JPH09166885A - Electrostatic charge image developing toner, image forming method, developing device unit and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an image which shows stable density from the initial period of formation and has uniform density without fog or irregularity even under low humidity or high humidity conditions, to prevent deposition, melt sticking or filming of a toner on a photoreceptor even when the toner is used for a long time, and to decrease abrasion or scratches on the photoreceptor compared to a conventional method. SOLUTION: This toner consists of an inorg. fine powder and toner particles containing at least a binder resin and a coloring agent. The inorg. fine powder is treated with such a silicone oil that its mol.wt. distribution by GPC has at least one max. in the region from 500 to 15000mol.wt. and at least one max. larger than the first max. above described or a shoulder in the region from 3000 to 100000mol.wt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner used in an image forming apparatus such as a printer, a copying machine and a facsimile using an electrophotographic method, an image forming apparatus using the toner, and a developing apparatus. The present invention relates to a unit and a process cartridge.

[0002]

2. Description of the Related Art Conventionally, many electrophotographic methods are known, but generally, an electrostatic latent image is formed on a photoconductor having a photoconductive substance by various means, and then the latent image is formed. The image is developed with toner to make it a visible image, and if necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat and pressure to obtain a copy. is there.

In recent years, image forming apparatuses using electrophotography have been applied as printers and facsimiles in addition to conventional copying machines, and have come to be used in general offices and homes.

In office copying machines, higher speed and stabilization are always desired, and high-speed use and stability of image density and image quality from the initial stage to the long-term use have become important. . In particular, stability of image quality under high humidity / high temperature, low humidity / low temperature, stability of image quality immediately after the apparatus main body is switched on, and stability of image quality before and after toner replenishment are required.

Conventionally, as a developing system for electrophotography,
A one-component developing method and a two-component developing method are known.
Above all, a one-component developing system is being adopted from the viewpoint that the structure of the developing device can be simplified while ensuring high reliability.

However, in the one-component developing system, it is necessary to uniformly coat the surface of a roll-shaped toner carrier such as a developing sleeve with a toner layer thickness regulating member in a thin layer. For this reason, a strong rubbing force is applied to the toner, and deterioration of the toner or the surface of the toner carrier easily occurs due to long-term use, and it is an object to further suppress deterioration of durability characteristics. Therefore, a technique for further improving this durability characteristic is desired.

As a charging means in electrophotography, a means utilizing corona discharge has been generally used. However, since the use of corona discharge generates a large amount of ozone, it is necessary to provide a filter, and there is a problem that the device becomes large or the running cost increases.

As a technique for solving such a problem, a charging member such as a roller or a blade is brought into contact with the surface of the photosensitive member to form a narrow space in the vicinity of the contact portion, and the so-called passion law is used. A charging method has been developed in which ozone generation is suppressed as much as possible by forming a discharge that can be interpreted. Among these, a roller charging method using a charging roller as a charging member is particularly preferably used from the viewpoint of charging stability.

The contact charging method and the contact transfer method are described in, for example, JP-A-63-149669 and JP-A-2-
No. 123385 has been proposed. In these, a conductive elastic roller is brought into contact with the electrostatic latent image carrier, the electrostatic latent image carrier is uniformly charged while applying a voltage to the conductive roller, and then a toner image is formed by exposure and development processes. After that, the transfer material was passed through while pressing another conductive roller to which a voltage was applied to the electrostatic latent image carrier to transfer the toner image on the electrostatic latent image carrier to the transfer material. After that, a copied image is obtained through a fixing process.

However, even in such a contact charging device, since the essential charging mechanism uses the discharging phenomenon from the charging member to the photosensitive member, the voltage required for charging as described above. Is required to have a value equal to or higher than the surface potential of the photoconductor. Furthermore, when AC charging is performed for uniform charging, vibration of the charging member and the photoconductor due to an electric field of AC voltage, generation of noise (hereinafter referred to as AC charging sound), and
Deterioration of the surface of the photoconductor due to electric discharge becomes remarkable, and accordingly, fusion or filming in which toner or a part of the toner component adheres to the surface of the photoconductor becomes a new problem.

Further, in such a roller transfer system which does not use corona discharge, since a transfer member such as a roller is brought into contact with a photoconductor through a transfer material such as paper at the time of transfer, idle rotation before and after passing the paper is performed. At times, filming occurs due to rubbing against the toner that is photosensitively attached, and when the toner image formed on the photoconductor is transferred to the transfer material, the toner image is subjected to pressure. A partial transfer defect called omission occurs, which is a serious problem in image quality.

In order to solve this problem, Japanese Patent Laid-Open Publication No.
No. 62 proposes an image forming apparatus using a developer containing hydrophobic inorganic fine powder treated with silicone oil. However, with a thick transfer paper or OHP sheet having a weight per unit of more than 100 g / m ² such as a postcard or a Kent paper, it is still sufficiently improved, and higher image quality is required.

Further, since the charging member and the contact transfer member in contact with each other are in contact with each other, the transfer residual toner and the toner which has passed through the cleaner adhere to the charging member and the transfer member, and when a large amount is accumulated, they are uniformly charged and evenly charged. The transfer is alienated, and streaks or unevenness appear in the halftone image.

Toner particles that have not been transferred onto the transfer material and remain on the photosensitive member are removed from the photosensitive member by a cleaning process. Regarding this cleaning process, conventional blade cleaning, fur brush cleaning or roller cleaning is used. Was used. However,
In any of the cleaning methods, the transfer residual toner is mechanically scraped off or dammed to be collected in a waste toner container. Therefore, due to such a cleaning member being pressed against the surface of the photoconductor, for example, by pressing the member strongly, the photoconductor is worn and scratches are generated on the photoconductor, and the toner appears on the image. There are problems that they are easily fixed (fused) on the surface and that external additives such as liberated silica adhere to the drum surface (filming).

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic charge image, an image forming method using the toner, a developing device unit and a process cartridge which solve the above-mentioned problems. is there.

The object of the present invention is to stabilize the concentration from the beginning,
To provide an electrostatic charge image developing toner capable of obtaining an image having a uniform density without fog or unevenness even under low humidity and high humidity, an image forming method using the toner, a developing device unit and a process cartridge. .

An object of the present invention is to provide a toner for developing an electrostatic charge image, which has a high fluidity, a high resolution, a high sharpness and forms an image faithful to an original, and an image using the toner. It is to provide a forming method, a developing device unit, and a process cartridge.

An object of the present invention is to provide a toner for developing an electrostatic image which is uniform and free of roughness in halftone images and solid images, an image forming method using the toner, a developing device unit and a process cartridge. .

An object of the present invention is to provide an electrostatic charge image developing toner having a high transfer efficiency with no image dropout during transfer and high image transfer efficiency in an image forming method using a contact charging means, and an image forming method using the toner. , A developing device unit and a process cartridge.

An object of the present invention is to provide a toner for developing an electrostatic charge image, which prevents toner adhesion, fusion and filming to a photoreceptor even after long-term use and reduces abrasion and scratches on the photoreceptor as compared with conventional toners. An object of the present invention is to provide an image forming method, a developing device unit and a process cartridge used.

[0021]

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

That is, the present invention provides a toner for developing an electrostatic image comprising toner particles containing at least a binder resin and a colorant, and an inorganic fine powder, wherein the inorganic fine powder is:
In the molecular weight distribution by GPC, the molecular weight is 500 to 1
It has at least one local maximum in the region of 5,000 and is larger than the local maximum, and has a molecular weight of 3,000 to 1,000.
The toner for developing an electrostatic charge image is characterized by being treated with a silicone oil having at least one local maximum or shoulder in the area 00.

The present invention also includes a charging step of charging the latent image holding member by a charging member, a latent image forming step of forming an electrostatic latent image on the charged latent image holding member by a latent image forming means, and a toner image. In the image forming method including a developing step of developing the electrostatic latent image with a toner to form a toner and a step of transferring the toner image to a transfer material by a transfer member, the toner contains at least a binder resin and a colorant. It has toner particles and inorganic fine powder contained therein, and the inorganic fine powder is G
In the molecular weight distribution by PC, the molecular weight is 500 to 15
000 region, at least one maximum value, and larger than the maximum value, the molecular weight is 3,000 to 10,000.
The present invention relates to an image forming method characterized by being treated with a silicone oil having at least one maximum value or shoulder in the 0 region.

Further, according to the present invention, the toner for developing the electrostatic latent image, the toner container for accommodating the toner and the toner contained in the toner container are carried, and the electrostatic latent image is formed. In a developing device unit having a toner carrier for carrying to a developing area where development is to be performed,
The toner has toner particles containing at least a binder resin and a colorant, and an inorganic fine powder, and the inorganic fine powder has a molecular weight of 500 in GPC molecular weight distribution.
Characterized in that it is treated with a silicone oil which has at least one local maximum in the region of 1 to 15,000 and is larger than the local maximum and has at least one local maximum or shoulder in the region of molecular weight 3000 to 100000. Developing device unit.

Further, according to the present invention, in a process cartridge detachable from the main body of the image forming apparatus, the process cartridge is held by a latent image holding member for holding an electrostatic latent image and the latent image holding member. A developing device for developing the electrostatic latent image, the developing device including a toner for developing the electrostatic latent image, a toner container for storing the toner, and a toner container for storing the toner. And a toner carrier for carrying the electrostatic latent image to a developing area where the electrostatic latent image is developed. The toner contains at least a binder resin and a colorant. Toner particles and inorganic fine powder are included, and the inorganic fine powder has at least one local maximum in the molecular weight range of 500 to 15,000 in the molecular weight distribution by GPC,
And has a molecular weight of 3000 to 10 which is larger than the maximum value.
The present invention relates to a process cartridge characterized by being treated with a silicone oil having at least one local maximum or shoulder in the area of 0000.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive investigations by the present inventors,
In the molecular weight distribution by GPC, the molecular weight is 500 to 1
Have at least one or more local maxima in the 5000 region,
And has a molecular weight of 3000 to 10 which is larger than the maximum value.
By externally adding the inorganic fine powder treated with silicone oil having at least one maximum value or shoulder in the region of 0000 to the toner particles, the toner has a high fluidity, and the toner has a high fluidity during development. The amount of charge rises quickly, the durable density is stable, and it is possible to form a clear image without fog or graze.Furthermore, even under low humidity and high humidity, there is no fog or density reduction, It has been found that it is possible to form a high-resolution image that is evenly coated and that is faithful to the latent image.

Further, when the above toner is used in an image forming method using a contact transfer means, the present inventors provide high transfer efficiency with no defects in images during transfer and no image defects, and toner or other materials. Since the additive does not contaminate the charging member and the transfer member, streaks and unevenness due to uneven charging and uneven transfer can be eliminated, and a uniform halftone image can be formed. It has been found to prevent toner fusing.

Further, when the above-mentioned toner is used in a component type developing device, the inventors of the present invention do not contaminate a developer carrying member such as a developing sleeve in a one-component developing system, and a toner coating method using an elastic blade. It was also found that, even in the case of halftone and solid black images, a uniform image without white stripes can be formed, and an image with a uniform image density can be formed even when continuous copying of solid black images is performed.

Further, when fixing the toner image formed by using the above-mentioned toner, the present inventors suppress the scattering of the line image and the character image at the time of fixing and improve the electrostatic charge offset property. I found it.

The inventors of the present invention have examined the silicone oil-treated inorganic fine powder to be externally added to the toner. As a result, the toner characteristics largely change depending on the molecular weight of the silicone oil to be treated, and the higher the molecular weight, the higher the charge amount. It has been found that the mold releasability from the body is also excellent.

However, the higher the molecular weight of the silicone oil, the more difficult it becomes to uniformly process the inorganic fine powder, resulting in lumps, deterioration of the hydrophobicity of the treated fine powder, and fogging of the toner obtained by addition. It happens.
Dama may cause uneven coating or fog in low humidity when the toner is coated on the sleeve of the toner carrier, and further causes dot-shaped blank areas in a solid black image. The decrease in hydrophobicity causes a decrease in image density due to durability under high humidity.

In the present invention, since the inorganic fine powder obtained is treated with a silicone oil containing a low molecular weight component together with a high molecular weight component, the obtained inorganic fine powder has suppressed lumps and has sufficient hydrophobicity, and In addition to the fact that the toner obtained by adding the toner has less fogging, the toner has a high charge amount, the charge rises quickly, and the releasability of the toner from the photoconductor is good.

Although the reason for this is not clear, the presence of the low molecular weight component makes the coating of the high molecular weight component on the inorganic fine powder uniform, and the coexistence of the low molecular weight component causes the high molecular weight component to rise quickly. It is considered that this is because the charging performance and the high releasing performance for the photoconductor are brought out.

The silicone oil used in the present invention is
In the molecular weight distribution by GPC, the molecular weight is 500 to 1
In the region of 5000, preferably a molecular weight of 1000 to 1
More preferably in the region of 5000, more preferably at least one maximum in the region of molecular weight 2000 to 10000, and larger than the maximum, the region of molecular weight 3000 to 100000, preferably the region of molecular weight 5000 to 100000, More preferably, the molecular weight is 100.
By having at least one maximum value or shoulder in the area of 00 to 100,000, filming on the photoconductor, toner fusion, and contamination of the developing sleeve as the toner carrier can be prevented.

The maximum value on the low molecular weight side is a molecular weight of 500 to 1.
If it does not exist in the region of 5000 and has a molecular weight of less than 500, the amount of volatile components increases, the amount of silicone oil treated on the surface of the inorganic fine powder becomes unstable, and uneven charging is likely to occur. The maximum value on the low molecular weight side is molecular weight 5
It does not exist in the region of 00 to 15,000 and has a molecular weight of 150.
When it is in the range of more than 00, it becomes impossible to uniformly treat the high molecular weight component of the silicone oil into the inorganic fine powder, and lumps occur, or the hydrophobicity of the treated inorganic fine powder becomes low, resulting in high humidity. Causes image density loss below.

Further, the maximum value or shoulder on the high molecular weight side does not exist in the region of the molecular weight of 3000 to 100000. When the molecular weight is less than 3000, the charging property and the releasability from the photoconductor are likely to be lowered. . When the maximum value or shoulder on the high molecular weight side exceeds 100,000,
It is difficult to uniformly treat the high molecular weight component of the silicone oil into the inorganic fine powder.

The silicone oil used in the present invention is
In the molecular weight distribution by GPC, weight average molecular weight / number average molecular weight (Mw / Mn) is preferably 2 to 40,
More preferably 2 to 30, still more preferably 2 to 2
Within the range of 0, filming and fusion can be suppressed.

If Mw / Mn is less than 2, a decrease in concentration may occur during toner replenishment under high temperature and high humidity, and if Mw / Mn exceeds 40, lumps are likely to occur. Filming and fusion may occur.

The silicone oil used in the present invention is
In the molecular weight distribution by GPC, the average molecular weight / number average molecular weight (Mz / Mn) is preferably 3 to 100,
More preferably, it is in the range of 4 to 30.

That is, the molecular weight of the silicone oil is 5
The component having the maximum value in the range of 00 to 15000, by itself, has a low viscosity, so that it migrates from the inorganic fine powder to the developing sleeve and adheres during development, resulting in a decrease in image density as image formation is repeated. May cause However, it contains a high-molecular weight component having a maximum value or peak in the molecular weight range of 3000 to 100,000, and has a Mz / Mn in the molecular weight distribution by GPC.
It is considered that when 3 is 3 or more, the silicone oil on the inorganic fine powder has increased viscoelasticity and is less likely to adhere to the sleeve. Therefore, the inorganic fine powder treated with the silicone oil having Mz / Mn of 3 or more reduces generation of lumps and enables uniform treatment to reduce liberation of the inorganic fine powder from the toner particles. It is possible to prevent the inorganic fine powder from adhering to the photosensitive member and prevent filming and toner fusion. Furthermore, since the amount of toner on the line image decreases by accelerating the rise of charging, the height of the toner on the line image before fixing becomes low, and the scattering at the time of fixing and the offset also decrease. Conceivable.

Further, when Mz / Mn is 100 or less, the lubricity of the cleaner is good, so that the occurrence of scratches on the photoconductor can be reduced.

If the Mz / Mn is less than 3, the developing sleeve may be contaminated and the image density may be lowered. If the Mz / Mn exceeds 100, the photoconductor may be scratched. Cheap.

Further, in the present invention, as shown in FIG. 1, in the molecular weight distribution of silicone oil by GPC, it has a maximum value in the region of molecular weight of 500 to 15,000 and is larger than the maximum value, and the molecular weight of 3,000 to 100,000. When the region has a maximum value, the distance from the apex of the maximum value existing in the molecular weight range of 500 to 15,000 to the baseline is A, and the maximum value that is larger than the maximum value and exists in the molecular weight range of 3000 to 100,000. The distance from the peak of the value to the baseline is B, and the base is from the bottom point of the minimum value existing between the maximum value existing in the molecular weight range of 500 to 15,000 and the maximum value existing in the molecular weight range of 3000 to 100000. When the distance to the line is C, A, B and C are preferably the following conditions A: B : C = 1: 0.01 to 1.0: 0.001 to 0.
70 is preferably satisfied, and more preferably the following condition A: B: C = 1: 0.08 to 0.5: 0.02 to 0.4.
It is good to satisfy 5.

In the relationship between A, B and C when there are two maximum values, when A is 1 and B is less than 0.01, the high molecular weight is small and the high molecular weight is high. I can not expect sex.

When A exceeds 1 and B exceeds 1.0, the amount of high molecular weight is too large, which makes it difficult to uniformly process the inorganic fine powder, and tends to cause lumps and decrease in hydrophobicity.

When A is 1 and C is less than 0.001, it is difficult to uniformly disperse the inorganic fine powder having a high molecular weight, and fog or blotch is likely to occur due to uneven charging.

When A exceeds 1 and C exceeds 0.5, as a result, the amount of high molecular weight is too large, and lumps are likely to occur.

Further, in the present invention, as shown in FIG. 2, in the molecular weight distribution of silicone oil by GPC, it has a maximum value in the region of molecular weight of 500 to 15,000 and is larger than the maximum value, and a molecular weight of 3000 to 1 is obtained.
In the case of having a shoulder in the region of 00000, the distance from the peak of the maximum value existing in the region of the molecular weight of 500 to 15,000 to the baseline is A, and the molecular weight is 3,000.
It is preferable that A and B satisfy the following condition A: B = 1: 0.1 to 0.7, where B is the distance from the inflection point of the shoulder existing in the region of 100 to 100000 to the baseline. More preferably, the following condition A: B = 1: 0.1 to 0.5 should be satisfied.

The above A when the maximum value and the shoulder are provided
In the relationship between B and B, when A is 1 and B is less than 0.1, the high molecular weight is small and the charging property is low.

When A exceeds 1 and B exceeds 0.7, the amount of high molecular weight increases and the uniform treatment of the inorganic fine powder becomes inferior, which causes lumps and lowers the hydrophobicity. It will be easier.

In the present invention, in the above GPC molecular weight distribution, when there are a plurality of maximum values or shoulders in each molecular weight region, an inflection point of the highest peak or shoulder in each molecular weight region, Is A or B, and when there are a plurality of local minimum values, the bottom point of the smallest local minimum value is C.

The shoulder according to the present invention is judged from the point where the differential value of the GPC chromatogram curve becomes the extreme value, that is, the inflection point.

In the present invention, the silicone oil GP
The molecular weight distribution of the chromatogram by C (gel permeation chromatography) is measured under the following conditions using toluene as a solvent.

That is, the column is stabilized in a heat chamber at 40 ° C., and toluene as a solvent is flowed through the column at a temperature of 1 ml / min, and a toluene sample solution of about 50 to 300 μl is injected for measurement. The molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. In that case, as the standard polystyrene sample for preparing the calibration curve, the molecular weight manufactured by Tosoh Corporation is 1 × 10 ² to
It is suitable to use a standard polystyrene sample of at least about 10 points, using a sample of about 1 × 10 ⁷ . An RI (refractive index) detector is used as the detector. As the column, a combination of a plurality of commercially available polystyrene gel columns may be used, and Shodex K-80 manufactured by Showa Denko KK
A combination of M and K-802 is used.

The sample is prepared as follows.

The sample is placed in toluene, left to stand for 30 minutes, shaken sufficiently, well mixed with toluene, and left still for 1 hour. After that, a sample that has passed through a sample processing filter (for example, Mysholydisk H-13-5; manufactured by Tosoh Corporation, Excicrodisk 25CR; manufactured by Gelman Science Japan Co., Ltd., etc.) can be used as a sample of GPC. The sample concentration is 0.5 to 5 mg / m
Adjust to be l.

The silicone oil used in the present invention is
It is represented by the following formula (1).

[0058]

[Outside 9] [In the formula, R ₁ represents a methyl group, another alkyl group, an aryl group or hydrogen, and independently, R ₂ represents a methyl group, another alkyl group, an aryl group, a vinyl group or an alkyl group having a functional group. A group, an aryl group having a functional group, or hydrogen is shown, and m and n are integers. ]

As the functional group, for example, an amino group; OH
Group; alkoxy group; polyether group; ester group; F,
Halogens such as Cl and Br.

Preferred silicone oils include, for example, dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl modified silicone oil, chloroalkyl modified silicone oil, chlorophenyl modified silicone oil,
Examples thereof include fatty acid-modified silicone oil, polyether-modified silicone oil, alkoxy-modified silicone oil, carbinol-modified silicone oil, amino-modified silicone oil and fluorine-modified silicone oil.

Particularly, from the viewpoint of preventing hollow defects, dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, fluorine-modified silicone oil, and alkyl-modified silicone oil are preferable.

The viscosity of silicone oil is 2 cS.
t-1,000,000 cSt is preferable.

The silicone oil used in the present invention is
It can be prepared by a conventionally known production method, and a low molecular weight component may be polymerized in the presence of a high molecular weight component,
In the presence of low molecular weight components, high molecular weight components may be polymerized,
Alternatively, two or more kinds of silicone oils having different average molecular weights may be mixed.

When the toner of the present invention is applied as a positively chargeable toner, the apparent amine equivalent of the silicone oil used is preferably in the range of 300 to 10000, more preferably 1000 to 6000. It is good to be inside.

When the amine equivalent of the silicone oil is less than 300, the charge amount becomes too high at low temperature and low humidity, which may cause coating unevenness on the relief, and when the amine equivalent of the silicone oil exceeds 10,000. Has a low charge amount under high temperature and high humidity,
The image density may decrease.

In the present invention, as the silicone oil having an amine equivalent of 300 to 10,000, an amino-modified silicone oil having at least a partial structure represented by the following formula (2) can be preferably used. These partial structures may be present at the end of the silicone oil.

[0067]

[Outside 10] Wherein, R ₃ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₄ represents an alkylene group or a phenylene group, R ₅ is R ₆ represents hydrogen, an alkyl group or an aryl group, R ₇ is A nitrogen-containing heterocyclic group is shown. The above alkyl group, aryl group, alkylene group or phenylene group may have an organo group having a nitrogen atom, or may have a substituent such as halogen within a range not impairing the charging property. .

Examples of the organo group having at least one nitrogen atom include an amino group having an organic group as a substituent, a nitrogen-containing heterocyclic group and a group having a nitrogen-containing heterocyclic group.

As the nitrogen-containing heterocyclic group, there are an unsaturated heterocyclic group and a saturated heterocyclic group, and known ones can be applied.

Examples of unsaturated heterocyclic groups include the following.

[0071]

[Outside 11]

Examples of the saturated heterocyclic group include the followings.

[0073]

[Outside 12] The heterocyclic group used in the present invention is preferably a 5- or 6-membered ring in consideration of stability.

The viscosity of the amino-modified silicone oil is preferably 2 cSt to 1,000,000 cSt.

In the present invention, as the silicone oil having an amino equivalent in the range of 300 to 10,000, it is preferable to use a combination of the above amino-modified silicone oil and a silicone oil having no amino group. It is preferable because it decreases.

Examples of the amino group-free silicone oil used in combination with the amino-modified silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil and vinyl group-containing silicone. Oil is included.

The dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil and vinyl group-containing silicone oil used in the present invention have the following formula (3).
Is indicated by.

[0078]

[Outside 13] [In the formula, R ₈ represents a methyl group, another alkyl group, an aryl group or hydrogen, and R ₉ independently has a methyl group, another alkyl group, an aryl group, a vinyl group or a hydroxyl group. Is an alkyl group or an aryl group, or hydrogen, and m and n are integers. ]

Among them, dimethylsilicone oil, methylphenylsilicone oil and methylhydrogensilicone oil are preferable from the viewpoint of hollowness, and dimethylsilicone oil is particularly preferable.

In the present invention, the mixing ratio of the amino-modified silicone oil and the silicone oil having no amino group is preferably 1:20 to 10: 1.

The viscosity of the silicone oil obtained by mixing the amino-modified silicone oil and the silicone oil having no amino group is 2 cSt to 1,000,000 cS.
t is preferred.

In the present invention, the treatment amount of the silicone oil with respect to the inorganic fine powder cannot be unconditionally specified because the specific surface area of the inorganic fine powder also affects, but the silicone oil is added to 5 parts by weight of the silicone oil with respect to 100 parts by mass of the inorganic fine powder. ~ 70
It may be used in an amount of parts by mass, preferably 7-40 parts by mass. If it is less than 5 parts by mass, it is difficult to obtain sufficient hydrophobicity and 70
If it exceeds the mass part, lumps are generated, or the specific surface area becomes small, resulting in poor fluidity.

As the inorganic fine powder used in the present invention,
Metal oxides of metals such as silicon, titanium, aluminum, germanium, magnesium, zinc, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin, antimony, molybdenum, tungsten; oxides such as boron oxide; silicon nitride. , Nitrides such as germanium nitride; complex metal oxides such as calcium titanate, magnesium titanate, strontium titanate, phosphotungstic acid, phosphomolybdic acid; metal salts such as calcium carbonate, magnesium carbonate, aluminum carbonate; kaolin. Clay minerals; acid compounds such as apatite; carbides such as silicon carbide and titanium carbide; silicon compounds; carbon powders such as carbon black and graphite.

Specific examples thereof include silicon oxide, aluminum oxide, titanium oxide, cerium oxide, germanium oxide, zinc oxide, tin oxide, zirconium oxide, molybdenum oxide, tungsten oxide, strontium oxide, boron oxide, silicon nitride and titanium. Mention may be made of calcium acidate, magnesium titanate, strontium titanate, phosphotungstic acid, phosphomolybdic acid, calcium carbonate, magnesium carbonate and aluminum carbonate.

Among these inorganic fine powders, silicon oxide,
Aluminum oxide and titanium oxide are preferred. There are many forms and types of these, but among them, silica fine powder represented by SiO _{2 as a} main component, alumina fine powder represented by Al ₂ O ₃ and titania fine powder represented by TiO ₂ are preferable,
Silica fine powder is particularly preferable.

As the inorganic fine powder, it is possible to use an inorganic fine powder produced by a dry method or a wet method. The dry method mentioned here is a method for producing an inorganic fine powder produced by vapor-phase acid of a halide. For example, the reaction equation which is the basis of the method utilizing the thermal decomposition oxidation reaction of the halide gas in oxygen hydrogen is shown by the following equation (4).

MX _n + 1 / 2nH ₂ + 1/4 · nO ₂ → MO _{n / 2} + nHX (4) In this formula, for example, M is a metal, a metalloid element, X is a halogen element, and n is an integer. is there. Specifically, AlCl ₃ , TiCl ₄ , GeCl ₄ , SiCl
_{If 4} , POCl ₃ and BBr ₃ are used, Al ₂
O ₃ , TiO ₂ , GeO ₂ , SiO ₂ , P ₂ O ₅ , B ₂
O ₃ is obtained. At this time, if a mixture of halides is used, a composite compound can be obtained.

As another method for producing the inorganic fine powder, heat C
By applying a manufacturing method such as VD or plasma CVD, it is possible to obtain a dry fine powder. Among them, SiO ₂ ,
Al ₂ O ₃ and TiO ₂ are preferably used.

As the method for producing the inorganic fine powder used in the present invention by a wet method, various conventionally known methods can be applied. For example, a method of decomposing an acid of sodium silicate as shown in the following formula (5); Na ₂ O · xSiO ₂ + 2HCl + nH ₂ O → xSiO ₂ · nH ₂ O + 2NaCl (5) With an ammonium salt or an alkali salt of sodium silicate. Method of decomposing; Method of generating alkaline earth metal silicate from sodium silicate, then decomposing with acid to obtain silicic acid; Method of converting sodium silicate solution into silicic acid by ion exchange resin; Natural silicic acid or A method using silicate; In addition, a method of hydrolyzing a metal alkoxide can be mentioned. This general reaction formula (6) is shown below.

M (OR) _n O + 1/2 nH ₂ O → MO ₂ + nROH (6) In this formula, for example, M represents a metal or metalloid element, R represents an alkyl group, and n represents an integer. At this time, if two or more metal alkoxides are used, a composite can be obtained.

The average particle size of these inorganic fine powders is preferably in the range of 0.001 to 2.0 μm in number average of primary particles, and particularly preferably 0.002 to 0.002.
It is preferable that the thickness is within the range of 0.2 μm.

The untreated inorganic fine powder used in the present invention has a specific surface area of 30 by nitrogen adsorption measured by the BET method.
m ² / g or more, it is preferably used in particular in the range of 50 to 500 m ² / g.

The specific surface area of the inorganic fine powder was measured according to the BET method by using a specific surface area measuring device Auto Soap 1 (manufactured by Yuasa Ionics Co., Ltd.) to adsorb nitrogen gas on the sample surface, and then BE
The specific surface area was calculated using the T multipoint method.

In the present invention, the method for treating the inorganic fine powder with the silicone oil is, for example, a method in which the untreated inorganic fine powder and the silicone oil are directly mixed using a mixer such as a Henschel mixer; A method of spraying silicone oil on the treated inorganic fine powder; or a method of dissolving or dispersing the silicone oil in an appropriate solvent and then adding untreated inorganic fine powder and mixing to remove the solvent.

The treated inorganic fine powder has a specific surface area by nitrogen adsorption measured by the BET method of 40 to 400 m ² / g.
Is preferably within the range.

The inorganic fine powder thus treated has a hydrophobicity of preferably 60% or more, more preferably 80% or more. 60% hydrophobicity
If it is less than 100%, the image density may be reduced under high humidity conditions.

To measure the hydrophobicity, 1.0 g of the sample and 100 g of ion-exchanged water are put in a 200 ml bottle and vigorously stirred for 1 minute. Then, after leaving still for 5 minutes, it is fractionated in a UV cell having a thickness of 10 mm. The light transmittance at 500 nm is measured using ion-exchanged water as a reference, and this light transmittance is taken as the hydrophobicity.

The treated inorganic fine powder used in the present invention is preferably added and mixed in an amount of 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the toner particles. And particularly preferably 0.2 to 3 parts by mass. If it is less than 0.01 parts by mass, the effect of improving toner aggregation will be poor, and if it exceeds 10 parts by mass, problems such as toner scattering between fine lines, contamination inside the machine, and scratches and abrasion of the photoconductor tend to occur. Is.

The inorganic fine powder used in the present invention may be treated with a treating agent such as a silane coupling agent or an organosilicon compound for the purpose of hydrophobizing, if necessary. As the treatment method, a known method is used, and the inorganic fine powder is treated with the above-mentioned treatment agent which reacts with or physically adsorbs to the inorganic fine powder. Examples of the treating agent include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, and bromomethyl. Dimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane , Diphenyldiethoxysilane,
Examples include hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, and 1,3-diphenyltetramethyldisiloxane. These are used in one kind or in a mixture of two or more kinds.

The toner of the present invention has toner particles containing a binder resin and a colorant. Examples of the binder resin used in the present invention include homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene and their substitution products; styrene-p-chlorostyrene copolymers, styrene-vinyl. Toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, Styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-
Styrene-based copolymers such as isoprene copolymer and styrene-acrylonitrile-indene copolymer; polyvinyl chloride; phenol resin; natural modified phenol resin; natural resin modified maleic acid resin; acrylic resin; methacrylic resin; polyvinyl acetate; Polysilicone resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, and petroleum-based resin can be used. Of these, styrene-based copolymers are preferable.

As a comonomer for the styrene monomer of the styrene copolymer, a vinyl monomer is preferable.

Examples of vinyl monomers include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate,
2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate,
A monocarboxylic acid having a double bond such as acrylonitrile, methacrylonitrile and acrylamide or a substituted product thereof; for example, a dicarboxylic acid having a double bond such as maleic acid, butyl maleate, methyl maleate and dimethyl maleate, and Substitutes thereof; vinyl esters such as vinyl chloride, vinyl acetate, vinyl benzoate, ethylene olefins such as ethylene, propylene and butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone Kind;
Examples thereof include vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether.

In the present invention, a crosslinking agent can be used in the styrene copolymer.

As the cross-linking agent, a compound mainly having two or more polymerizable double bonds can be used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate, Ethylene glycol dimethacrylate,
A carboxylic acid ester having two double bonds such as 1,3-butanediol dimethacrylate; a divinyl compound such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and a compound having three or more vinyl groups; Can be used alone or as a mixture.

Among the above styrene-based copolymers, a styrene-acrylic copolymer mainly using acrylic acid ester, acrylic acid, acrylic acid amide, methacrylic acid ester, methacrylic acid, methacrylic acid amide as a comonomer is preferable. Particularly preferred.

Further, a styrene-acrylic terpolymer containing maleic acid, maleic acid ester and maleic anhydride is one of the preferable forms.

The binder resin used in the present invention has at least one peak (Pa) in the molecular weight distribution of 5,000 to 50,000 in the molecular weight distribution measured by GPC.
And has at least one peak or shoulder (Pb) in a region having a molecular weight of 100,000 or more.

In the present invention, the molecular weight distribution of the binder resin GPC chromatogram is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent was flown into the column at this temperature at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution was injected. Measure. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is used.
It is appropriate to use about 0 standard polystyrene samples. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns, for example, shod manufactured by Showa Denko KK
ex GPC KF-801, 802, 803, 80
4,805,806,807,800P combination, Tosoh TSKgel G1000H (H _XL ),
G2000H (H _XL ), G3000H (H _XL ), G40
00H (H _XL ), G5000H (H _XL ), G6000H
(H _XL ), G7000H (H _XL ), TSKguardc
A combination of columns can be mentioned.

The sample is manufactured as follows.

After placing the sample in THF and leaving it to stand for several hours, it is shaken well, mixed well with THF (until the sample is no longer united), and left still for 12 hours or more. Then T
The time of leaving in HF is set to 24 hours or more.
After that, the sample processing filter (pore size 0.45
0.5 μm, for example, Myshoridisk H-25
-5 (manufactured by Tosoh Corporation, Exiclodisk 25CR manufactured by Germanic Science Japan) can be used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

As the method for synthesizing the binder resin according to the present invention, a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method can be used.

In the bulk polymerization method, it is possible to obtain a low molecular weight polymer by polymerizing at a high temperature to accelerate the termination reaction rate, but it is difficult to control the reaction. In the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer depending on the solvent, and by adjusting the amount of the initiator and the reaction temperature. It is preferable when a low molecular weight compound is obtained from the resin composition.

As the solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol, benzene and the like can be used. In the case of a styrene monomer mixture, xylene, toluene or cumene is preferred. It is appropriately selected depending on the polymer to be polymerized.

When a carboxylic acid monomer or an anhydride monomer is used, it is preferable to use the bulk polymerization method or the solution polymerization method in view of the nature of the monomer.

As the binder resin for toner used for pressure fixing, low molecular weight polyethylene, low molecular weight polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, higher fatty acid, polyamide resin, Examples thereof include polyester resins. These are preferably used alone or as a mixture.

In the present invention, conventionally known inorganic or organic dyes / pigments can be used as the colorant contained in the toner particles. Examples thereof include carbon black, aniline black, acetylene black and naphthol yellow. , Hansa Yellow, Rhodamun Lake, Alizarin Lake, red iron oxide, Phthalocyanine Blue, Induslen Blue. These are usually used in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

In the toner of the present invention, a magnetic material can be used as a colorant, if necessary.

As the magnetic material used in the present invention, iron oxide such as magnetite, γ-iron oxide, ferrite iron, and excess type ferrite; magnetic metal such as iron, cobalt and nickel; iron oxide or magnetic metal and cobalt and tin. ,Titanium,
Mention may be made of complex metal oxide alloys or mixtures with metals such as copper, lead, zinc, magnesium, manganese, aluminum, silicon.

The average particle size of these magnetic particles is preferably in the range of 0.05 to 1.0 μm, more preferably in the range of 0.1 to 0.6 μm, and further preferably in the range of 0.1 to 1.0 μm. It is preferable that the thickness is within the range of 0.4 μm.
These magnetic particles have a BET specific surface area by the nitrogen adsorption method of preferably 1 to 20 m ² / g, particularly 2.5.
To 12 m ² / g, and the Mohs hardness is preferably 5 to 7.

The shape of the magnetic particles may be octahedron, hexahedron, sphere, needle or scale, but the octahedron, hexahedron or sphere having less anisotropy is preferable.

When used as a magnetic toner, the magnetic toner particles containing the magnetic material preferably contain 10 to 150 parts by mass, preferably 20 to 120 parts by mass of the magnetic material with respect to 100 parts by mass of the binder resin.

The toner of the present invention is preferably used by blending (internally adding) the charge control agent with the toner particles or mixing with the toner particles (externally adding). The charge control agent enables optimal charge control according to the development system.
In particular, in the present invention, it is possible to further stabilize the balance between the particle size distribution and the charge amount.

As the charge control agent for controlling the toner to be negatively charged, for example, organic metal complex and chelate compound are effective, and monoazo metal complex, acetylacetone metal complex,
Examples thereof include aromatic hydroxycarboxylic acid-based metal complexes and aromatic dicarboxylic acid-based metal complexes. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, their anhydrides, their esters, and phenol derivatives such as bisphenol.

As the charge control agent for controlling the toner to be positively charged, a modified product of nigrosine and a fatty acid metal salt; tributylbenzylammonium-1-hydroxy-4-
Naphtosulfonates, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof and lake pigments thereof, triphenylmethane dyes and lake pigments thereof (lake forming agent). As, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid,
Tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide), metal salts of higher fatty acids; dibutyltin oxide, dioctyltin oxide, diorganotin oxides such as dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin. Diorgano tin borates such as borates; These can be used alone or in combination of two or more.

The above charge control agent is preferably used in the form of fine particles, and the number average particle diameter of the fine charge control agent is preferably 4 μm or less, more preferably 3 μm or less.
μm or less is preferable. When these charge control agents are internally added to the toner particles, the toner particles are preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the binder resin. It is preferable to contain the mass part.

From the viewpoint of improving the releasability from the fixing member during fixing and the fixing property, the toner particles preferably contain wax. Examples of the waxes include paraffin wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives. The derivatives include oxides, block copolymers with vinyl monomers, and graft modified products of vinyl monomers.

In addition, alcohols, fatty acids, acid amides,
Esters, ketones, hydrogenated castor oil and its derivatives, plant waxes, animal waxes, mineral waxes, petrolactam can also be used.

The toner of the present invention may contain a small amount of other additives within a range that does not have a substantial adverse effect. Examples of the additive include lubricant powders such as Teflon powder, zinc stearate powder, polyvinylidene fluoride powder; abrasives such as cerium oxide powder, silicon carbide powder and strontium titanate powder; for example, titanium oxide powder,
Examples thereof include fluidity imparting agents or anti-caking agents such as aluminum oxide powders; conductivity imparting agents such as carbon black powders, zinc oxide powders, tin oxide powders; and organic fine particles or inorganic fine particles of opposite polarity.

A known method is used for producing the toner according to the present invention. For example, a binder resin and a pigment, a dye or a magnetic material as a colorant, and if necessary, a charge control agent and a wax. , A metal salt or a metal complex, and other additives are sufficiently mixed with a mixer such as a Henschel mixer or a ball mill, and then melt-kneaded with a heat kneader such as a heating roll, a kneader or an extruder to mix the resins with each other. Metal compounds, pigments, dyes, etc.
A magnetic substance is dispersed or dissolved, and after cooling and solidification, pulverization and classification are performed to obtain toner particles, and the obtained toner particles, a silicone oil-treated inorganic fine powder and, if necessary, a desired additive are mixed with a Henschel mixer. The toner according to the present invention can be obtained by thoroughly mixing with a mixer such as the above.

The toner of the present invention can be used as a one-component type developer as it is or as a two-component type developer mixed with a carrier.

As the carrier used in the two-component developing method, those conventionally known can be used. Specifically, surface-oxidized or non-oxidized iron, cobalt, nickel, manganese, chromium and rare earth elements can be used. Such metals and their alloys or oxides. The carrier preferably has an average particle size within the range of 20 to 300 μm.

Further, in the present invention, a coated carrier in which a resin is coated or attached to the surface of these carrier particles can be used.

Examples of the binder resin coated or adhered to the surface of carrier particles include styrenes such as styrene and chlorostyrene; monoolefins such as ethylene, propylene, butylene and isobutylene; vinyl acetate, vinyl propionate and vinyl benzoate. Vinyl esters such as vinyl butyrate; methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate,
Α-Methylene aliphatic monocarboxylic acid esters such as phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and dodecyl methacrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether; vinyl methyl ketone, vinyl Vinyl ketones such as hexyl ketone and vinyl isopropenyl ketone; homopolymers or copolymers thereof can be mentioned. Particularly, as a typical binder resin, dispersibility of conductive fine particles and film forming property as a coat layer,
From the viewpoint of toner spent prevention and productivity, polystyrene, styrene-alkyl acrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyethylene and polypropylene are preferable. Further, polycarbonate, phenol resin, polyester, polyurethane, epoxy resin, polyolefin, fluororesin, silicone resin, and polyamide can be used. In particular, from the viewpoint of preventing spent, it is more preferable to contain a resin having a small critical surface tension, such as polyolefin, fluororesin, and silicone resin.

The content ratio of the resin having a small critical surface tension to the total amount of binder is preferably 1.0 to 60% by mass, particularly preferably 2.0 to 40% by mass. When the content is less than 1.0% by mass, the surface modification effect is insufficient and the toner spent is ineffective, and the content is 60% by mass.
If it exceeds, it is difficult to uniformly disperse both of them, so that partial unevenness occurs in the volume resistance value and the charging characteristics deteriorate.

Examples of the fluororesin used as the binder resin for coating the carrier include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, dichlorodifluoroethylene, tetrafluoroethylene, hexafluoropropylene and others. And a solvent-soluble copolymer with the monomer of.

The silicone resin used as the binder resin for coating the carrier is, for example, KR271, KR282, KR311, KR255, K manufactured by Shin-Etsu Silicone Co., Ltd.
R155 (Straight Silicone Varnish), KR21
1, KR212, KR216, KR213, KR21
7, KR9218 (modified silicone varnish), SA-
4, KR206, KR5206 (Silicone alkyd varnish), ES1001, ES1001N, ES100
2T, ES1004 (Silicone epoxy varnish), K
R9706 (Silicone acrylic varnish), KR520
3, KR5221 (silicone polyester varnish);
Alternatively, SR2100 and SR21 manufactured by Toray Silicone Co., Ltd.
01, SR2107, SR2110, SR2108, S
R2109, SR2400, SR2410, SR241
1, SH805, SH806A, SH840; are used.

When the resin coating layer is formed by coating or adhering the surface of the carrier particles with a resin, it is preferable that the resin coating layer contains conductive fine particles to control the electric resistance.

In the present invention, as a method for producing a carrier in which a resin coating layer containing conductive fine particles is formed on the surface of carrier particles, the conductive fine particles and the coating resin are dissolved in an appropriate solvent to prepare a coating layer solution. After soaking the carrier particles, use a spray dryer to volatilize the solvent to form a coat layer, or spray the coat layer solution while forming a fluidized bed by placing the carrier particles in a general fluidized bed coating device. While drying, the coating layer is gradually formed.

The image forming method using the toner of the present invention, the developing device unit and the process cartridge will be described in detail.

The image forming method using the toner of the present invention includes a method using a magnetic toner and a method using a non-magnetic toner.

First, a developing method using a one-component developer made of magnetic toner will be described.

In FIG. 5, the substantially right half peripheral surface of the toner carrier 102 is constantly in contact with the toner pool in the toner container 106, and the toner near the surface of the toner carrier is included in the toner carrier on the surface of the toner carrier. The magnetic force generated by the magnetism generating means 103 and / or the electrostatic force is used to attach and support. When the toner carrier 102 is driven to rotate, the magnetic toner layer on the surface of the toner carrier passes through the position of the doctor blade 104, which is a toner layer regulating member, to form a thin layer T ₁ having a uniform thickness in each part. To be done. The magnetic toner is charged mainly by frictional contact between the surface of the toner carrier and the magnetic toner in the toner pool in the vicinity of the surface of the toner carrier as the toner carrier 102 rotates, and the magnetic toner carried on the toner carrier 102 is the toner. As the carrier rotates, it is conveyed to the developing area A (where the electrostatic latent image is developed with magnetic toner), which is the closest position between the photoreceptor 101 as the latent image carrier and the toner carrier 102. The toner is carried on the toner carrier 102 in the process of passing through the developing area A. The magnetic toner flies by a bias electric field applied between the photoconductor 101 and the toner carrier 102, for example, a direct current and an alternating voltage, and a magnetic field is generated between the surface of the photoconductor 101 in the developing area A and the surface of the toner carrier 102 (gap α). Move back and forth. Finally, the magnetic toner on the side of the toner carrier 102 is transferred to the photoconductor 10.
A toner image T ₂ is sequentially formed by selectively adhering to the surface of one surface in accordance with the potential pattern of the latent image.

After passing through the developing area A, the thin toner layer on the surface of the toner carrier on which the magnetic toner has been selectively consumed returns to the toner reservoir of the toner container 106, so that the toner carrier can re-supply the magnetic toner. The magnetic toner thin layer T ₁ carried on the toner carrier 102 is received and conveyed to the developing area A, and the developing process is repeated. Reference numeral 105 is a toner stirring member.

As the toner layer thickness regulating member used in the present invention, a metal blade, a magnetic blade (for example, 104 shown in FIG. 5) or a surface of the toner carrier, which is arranged with a certain gap from the toner carrier. An elastic blade that elastically abuts against (for example, 203 shown in FIG. 6 and FIG. 7).
Any of 303) can be used.

As the elastic blade, silicone rubber,
A rubber elastic body such as urethane rubber or NBR; a synthetic resin elastic body such as polyethylene terephthalate; a metal elastic body such as stainless steel or steel can be used, and a composite body thereof can also be used. A rubber elastic body is preferable.

The material of the elastic blade has a great influence on the charging of the toner on the toner carrier. Therefore, an organic or inorganic substance may be added to the elastic body, and may be melt-mixed or dispersed. Examples of the substance to be added include metal oxides, metal powders, ceramics,
Examples include carbon allotropes, whiskers, inorganic fibers, dyes, pigments and surfactants. Further, in order to control the charging property of the toner, an elastic support such as rubber, synthetic resin, or metal elastic body may be contacted with a charge control substance such as resin, rubber, metal oxide, or metal on the contact portion of the toner carrier. You may use the one attached to. When durability is required for the elastic body and the toner carrier, it is preferable to bond the resin and rubber to the metal elastic body so as to contact the toner carrier contact portion.

When the toner is negatively charged, the elastic blade and the charge control substance are preferably urethane rubber, urethane resin, polyamide resin, nylon resin and the like, which are easily charged to the positive polarity. When the toner is positively charged, the elastic blade and the charge control substance are those that are easily negatively charged, such as urethane rubber, urethane resin, silicone rubber, silicone resin, polyester resin, fluorine resin, and polyimide resin. Is preferred.

When the toner carrier contacting portion is a resin or rubber molded body, in order to adjust the chargeability of the toner, a metal oxide such as silica, alumina, titania, tin oxide, zirconia, or zinc oxide is used. Thing, carbon black,
It is also preferable to include a charge control agent generally used in toner.

The base, which is the upper side of the elastic blade, is fixed and held on the toner container side, and the lower side is against the elastic force of the blade in the opposite direction to the rotation direction of the toner carrier (see FIG. 6) or in the forward direction. The surface is flexed in the direction (see FIG. 7) and brought into contact with the surface of the toner carrier with an appropriate elastic pressing force.

Incidentally, in FIGS. 6 and 7, 201 and 3
Reference numeral 01 represents a latent image carrier, and 202 and 302 represent toner carriers.

The contact pressure between the blade and the toner carrier is
As the linear pressure in the generatrix direction of the toner carrier, 0.98 N / m
(1 g / cm) or more, preferably 1.27 to 245N
/ M (3 to 250 g / cm), more preferably 4.9 to
118 N / m (5 to 120 g / cm) is effective. When the contact pressure is less than 0.98 N / m (1 g / cm), it becomes difficult to uniformly apply the toner, which causes fog and scattering. Contact pressure is 245 N / m (250 g / cm)
If it exceeds, a large pressure is applied to the toner, and deterioration of the toner easily occurs, which is not preferable.

The gap α between the photosensitive member and the toner carrying member is preferably set to, for example, 50 to 500 μm.

The layer thickness of the magnetic toner layer on the toner carrier is
It is preferable to make the gap smaller than the gap α between the photoconductor and the toner carrying member because fog is less likely to occur, but it is also possible to use it in a form in which a part of the toner layer is in contact with the photoconductor surface.

In the present invention, it is preferable that an electric field containing an AC component is applied as a developing bias between the toner carrier and the photoconductor. The peak-to-peak magnitude (Vpp) of the electric field at the closest portion of both the AC component between the toner carrier and the photoconductor is preferably 2-8 MV / m or more. The frequency of AC bias is 1.0 kHz
5.0 kHz, preferably 1.5 kHz to 3.0 kHz
Used in A rectangular wave, a sine wave, a sawtooth wave, and a triangular wave can be applied to the waveform of the AC bias. Asymmetrical AC biases having different positive / reverse voltage times can also be used.

In the present invention, the toner carrier is a metal,
Materials such as ceramics are used, but non-magnetic conductive metals such as aluminum and SUS are preferable from the viewpoint of chargeability to the toner. The toner carrier can be used as it is pulled out or cut, but in order to control the toner transporting property and the triboelectric charging property, polishing, roughening along the circumferential direction or the longitudinal direction, blasting or coating is performed. Be seen. In the present invention, blasting is preferably performed, and regular particles and irregular particles are used as a blasting agent, and each is used alone or in combination,
Overlapped ones are also available.

As the conductive fine particles contained in the resin coating layer for coating the surface of the toner carrier, carbon black,
A conductive metal oxide such as graphite and conductive zinc oxide and a conductive metal complex oxide are preferably used alone or in combination of two or more. As the resin in which the conductive fine particles are dispersed, phenol resin, epoxy resin, polyamide resin, polyester resin, polycarbonate resin, polyolefin resin, silicone resin, fluorine resin, styrene resin, acrylic resin Resin is used. Particularly, a thermosetting or photocurable resin is preferable.

Next, a developing method using a non-magnetic toner will be described.

FIG. 8 shows an apparatus for developing an electrostatic image formed on a photoconductor. Reference numeral 401 denotes a photosensitive member as a latent image holding member, and electrostatic latent image formation is formed by electrophotographic process means or electrostatic recording means (not shown). A toner carrier 402 is composed of a non-magnetic sleeve made of aluminum or stainless steel.

A coarse aluminum or stainless steel tube may be used as it is as the toner carrier, but preferably, its surface is uniformly roughened by spraying roughening particles such as glass beads, and its surface is mirror-finished. Alternatively, it is preferable that its surface is coated with a resin, which is similar to that used in the method for developing a magnetic toner.

The toner 406 is contained in the toner container 403, and is supplied onto the toner carrier by the supply roller 404. The supply roller is made of a foam material such as polyurethane foam, and with respect to the toner carrier,
The toner is supplied in the forward or reverse direction at a relative speed which is not 0, and the toner (undeveloped toner) after development on the toner carrier is stripped off as well. The toner supplied onto the toner carrier is uniformly and thinly applied by a toner application blade 405 as a toner layer thickness regulating member. Reference numeral 407 is a stirring member.
When 7 rotates in the direction of the arrow, the toner container 403
The toner 406 therein is agitated.

The material of the blade, the contact means, the material of the toner carrier, the distance between the photoconductor and the toner carrier, and the bias applied to the toner carrier are the same as those in the magnetic toner developing method.

In the present invention, among the components described in the developing method using the magnetic toner and the developing method using the non-magnetic toner, at least the toner for developing the electrostatic latent image and the toner are stored. And a toner carrier for carrying the toner contained in the toner container and carrying the toner contained in the toner container to the developing area where the electrostatic latent image is developed. Can be used as

This developing device unit is mounted on the main body of the image forming device, which will be described later, and is fixed by fixing means such as bolts and pins.

In the developing device unit of the present invention, in addition to the toner, the toner container and the toner carrier, a toner layer thickness regulating member or a toner supply roller may be integrally provided.

An example of a specific image forming apparatus that can be used for carrying out the image forming method in the present invention will be described with reference to FIG.

Reference numeral 1 is a rotary drum type photoconductor as a latent image carrier, and the photoconductor 1 has a conductive base layer 1b such as aluminum and a photoconductive layer 1a formed on the outer surface thereof as basic constituent layers. It is driven to rotate at a predetermined peripheral speed in the direction of the arrow.

Reference numeral 2 is a charging roller as a contact charging member, which is basically composed of a core metal bar 2b and a conductive elastic layer 2a whose outer periphery is made of a conductive resin material such as epichlorohydrin rubber containing carbon black. .

The charging roller 2 is pressed against the surface of the photoconductor 1 with a predetermined pressing force, and is driven to rotate as the photoconductor 1 rotates. Further, the charging roller 2 includes a cleaning member 1
Felt pad 2 is abutted. This cleaning member can be omitted in a low-speed machine or a medium-speed machine, which has a small number of durable sheets until the life of the apparatus.

Reference numeral 3 denotes a charging bias power source for applying a voltage to the charging roller 2, and by applying a charging bias to the charging roller 3, the surface of the photosensitive member 1 is uniformly charged with negative polarity.

Next, an electrostatic latent image is formed by image exposure 4 as a latent image forming means, and a developing device 5 as a developing means.
The electrostatic latent image is developed by the toner held in the toner and sequentially visualized as a toner image. Reference numeral 6 denotes a transfer roller as a contact transfer member, which has a central core metal 6b and an outer periphery of ethylene-propylene-containing carbon black.
The basic constitution is a conductive elastic layer 6a formed of a conductive resin material such as a butadiene copolymer.

The transfer roller 6 is brought into pressure contact with the surface of the photoconductor 1 with a predetermined pressing force and rotates at the same speed as the peripheral speed of the photoconductor 1 or with a peripheral speed difference. Further, a felt pad as a cleaning member 13 is in contact with the transfer roller 6. The cleaning member 13 can be omitted in a low-speed machine or a medium-speed machine whose durability is small until the life of the apparatus.

As the transfer material 8, for example, A4 size paper is used, which is conveyed between the photoconductor 1 and the transfer roller 6, and at the same time, a bias having a reverse polarity to the toner is applied to the transfer roller 6 from the transfer bias power source 7. By doing so, the toner image on the photoconductor 1 is transferred to the surface side of the transfer material 8.
Therefore, at the time of transfer, the transfer roller 6 is pressed against the photoconductor 1 via the transfer material 8.

Next, the transfer material 8 is transferred to a heat roller fixing device 11 as a fixing means having a fixing roller 11a having a halogen heater built therein and an elastic pressure roller 11b pressed against the fixing roller 11a as a fixing means. By being conveyed and passing between the fixing roller 11a and the pressure roller 11b, the toner image is fixed on the transfer material 8 and discharged as an image-formed product.

On the surface of the photoreceptor 1 after the transfer of the toner image, a cleaning device 9 equipped with an elastic cleaning blade made of an elastic material such as polyurethane rubber, which is in contact with the photoreceptor 1 in the counter direction, is attached to the adhered contaminants such as transfer residual toner. Then, the surface is cleaned by, and the charge is removed by the charge removing exposure device 10, and the image is repeatedly formed.

As the charging member 2 of the photosensitive member 1, it is preferable to use a contact charging member such as a charging roller that contacts and charges the photosensitive member, because the amount of ozone generated during charging can be suppressed, but an ozone filter is used. After being provided, it is also possible to use a corona charger that is generally widely used.

Further, the transfer member 6 is also preferably a contact transfer member such as a charging roller for contacting and transferring to the photoconductor via the transfer material, since the amount of ozone generated at the time of transfer can be suppressed, but the ozone filter is preferable. In addition to the above, it is also possible to use a generally widely used corona transfer charger.

In the present invention, instead of the heat roller fixing device as the fixing means of the image forming apparatus shown in FIG. 3, a fixedly supported heating member and a heating member opposed to and in pressure contact with the heating member are interposed. It is possible to use a film heat fixing device that heat-fixes the toner by using a pressure member that brings the transfer material into close contact with the heating body.

FIG. 4 shows an example of the above film heating and fixing device.
Shown in

In the film heating and fixing device shown in FIG. 4, the heating element has a smaller heat capacity than the conventional heat roll and has a linear heating part, and the maximum temperature of the heating part is 100 to 300 ° C. It is preferable.

The film located between the heating element and the pressing member is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. Examples of these heat-resistant sheets include polyester, PET (polyethylene) having high heat resistance. Terephthalate), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), PTFE (polytetrafluoroethylene), polymer sheet such as polyimide, polyamide, metal sheet such as aluminum, and metal sheet and polymer sheet A laminated sheet is used.

A more preferable film structure is that these heat resistant sheets have a release layer and / or a low resistance layer.

A specific example of the fixing device will be described with reference to FIG.

Reference numeral 111 denotes a low-heat-capacity linear heating element fixedly supported by the apparatus, and has a thickness of 1.0 mm and a width of 1 as an example.
A resistance material 119 having a width of 1.0 mm is applied to an alumina substrate 120 having a length of 0 mm and a length of 240 mm, and electricity is applied from both ends in the longitudinal direction. For energization, for example, a pulsed waveform with a cycle of 20 msec of DC 100 V and a pulse corresponding to a desired temperature and energy release amount controlled by the temperature measuring element 121 is given by changing its pulse width. The approximate pulse width is 0.5 msec to 5 msec. By contacting the heating element 111 whose energy and temperature are controlled in this way,
The fixing film 112 moves in the direction of the arrow in the figure.

An example of this fixing film has a thickness of 2
It is an endless film in which a release layer made by adding a conductive material to a 0 μm heat-resistant film (for example, polyimide, polyetherimide, PES or PFA and at least a fluororesin such as PTFE or PFA on the image contact surface side) is coated to 10 μm. Generally, the total thickness is less than 100 μm, more preferably less than 40 μm. The film is driven by the drive roller 113 and the driven roller 114 and tensioned to move in the arrow direction without wrinkles.

Reference numeral 115 denotes a pressure roller having a rubber elastic layer having a good releasability, such as silicone rubber, having a total pressure of 4 to 2
The heating element is pressed through the film with 0 kg, and is rotated in pressure contact with the film. Unfixed toner 117 on transfer material 116
Is to be guided to the fixing section by the entrance guide 118 and to obtain a fixed image by the above heating.

Although the endless belt has been described above,
A sheet feeding shaft and a winding shaft are used, and the fixing film may be an end film.

In the image forming apparatus shown in FIG. 3, the developing device unit described above of the present invention can be used as the developing device 5 as the developing means.

FIG. 9 shows a specific example of the process cartridge of the present invention.

In the following description of the process cartridge, components having the same functions as the components of the image forming apparatus described in FIG. 3 will be described using the same reference numerals as those in FIG.

The process cartridge of the present invention is one in which at least the developing device and the latent image holding member are integrally formed into a cartridge, and is attached to and detached from the image forming apparatus main body (eg, copying machine, laser beam printer, facsimile apparatus). It is configured to be possible.

In the embodiment shown in FIG. 9, the developing device 5,
A process cartridge C in which a drum-shaped latent image holder (photosensitive drum) 1, a cleaning device 9 having a cleaning blade 91 as a cleaning member, and a charging roller 2 as a charging member are integrated is exemplified.

In the present embodiment, the developing device 5 has an elastic regulating blade 51 as a toner layer thickness regulating means and a toner 53 in the toner container 52. The toner 53 is used and a bias applying means is used for developing. The photosensitive drum 1 and the developing sleeve 5 as a toner carrier are controlled by the developing bias voltage.
A predetermined electric field is formed between the electric field and the magnetic field 4 and the developing process is performed. The distance between the photosensitive drum 1 and the developing sleeve 54 is very important in order to appropriately carry out this developing step.

In the above description, the embodiment in which the four components of the developing device 5, the latent image holding member 1, the cleaning means 9 and the charging member 2 are integrated into a cartridge has been described. It suffices that at least two constituent elements of the latent image holding member are integrally made into a cartridge, and three constituent elements of the developing device, the latent image holding member and the cleaning means, the developing device, the latent image holding member and the charging. It is also possible to add three components of the member or other components to integrally form a cartridge.

In FIG. 3, the optical image exposure 4 as a latent image forming means is reflected light or transmitted light from an original, or when the image forming apparatus is used as a copying machine or a printer.
The original is read and converted into a signal, and the signal is used to scan the laser beam, drive the LED array, or drive the liquid crystal shutter array.

When used as a printer for a facsimile, the optical image exposure 4 is exposure for printing received data. FIG. 10 is a block diagram showing an example of this case.

The controller 511 controls the image reading section 510 and the printer 119. The entire controller 511 is controlled by the CPU 517. The read data from the image reading unit is transmitted to the partner station via the transmission circuit 513. The data received from the partner station is sent to the printer 519 through the receiving circuit 512. Predetermined image data is stored in the image memory. Printer controller 5
18 controls the printer 519. Reference numeral 514 is a telephone.

The image received from the line 515 (image information from the remote terminal connected via the line) is demodulated by the receiving circuit 512, and then the CPU 517 decodes the image information and sequentially processes the image memory 516. Stored in. When the image of at least one page is stored in the memory 516, the image of that page is recorded. CPU517
Reads one page of image information from the memory 516 and sends the combined one page of image information to the printer controller 518. The printer controller 518 is C
When receiving the image information of one page from the PU 517, the printer 519 is controlled to record the image information of the page.

The CPU 517 is receiving the next page during recording by the printer 519.

As described above, the image is received and recorded.

[0201]

EXAMPLES The present invention will be specifically described below with reference to production examples and examples, but the present invention is not limited thereto. All parts in the following formulations are parts by mass.

Example 1 Production Example 1 of Silica Silicone oil (1) was prepared by mixing 75% of dimethyl silicone oil having a peak at a molecular weight of 2000 and 25% of dimethyl silicone oil having a peak at a molecular weight of 41,000. When GPC of this silicone oil was measured, it had peaks at a molecular weight of 2100 and a molecular weight of 41000, respectively.
The height A from the peak of 00 to the baseline is 1
On the other hand, the height B from the peak of the molecular weight of 41,000 to the baseline is 0.30, and the height C from the bottom point of the minimum value C between the two peaks to the baseline is 0.1.
2 (see FIG. 1). The results of GPC measurement are shown in Table 1.

While stirring 100 parts of silica fine powder (trade name Aerosil # 200; specific surface area of about 200 m ² / g manufactured by Nippon Aerosil Co., Ltd.) produced by the dry method, the temperature was about 6
The solution was kept at 0 ° C., a solution of 20 parts of silicone oil (1) -20 parts of hexane was sprayed, and the solvent was dried while stirring. Then heat to 300 ° C. with stirring, 3
Treatment at 00 ° C. for 1 hour gave silica (1). Table 2 shows the processing conditions, hydrophobicity, and BET surface area of this silica.

Toner Production Example 1 Styrene-n-butyl acrylate copolymer 100 parts (St / BA = 84/16, peak molecular weight Pa = 12000, peak molecular weight Pb = 355000, Mn = 8600, Mw = 178000) Magnetic iron oxide 80 parts Polypropylene wax 4 parts Metal complex of monoazo dye 1 part

The above materials were well premixed by a Henschel mixer, and then melt-kneaded by a twin-screw kneading extruder set at 140 ° C. The obtained kneaded product is cooled and coarsely pulverized by a cutter mill, then finely pulverized by a fine pulverizer using a jet stream, and the obtained fine pulverizer is further classified by an air classifier to obtain a weight. Toner particles (1) having an average particle size of 8.4 μm were obtained.

To 100 parts of the obtained toner particles (1), 0.8 part of silica (1) was added and mixed with a Henschel mixer to obtain a negatively chargeable toner.

A commercially available laser printer LBP-A404 having a developing device shown in FIG.
It was filled in a cartridge for GII (manufactured by Canon Inc.) and the image was evaluated.

<Durability Test> A durability test of 3000 sheets was carried out under various environmental conditions of normal temperature / normal humidity, low temperature, low humidity, high temperature / high humidity. The image density and fog in each environment are evaluated, and the image dropout level (reproducibility of character images) at room temperature and humidity, the uniformity of halftone images and the uniformity of solid black images (unevenness,
The presence or absence of dot-shaped white spots, white stripes, filming and fusion on the photoconductor, and electrostatic offset were evaluated. Further, the sleeve contamination was evaluated after the durability test under high temperature and high humidity environment, and the negative development was evaluated after the durability test under low temperature and low humidity environment.

Further, after a durability test at room temperature and normal humidity, five solid black images were continuously printed, the uniformity of the solid black images during continuous copying was evaluated, and the photoreceptor drum was visually scratched. evaluated.

Furthermore, 10 sheets of character and line images were continuously copied using Cangas paper which had been left for 1 week or more under high temperature and high humidity environment and absorbed moisture, and the scattering level at the time of fixing was evaluated. .

Each of the above evaluations was evaluated based on the following evaluation methods.

Image Density A square image having a side of 5 mm or a circular black image having a diameter of 5 mm is used as an image density measuring instrument RD91 manufactured by Macbeth.
8 was used to measure the image density.

The extent of the amount of developing toner to the non-image area was evaluated by visual observation of fogging . (Evaluation Criteria) A: No fogging is visually observed B: No fogging is observed unless the subject is closely watched C: Fogging is present but practically no problem D: Fogging is noticeable

Sleeve Contamination On a part of the developing sleeve, the toner was removed, the part was wiped with sillbon paper, and when a solid black image was produced, the difference in shade was visually evaluated between the wiped part and the other part. . (Evaluation Criteria) A: Density does not change B: There is a difference in light and shade when gazing C: There is a difference in light and shade, but there is no practical problem D: Significantly higher density

Negative development : Three types of images, a solid black image, a 2 dot-1 space halftone image, and a 1 dot-1 space halftone image, are output on the same recording paper so as to be continuous 10 mm each in the feed direction. The gradation images were used and evaluated based on the following evaluation criteria by the order of the image densities of the three types of images. (Evaluation Criteria) A: The difference in gray level is exactly the same as the gradation output. B: There is a portion where some gray levels are reversed. C: There is some point where some gray levels are reversed, but there is no practical problem. D: The shade difference is reversed at multiple points

Uniformity of Halftone Image The uniformity of the halftone image was evaluated. (Evaluation Criteria) A: Almost visually uniform B: Some streak-like unevenness is slightly seen C: Some streak-like unevenness is seen but practically no problem D: Unevenness is noticeable

Uniformity of solid black image The uniformity of the solid black image was evaluated. (Evaluation Criteria) A: Uniform solid black image B: Partially spotted white spots or faint white streaks and unevenness C: Partial spotted white spots, white streaks and unevenness are seen, but practical There is no problem on the top. D: White spots, white lines, and unevenness are noticeable.

Filming and Fusion to Photoreceptor The occurrence of filming and fusion was observed by a solid white image. (Evaluation Criteria) A: No filming fusion is observed B: Some are seen when the density is increased C: Vividly visible in a normal solid white image D: Conspicuous in a normal solid white image

Thick paper (200 g / m ² paper) was used as a transfer material in the image, and the hollow portions of the line portion and the character portion were evaluated. (Evaluation Criteria) A: Almost no hollow area is seen B: No hollow area is observed unless gazing C: Some areas are missing, but there is no problem in practical use D: Clear areas are clearly recognizable

Fixing scattered humidity is left under 80% RH, and a line image parallel to the fixing longitudinal direction (200 μm width every 1 cm is set so that the rough side of the transfer paper of 80 g / m ² whose humidity is adjusted becomes the transfer surface. To 2
It was evaluated by using 0). (Evaluation criteria) A: Scattered location 0 to 1 location B: Scattered location 2 to 10 location C: Scattered location 11 to 30 location D: Scattered location Over 30 location

100 sheets of A4 paper forward 60% halftone images were printed so that the rough surface of the transfer paper (A4 vertical feed) having an electrostatic offset of 80 g / m ² became the transfer surface. The stain on the white background portion and the stain on the back surface were evaluated. (Evaluation Criteria) A: No stain or stain on the white background is visually observed. B: No stain or stain on the white background is observed unless attention is paid. C: Slight stain or stain on the white background can be seen, but it is practical. No problem D: Dirt on the white background is noticeable

Photosensitive drum scratch Evaluation was made by a solid white image and a halftone image. (Evaluation Criteria) A: No scratches appearing on the image B: Slight scratches appearing on the halftone part (up to 3) C: Scratches appearing on the halftone part D: Scratches appearing on the normal image

The evaluation results are shown in Table 3.

[Example 2] 90% dimethyl silicone oil having a peak at a molecular weight of 2000 and a molecular weight of 1100
Silicone oil (2) was prepared in the same manner as in Example 1 except that 10% of dimethyl silicone oil having a peak at 0 was used to obtain silica (2).

0.8 part of this silica (2) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

[Example 3] 73% of dimethyl silicone oil having a peak at a molecular weight of 1200 and a molecular weight of 7,000
Silicone oil (3) was prepared in the same manner as in Example 1 except that 27% of dimethyl silicone oil having a peak at was used to obtain silica (3).

0.8 part of this silica (3) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

Example 4 Methylphenylsilicone oil 60% having a peak at a molecular weight of 550 and a molecular weight of 35
Dimethyl silicone oil having a peak at 00 40%
A silicone oil (4) was prepared in the same manner as in Example 1 except that was used to obtain silica (4).

0.8 part of the silica (4) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

[Example 5] 70% dimethyl silicone oil having a peak at a molecular weight of 6000 and a molecular weight of 2800
Methylphenyl silicone oil 3 having a peak at 0
A silicone oil (5) was prepared in the same manner as in Example 1 except that 0% was used to obtain silica (5).

0.8 part of the silica (5) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was conducted using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. The evaluation results are shown in Table 3.

Example 6 55% of dimethyl silicone oil having a peak at a molecular weight of 12,000 and a molecular weight of 890
Dimethyl silicone oil having a peak at 00 45%
A silicone oil (6) was prepared in the same manner as in Example 1 except that was used to obtain silica (6).

0.8 part of the silica (6) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

Example 7 65% of dimethyl silicone oil having a peak at a molecular weight of 1400 and a molecular weight of 8900
Silicone oil (7) was prepared in the same manner as in Example 1 except that 35% of dimethyl silicone oil having a peak at 0 was used to obtain silica (7).

0.8 part of the silica (7) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

Example 8 Using titania as a fine powder matrix, 15 parts of silicone oil (1) was treated in the same manner as in Example 1 to obtain titania (8).

0.8 part of the titania (8) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

Example 9 Using alumina as a fine powder matrix, 12 parts of silicone oil (1) was treated in the same manner as in Example 1 to obtain alumina (9).

0.8 part of this alumina (9) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

Comparative Example 1 Silica (10) was obtained in the same manner as in Example 1 except that only dimethyl silicone oil (8) having a peak at a molecular weight of 2000 was used.

0.8 part of the silica (10) was added to 100 parts of the toner Rumi (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

Comparative Example 2 Silica (11) was obtained in the same manner as in Example 1 except that only dimethyl silicone oil (9) having a peak at a molecular weight of 50,000 was used.

0.8 part of the silica (11) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

[Comparative Example 3] 60% dimethyl silicone oil having a peak at a molecular weight of 450 and a molecular weight of 12500
A silicone oil (10) was prepared in the same manner as in Example 1 except that 40% of dimethyl silicone oil having a peak at was used to obtain silica (12).

0.8 part of this silica (12) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

[Comparative Example 4] 65% dimethyl silicone oil having a peak at a molecular weight of 17500 and a molecular weight of 890
Dimethyl silicone oil having a peak at 00 35%
Silicone oil (11) was prepared in the same manner as in Example 1 except that was used to obtain silica (13).

0.8 part of the silica (13) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

[Comparative Example 5] 75% of dimethyl silicone oil having a peak at a molecular weight of 1200 and a molecular weight of 2100
A silicone oil (12) was prepared in the same manner as in Example 1 except that 25% of dimethyl silicone oil having a peak at was used to obtain silica (14).

0.8 part of the silica (14) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

[Comparative Example 6] 65% dimethyl silicone oil having a peak at a molecular weight of 1200 and a molecular weight of 1050
Dimethyl silicone oil having a peak at 00 35%
A silicone oil (13) was prepared in the same manner as in Example 1 except that was used to obtain silica (15).

0.8 part of this silica (15) was added to 100 parts of the toner particles (1) and mixed with a Henschel mixer to obtain a negatively chargeable toner.

Example 1 was carried out using the obtained negatively chargeable toner.
The image was evaluated in the same manner as. Table 3 shows the evaluation results.

[0266]

[Table 1]

[0267]

[Table 2]

[0268]

[Table 3]

Example 10 Silica Production Example 16 Silicone oil (14) was prepared by mixing 70% of amino-modified silicone oil having a peak at a molecular weight of 5500 and 30% of amino-modified silicone oil having a peak at a molecular weight of 37,000. . GP of this silicone oil
When C is measured, the molecular weight distribution shows a molecular weight of 5500
It has a peak at a molecular weight of 37,000 and a shoulder at a molecular weight of 3500, and the height A from the peak of the molecular weight of 5500 to the baseline is 1, while the shoulder position (inflection point) at the molecular weight of 37,000 is at the baseline. Height B
Was 0.44. The results of GPC measurement and amine equivalents are shown in Table 4.

While stirring 100 parts of silica fine powder (commercial name Aerosil # 200; specific surface area of about 200 m ² / g manufactured by Nippon Aerosil Co., Ltd.) produced by the dry method, the temperature was about 6
The solution was kept at 0 ° C., 20 parts of silicone oil (14) -20 parts of hexane was sprayed, and the solvent was dried while stirring. Then, raise the temperature to 250 ° C. with stirring,
Treatment at 250 ° C. for 1 hour gave silica (16). Table 4 shows the treatment conditions, hydrophobicity, and BET surface area of this silica.

Toner Production Example 2 Styrene-n-butyl acrylate copolymer 100 parts (St / BA = 83/17, peak molecular weight Pa = 11,000, peak molecular weight Pb = 340000, Mn = 8800, Mw = 180000) Magnetic iron oxide 80 parts Polypropylene wax 4 parts Nigrosine dye 2 parts

The above materials were well premixed by a Henschel mixer, and then melt-kneaded by a twin-screw kneading extruder set at 140 ° C. The obtained kneaded product is cooled and coarsely pulverized by a cutter mill, then finely pulverized by a fine pulverizer using a jet stream, and the obtained fine pulverizer is further classified by an air classifier to obtain a weight. Toner particles (2) having an average particle diameter of 8.6 μm were obtained.

To 100 parts of the obtained toner particles (2), 0.8 part of silica (16) was added and mixed with a Henschel mixer to obtain a positively chargeable toner.

The developing device unit shown in FIG. 5 of a commercially available copying machine NP6030 (manufactured by Canon Inc.) modified from the image forming apparatus shown in FIG. An image was evaluated by applying a chargeable toner.

<Durability Test> A durability test of 10,000 sheets was carried out under various environmental conditions of normal temperature / normal humidity, low temperature / low humidity, high temperature / high humidity. Image density and fog in each environment are evaluated, and the density difference before and after toner replenishment (minimum value after 200 sheets of replenishment), low temperature
The coat state on the sleeve under low humidity and the sleeve contamination under high temperature and high humidity were evaluated. Furthermore, the level of image dropouts (reproducibility of character images) at room temperature and humidity, the uniformity of halftone images, and the uniformity of solid black images (unevenness, dot-like voids,
White streaks) were evaluated, and after the durability test, 5 solid black images were continuously printed, and the uniformity during continuous copying was evaluated.

Further, the presence or absence of filming and fusion on the photoconductor was evaluated, the charging member was cleaned and a halftone image was displayed to evaluate the state of occurrence of scratches on the photoconductor drum.

In each of the above evaluations, image density, fog, sleeve contamination, image dropout, uniformity of halftone image and uniformity of solid black image, occurrence of filming and fusion on the photoreceptor, and The scratches on the photosensitive drum were evaluated by the same evaluation method as in Example 1, and the coat state on the sleeve was evaluated by the following method.

The coated toner on the sleeve was put in a hopper container, an empty developing device was set in the main body, and the toner was put in the developing container by a usual setting method.

The toner coat state on the developing device sleeve was visually observed and evaluated by a halftone image and a solid white image. (Evaluation Criteria) A: Uniform on the sleeve and uniform image B: Slightly uneven coating on the sleeve but not seen in the image C: Slight unevenness in the halftone image is visible, but is a practical problem No D: Unevenness is seen on the image

The evaluation results are shown in Table 6.

[Example 11] Amino-modified silicone oil having a peak at a molecular weight of 3,500 and 75% and a molecular weight of 14
-Modified silicone oil 2 having a peak at 000
A silicone oil (15) was prepared in the same manner as in Example 10 except that 5% was used to obtain silica (17).

0.8 part of this silica (17) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was performed using the obtained positively chargeable toner.
The image was evaluated in the same manner as 0. Table 6 shows the evaluation results.

Example 12 Amino-modified silicone oil having a peak at a molecular weight of 1500 and 70% and a molecular weight of 60
Amino-modified silicone oil 30 having a peak at 00
A silicone oil (16) was prepared in the same manner as in Example 10 except that 100% was used to obtain silica (18).

0.8 part of this silica (18) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was performed using the obtained positively chargeable toner.
The image was evaluated in the same manner as 0. Table 6 shows the evaluation results.

[Example 13] 80% amino-modified silicone oil having a peak at a molecular weight of 12,000 and a molecular weight of 8
A silicone oil (17) was prepared in the same manner as in Example 10 except that 20% of amino-modified silicone oil having a peak at 9000 was used. Using titania as a fine powder matrix, 15 parts of silicone oil (17) was treated to obtain titania (19). The processing conditions and physical properties are shown in Table 5.

0.8 part of the titania (19) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
The image was evaluated in the same manner as 0. Table 6 shows the evaluation results.

Example 14 Amino-modified silicone oil 85% having a peak at a molecular weight of 1500 and a molecular weight of 89
-Modified silicone oil 1 having a peak at 000
A silicone oil (18) was prepared in the same manner as in Example 10 except that 5% was used to obtain silica (20).

0.8 part of this silica (20) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
The image was evaluated in the same manner as 0. Table 6 shows the evaluation results.

[Example 15] 80% amino-modified silicone oil having a peak at a molecular weight of 5100 and a molecular weight of 76
-Modified silicone oil 2 having a peak at 000
A silicone oil (19) was prepared in the same manner as in Example 10 except that 0% was used to obtain silica (21).

0.8 part of this silica (21) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
The image was evaluated in the same manner as 0. Table 6 shows the evaluation results.

[Example 16] 91% of amino-modified silicone oil having a peak at a molecular weight of 1,000 and a molecular weight of 60
Amino-modified silicone oil having a peak at 00 9%
A silicone oil (20) was prepared in the same manner as in Example 10 except that was used to obtain silica (22).

0.8 part of this silica (22) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
The image was evaluated in the same manner as 0. Table 6 shows the evaluation results.

Comparative Example 7 Silica (2) was prepared in the same manner as in Example 10 except that only the amino-modified silicone oil (21) having a peak at a molecular weight of 5,500 was used.
3) was obtained.

0.8 part of the silica (23) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
The image was evaluated in the same manner as 0. Table 6 shows the evaluation results.

Comparative Example 8 Silica (2) was prepared in the same manner as in Example 10 except that only amino-modified silicone oil (22) having a peak at a molecular weight of 37,000 was used.
4) was obtained.

0.8 part of this silica (24) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Using the thus obtained positively chargeable toner, image evaluation was carried out in the same manner as in Example 10. Table 6 shows the evaluation results.

[Comparative Example 9] 20% amino-modified silicone oil having a peak at a molecular weight of 450 and a molecular weight of 2700
80% amino-modified silicone oil with a peak at 0
A silicone oil (23) was prepared in the same manner as in Example 10 except that the above was used to obtain silica (25).

0.8 part of this silica (25) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
The image was evaluated in the same manner as 0. Table 6 shows the evaluation results.

[Comparative Example 10] 80% amino-modified silicone oil having a peak at a molecular weight of 17500 and a molecular weight of 8
A silicone oil (24) was prepared in the same manner as in Example 10 except that 20% of amino-modified silicone oil having a peak at 9000 was used, and silica (26) was prepared.
I got

0.8 part of this silica (26) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
The image was evaluated in the same manner as 0. Table 6 shows the evaluation results.

[Comparative Example 11] 65% amino-modified silicone oil having a peak at a molecular weight of 1400 and a molecular weight of 21
Amino-modified silicone oil 35 having a peak at 00
Silicone oil (25) and silica (27) were obtained in the same manner as in Example 10 except that 10% was used.

0.8 part of this silica (27) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was performed using the obtained positively chargeable toner.
The image was evaluated in the same manner as 0. Table 6 shows the evaluation results.

[Comparative Example 12] 60% amino-modified silicone oil having a peak at a molecular weight of 1400 and a molecular weight of 12
A silicone oil (26) was prepared in the same manner as in Example 10 except that 40% of amino-modified silicone oil having a peak at 5000 was used, and silica (28) was prepared.
I got

0.8 part of this silica (28) was added to 100 parts of the toner particles (2) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was performed using the obtained positively chargeable toner.
The image was evaluated in the same manner as 0. Table 6 shows the evaluation results.

[0317]

[Table 4]

[0318]

[Table 5]

[0319]

[Table 6]

Example 17 Using alumina as a fine powder matrix, 12 parts of silicone oil (14) shown in Table 4 was treated in the same manner as in Example 10 to obtain alumina (29) shown in Table 7. It was

Toner Production Example 3 Styrene-n-butyl acrylate copolymer 100 parts (St / BA = 85/15, peak molecular weight P _a = 9000, peak molecular weight P _b = 285000, Mn = 8100, Mw = 169000)・ Polyethylene wax 4 parts ・ Phthalocyanine 4 parts ・ Quaternary ammonium salt 2 parts

Using the above materials, a toner particle powder (3) having a weight average particle diameter of 8.4 μm was obtained in the same manner as in Example 10.

0.8 part of alumina (29) was added to 100 parts of toner particles (3) and mixed with a Henschel mixer to obtain a positively chargeable toner.

The obtained positively charged toner was used for image evaluation with a commercially available copying machine FC330 (manufactured by Canon Inc.) having a developing device shown in FIG.

A durability test of 1,000 sheets was carried out under various environmental conditions of normal temperature / normal humidity, low temperature / low humidity, high temperature / high humidity. Image density and fog in each environment were evaluated. Furthermore, we evaluated the level of image dropouts (reproducibility of character images) at room temperature and humidity, the uniformity of halftone images and the uniformity of solid black images, and the occurrence of filming and fusion on the photoconductor. did.

Each evaluation was performed in the same manner as the evaluation performed in Example 1.

The evaluation results are shown in Table 8.

[0328]

[Table 7]

[0329]

[Table 8]

Example 18 Production Example 30 of Silica A silicone oil (27) was prepared by mixing 80% of amino-modified silicone oil having a peak at a molecular weight of 4400 and 20% of dimethyl silicone oil having a peak at a molecular weight of 48,000. GPC of this silicone oil
It has peaks at molecular weights 4400 and 48000 in the molecular weight distribution, and the height A from the peak apex of the molecular weight 4400 to the baseline is 1, while the height A from the peak apex of the molecular weight 48000 is high. The height B is 0.32, and the height C from the bottom point of the minimum value C between the two peaks to the baseline is 0.2.
It was 2. The measurement result of GPC and the amine equivalent are 9th.
It is shown in the table.

While stirring 100 parts of fine silica powder (trade name Aerosil # 200; specific surface area of about 200 m ² / g Nippon Aerosil Co., Ltd.) produced by the dry method, the temperature was about 6
Silicone oil (27) shown in Table 9 kept at 0 ° C
A solution of 20 parts-hexane 20 parts was sprayed and the solvent was dried while stirring. Then 250 ° C with stirring
The temperature is raised to 250 ° C. and treated at 250 ° C. for 1 hour to obtain silica (30)
I got Table 10 shows the processing conditions, hydrophobicity, and BET surface area of this silica.

Toner Production Example 4 Styrene-n-butyl acrylate copolymer 100 parts (St / BA = 83/17, peak molecular weight P _a = 10500, peak molecular weight P _b = 360000, Mn = 8800, Mw = 180,000)・ Magnetic iron oxide 80 parts ・ Polypropylene wax 4 parts ・ Nigrosine dye 2 parts

The above materials were well premixed by a Henschel mixer, and then melt-kneaded by a twin-screw kneading extruder set at 140 ° C. The obtained kneaded product is cooled and coarsely pulverized by a cutter mill, then finely pulverized by a fine pulverizer using a jet stream, and the obtained fine pulverizer is further classified by an air classifier to obtain a weight. Toner particles (4) having an average particle diameter of 8.3 μm were obtained.

To 100 parts of the obtained toner particles (4), 0.8 part of silica (30) was added and mixed with a Henschel mixer to obtain a positively chargeable toner.

Commercially available copying machine NP160 (manufactured by Canon Inc.)
The process cartridge having the developing device shown in FIG. 6 for modification is modified so that the toner can be replenished, and 150 g of the obtained positively charged toner is filled in the process cartridge shown in FIG.
The image was evaluated by applying it to the copying machine NP160 as the image forming apparatus shown in FIG.

<Durability Test> After printing 2000 sheets at ambient temperature / normal humidity, low temperature / low humidity, high temperature / high humidity, 150 g of toner is supplied, and further 2000 sheets are printed. Was replenished with 300 g, and further 6000 sheets were printed, and a durability test was conducted. The image density and fog in each environment were evaluated after the initial durability of 4000 sheets and after the durability of 10,000 sheets, respectively, and the density difference before and after replenishing 2000 sheets of toner (the minimum value after 200 sheets of replenishment) was evaluated. In addition, after 4000 sheets were run, negative development occurred at low temperature and low humidity, sleeve contamination at high temperature and high humidity was evaluated, and the level of image dropout at normal temperature and normal humidity (character image reproduction) Property), the uniformity of halftone images and the uniformity of solid black images (unevenness, dot white spots, white streaks) are evaluated, and five solid black images are continuously printed before toner replenishment during durability test. Then, the uniformity during continuous copying was evaluated.

After the end of 2000 sheets, the presence or absence of filming and fusion on the photoconductor is evaluated, the charging member is cleaned, a halftone image is displayed, and the state of occurrence of scratches on the photoconductor drum is checked. evaluated.

Using a transfer paper left under high temperature and high humidity for one week, fixing scattering and offset were evaluated.

In each of the above evaluations, image density, fog, sleeve contamination, image dropout, uniformity of halftone image and uniformity of solid black image, occurrence of filming and fusing on photoconductor, exposure to light The state of occurrence of body drum scratches, fixing scattering, and offset were evaluated in the same manner as in Example 1, and negative development was evaluated based on the following evaluation method.

<Negative development> Image density is 0.3, 0.4,
A4 circle with a diameter of 5 mm showing 0.5, 0.75, 1.1
The originals arranged at both ends of the image and at the center of the image were used to evaluate the density of the formed image.

<Evaluation Criteria> A: The density difference is as in the order of the document density. B: There are places where the circles of original density 0.75 and 1.1 are within 0.03 on the image. C: The order of the original density and the order on the image are reversed in a small part, but there is no problem in practical use. D: The order of the document density and the order on the image are reversed.

The evaluation results are shown in Table 11.

Example 19 80% dimethyl silicone oil having a peak at a molecular weight of 2400 and a molecular weight of 120
Amino-modified silicone oil 20 having a peak at 00
A silicone oil (28) was prepared in the same manner as in Example 18 except that 100% was used to obtain silica (31).

0.8 part of the silica (31) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

[Example 20] 80% amino-modified silicone oil having a peak at a molecular weight of 1600 and a molecular weight of 11
Dimethyl silicone oil 20 having a peak at 000
A silicone oil (29) was prepared in the same manner as in Example 18 except that the percentage (%) was used to obtain silica (32).

0.8 part of this silica (32) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

Example 21 Amino-modified silicone oil 60% having a peak at a molecular weight of 970 and a molecular weight of 700
A silicone oil (30) was prepared in the same manner as in Example 18 except that 40% of dimethyl silicone oil having a peak at 0 was used to obtain silica (33).

0.8 part of the silica (33) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

[Example 22] 80% amino-modified silicone oil having a peak at a molecular weight of 13500 and a molecular weight of 8
Dimethyl silicone oil 2 having a peak at 9000
A silicone oil (31) was prepared in the same manner as in Example 18 except that 0% was used to obtain silica (34).

0.8 part of the silica (34) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Image evaluation was carried out in the same manner as in Example 18 using the obtained positively chargeable toner. The evaluation results are shown in Table 11.

Example 23 In the same manner as in Example 18, using titania as the fine powder matrix, the silicone oil (2
15 parts of 7) was processed to obtain titania (35).

0.8 part of the titania (35) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Using the obtained positively chargeable toner, image evaluation was carried out in the same manner as in Example 18. The evaluation results are shown in Table 11.

Example 24 70% dimethyl silicone oil having a peak at a molecular weight of 6000 and a molecular weight of 500
Amino-modified silicone oil 30 having a peak at 00
A silicone oil (32) was prepared in the same manner as in Example 18 except that the percentage (%) was used to obtain silica (36).

0.8 part of the silica (36) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

[Example 25] 90% amino-modified silicone oil having a peak at a molecular weight of 550 and a molecular weight of 700
A silicone oil (33) was prepared in the same manner as in Example 18 except that 10% of dimethyl silicone oil having a peak at 0 was used to obtain silica (37).

0.8 part of this silica (37) was added to 100 parts of the toner particles (4) and mixed by a Henschel mixer to obtain a positively chargeable toner.

Example 1 was performed using the obtained positively chargeable toner.
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

[Comparative Example 13] Amino-modified silicone oil having a peak at a molecular weight of 2400, 65%, and a molecular weight of 21
Dimethyl silicone oil having a peak at 00 35%
A silicone oil (34) was prepared in the same manner as in Example 18 except that was used to obtain silica (38).

0.8 part of this silica (38) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

Comparative Example 14 Amino-modified silicone oil having a peak at a molecular weight of 2,400 and 85% and a molecular weight of 12
Dimethyl silicone oil 1 having a peak at 5000
A silicone oil (35) was prepared in the same manner as in Example 18 except that 5% was used to obtain silica (39).

0.8 part of this silica (39) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

[Comparative Example 15] 90% amino-modified silicone oil having a peak at a molecular weight of 400 and a molecular weight of 600
Methylphenyl silicone oil having a peak at 0 1
A silicone oil (36) was prepared in the same manner as in Example 18 except that 0% was used to obtain silica (40).

0.8 part of this silica (40) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

[Comparative Example 16] 65% amino-modified silicone oil having a peak at a molecular weight of 16000 and a molecular weight of 8
Dimethyl silicone oil 3 having a peak at 9000
A silicone oil (37) was prepared in the same manner as in Example 18 except that 5% was used to obtain silica (41).

0.8 part of this silica (41) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 Using the Obtained Positively Chargeable Toner
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

[Comparative Example 17] 40% amino-modified silicone oil having a peak at a molecular weight of 450 and a molecular weight of 480
A silicone oil (38) was prepared in the same manner as in Example 18 except that 60% of dimethyl silicone oil having a peak at 0 was used to obtain silica (42).

0.8 part of the silica (42) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

Comparative Example 18 Silica (4) was prepared in the same manner as in Example 18 except that only the amino-modified silicone oil (39) having a peak at a molecular weight of 1600 was used.
3) was obtained.

0.8 part of the silica (43) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

[Comparative Example 19] Silica (44) was obtained in the same manner as in Example 18 except that only the amino-modified silicone oil (40) having a peak at a molecular weight of 28,000 was used.

0.8 part of the silica (44) was added to 100 parts of the toner particles (4) and mixed with a Henschel mixer to obtain a positively chargeable toner.

Example 1 was carried out using the obtained positively chargeable toner.
Image evaluation was performed in the same manner as in No. 8. The evaluation results are shown in Table 11.

[0385]

[Table 9]

[0386]

[Table 10]

[0387]

[Table 11]

[0388]

[Table 12]

Example 26 Alumina (45) shown in Table 12 was obtained by treating 12 parts of silicone oil (27) shown in Table 9 in the same manner as in Example 18 using alumina as the fine powder matrix. It was

Toner Production Example 5 Styrene-n-butyl acrylate copolymer 100 parts (St / BA = 83/15, peak molecular weight P _a = 10000, peak molecular weight P _b = 345000, Mn = 8500, Mw = 175000) Polyethylene wax 4 parts ・ Phthalocyanine 4 parts ・ Quaternary ammonium salt 2 parts

Using the above materials, toner particles (5) having a weight average particle diameter of 8.5 μm were obtained in the same manner as in Example 18.

0.8 part of alumina (45) was added to 100 parts of toner particles (5) and mixed with a Henschel mixer to obtain a positively chargeable toner.

The obtained positively charged toner was used for image evaluation with a commercially available copying machine FC330 (manufactured by Canon Inc.) having a developing device shown in FIG.

A durability test of 1,000 sheets was carried out under ambient temperature / normal humidity, low temperature / low humidity, high temperature / high humidity environmental conditions. Image density and fog in each environment were evaluated. Furthermore, we evaluated the level of image dropouts (reproducibility of character images) at room temperature and humidity, the uniformity of halftone images and the uniformity of solid black images, and the occurrence of filming and fusion on the photoconductor. did.

Each evaluation was performed in the same manner as the evaluation performed in Example 1.

The evaluation results are shown in Table 13.

[0397]

[Table 13]

[0398]

[Table 14]

[0399]

According to the present invention, since the toner has a mixture of inorganic fine powder and toner particles treated with silicone oil having a specific molecular weight distribution in the GPC molecular weight distribution, (i) the image from the initial stage The density is stable, and even under low temperature / low humidity, room temperature / normal humidity and high temperature / high humidity environments, and even when toner is replenished, a high density image with excellent image quality without fog can be obtained for a long time. It is possible to form (ii) an image that is free from image defects such as voids in transfer, and free from scatter, offset, and filming. (Iii) Even in a halftone image or a solid black image, It is possible to form an excellent image that is uniform and has no unevenness, streak-like white spots, or dot-like white spots.

[Brief description of the drawings]

FIG. 1 is a view showing a GPC chromatogram of silicone oil (1) used in Example 1 of the present invention.

FIG. 2 shows a GPC chromatogram of silicone oil (14) used in Example 10 of the present invention.

FIG. 3 is a schematic view of an image forming apparatus for explaining the image forming method of the present invention.

FIG. 4 is a schematic view for explaining another form of fixing means applicable as the fixing means of the image forming apparatus shown in FIG.

FIG. 5 is a schematic view of a developing device unit of the present invention using a magnetic one-component developing system.

FIG. 6 is a schematic view of a developing device unit of another embodiment of the present invention using an elastic blade.

FIG. 7 is a schematic view of a developing device unit according to another embodiment of the present invention using an elastic blade.

FIG. 8 is a schematic view of a developing device unit of the present invention using a non-magnetic one-component developing system.

FIG. 9 is a diagram showing one specific example for explaining the process cartridge of the present invention.

FIG. 10 is a diagram showing a block diagram when the image forming method of the present invention is applied to a printer of a facsimile apparatus.

[Explanation of Codes] 1 Latent Image Holder 2 Charging Member 3 Charging Bias Power Supply 4 Latent Image Forming Means 5 Developing Device 6 Transfer Member 7 Transfer Bias Power Supply 8 Recording Material 9 Cleaning Device 10 Discharge Exposure Device 11 Fixing Device 51 Toner Layer Thickness Regulation Means 52 Toner container 53 Toner 54 Toner carrier 91 Cleaning member 101, 201, 301 Latent image carrier 102, 202, 302 Toner carrier 103 Magnetic generation means 104 Toner layer thickness regulating member (magnetic blade) 105 Toner stirring member 106 Toner Containers 203 and 303 Toner layer thickness regulating member (elastic blade) 401 Latent image holder 402 Toner carrier 403 Toner container 404 Supply roller 405 Toner layer thickness regulating member 406 Toner 407 Agitating member A Development area C Process cartridge T ₁ Toner thin layer T ₂ toner image

Claims (68)

[Claims] 1. A toner for electrostatic image development comprising toner particles containing at least a binder resin and a colorant, and an inorganic fine powder, wherein the inorganic fine powder has a molecular weight distribution of 500 to 15,000 in GPC molecular weight distribution. Has at least one local maximum and has a molecular weight of more than 30
A toner for developing an electrostatic charge image, which is treated with a silicone oil having at least one local maximum or shoulder in the range of 00 to 100,000. 2. The electrostatic image developing toner according to claim 1, wherein the silicone oil has a weight average molecular weight / number average molecular weight (Mw / Mn) of 2 to 40. 3. The toner for developing an electrostatic charge image according to claim 1, wherein the silicone oil has a Z average molecular weight / number average molecular weight (Mz / Mn) of 3 to 100. 4. In the molecular weight distribution by GPC, the silicone oil has a distance from the peak of the maximum value existing in the molecular weight range of 500 to 15,000 to the baseline as A, which is larger than the maximum value and has a molecular weight of 3,000 to 100,000. The distance from the peak of the maximum value existing in the region of to the baseline is B, and the molecular weight is 500 to 1500.
When the distance from the bottom point of the minimum value existing between the maximum value existing in the area of 0 and the maximum value existing in the area of the molecular weight of 3000 to 100000 to the baseline is C, A, B and C are the following conditions A: B:
4. The electrostatic image developing toner according to claim 1, wherein C = 1: 0.01 to 1.0: 0.001 to 0.70 is satisfied. 5. In the molecular weight distribution by GPC, the silicone oil has a distance A from a peak of a maximum value existing in a molecular weight range of 500 to 15,000 to a base line, which is larger than the maximum value and has a molecular weight of 3,000 to 100,000. Assuming that the distance from the inflection point of the shoulder in the area of B to the baseline is B, A and B
The toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein the following condition A: B = 1: 0.1 to 0.7 is satisfied. 6. The silicone oil has the following formula (1): [In the formula, R ₁ represents a methyl group, another alkyl group, an aryl group or hydrogen, and independently, R ₂ represents a methyl group, another alkyl group, an aryl group, a vinyl group or an alkyl group having a functional group. , Represents an aryl group having a functional group, or hydrogen, and m and n represent integers. ] The silicone oil shown by these is included, The 1 thru | or 5 characterized by the above-mentioned.
The toner for developing electrostatic images according to any one of the above. 7. The silicone oil is dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl modified silicone oil, chloroalkyl modified silicone oil, chlorophenyl modified silicone oil, fatty acid modified silicone oil, polyether modified silicone. 7. One or more silicone oils selected from the group consisting of oils, alkoxy-modified silicone oils, carbinol-modified silicone oils, amino-modified silicone oils and fluorine-modified silicone oils.
3. The toner for developing an electrostatic image according to item 1. 8. The silicone oil contains at least one silicone oil selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, fluorine-modified silicone oil and alkyl-modified silicone oil. 7. The toner for developing an electrostatic charge image according to claim 6, wherein 9. The silicone oil is 300 to 10
2. An amine equivalent of 000.
6. The electrostatic image developing toner according to any one of items 1 to 5. 10. The toner for developing an electrostatic charge image according to claim 9, wherein the toner has a positive charging property. 11. The silicone oil has the following formula (2): [Wherein R ₃ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₄ represents an alkylene group or a phenylene group, R ₅ and R ₆ represent hydrogen, an alkyl group or an aryl group, and R ₇ represents A nitrogen-containing heterocyclic group is shown. ] The toner for developing an electrostatic charge image according to claim 9, further comprising an amino-modified silicone oil represented by the formula [10]. 12. The toner for developing an electrostatic charge image according to claim 9, wherein the silicone oil contains a mixture of an amino-modified silicone oil and a silicone oil having no amino group. 13. The silicone oil is one or more selected from the group consisting of amino-modified silicone oil, dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil and vinyl group-containing silicone oil. 10. The toner for developing an electrostatic charge image according to claim 9, which contains a mixture with the silicone oil of. 14. The silicone oil selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil and vinyl group-containing silicone oil has a molecular weight distribution by GPC of
The toner for developing an electrostatic charge image according to claim 13, which has at least one maximum value in a region having a molecular weight of 1,000 or more. 15. The amino-modified silicone oil is G
In the molecular weight distribution by PC, the molecular weight is 500 to 15
15. The toner for developing an electrostatic charge image according to claim 11, which has at least one maximum value in the area of 000. 16. A charging step of charging a latent image holding member by a charging member, a latent image forming step of forming an electrostatic latent image on the charged latent image holding member by a latent image forming means, and a toner image forming step. An image forming method including a developing step of developing the electrostatic latent image with toner and a step of transferring the toner image to a transfer material by a transfer member, wherein the toner is toner particles containing at least a binder resin and a colorant. , And inorganic fine powder, which has at least one local maximum in the molecular weight range of 500 to 15,000 and has a molecular weight of 30 or more in the molecular weight distribution by GPC.
An image forming method characterized by being treated with a silicone oil having at least one local maximum or shoulder in a region of 00 to 100,000. 17. The image forming method according to claim 16, wherein the silicone oil has a weight average molecular weight / number average molecular weight (Mw / Mn) of 2 to 40. 18. The silicone oil is 3 to 100.
17. The image forming method according to claim 16, wherein the image forming method has a Z average molecular weight / number average molecular weight (Mz / Mn). 19. In the molecular weight distribution by GPC of the silicone oil, the distance from the peak of the maximum value existing in the molecular weight range of 500 to 15,000 to the baseline is A, which is larger than the maximum value and the molecular weight is 3000 to 100,000. Let B be the distance from the peak of the maximum value existing in the region of to, and the molecular weight is 500 to 150.
When the distance from the bottom point of the minimum value existing between the maximum value existing in the area of 00 and the maximum value existing in the area of the molecular weight of 3000 to 100000 to the baseline is C, A, B and C are the following condition A:
B: C = 1: 0.01 to 1.0: 0.001 to 0.70
The image forming method according to any one of claims 16 to 18, characterized in that: 20. In the molecular weight distribution by GPC of the silicone oil, the distance from the peak of the maximum value existing in the molecular weight range of 500 to 15,000 to the baseline is A, which is larger than the maximum value and the molecular weight is 3000 to 100,000. Assuming that the distance from the inflection point of the shoulder in the area of B to the baseline is B, A and B
19. The image forming method according to claim 16, wherein the following condition A: B = 1: 0.1 to 0.7 is satisfied. 21. The silicone oil has the following formula (1): [In the formula, R ₁ represents a methyl group, another alkyl group, an aryl group or hydrogen, and independently, R ₂ represents a methyl group, another alkyl group, an aryl group, a vinyl group or an alkyl group having a functional group. , Represents an aryl group having a functional group, or hydrogen, and m and n represent integers. ] The image forming method according to any one of claims 16 to 20, further comprising a silicone oil represented by the above. 22. The silicone oil is dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, alkyl modified silicone oil, chloroalkyl modified silicone oil,
One or more silicone oils selected from the group consisting of chlorophenyl modified silicone oil, fatty acid modified silicone oil, polyether modified silicone oil, alkoxy modified silicone oil, carbinol modified silicone oil, amino modified silicone oil and fluorine modified silicone oil. 3. The method according to claim 2, wherein
1. The image forming method described in 1. 23. The silicone oil contains at least one silicone oil selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, fluorine-modified silicone oil and alkyl-modified silicone oil. The image forming method according to claim 21, wherein: 24. The silicone oil is 300 to 1
The image forming method according to any one of claims 16 to 20, wherein the image forming method has an amine equivalent of 0000. 25. The image forming method according to claim 24, wherein the toner has a positive charging property. 26. The silicone oil has the following formula (2): [Wherein R ₃ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₄ represents an alkylene group or a phenylene group, R ₅ and R ₆ represent hydrogen, an alkyl group or an aryl group, and R ₇ represents A nitrogen-containing heterocyclic group is shown. The image forming method according to claim 24, further comprising an amino-modified silicone oil represented by 27. The image forming method according to claim 24, wherein the silicone oil contains a mixture of an amino-modified silicone oil and a silicone oil having no amino group. 28. The silicone oil is one or more selected from the group consisting of amino-modified silicone oil, dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil and vinyl group-containing silicone oil. 25. The image forming method according to claim 24, wherein the image forming method comprises a mixture with the silicone oil. 29. The silicone oil selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil and vinyl group-containing silicone oil has a molecular weight distribution by GPC,
29. The image forming method according to claim 28, which has at least one maximum value in a region having a molecular weight of 1000 or more. 30. The amino-modified silicone oil is G
In the molecular weight distribution by PC, the molecular weight is 500 to 15
30. The image forming method according to any one of claims 26 to 29, wherein the image forming method has at least one local maximum value in the area of 000. 31. A toner for developing an electrostatic latent image, a toner container for accommodating the toner, a toner contained in the toner container, and a place for developing the electrostatic latent image. In a developing device unit having a toner carrier for transporting to a developing area, the toner includes toner particles containing at least a binder resin and a colorant, and inorganic fine powder, and the inorganic fine powder is In the molecular weight distribution by GPC, at least one local maximum value is present in the molecular weight range of 500 to 15,000, and is larger than the local maximum value, the molecular weight is 30
A developing device unit treated with a silicone oil having at least one local maximum or shoulder in a region of 00 to 100,000. 32. The developing device unit according to claim 31, wherein the silicone oil has a weight average molecular weight / number average molecular weight (Mw / Mn) of 2 to 40. 33. The silicone oil is 3 to 100.
32. The developing device unit according to claim 31, having a Z average molecular weight / number average molecular weight (Mz / Mn). 34. In the molecular weight distribution by GPC of the silicone oil, the distance from the apex of the maximum value existing in the molecular weight range of 500 to 15,000 to the baseline is A, which is larger than the maximum value and has a molecular weight of 3,000 to 100,000. Let B be the distance from the peak of the maximum value existing in the region of to, and the molecular weight is 500 to 150.
When the distance from the bottom point of the minimum value existing between the maximum value existing in the area of 00 and the maximum value existing in the area of the molecular weight of 3000 to 100000 to the baseline is C, A, B and C are the following condition A:
B: C = 1: 0.01 to 1.0: 0.001 to 0.70
34. The developing device unit according to any one of claims 31 to 33, characterized in that 35. In the molecular weight distribution of GPC, the silicone oil has a distance from the peak of the maximum value existing in the molecular weight range of 500 to 15,000 to the baseline as A, which is larger than the maximum value and has a molecular weight of 3,000 to 100,000. Assuming that the distance from the inflection point of the shoulder in the area of B to the baseline is B, A and B
34. The developing device unit according to claim 31, wherein the following condition A: B = 1: 0.1 to 0.7 is satisfied. 36. The silicone oil has the following formula (1): [In the formula, R ₁ represents a methyl group, another alkyl group, an aryl group or hydrogen, and independently, R ₂ represents a methyl group, another alkyl group, an aryl group, a vinyl group or an alkyl group having a functional group. , Represents an aryl group having a functional group, or hydrogen, and m and n represent integers. ] The developing device unit according to any one of claims 31 to 35, wherein the developing device unit contains a silicone oil. 37. The silicone oil is dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, alkyl modified silicone oil, chloroalkyl modified silicone oil,
At least one silicone oil selected from the group consisting of chlorophenyl modified silicone oil, fatty acid modified silicone oil, polyether modified silicone oil, alkoxy modified silicone oil, carbinol modified silicone oil, amino modified silicone oil and fluorine modified silicone oil. The developing device unit according to claim 36, comprising: 38. The silicone oil contains at least one silicone oil selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, fluorine-modified silicone oil, and alkyl-modified silicone oil. 37. The developing device unit according to claim 36. 39. The silicone oil is 300 to 1
The developing device unit according to any one of claims 31 to 35, having an amine equivalent of 0000. 40. The developing device unit according to claim 39, wherein the toner has a positive charging property. 41. The silicone oil has the following formula (2): [Wherein R ₃ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₄ represents an alkylene group or a phenylene group, R ₅ and R ₆ represent hydrogen, an alkyl group or an aryl group, and R ₇ represents A nitrogen-containing heterocyclic group is shown. 40. The developing device unit according to claim 39, further comprising an amino-modified silicone oil represented by 42. The developing device unit according to claim 39, wherein the silicone oil contains a mixture of amino-modified silicone oil and silicone oil having no amino group. 43. The silicone oil is one or more selected from the group consisting of amino-modified silicone oil, dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil and vinyl group-containing silicone oil. 35. The developing device unit according to claim 34, wherein the developing device unit contains a mixture with the silicone oil of. 44. The silicone oil selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil and vinyl group-containing silicone oil has a molecular weight distribution by GPC,
The developing device unit according to claim 43, which has at least one local maximum in a region having a molecular weight of 1,000 or more. 45. The amino-modified silicone oil is G
In the molecular weight distribution by PC, the molecular weight is 500 to 15
The developing device unit according to any one of claims 41 to 44, wherein the developing device unit has at least one maximum value in the area of 000. 46. The developing device unit according to claim 31, wherein the developing device unit is mounted on an image forming apparatus main body and is fixed by fixing means. 47. The developing device unit according to claim 46, wherein the developing device unit is fixed to the image forming apparatus main body by using a bolt as the fixing means. 48. The developing device unit according to claim 46, wherein the developing device unit is fixed to the image forming apparatus main body by using a pin as the fixing means. 49. A process cartridge attachable to and detachable from an image forming apparatus main body, wherein the process cartridge has a latent image holding property for holding an electrostatic latent image and an electrostatic latent image held by the latent image holding member. And a toner container for accommodating the toner, and a toner contained in the toner container. The toner has a toner carrier for carrying and carrying it to a developing area where an electrostatic latent image is developed. The toner is toner particles containing at least a binder resin and a colorant, and an inorganic fine powder. The inorganic fine powder has at least one local maximum in the molecular weight range of 500 to 15,000 in the molecular weight distribution by GPC, and has a molecular weight of 3 or more.
A process cartridge characterized by being treated with a silicone oil having at least one local maximum or shoulder in the range of 00 to 100,000. 50. The process cartridge according to claim 49, wherein the silicone oil has a weight average molecular weight / number average molecular weight (Mw / Mn) of 2 to 40. 51. The silicone oil is 3 to 100.
50. The process cartridge according to claim 49, wherein the process cartridge has a Z-average molecular weight / number-average molecular weight (Mz / Mn). 52. In the molecular weight distribution by GPC, the silicone oil has a distance from a peak of a maximum value existing in a molecular weight range of 500 to 15,000 to a base line as A, which is larger than the maximum value and has a molecular weight of 3,000 to 100,000. Let B be the distance from the peak of the maximum value existing in the region of to, and the molecular weight is 500 to 150.
When the distance from the bottom point of the minimum value existing between the maximum value existing in the area of 00 and the maximum value existing in the area of the molecular weight of 3000 to 100000 to the baseline is C, A, B and C are the following condition A:
B: C = 1: 0.01 to 1.0: 0.001 to 0.70
The process cartridge according to any one of claims 49 to 51, characterized in that: 53. In the molecular weight distribution by GPC of the silicone oil, the distance from the apex of the maximum value existing in the molecular weight range of 500 to 15,000 to the baseline is A, and the silicone oil is larger than the maximum value and has a molecular weight of 3,000 to 100,000. Assuming that the distance from the inflection point of the shoulder in the area of B to the baseline is B, A and B
52. The process cartridge according to claim 49, wherein the following condition A: B = 1: 0.1 to 0.7 is satisfied. 54. The silicone oil has the following formula (1): [In the formula, R ₁ represents a methyl group, another alkyl group, an aryl group or hydrogen, and independently, R ₂ represents a methyl group, another alkyl group, an aryl group, a vinyl group or an alkyl group having a functional group. , Represents an aryl group having a functional group, or hydrogen, and m and n represent integers. ] The process cartridge according to any one of claims 49 to 53, wherein the process cartridge contains a silicone oil represented by the above. 55. The silicone oil is dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, chloroalkyl-modified silicone oil,
At least one silicone oil selected from the group consisting of chlorophenyl modified silicone oil, fatty acid modified silicone oil, polyether modified silicone oil, alkoxy modified silicone oil, carbinol modified silicone oil, amino modified silicone oil and fluorine modified silicone oil. 55. The process cartridge of claim 54, comprising: 56. The silicone oil contains at least one silicone oil selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, fluorine-modified silicone oil and alkyl-modified silicone oil. The process cartridge according to claim 54, wherein: 57. The silicone oil is 300 to 1
54. A process cartridge according to any of claims 49 to 53 having an amine equivalent weight of 0000. 58. The process cartridge according to claim 57, wherein the toner has a positive charging property. 59. The silicone oil has the following formula (2): [Wherein R ₃ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₄ represents an alkylene group or a phenylene group, R ₅ and R ₆ represent hydrogen, an alkyl group or an aryl group, and R ₇ represents A nitrogen-containing heterocyclic group is shown. The process cartridge according to claim 57, further comprising an amino-modified silicone oil represented by the formula. 60. The process cartridge according to claim 57, wherein the silicone oil contains a mixture of an amino-modified silicone oil and a silicone oil having no amino group. 61. The silicone oil is one or more selected from the group consisting of amino-modified silicone oil and dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, and vinyl group-containing silicone oil. 58. A process cartridge according to claim 57, comprising a mixture with a silicone oil according to claim 57. 62. The silicone oil selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, and vinyl group-containing silicone oil has a molecular weight distribution measured by GPC of
The process cartridge according to claim 61, which has at least one local maximum in a region of a molecular weight of 1000 or more. 63. The amino-modified silicone oil is G
In the molecular weight distribution by PC, the molecular weight is 500 to 15
63. The process cartridge according to claim 59, wherein the process cartridge has at least one maximum value in the area of 000. 64. The process cartridge integrally has, in addition to the latent image carrier and the developing device, a cleaning means for cleaning the surface of the latent image carrier. 64. The process cartridge according to any one of claims 49 to 63. 65. The process cartridge according to claim 64, wherein the cleaning means is a cleaning blade. 66. The process cartridge further comprises, in addition to the latent image holding member and the developing device, an integral charging member for charging the latent image holding member. Item 64. The process cartridge according to any one of items 49 to 63. 67. The process cartridge comprises, in addition to the latent image carrier and the developing device, a cleaning unit for cleaning the surface of the latent image carrier and a charging device for charging the latent image carrier. 64. The process cartridge according to claim 49, further comprising a member integrally. 68. The process cartridge according to claim 67, wherein the cleaning means is a cleaning blade.