and the sub-scanning direction has an extremely narrow round or elliptical shape of 20 to 100 μm.

[Fixing Apparatus] The toner of the present invention comprises an image forming method including a step of fixing a transfer sheet having a toner image formed thereon by passing the transfer sheet between a heating roller and a pressure roller constituting a fixing device. It is suitably used in the image forming method of the present invention).

FIG. 6 is a sectional view showing an example of a fixing device used in the image forming method of the present invention.

In the figure, the fixing device (fixing device) includes a heating roller 70 and a pressure roller 72 that comes into contact with the heating roller 70. Here, T is a toner image formed on the transfer paper (image forming support) 18.

[0331] The heating roller 70 has a coating layer 82 made of a fluororesin or an elastic body formed on the surface of a metal core 81, and includes a heating member 75 made of a linear heater.

The core bar 81 is made of metal and has an inner diameter of 10 to 70 mm. The metal constituting the metal core 81 is not particularly limited, but examples thereof include metals such as iron, aluminum, and copper, and alloys thereof.

The thickness of the core bar 81 is 0.1 to 15 mm, and is determined in consideration of the balance between the demand for energy saving (thinning) and the strength (depending on the constituent materials). For example,
In order to maintain a strength equivalent to that of a 0.57 mm iron core with an aluminum core, the wall thickness must be 0.8 mm.

Examples of the fluorine resin constituting the surface layer of the coating layer 82 include PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer).

The thickness of the surface layer of the coating layer 82 made of fluororesin is 10 to 500 μm, preferably 15 to 40 μm.
0 μm.

If the thickness of the surface layer of the coating layer 82 made of fluororesin is less than 10 μm, the function as the coating layer cannot be sufficiently exhibited, and the durability as a fixing device cannot be secured. . On the other hand, if it exceeds 500 μm,
The thermal conductivity of the roller is reduced, and the melting of the toner becomes insufficient.

It is preferable to use silicone rubber and silicone sponge rubber having good heat resistance, such as LTV, RTV, and HTV, as the elastic body constituting the coating layer 82.

An elastic Asker C constituting the coating layer 82
The hardness is less than 80 °, preferably less than 60 °. The thickness of the coating layer 82 made of an elastic material is 0.1 to
It is 30 mm, preferably 0.1 to 20 mm.

The elastic Asker C constituting the coating layer 82
If the hardness exceeds 80 ° and the thickness of the coating layer 82 is less than 0.1 mm, the nip for fixing cannot be increased, and the effect of soft fixing (for example, Improvement effect of color reproducibility by toner layer)
Cannot be demonstrated.

As the heating member 75, a halogen heater can be suitably used. The pressure roller 72 is
A coating layer 84 made of an elastic material is formed on the surface of the core bar 83. The elastic body constituting the coating layer 84 is not particularly limited, and may be various soft rubbers such as urethane rubber and silicone rubber and sponge rubber. And it is preferable to use silicone sponge rubber.

An elastic Asker C constituting the coating layer 84
The hardness is less than 80 °, preferably less than 70 °, more preferably less than 60 °. The thickness of the coating layer 84 is 0.1 to 30 mm, preferably 0.1 to 20 mm.
mm.

Elastic Asker C constituting the coating layer 84
When the hardness exceeds 80 ° and when the thickness of the coating layer 84 is less than 0.1 mm, the nip for fixing cannot be increased, and the effect of soft fixing cannot be exhibited.

The material constituting the core bar 83 is not particularly limited, but examples thereof include metals such as aluminum, iron and copper or alloys thereof.

The contact load (total load) between the heating roller 70 and the pressure roller 72 is usually 40 to 350 N, preferably 50 to 300 N, more preferably 50 to 300 N.
２５０250N. This contact load is applied to the heating roller 1
It is defined in consideration of the strength of 0 (thickness of the core metal 75). For example, in the case of a heating roller having a core metal made of 0.3 mm iron, the heating roller is preferably set to 250 N or less.

From the viewpoint of offset resistance and fixability, the nip width is preferably 4 to 10 mm, and the surface pressure of the nip is 0.6 × 10 ^{5 to} 1.5 × 10 ^5.
It is preferably Pa.

An example of the fixing conditions by the fixing device shown in FIG. 6 is as follows. Fixing temperature (surface temperature of heating roller 70)
Is 150 to 210 ° C., and the fixing linear velocity is 80 to 640 m.
m / sec.

The fixing device used in the present invention may be provided with a cleaning mechanism as needed. In this case, as a method of supplying the silicone oil to the upper roller (heating roller) of the fixing unit, a method of supplying and cleaning with a pad, a roller, a web, or the like impregnated with the silicone oil can be used.

As the silicone oil, those having high heat resistance are used, and polydimethyl silicone, polyphenylmethyl silicone, polydiphenyl silicone and the like are used. Since those having a low viscosity have a large outflow during use, those having a viscosity at 20 ° C. of 1 to 100 Pa · s are preferably used.

However, the effect of the present invention is particularly remarkably exhibited when an image is formed by a fixing device in which silicone oil is not supplied or a silicone oil supply amount is extremely low. Therefore, even when the silicone oil is supplied, the supply amount is preferably 2 mg or less per A4 sheet.

By setting the supply amount of the silicone oil to 2 mg or less per A4 sheet, the amount of the silicone oil adhering to the transfer paper (image support) after fixing is reduced, and the ballpoint pen is formed by the silicone oil adhering to the transfer paper. There is no difficulty in writing with an oil-based pen, etc., and the writing performance is not impaired.

In addition, it is possible to avoid problems such as deterioration of the offset resistance with time due to deterioration of the silicone oil and contamination of the optical system and the band electrode by the silicone oil.

Here, the supply amount of the silicone oil was determined by transferring the transfer paper (A) to a fixing device (between rollers) heated to a predetermined temperature.
100 sheets of 4 size white paper) are continuously passed, and the mass change (Δw) of the fixing device before and after the paper passing is measured and calculated (Δw / 100).

[0353]

EXAMPLES The present invention will be described specifically with reference to Examples.
Embodiments of the present invention are not limited to these.

"Production Example 1 of Fatty Acid Metal Salt" (Example of Zinc Stearate) As raw materials, a 1% by mass aqueous solution of sodium stearate (solution a) and a 0.2% by mass aqueous solution of zinc sulfate (solution b) were used. Got ready. Next, a 2 L container with a stirring device having a turbine blade having a diameter of 6 cm was prepared, and the turbine blade was rotated at 350 revolutions / minute. This container has a liquid temperature of 80 ° C.
The solution a and the solution b heated at the same time were added simultaneously from different directions so that the equivalent ratio became 1: 1. In addition, the time to supply the whole amount is 1
Performed within 0 seconds. After charging the whole amount, 1 at 80 ° C
After aging for 0 minutes, the reaction was terminated to prepare a zinc stearate slurry. Next, the zinc stearate slurry was filtered, washed twice with water, and then washed with methanol. After washing, it was dried at 90 ° C. under normal pressure to produce “zinc stearate”. The crystal transition onset temperature of the obtained “zinc stearate” was 100 ° C.

"Production Example 2 of Fatty Acid Metal Salt" (Example of Calcium Stearate) In Production Example 1 of fatty acid metal salt, solution b was changed to a 0.5% by mass aqueous solution of calcium chloride, and the solution temperature was changed to 65 ° C. "Calcium stearate" was produced in the same manner as in Production Example 1 except that the drying was changed to 65 ° C. The crystal transition onset temperature of the obtained “calcium stearate” is 73
° C.

"Production Example 3 of Fatty Acid Metal Salt" (Example of Lithium Stearate) In Production Example 1 of fatty acid metal salt, solution b was changed to a 0.5% by mass aqueous solution of lithium hydroxide, and the solution temperature was changed to 70%. ° C, washing was not carried out with methanol, and "Lithium stearate" was produced in the same manner as in Production Example 1 except that drying was changed to 70. The crystal transition onset temperature of the obtained “lithium stearate” was 76 ° C. It was 100 ° C.

"Production Example 1 of Comparative Fatty Acid Metal Salt" (Example of Comparative Zinc Stearate) As raw materials, a 5% by weight aqueous solution of sodium stearate (solution c) and a 2% by weight aqueous solution of zinc sulfate (solution d) )
Was prepared. Next, a 2 L vessel equipped with a stirring device having a turbine blade having a diameter of 6 cm was prepared, and the turbine blade was set to 3.
It was rotated at 50 revolutions / minute. Solution c and solution d heated to a temperature of 80 ° C. were simultaneously charged into this container from different directions so that the equivalent ratio became 1: 1. In addition, the time for feeding the whole amount is 10
Went within seconds. After charging the entire amount, 10 at 80 ° C
After aging for a minute, the reaction was terminated to prepare a zinc stearate slurry. Next, the zinc stearate slurry was filtered, washed twice with water, and then washed with methanol. After washing, drying at 110 ° C under normal pressure, “Zinc stearate for comparison”
Was manufactured. The crystal transition start temperature of the obtained “zinc stearate for comparison” was 100 ° C.

The obtained “Production Examples 1 to 3 of fatty acid metal salts”,
Table 1 shows the physical property values of "Comparative Fatty Acid Metal Salt Production Example 1".

[0359]

[Table 1]

"Example of the production of inorganic / organic composite fine particles" The primary particle diameter was 30 n per 100 g of styrene / acryl organic fine particles (glass transition point: 95 ° C) having an average particle diameter of 1.2 µm.
oxide particles "ET-3", the surface of which has been treated with tin oxide.
After adding 40 g of "00W" (manufactured by Ishihara Sangyo Co., Ltd.) and mixing with a turbula mixer for 40 minutes, the mixture was mixed with a vibration mill for 60 minutes. Next, the powder surface reformer "Hybridizer"
(Nara Machinery Co., Ltd.) at a peripheral speed of 80 m / sec and 90 ° C. for 3 minutes to produce “inorganic / organic composite fine particles” having titanium oxide fixed on the surface of the organic fine particles.

The “inorganic / organic composite fine particles” had a circularity coefficient of 0.950 and a fixation rate of 53.4%.

“Metal oxide (strontium titanate)
Production Example "600 g of strontium carbonate and titanium oxide 32
0 g was wet-mixed in a ball mill for 8 hours and then filtered and dried. This mixture is molded by applying a force of 50 N / cm ² ,
Calcination was performed at a temperature of 1100 ° C. for 8 hours. Thereafter, mechanical crushing was performed to produce "strontium titanate".

The “strontium titanate” had a number average particle size of 0.7 μm and a circularity coefficient of 0.954.

[Example of Production of Hydrophobic Silica a] 100 parts by mass of fumed silica having a primary particle diameter of 0.007 μm was placed in a vessel having a high-speed mixer, and placed in a nitrogen atmosphere at 8500 parts.
While stirring at rpm, 20 parts by mass of dimethyldichlorosilane was sprayed, and stirring was further continued for 5 minutes. Then, the obtained powder liquid was refluxed and stirred at 200 ° C. for 3 hours under a nitrogen stream. Thereafter, the mixture was cooled to room temperature to produce “hydrophobic silica a”.

"Production Example of Hydrophobic Silica b" In the production example of "hydrophobic silica a", the primary particle diameter was 0.033 μm instead of the fumed silica having a primary particle diameter of 0.007 μm.
Except that octyltrimethoxysilane was used instead of dimethyldichlorosilane.
"Hydrophobic silica b" was produced in the same manner as "hydrophobic silica a".

[Example of Production of Hydrophobic Titanium Oxide c] In a round bottom flask equipped with a magnetic stirrer and a trap, 1
5 parts by mass of titanium oxide (anatase type titanium oxide having a number average particle size of 0.030 μm) dried at 10 ° C. for 24 hours
Was added with 150 parts by weight of dehydrated toluene and 1.5 parts by weight of normal butyltrimethoxysilane, and 0.5 part by weight of acetic acid was further added as a buffer. The resulting suspension is
The mixture was refluxed at 60 ° C. for 7 hours, cooled to room temperature, and then filtered by suction.

Subsequently, the residue was washed with toluene and heated at 110 ° C.
For 4 hours. Further, the solution was suction-filtered with ethanol, dried at 110 ° C. for 4 hours, and pulverized in an agate mortar to produce “hydrophobic titanium oxide c” as a white powdery substance. Manufactured.

"Example of Production of Hydrophobic Titanium Oxide d" In the production of "hydrophobic titanium oxide c", the number average particle diameter was 0.03.
A titanium oxide having a number average particle size of 0.092 μm (rutile, anatase ratio 60:40) was used instead of 0 μm anatase-type titanium oxide, and octyltrimethoxysilane was used in place of normal butyltrimethoxysilane. "Hydrophobic titanium oxide d" was produced.

"Production Example of Toner Particles" (Latex: 1HML) (1) Preparation of core particles (first-stage polymerization) A 5-L separable flask equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device was placed in a 5-liter separable flask. 6. Anionic surfactant (sodium dodecyl sulfonate: SDS)
A surfactant solution (aqueous medium) in which 08 g was dissolved in 3010 g of ion-exchanged water was charged, and the solution was supplied at 230 rpm under a nitrogen stream.
The internal temperature was raised to 80 ° C. while stirring at a stirring speed of.

To this surfactant solution was added 9.2 g of a polymerization initiator (potassium persulfate: KPS) in 200 g of ion-exchanged water.
Was added, and the temperature was adjusted to 75 ° C., and then 70.1 g of styrene and n-butyl acrylate 1 were added.
A monomer mixture composed of 9.9 g and 10.9 g of methacrylic acid was added dropwise over 1 hour, and the system was heated and stirred at 75 ° C. for 2 hours to perform polymerization (first-stage polymerization). Latex (a dispersion of resin particles composed of a high molecular weight resin) was prepared. This is designated as “latex (1H)”.

(2) Formation of Intermediate Layer (Second Stage Polymerization) In a flask equipped with a stirrer, styrene 1
In a monomer mixture comprising 05.6 g, 30.0 g of n-butyl acrylate, 6.4 g of methacrylic acid, and 5.6 g of n-octyl-3-mercaptopropionate, the release agent “exemplified compound 19” was added. 72.0 g was added, and 8
The mixture was heated to 0 ° C. and dissolved to prepare a “monomer solution”.

On the other hand, an anionic surfactant (SDS)
A surfactant solution obtained by dissolving 1.6 g in 2700 mL of ion-exchanged water was heated to 80 ° C.
After adding 28 g of a latex (1H), which is a dispersion of core particles, in terms of solid content, the mechanical dispersion machine CLEARMIX having a circulation path (CLEARMIX) (manufactured by M-Technic Co., Ltd.) was used. The “dispersion liquid (emulsion liquid)” containing emulsified particles (oil droplets) having a uniform dispersion particle diameter (284 nm) was prepared by mixing and dispersing the “dispersion solution”.

Next, 5.1 g of a polymerization initiator (KPS) was added to 240 mL of ion-exchanged water in the “dispersion liquid (emulsion liquid)”.
The polymerization (second stage polymerization) is carried out by adding an initiator solution dissolved in water and 750 mL of ion-exchanged water, and heating and stirring the system at 80 ° C. for 3 hours to form a latex (comprising a high molecular weight resin). A dispersion of composite resin particles having a structure in which the surface of the resin particles is coated with an intermediate molecular weight resin was manufactured. This is referred to as “latex (1HM)”.

(3) Formation of outer layer (third stage polymerization) [Latex (1HM)] obtained as described above
And 7.4 g of a polymerization initiator (KPS) in 20 ion-exchanged water.
An initiator solution dissolved in 0 mL was added, and under a temperature condition of 80 ° C., 300 g of styrene, 95 g of n-butyl acrylate, 15.3 g of methacrylic acid, and n-octyl-3-amine.
A monomer mixture composed of 10.4 g of mercaptopropionate was added dropwise over 1 hour.

After completion of the dropwise addition, polymerization (third stage polymerization) was carried out by heating and stirring for 2 hours, and then cooled to 28 ° C. to form a latex (a central portion composed of a high molecular weight resin and an intermediate layer composed of an intermediate molecular weight resin). And an outer layer made of a low-molecular-weight resin, and a dispersion liquid of composite resin particles containing the exemplary compound 19) in the intermediate layer was produced. This latex is referred to as “latex (1HML)”.

The composite resin particles constituting the “latex (1HML)” have peak molecular weights of 138,000, 80,000 and 13,000,
The number average particle size of the composite resin particles was 102 nm.

[Production Example of Toner Particles 1 to 5] 57.0 g of sodium n-dodecyl sulfate was added to 1700 m of deionized water.
L. While stirring this solution, carbon black “REGAL 330” (manufactured by Cabot) 42
0.0 g slowly added, then "Clear mix"
A dispersion of colorant particles (hereinafter, also simply referred to as “colorant dispersion”) was prepared by performing a dispersion treatment using (manufactured by M-Technic). The particle size of the colorant particles in the “colorant dispersion” was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), and was found to be 112 nm in weight average particle size.

420.7 g of “latex (1HML)” obtained in the production example of resin particles for toner (solid basis)
, 900 g of ion-exchanged water, and “colorant dispersion” 166
g was placed in a reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, a stirrer, a particle size and shape monitoring device (two-stage stirrer plate, the cross angle α of which was 25 °), and stirred. After adjusting the internal temperature to 30 ° C, 5 m
ol / L aqueous sodium hydroxide solution to adjust the pH to 1
Adjusted to 1.0.

Subsequently, magnesium chloride hexahydrate
An aqueous solution obtained by dissolving 1 g in 1000 mL of ion-exchanged water is
The solution was added at 30 ° C. over 10 minutes with stirring. After standing for 3 minutes, heating was started, and the system was heated to 90 ± 3 ° C. over 6 to 10 minutes (heating rate: 10 ° C./min).

[0380] In that state, "Coulter counter TA
-2 ", the particle size of the associated particles was measured, and when the volume average particle size became 5.5 μm, 80.4 g of sodium chloride
Was dissolved in 1,000 mL of ion-exchanged water to stop the particle growth, and further, as a ripening treatment, the mixture was heated and stirred at a liquid temperature of 85 ± 2 ° C. for 0.5 to 15 hours to continue the fusion. . Thereafter, the mixture was cooled to 30 ° C. under the condition of 8 ° C./min, the pH was adjusted to 2.0 by adding hydrochloric acid, and the stirring was stopped. The generated associated particles are filtered using a Nutsche, washed repeatedly with ion-exchanged water, and then, using a flash jet drier, with an intake air temperature of 6.
Dry at 0 ° C. and then use a fluid bed drier at 60 ° C.
At a temperature of to produce "toner particles".

In the monitoring of the salting-out / fusion step and the shape control step, the coefficient of variation of the shape and the shape factor is controlled by controlling the number of rotations of stirring and the heating time, and the variation coefficient of the particle size and the particle size distribution are controlled. Were adjusted to produce "toner particles 1 to 5".

Table 2 shows the particle diameter, shape coefficient, variation coefficient, and the like of “toner particles 1 to 5”.

[0383]

[Table 2]

"Production Example of Toner" To the "toner particles 1 to 5" obtained as described above, a fatty acid metal salt, an abrasive external additive, and an external additive were added at the ratios shown in Tables 3 to 5. ,
Using a 10L Henschel mixer, the peripheral speed of the rotor was 40m /
Secondly, the mixture was mixed for 10 minutes to produce "Toners 1 to 5".

Tables 3 to 5 show the addition amounts of external additives, the circularity count, and the like of "Toners 1 to 5".

[0386]

[Table 3]

[0387]

[Table 4]

[0388]

[Table 5]

[Example of Production of Resin-Coated Carrier] Ferrite core material particles contained 22 mol% of MnO and 78 m ₂ of Fe ₂ O ₃ .
ol% was pulverized, mixed and dried in a wet ball mill for 2 hours, calcined by holding at 900 ° C. for 2 hours, and pulverized in a ball mill for 3 hours to form a slurry. Is added, granulated by a spray drier and dried.
Main firing was performed for 3 hours to produce. The resistance of the ferrite core material particles was 4.3 × 10 ⁸ Ω.

First, cyclohexyl methacrylate was prepared by an emulsion polymerization method using sodium benzenesulfonate having an alkyl group having 12 carbon atoms as a surfactant at a concentration of 0.3% by mass in an aqueous medium. / Methyl methacrylate (copolymerization ratio 5/5). The volume average primary particle size of the coating resin fine particles is 0.1 μm, and the weight average molecular weight (Mw) is 20.
000, number average molecular weight (Mn) is 91,000, M
w / Mn = 2.2, softening point temperature (Tsp) is 230 ° C.,
Glass transition temperature (Tg) was 110 ° C.

Next, 100 parts by mass of the ferrite core material particles and 2 parts by mass of the coating resin fine particles were charged into a high-speed stirring mixer equipped with stirring blades, and were stirred and mixed at 120 ° C. for 30 minutes to obtain a mechanical impact. Was used to produce a “resin-coated carrier” having a volume average particle size of 61 μm.

"Example of Production of Developer" Each of "Toners 1 to 5" to which an additive was added and "Resin-coated carrier" were mixed to form "Developers 1 to 5" having a toner concentration of 6% by mass. Was manufactured.

"Production Example of Photosensitive Member" 30 g of polyamide resin "Amilan CM-8000" (manufactured by Toray Industries, Inc.) was charged into a mixed solvent of 900 mL of methanol and 100 mL of 1-butanol, and dissolved by heating at 50 ° C. This liquid has an outer diameter of 60 mm,
It was applied on a 360 mm long cylindrical aluminum conductive support to form a 0.5 μm thick “intermediate layer”.

Next, the silicone resin “KR-5240”
10 g of t-butyl acetate (manufactured by Shin-Etsu Chemical Co., Ltd.)
And titanyl phthalocyanine “Y-TiO 2
Pc "(described in JP-A-64-17066) was mixed and dispersed for 20 hours using a sand mill to prepare a coating liquid. Using this liquid, apply on the “intermediate layer”,
A “charge generation layer” having a thickness of 0.3 μm was formed.

Next, 150 g of CTM “T-1” (N- (4-methylphenyl) -N- {4- (β-phenylstyryl) phenyl} -p-toluidine) and a polycarbonate resin having a viscosity average molecular weight of 20,000 "Iupilon Z-200"
200 g (manufactured by Mitsubishi Gas Chemical Company) was dissolved in 1,000 mL of 1,2-dichloroethane to prepare a charge transport layer coating solution. This solution was applied using a circular slide hopper and then dried at 100 ° C. for 1 hour to form a 22 μm thick “charge transport layer”.

Next, 30 g of CTM “T-1” and a polycarbonate resin having a viscosity average molecular weight of 80,000 “Iupilon Z-
800 "(manufactured by Mitsubishi Gas Chemical Co., Ltd.) in 1000 mL of 1,2-dichloroethane was coated with a coating solution on the" charge transport layer "using a circular slide hopper.
After drying at 100 ° C. for 1 hour, an “overcoat layer” having a thickness of 5 μm was formed to produce a “photoreceptor”.

"Evaluation of actual photography" A commercially available digital copying machine "KonicaSiti" equipped with a toner recycling system
os 7020 "(manufactured by Konica Corporation) (remodeled cleaning unit: a cleaning method using an elastic cleaning blade, the intersection angle φ between the holder and the image forming body is 25 °). And "developer 1
5 ”, and after printing 300,000 sheets of images with a pixel rate of 8% continuously in a high-temperature and high-humidity environment (temperature 33 ° C., relative humidity 80%) using“ toners 1 to 5 ”, Image blur, fog, uniformity of halftone, toner scattering of fine dots, and the like were evaluated.

<Amount of Wear of Cleaning Blade> After printing 100,000 sheets, the cleaning blade was removed from the cleaning device, and the portion disappeared due to wear was measured with a laser microscope. If the amount of wear is within 15 μm, there is no problem.

<Photoreceptor Wear> The wear of the photoconductor was calculated from the difference between the outer diameter of the photoconductor before starting printing and the outer diameter of the photoconductor after printing 300,000 sheets. If the amount of wear is within 10 μm, there is no problem.

<Toner slippage> [0400] Evaluation was made based on the number of sheets where toner slipped from the cleaning device onto the photoreceptor in the white area of the image and was detected as image stain.

<Toner Filming of Photoconductor> Each 10,000 prints were evaluated by observing the photoconductor surface with the naked eye.

<Lifetime of Photoconductor> Evaluation was made based on the number of prints when the fog density (the relative density of the non-image area with respect to the transfer paper) when the exposure amount was maximized exceeded 0.01. The fog density was measured with "Densitometer PDA-65" (manufactured by Konica Corporation).

<Image blur> A character image having a character size of 5 points was formed on the entire image, and evaluation was made based on the number of prints until the image was blurred locally or a portion where toner spreads around the image was detected.

<Fog> A character image having a character size of 5 points was formed on the entire image, and the fog in the non-image portion was visually evaluated.

Rank ：: good without fog Rank ：: good without fog, practically no problem Rank x: practically problematic with fog <Homogeneity of halftone> Uniformity of halftone is visually judged. The uniformity of the halftone image was visually evaluated.

Rank A: uniform image without unevenness Rank B: presence of thin stripe-like unevenness Rank C: presence of several thin stripe-like unevenness Rank D: presence of several or more clear stripe-like unevenness <fine Dot toner scattering> A 10% halftone dot image was formed on the entire image, and toner scattering around the dots was observed with a loupe.

Rank ：: toner scattering is hardly detectable. Rank ：: toner scattering is slight, but not noticeable unless gazing. Rank ×: toner scattering is easily detected, and the level of practical problems is evaluated. It is shown in Table 6.

[0408]

[Table 6]

The continuous printing of an image having a low pixel rate under a high-temperature and high-humidity environment using a printer equipped with a toner recycling system is a severe condition because embedding of external additives is promoted. 3 (Examples 1-3)
It was found that both of the toners were at a level having no practical problem, whereas the toners 4 and 5 (Comparative Examples 1 and 2) outside the present invention were at a level having a practical problem.

[0410]

As demonstrated in the examples, the image forming method and the toner according to the present invention reduce the wear of the cleaning blade, do not cause the toner to slip through for a long period of time, reduce the wear of the photosensitive member, and reduce the toner filming. By eliminating the occurrence of blemishes, the life of the photoreceptor can be extended, and even when printed at high temperature and high humidity, there is no image fogging or image blur, an excellent halftone, and an excellent effect of obtaining an image with little toner scattering of fine dots. Have.

[Brief description of the drawings]

FIG. 1 is a configuration diagram illustrating an example of a cleaning mechanism according to the present invention.

FIG. 2 is a diagram illustrating a situation where toner on an image forming body is scraped off by an elastic cleaning blade.

FIG. 3 is a diagram illustrating an intersection angle φ between a holder 3 of an elastic cleaning blade 1 and an image forming body 2.

FIG. 4 is a cross-sectional configuration diagram illustrating an example of an image forming apparatus used in the image forming method of the present invention.

FIG. 5 is a perspective view of a member showing an example of a toner recycling device.

FIG. 6 is a sectional view showing an example of a fixing device used in the image forming method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Elastic cleaning blade 2 Image forming body (photosensitive drum) 3 Holder 4 Member for applying contact pressure 5 Waste toner conveying section 6 Guide plate 11 Cleaning device 12 Pre-charge exposure (PCL) 13 fθ lens 16 Developing device 17 Transfer Container 18 transfer paper φ intersection angle

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G03G 15/08 507 G03G 15/08 507L 21/10 507D 21/00 318 326 (72) Inventor Tomomi Oshiba Hachioji-shi, Tokyo 2970, Ishikawacho Konica Co., Ltd. (72) Inventor Hiroyuki Kozuru, 2970, Ishikawacho, Hachioji-shi, Tokyo Konica Co., Ltd. 2H005 AA08 AA15 AB06 CA02 CA14 CA30 CB07 CB08 CB13 DA07 EA05 EA07 EA10 2H077 AA37 AC16 EA14 2H134 GA01 GB02 HD01 HD02 HD04 HD05 HD06 HD11 HD19 JA02 JA11 KD08 KF07 KG07 KH15 KH17

Claims (33)

[Claims] 1. A latent image on an image forming body having an organic photosensitive layer is developed using toner to form a toner image, and the toner image is transferred to a transfer material. In the image forming method including a step of cleaning the residual toner, the cleaning is performed by bringing a tip of an elastic cleaning blade having a base supported by a holder into contact with the image forming body, and an intersection formed between the holder of the elastic cleaning blade and the image forming body. The angle φ is less than 90 °, the toner component has a number average particle size of 4 to 9 μm, and contains 1.0 to 7.0% by number of the toner component with a number standard particle size of 3.17 μm or less. An image forming method using a toner containing a fatty acid metal salt having an average particle size of 0.5 to 4.0 μm. 2. The image forming method according to claim 1, wherein the toner contains an abrasive external additive and an external additive. 3. The image forming method according to claim 1, wherein the cleaned toner is returned to a developing step and reused. 4. A toner containing 1 to 4.5% of toner particles having a number-based particle size of 3.17 μm or less and containing a fatty acid metal salt having a number-average particle size of 0.5 to 3.0 μm. The image forming method according to claim 1, wherein: 5. The toner according to claim 1, wherein the toner contains 0.02 to 2.0 parts by mass of the fatty acid metal salt.
The image forming method according to any one of Items 1 to 4, wherein 6. The toner according to claim 1, wherein the toner contains 0.04 to 1.0 parts by mass of the fatty acid metal salt.
The image forming method according to any one of claims 1 to 5, wherein 7. The circularity coefficient is 0.750 to 0.960.
The image forming method according to any one of claims 1 to 6, wherein the abrasive external additive is contained in a toner. 8. The image forming method according to claim 1, wherein the external additive having abrasive properties is a toner that is strontium titanate. 9. The toner according to claim 1, wherein the toner contains, on the surface of the organic fine particles, inorganic / organic composite fine particles in which inorganic fine particles having a number average primary particle diameter of 5 to 100 nm are fixed to a fixing degree of 20 to 75%. An image forming method according to claim 1. 10. An external additive present on the surface of toner particles having a particle size of 0.005 to 0.025 μm is from 65 to 95.
4% to 34% in number%, 0.025 to 0.080 μm
Number%, 0.080 ~ 0.500μm 0.3 ~
The number average particle diameter of the toner particles adhering to 10% by number is 0.1%.
The image forming method according to any one of claims 1 to 9, wherein a toner containing an abrasive external additive of 5 to 5.0 µm is used. 11. The number average particle size is 0.005 to 0.01.
5 μm silica a having a number average particle size of 0.020 to 0.0
80 μm silica b, having a number average particle size of 0.015 to 0.5 μm.
070 μm titanium oxide c, having a number average particle size of 0.08 to
The toner according to claim 1, wherein the toner particles have a number average particle diameter of 0.5 to 5.0 µm, and the toner particles have an external additive of 0.2 µm titanium oxide d. The image forming method according to any one of items 1 to 10. 12. The proportion of toner particles having a shape coefficient variation coefficient of 16% or less, a number variation coefficient in the number particle size distribution of 27% or less, and a shape coefficient in the range of 1.0 to 1.6. The image forming method according to any one of claims 1 to 11, wherein a toner having a ratio of 65% by number or more is used. 13. The ratio of toner particles having no corners is 50% by number or more, the number variation coefficient in the number particle size distribution is 27% or less, and the shape factor is in the range of 1.0 to 1.6. 13. The toner according to claim 1, wherein a toner having a ratio of toner particles of 65% by number or more is used.
Item. 14. A toner comprising toner particles having a shape coefficient in the range of 1.2 to 1.6, wherein the proportion of toner particles is 65% by number or more and the coefficient of variation of the shape coefficient is 16% or less. The image forming method according to claim 1, wherein: 15. When the particle diameter of toner particles is D (μm), the natural logarithm lnD is plotted on the horizontal axis, and the horizontal axis is 0.2.
The relative frequency (m1) of the toner particles included in the most frequent class in the histogram showing the number-based particle size distribution divided into a plurality of classes at three intervals, and the toner particles included in the class having the second highest frequency after the most frequent class The image forming method according to any one of claims 1 to 14, wherein a toner having a sum (M) of 70% or more with respect to a relative frequency (m2) is used. 16. The image forming method according to claim 1, wherein a toner obtained by forming particles in an aqueous medium is used. 17. The method according to claim 1, wherein a toner obtained by aggregating and fusing the resin particles in an aqueous medium is used.
17. The image forming method according to any one of items 16 to 16. 18. A toner image is formed by developing a latent image on an image forming body provided with an organic photosensitive layer using a toner, and transferring the toner image to a transfer material. In a toner used in an image forming method having a step of cleaning residual toner, the cleaning is performed by bringing a tip of an elastic cleaning blade supported by a holder into contact with an image forming body, and forming the image with the holder of the elastic cleaning blade. The toner has a crossing angle φ of less than 90 °, a toner number average particle diameter of 4 to 9 μm, and a number-based particle diameter of 3.17 μm or less.
% To 7.0% by number, and the number average particle size is 0.5 to 4.0.
A toner comprising a fatty acid metal salt of μm. 19. The toner according to claim 18, wherein the toner contains an abrasive external additive and an external additive.
The toner according to 1. 20. The toner according to claim 1, wherein the toner has 1 to 4.5% of toner particles having a number-based particle size of 3.17 μm or less, and has a number-average particle size of 0.
The toner according to claim 18, further comprising a fatty acid metal salt of 5 to 3.0 μm. 21. The fatty acid metal salt is added in an amount of 0.02 to 2.0.
The toner according to any one of claims 18 to 20, wherein the toner is contained in parts by mass. 22. The fatty acid metal salt is added in an amount of 0.04 to 1.0.
The toner according to any one of claims 18 to 21, wherein the toner is contained in parts by mass. 23. A circularity coefficient of 0.750 to 0.96
The toner according to any one of claims 18 to 22, wherein the abrasive external additive of 0 is contained in the toner. 24. The abrasive external additive according to claim 18, wherein the external additive is strontium titanate.
The toner according to any one of the above items. 25. The organic fine particles according to claim 18, further comprising inorganic / organic composite fine particles having inorganic fine particles having a number average primary particle diameter of 5 to 100 nm fixed to a fixing degree of 20 to 75% on the surface of the organic fine particles. The toner according to claim 1. 26. The toner according to claim 26, wherein the external additive present on the surface of the toner particles is from 0.005 to 0.025 μm.
4% to 34% in number%, 0.025 to 0.080 μm
Number%, 0.080 ~ 0.500μm 0.3 ~
The number average particle size of the toner particles adhered to 10% by number is 0.1%.
The toner according to any one of claims 18 to 25, further comprising an abrasive external additive of 5 to 5.0 µm. 27. The number average particle size is 0.005 to 0.01.
5 μm silica a having a number average particle size of 0.020 to 0.0
80 μm silica b, having a number average particle size of 0.015 to 0.5 μm.
070 μm titanium oxide c, having a number average particle size of 0.08 to
The toner particles to which an external additive of titanium oxide d having a thickness of 0.2 μm is externally added include an abrasive external additive having a number average particle diameter of 0.5 to 5.0 μm. 27. The toner according to any one of items 26 to 26. 28. A ratio of toner particles having a shape coefficient variation coefficient of 16% or less, a number variation coefficient in a number particle size distribution of 27% or less, and a shape coefficient in a range of 1.0 to 1.6. The toner according to any one of claims 18 to 27, wherein is less than 65% by number. 29. The ratio of toner particles having no corners is 50% by number or more, and the number variation coefficient in the number particle size distribution is 2%.
29. The toner according to claim 18, wherein the ratio of toner particles having a shape factor in the range of 1.0% to 1.6% is 65% by number or more. toner. 30. The toner according to claim 30, wherein the proportion of toner particles having a shape factor in the range of 1.2 to 1.6 is 65% by number or more and the variation coefficient of the shape coefficient is 16% or less. The toner according to any one of claims 18 to 29, wherein 31. When the particle diameter of the toner particles is D (μm), the natural logarithm lnD is plotted on the horizontal axis, and the horizontal axis is 0.2.
The relative frequency (m1) of the toner particles included in the most frequent class in the histogram showing the number-based particle size distribution divided into a plurality of classes at three intervals, and the toner particles included in the next most frequent class after the most frequent class 20. The sum (M) of the relative frequency (m2) and the relative frequency (m2) is 70% or more.
31. The toner according to any one of items 30 to 30. 32. The toner according to claim 18, which is obtained by forming particles in an aqueous medium. 33. The toner according to claim 18, which is obtained by aggregating and fusing resin particles in an aqueous medium.