JP3481028B2 - Toner and image forming method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner, a developer and an image forming method used when developing an electrostatic latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc. The present invention relates to a toner, a developer and an image forming method suitable for forming a color image of an intermediate color on a recording material by performing color superposition using a plurality of toners of two or more colors.

[0002]

BACKGROUND OF THE INVENTION Electrophotography is described, for example, in US Pat.
No. 7,691 and No. 2,357,809, an electrostatic latent image is formed on the surface of a photoconductor, and the electrostatic latent image is formed into a toner image by a dry developer containing colored particles. In addition, after the toner image is transferred onto paper or the like, the toner image is permanently fixed by heating or pressing to form a copied image.

Inorganic photoconductors such as selenium, zinc oxide, and cadmium sulfide, organic photoconductors, and the like are known as photoconductors used in such electrophotography, but in recent years, the manufacturing cost is low and the cost is high. Organic photoconductors made of organic semiconductors, which have advantages such as sensitivity, durability, heat resistance, and non-toxicity to human body, and have good film-forming properties, have been used.

When an organic photoreceptor is used, a negative electrostatic latent image is generally used. As a developer used for developing a negative electrostatic latent image, a toner constituting the developer must be positively charged. In order to positively charge the toner, a carrier that can positively charge the toner is selected.

However, simply selecting a carrier (friction charging member) for positively charging the toner cannot provide a good image for a long period of time. The toner is charged by rubbing against the friction charging member,
When used for a long period of time, some of the components that make up the toner migrate to the triboelectrification member due to friction, contaminate the triboelectrification member surface, and gradually it becomes impossible to impart an appropriate triboelectric charge to the toner, causing fogging. It tends to occur.

In order to solve the above problems, Japanese Patent Publication No. 53-2
No. 2447 and JP-A-53-66235, it is proposed that inorganic fine particles treated with an aminosilane coupling agent are added to the toner to impart positive chargeability. However, it was not possible to impart an appropriate positive charging property over a long period of time, and if it was repeatedly used many times, the charging property was lost, causing fog or toner scattering. It contaminates the image. It has been found that the above-mentioned drawback becomes more remarkable in an environment of higher humidity. Further, JP-A-56-123550 and JP-A-59-34539 disclose,
Proposed to improve charge stability, environmental stability, durability, etc. by adding silica fine particles treated with an aminosilane coupling agent or a silane coupling agent for hydrophobicity to the toner. Has been
When the present inventors studied, it was not possible to block all of Si—OH, which is a hydrophilic group on the surface of silica particles, and a considerable amount of —OH groups remained on the surface of silica particles,
It was found that the effect of humidity could not be completely prevented and it was unstable to environmental changes. In addition, JP-A-59-201063 discloses that by adding fine silicic acid powder treated with silicone oil having an amine side chain to a toner, it has durability and is stable against changes in environmental conditions. Although it has been proposed that the silicone oil has tackiness, the present inventors have studied.
It adheres to and contaminates the surface of the photoconductor, carrier particles, developer, carrier, etc., destabilizes the triboelectric chargeability of the toner, lowers the durability, and lowers the cleaning property of the surface of the photoconductor. found.

As described above, it does not have a positive charging property which is sufficiently stable against environmental changes, the charging efficiency is poor, the initial charging rise is poor, and cleaning failure is likely to occur.
As a solution to the drawbacks such as poor durability
In the 1-114857 publication, it is proposed to add inorganic fine particles whose surface is treated with an organopolysiloxane having a component having an ammonium salt as a functional group as a cocondensation component to a developer. , It was not possible to give a sufficient positive charge. The reason why it is not possible to give a sufficient positive charge, the co-condensation polysiloxane described in JP-A 1-114857, the ammonium salt functional group is in the side chain of the molecular chain of the polysiloxane,
It is considered that this is because the functional group of the ammonium salt forms a form coordinated to the surface of the fine particles by hydrogen bond.

Then, the inventors of the present invention studied and found that the above-mentioned drawbacks can be solved by using inorganic fine particles treated with a specific organopolysiloxane having an ammonium functional group at the terminal.

Further, these conventionally known toners are formed by using a plurality of toners of two or more colors to form a toner image of an intermediate color on a recording material by carrying out color superposition and fixing the toner image to form a color image. When used in a color image forming method to be formed, there is a problem in that color misregistration and color mixture of superposed images occur.

Therefore, an appropriate amount of positive charge can be quickly applied, and the positive charge can be stably maintained. By using a plurality of toners of two or more colors and superimposing colors, intermediate colors on the recording material can be obtained. When used in a color image forming method for forming a toner image, it has been desired to develop a toner capable of obtaining a high-definition image with high image density for a long period of time without causing color misregistration or color mixture of superposed images.

[0011]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a proper amount of positive charges rapidly, maintain a proper amount of positive charges stably for a long period of time, and prevent toner scattering and image fogging. Another object of the present invention is to provide a toner for electrophotography and a developer for developing an electrostatic charge image, which can form a high-definition image free from image defects such as character dust.

Another object of the present invention is to form a high-definition image with a high image density, without causing color misregistration or color mixture of superposed images, and superimposing colors using a plurality of toners of two or more colors. The purpose is to provide a toner that forms a toner image of an intermediate color on a recording material.

Another object of the present invention is to perform color superimposition using a plurality of toners of two or more colors without causing color misregistration or color mixture of superposed images, and to obtain a high-definition image with high image density. It is to provide a color image forming method capable of forming a color image.

Another object of the present invention is to provide a fixing method capable of forming a high-definition image without toner scattering, image fogging, and image defects such as character dust.

[0015]

The above objects of the present invention are: (1) Colored particles comprising at least a resin and a colorant,
A toner obtained by adding inorganic fine particles treated with an organopolysiloxane having an ammonium functional group at the terminal represented by the following formula 1 .

[0016]

[Chemical 4] [Wherein Y and Z are the number of substituted and unsubstituted carbon atoms, respectively]
1 to 8 represents an alkyl group or an aryl group. A and
B is a hydrogen atom, a substituted or unsubstituted C1-4 carbon atom, respectively.
Have one alkyl group or ammonium salt structure
Represents a group. However, at least one of A and B is
It is a group having an ammonium salt structure. n is an integer of 5 to 400
Represents a number. The toner according to (2) using a plurality of toners of two or more colors, above, wherein the on the recording medium by performing color superimposition is toner used to form an intermediate color of the toner image (1) . (3) inorganic fine particles treated with organopolysiloxane having terminal ammonium functional groups, above, wherein the inorganic fine particles treated with a hydrophobic treatment agent (1) or
Or the toner according to (2) . (4) A developer for electrostatic charge image development comprising the toner according to any one of (1) to (3) and a carrier. (5) The carrier according to the above (4), wherein the carrier is a carrier in which the core surface having a fluorine atom content rate of 30 atom% or more on the carrier surface is coated with a fluororesin. Developer for charge image development. (6) The fluorinated resin is a fluorinated acrylate resin or fluorinated methacrylate resin containing a repeating unit represented by the following formula 2, or vinylidene fluoride resin, hexafluoropropylene resin, or vinylidene fluoride and hexafluoropropylene. The developer for electrostatic charge image development according to (5) above, which is a copolymer resin of

[0017]

[Chemical 5] [In the formula, R represents a hydrogen atom or a methyl group, and Rf represents an alkyl group substituted with a fluorine atom. (7) The fluorinated resin is a fluorinated methacrylate resin having a repeating unit represented by the following formula 3 of 75% by weight or more,
Alternatively, it is a copolymer resin of vinylidene fluoride and hexafluoropropylene (5) or
Is the developer for developing an electrostatic charge image according to (6) .

[0018]

[Chemical 6] [In the formula, Rf represents an alkyl group substituted with a fluorine atom. (8) A color image forming method for forming an image by forming a toner image of an intermediate color on a recording material by performing color superposition using a plurality of toners of two or more colors, and forming the image by fixing the toner image, As toner, the above (1) to (3)
A color image forming method, characterized in that the toner described in any one of the above is used. (9) Any one of the above (1) to (3) is provided between the rotating fixing roller and the pressure-bonding roller that is pressed against the fixing roller .
Thermal fixing method characterized in that passed through a recording material bearing a toner image according to fix the toner image on the recording material. (10) A movable film material is disposed between a fixedly arranged heating body and a pressure member that presses against and rotates against the heating body, and a toner image is provided between the film material and the pressure member. Any of the above (1) to (3) so that the film contacts the film material .
Thermal fixing method characterized in that passed through a recording material bearing a toner image according to fix the toner image on the recording material. Can be achieved by

The present invention will be described in detail below.

In the present invention, the toner has the above formula 1
Organopolysiloxane having an ammonium functional group at the terminal represented (hereinafter, simply referred to as an ammonium functional group at the terminal
Sometimes referred to as an organopolysiloxane having. )
Inorganic fine particles treated with are used.

In the present invention, by using the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the terminal, the positive chargeability of the inorganic fine particles is increased, and when the inorganic fine particles are added to the colored particles to form a toner, An appropriate amount of positive charge can be quickly applied and the positive charge can be stably maintained.

When inorganic fine particles treated with an organopolysiloxane having an ammonium functional group only on the side chain are used, the above effects are not observed, whereas treatment with an organopolysiloxane having an ammonium functional group at the end is used. The reason why the above effect is obtained when the above-mentioned inorganic fine particles are used has not been clarified in detail, but it can be estimated as follows.

That is, when an organopolysiloxane having an ammonium functional group only in its side chain is used for treating the inorganic fine particles, the ammonium functional group is present only in the side chain of the organopolysiloxane molecule. In addition, when the inorganic fine particles are treated, the ammonium functional group approaches a polar group such as a hydroxyl group on the surface of the base inorganic fine particles, which facilitates coordination, and as a result, the positively charged property of the ammonium functional group is not sufficiently exhibited. It is presumed that.
On the other hand, when the ammonium functional group is present at the end of the organopolysiloxane, the ammonium functional group does not selectively approach the polar group on the surface of the inorganic fine particles and is coordinated, so that the ammonium functional group is not present in the inorganic fine particles. It is presumed that it is possible to exist on the surface.

By allowing the ammonium functional group to exist on the outermost surface of the inorganic fine particles, the positive charging property of the ammonium functional group can be sufficiently involved in the triboelectric charging, and the positive charging property of the inorganic fine particles is increased, so that the coloring particles are added. When added as a toner, an appropriate amount of positive charge can be quickly applied and the positive charge can be stably maintained, and the toner can be used as an electrostatic latent image formed on an electrostatic image support. When used as a developer for developing, it is considered that a high-definition image with high image density and no image fog can be obtained for a long period of time without toner scattering.

Further, when the toner image is fixed on the recording material by passing through the recording material carrying the toner image, if the curvature becomes small at the peeling portion, the electric charge generated by the peeling from the heating portion increases and the character dust is generated. However, the toner of the present invention has the effect of stabilizing the charge amount over a long period of time, and does not cause character dust.

Therefore, a fixedly arranged heating element, a pressure member that is pressed against and rotates against the heating element, and a movable film material are arranged for fixing, or the curvature of the fixing roller during roller fixing. If you reduce the
Character dust does not occur.

In addition, a proper amount of positive charge is rapidly applied,
In addition, the positive charge can be stably maintained, a toner image of an intermediate color is formed on the recording material by performing color superposition using a plurality of toners of two or more colors, and the toner image is fixed to form a color image. It is considered that when it is formed, the development efficiency is stably maintained without being lowered, and a high-definition image with high image density and without color shift or color mixture of a superimposed image can be obtained for a long time.

Next, the inorganic fine particles used in the present invention which are added to the colored particles and which are treated with the organopolysiloxane having an ammonium functional group at the terminal will be described.

The inorganic fine particles used for the treatment with the organopolysiloxane having an ammonium functional group at the end are preferably those having a number average primary particle diameter of 3 to 500 nm, more preferably 5 to 100 nm. Those are preferable.

The organopolysiloxane having an ammonium functional group at the terminal used in the present invention can be obtained by modifying the terminal group of the organopolysiloxane so that at least one of the terminals has an ammonium functional group.

In the present invention, the term "terminal" refers to the end of the organopolysiloxane molecular chain, not the end of the side chain of the organopolysiloxane molecular chain.

The powder represented by the following formula 1 used in the present invention
Organopolysiloxaes with ammonium functional groups at the ends
Will be described in more detail.

[0033]

[Chemical 7] [In the formula, Y and Z each represent a substituted or unsubstituted alkyl group or aryl group having 1 to 8 carbon atoms. A and B are each a hydrogen atom, a substituted or unsubstituted carbon atom number 1 to 4
Represents an alkyl group or a group having an ammonium salt structure. However, at least one of A and B is a group having an ammonium salt structure. n represents an integer of 5 to 400 . Furthermore, as the organopolysiloxane used in the present invention, those represented by the following formulas 4 and 5 are preferable.

[0034]

[Chemical 8]

In the formulas 4 and 5, Y and Z each represent a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or an aryl group (for example, a phenyl group), and R ¹ has a carbon atom number of 1 to 8 represents an alkylene group or an arylene group (for example, a phenylene group), and R ² , R ³ and R
⁴ is a hydrogen atom, an aryl group (for example, a phenyl group),
An alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms having an amino group, an aryl group having an amino group (for example, a phenyl group), an alkyl group having 1 to 30 carbon atoms having an ammonium salt structure Group or an aryl group having an ammonium salt structure (for example, a phenyl group), R
⁵ represents an alkyl group having 1 to 4 carbon atoms, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X 6
^- represents counter anion (e.g., halide ions, sulfo ions). a, b, c and d represent an integer of 1 to 3. However, a + b = 3 and c + d = 3. n is 5
It is an integer of 400 . In addition, R ^{1 to} R ⁶ may have any substituent such as an alkyl group and an aryl group.

In equations 4 and 5

[0037]

[Chemical 9] For example, the following may be mentioned.

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040] In the present invention, the organopolysiloxane may be used any viscosity, preferably those kinematic viscosity at 25 ° C. is 5 to 500 mm ² / sec, more 10 to 100 mm ² / Better is something in the range of seconds
Good By setting the kinematic viscosity of the organopolysiloxane and the polymerization degree of the diorganosiloxane unit within the above ranges, the treatment of the inorganic fine particles can be achieved without impairing the fluidity.

The organopolysiloxane having an ammonium functional group at the terminal used in the present invention can be produced by a conventionally known method. For example, a silanol group at the terminal of the organopolysiloxane molecular chain is reacted with an organoalkoxysilylammonium compound, and in some cases, a silanol group at the terminal of the organopolysiloxane molecular chain is treated with an organoalkoxysilylamine compound and a hydrogen halide. It can be produced by reacting in the presence of an acid such as an acid and another inorganic or organic acid.

The organoalkoxysilylammonium compound can be produced by a known method, for example, by reacting an alkoxysilylalkylhalogenide or an alkoxysilylalkylsulfonate with an amine, particularly a tertiary amine.
Further, the organoalkoxysilylamine compound can also be produced by a known method, and a part thereof can be obtained as a commercial product.

The positive charge imparting property can be controlled by variously changing the reaction ratio between the organoalkoxysilylammonium compound or the organoalkoxysilylamine compound and the dimethylpolysiloxane having silanol groups at both ends.

The inorganic fine particles to be treated with the organopolysiloxane having an ammonium functional group at the end of the present invention include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, Examples thereof include fine particles of chromium oxide, cerium oxide, antimony trioxide, tin oxide, zirconium oxide, silicon carbide and the like. These can be used alone or as a mixture.

The above-mentioned base inorganic fine particles can be used regardless of whether they are produced by a dry method or a wet method.

Examples of the dry method include a method of producing inorganic fine particles by vapor-phase oxidation of a halide of a metal element or a semimetal, and for example, a halogen by utilizing a thermal decomposition oxidation reaction in oxygen or hydrogen. It is a method for producing inorganic fine particles from a compound gas, and the reaction formula is shown as follows.

MX _n +1/2 nH ₂ +1/4 nO ₂ →
MO _{1 / 2n} + nHCl In this reaction formula, M represents a metal atom or a metalloid atom, X represents a halogen atom, and n represents a positive integer.

When the inorganic fine particles are produced by the dry method, the vapor-phase-oxidized halide may be SiCl ₄ ,
By using TiCl ₄ , AlCl ₃ and BaCl ₂ , fine particles of SiO ₂ , TiO ₂ , Al ₂ O ₃ and BaO can be obtained respectively. In the case of vapor phase oxidation, a corresponding compound oxide can be obtained by mixing and using a halide.

Examples of the wet method include a method in which an aqueous solution of sodium silicate is used and decomposed with an acid and / or an alkali salt to produce inorganic fine particles.

As the base inorganic fine particles, silica, alumina, and titanium oxide are preferable because they have an appropriate electric resistance. Furthermore, silica fine particles produced by the dry method are more preferable in that they have an appropriate electric resistance. Further, the term "silica" includes not only silicon dioxide (silica) but also silicates such as aluminum silicate, sodium silicate, magnesium silicate, potassium silicate, calcium silicate, and zinc silicate. It is preferable that the content of SiO ₂ is 85% by weight or more.

As the inorganic fine particles used for the treatment with the organopolysiloxane having an ammonium functional group at the terminal, those having a number average primary particle diameter of 3 to 500 nm are used in order to improve the fluidity of the toner. More preferably, it is more preferably in the range of 5 to 100 nm. Here, the number average primary particle diameter refers to the number average particle diameter of the primary particles (particles in the state of being separated into individual unit particles) of the inorganic fine particles present in the form of fine particles, for example, a transmission electron microscope ( The TEM image can be obtained by importing it into an image analysis device.

In the base inorganic fine particles used in the present invention, the surface of the base inorganic fine particles may be appropriately treated with a hydrophobizing agent in order to reduce the influence of the chargeability fluctuation caused by the base inorganic fine particles themselves due to environmental changes. preferable.

When the inorganic fine particles used in the present invention are hydrophobized with a hydrophobizing agent before being treated with the organopolysiloxane having an ammonium functional group at the terminal, the adsorption of water on the surface of the inorganic fine particles can be remarkably suppressed. As a result, it is possible to make the fluctuation of the charging characteristic due to the fluctuation of the humidity extremely small.

When the surface of the inorganic fine particles is subjected to a hydrophobic treatment with a hydrophobizing agent, the hydroxyl groups present on the surface of the inorganic fine particles are modified to a non-polar group, and then treated with an organopolysiloxane having an ammonium functional group at the end. , The ammonium functional group present at the end of the organopolysiloxane is prevented from selectively approaching and coordinating with the polar group present on the surface of the inorganic fine particles, and the ammonium functional group can be present on the outermost surface. The positive chargeability of the ammonium functional group can be remarkably exhibited.

As described above, by performing the hydrophobizing treatment with the hydrophobizing agent before the treatment with the organopolysiloxane having an ammonium functional group at the terminal, a proper amount of positive charge can be rapidly imparted to the toner, and Since the positive charge can be stably maintained even when the humidity environment changes, there is no toner scattering in the device for a long period of time even in various usage environments, and high-definition images with high image density and no image fog Can be obtained.

In the present invention, as a hydrophobizing agent that can be used, a compound that easily reacts with a hydroxyl group existing on the surface of the inorganic fine particles and can bond an organic group to oxygen of the hydroxyl group is used. . Generally, as a hydrophobizing agent, a silane coupling agent such as a silane compound or a disilazane compound represented by the following formula 6 or the following formula 7
Examples of the titanium-based coupling agent such as a titanium compound represented by the formula (3) are preferable, and among these, a silane coupling agent is preferably used.

[0057]

[Chemical 12] In the above formula 6, R ¹ represents halogen or an alkoxyl group having 1 to 5 carbon atoms, R ² represents an alkyl group having 1 to 5 carbon atoms, R ³ is a substituted or unsubstituted alkyl group,
It represents an aryl group, an alkylaryl group or an arylalkyl group, and n represents a positive integer of 1 to 3.

[0058]

[Chemical 13] In the above formula 7, R ¹ represents halogen or an alkoxyl group having 1 to 5 carbon atoms, R ² represents an alkyl group having 1 to 5 carbon atoms, R ³ is a substituted or unsubstituted alkyl group,
It represents an aryl group, an alkylaryl group or an arylalkyl group, and n represents a positive integer of 1 to 3.

Specific examples of the silane coupling agent include:
For example, halogenated silane compounds such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, methyltribromosilane, dimethyldibromosilane, trimethylbromosilane, diethyldichlorosilane, allyldimethylchlorosilane, and allylphenyldichlorosilane, and hexyltrimethoxysilane. Alkoxysilane compounds such as octyltrimethoxysilane, dioctyldimethoxysilane, vinyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane, and hexamethyldisilazane, hexaethyldisilazane,
Examples include disilazane compounds such as hexapropyldisilazane. Any of these can be preferably used, and among these, dimethyldichlorosilane, octyltrimethoxysilane, and hexamethyldisilazane are particularly preferable because of easy reaction with the hydroxyl group on the surface of the inorganic fine particles and availability at low cost.

In order to perform the hydrophobic treatment on the base inorganic fine particles by using the hydrophobic treatment agent, the inorganic fine particles are made into a cloud shape by stirring or the like, and the hydrophobic treatment agent which is made into a solution using alcohol or the like is sprayed or It is possible to use a conventionally known method such as a dry process in which a vaporized hydrophobizing agent is brought into contact with the reaction to cause a reaction, or a wet treatment in which inorganic particles are dispersed in a solvent and a hydrophobizing agent is dropped to react.

The base inorganic fine particles are preferably treated with a hydrophobizing agent so that the surface thereof has an appropriate hydrophobicity, and the degree of hydrophobization as a measure of wettability with methanol is 30 to 70%. It is preferable that the treatment is performed within the range. By setting the degree of hydrophobicity of the base inorganic fine particles in the above range, the moisture resistance of the base inorganic fine particles is appropriately improved, and when the base inorganic fine particles are treated with the organopolysiloxane having an ammonium functional group at the end, The adhesion of organopolysiloxanes having ammonium functional groups is increased.

When the degree of hydrophobicity of the base inorganic fine particles is less than 30%, the moisture resistance of the inorganic fine particles is not sufficient, the chargeability is apt to change due to environmental changes, and the degree of hydrophobicity is 70%. When it exceeds the above range, the adhesion between the organopolysiloxane having an ammonium functional group at the terminal and the base inorganic fine particles is deteriorated, and the long-term positive charge is likely to be insufficient.

The degree of hydrophobicity of the above-mentioned inorganic fine particles is calculated as follows. <Calculation of Hydrophobicity> 50 ml of distilled water is placed in an Erlenmeyer flask, and 0.200 g of inorganic fine particles to be measured is precisely weighed and added. While stirring with a magnetic stirrer, methanol is dripped from a buret whose tip is immersed in a liquid until the inorganic fine particles become wet. When the inorganic fine particles are completely wet with the solution, the dropping of methanol is terminated, the amount of dropped methanol (ml) is read, and the hydrophobicity is calculated by the following formula.

Hydrophobicity (%) = [a / (50 + a)] × 100 a; Amount of methanol dropped (milliliter) The inorganic fine particles are treated with organopolysiloxane having an ammonium functional group at the end to form the base inorganic fine particles. for
Preference is given to using 1 to 50% by weight, preferably 3 to 40%, of terminal organofunctional polysiloxanes. By setting the amount within the above range, a preferable positive charge imparting property can be imparted without impairing the fluidity of the treated inorganic fine particles.

The treatment of the base inorganic fine particles with the organopolysiloxane having an ammonium functional group at the terminal is performed by dissolving the organopolysiloxane having an ammonium functional group at the terminal in an alcohol, for example, an alcohol having 1 to 5 carbon atoms. Can be carried out by treating the base inorganic fine particles. The alcohol used for dissolution is preferably methanol, ethanol, isopropanol or a mixture thereof. This treatment includes a method of spraying the above-mentioned alcohol solution on the base inorganic fine particles and drying, or a method of immersing the base inorganic fine particles in the alcohol solution and drying.

The concentration of the terminal organofunctional polysiloxane in the solution used for the treatment is
Depending on the solubility and the properties, it is generally from 1 to 90% by weight, preferably from 10 to 50% by weight.

The treatment of the base inorganic fine particles with the organopolysiloxane having an ammonium functional group at the terminal is
After mixing, the ambient temperature is preferably 20 to 250 ° C, more preferably 80 to 220 ° C. By setting the atmosphere temperature of the treatment within the above range, the crosslinking of the organopolysiloxane having an ammonium functional group at the terminal proceeds properly, and the base inorganic fine particles are firmly and uniformly coated.

Although the treatment time depends on the ambient temperature, it is usually
10 minutes to 6 hours. The preferable treatment time is 0.5 to 6 hours when the ambient temperature is in the range of 80 to 220 ° C. Any suitable equipment can be used for the treatment, for example a circulating air drying chamber, a heating mixer or a disc dryer.

Further, it has an ammonium functional group at the terminal.
Inorganic fine particles treated with organopolysiloxane are optional
BE with a surface area of
T specific surface area 10 to 400 m² / G is preferred, 50
~ 350m² The range of / g is more preferable. BET ratio
Surface area is 10m²If less than / g, the fluidity of the toner is secured.
Can be difficult, and 400m²When / g is exceeded
Charging of inorganic fine particles after treatment due to water content in air
It tends to be unstable. BET specific surface area
Is a Micromeritics manufactured by Micromeritics.
Measured by Cousse Flowthorpe II 2300
Is.

The inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the end of the present invention are added to colored particles containing at least a binder resin and a colorant to be used as a toner. The proportion of the fine particles added is preferably 0.1 to 5% by weight, more preferably 0.1 to 4% by weight, based on the colored particles.

When the content of the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the end of the present invention is less than 0.1% by weight, the fluidity and the positive charging property of the toner are not sufficient, which results in However, the triboelectric chargeability of the toner becomes poor, and it becomes impossible to apply a proper amount of positive charge to the toner, and toner scattering and image fogging easily occur. Further, when the content of the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the terminal is larger than 5% by weight, a part of the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the terminal is partially contained. It becomes a state of being released from the colored particles, and as a result, a part of the released inorganic fine particles adheres to the carrier, the developing sleeve, the regulating blade or the photoconductor to hinder the triboelectrification property of the toner. In some cases, the amount of positive charge cannot be applied and toner scattering or image fogging may occur. Further, in some cases, the positive charge is excessively applied to the toner, so that the image density is lowered.

The resin constituting the colored particles is not particularly limited, and various conventionally known resins can be used. Examples of these resins include styrene resins, acrylic resins, styrene / acrylic resins, polyester resins,
Examples thereof include styrene / butadiene resin.

The colorant of the toner of the present invention is not particularly limited, and various conventionally known materials can be used. Examples of these colorants include carbon black, nigrosine dye, aniline blue, calcoil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, and rose bengal. In the case of forming an intermediate color on a recording material by carrying out color superposition, a colorant described later is preferably used.

The colored particles of the present invention can contain, in addition to the resin and the colorant, other additives used in the colored particles used in the toner.

As the above-mentioned other additives which can be added to the colored particles of the present invention, a releasing agent can be mentioned. As the releasing agent, a number average molecular weight (the number average molecular weight is high temperature GP
The polystyrene molecular weight conversion value in C is shown. ) Is from 1,500
5,000 polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polyethylene-polypropylene copolymer, etc., high melting point paraffin waxes such as microwax, Fischer-Tropsch wax, fatty acid lower alcohol ester, fatty acid higher alcohol ester, fatty acid Ester waxes such as polyhydric alcohol esters and amide waxes can be used alone or in combination.

Examples of other additives include salicylic acid derivatives, azo metal complexes, charge control agents such as quaternary ammonium salts, and fixability improving agents such as low molecular weight polyolefins and carnauba wax.

The toner of the present invention can form an intermediate color on a recording material by performing color superposition.

When four color toners of yellow, magenta, cyan and black are used, the color reproduction range is widest, which is preferable. Single color images of yellow, magenta, cyan and black are
Although it can be reproduced as usual without performing color superimposition, an image of an intermediate color, for example, an image of green, red, blue, orange, brown or the like can be reproduced by superimposing two or more colors.

If necessary, other colors such as orange, brown, silver and gold can be added.

Among the four color toners of yellow, magenta, cyan and black, as a colorant for obtaining a black toner, carbon black such as channel black, furnace black, acetylene black, thermal black, lamp black, magnetic substance, Examples thereof include black pigments such as titanium black and dyes such as nigrosine.

As the colorant for obtaining the yellow toner, C.I. I. Solvent Yellow 19, 44, 7
7, ibid 79, ibid 81, ibid 82, ibid 93, ibid 98, ibid 10
3, dyes 104, 112, 162 and the like, C.I. I.
Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 93, Pigment Yellow 93, Pigment Yellow 138, and the like.

As the colorant for obtaining the magenta toner, C.I. I. Solvent Red 1, Dye 49, Dye 52, Dye 58, Dye 63, Dye 111, Dye 122, C.I. I.
Pigment Red 5, Same 48: 1, Same 53: 1, Same 5
7: 1, 122, 139, 144, 149, 166, 177, 178, 222, C.I. I. Pigment Orange 31, Pigment Orange 43, and the like.

As the colorant for obtaining the cyan toner, C.I. I. Solvent Blue 25, 36, 60,
Dyes such as 70, 93, and 95, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 3, 6
Pigments such as 0 are listed.

When a toner of a special color is obtained, a mixture of the above colorants, gold powder, silver powder, fish scales, etc. can be used as the colorant. The particle size of the fine powder colorant varies depending on the type, but the number average primary particle size is generally 10 to
About 200 nm is preferable.

The volume average particle diameter of the colored particles is usually 1 to 30 μm, preferably 5 to 20 μm. The volume average particle diameter of the colored particles is the Coulter counter T
It was measured with an A-II type (manufactured by Coulter, Inc.) using an aperture of 100 μm.

Styrene-acrylic resin fine particles having a number average primary particle size of 0.1 to 2.0 μm or higher fatty acid metal salt such as zinc stearate may be added to the toner as a cleaning aid.

When a magnetic toner is obtained, magnetic particles are contained. As the magnetic particles, particles such as ferrite magnetite having an average primary particle diameter of 0.1 to 2.0 μm are used. The addition amount of these magnetic particles is 20 to 70% by weight in the colored particles.

The toner of the present invention can be used as a one-component developer, but can also be mixed with a carrier and used as a two-component developer.

The carrier used for the two-component developer is
Although various known structures can be used,
Preferred examples include a magnetic carrier, for example, an uncoated carrier composed only of magnetic material particles such as iron and ferrite, a resin-coated carrier obtained by coating the surface of magnetic material particles with a resin, or the above magnetic material and resin. A magnetic powder-dispersed carrier obtained by melt-kneading, pulverizing, and classifying can be mentioned.

If necessary, various additives such as a dispersion aid and a resistance control agent can be added to the carrier.

In the present invention, when the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the terminal are used for the toner, a relatively high charge amount can be imparted to the toner and toner scattering and image fogging can be prevented. In a two-component developer that uses the carrier as a frictional charge imparting member, the electrostatic binding force of the carrier increases, and if the developer is used for a long period of time, the toner that cannot participate in the development receives mechanical stress and the carrier surface is It may be contaminated and the function of the carrier as a triboelectric charging member may be diminished.

These drawbacks can be solved by using, as a carrier, a carrier in which the core surface having a fluorine atom content on the carrier surface of 30 atom% or more is coated with a fluororesin, and the carrier satisfying the above conditions is satisfied. By using, it is possible to sufficiently suppress the contamination of the carrier surface, to stably provide positive charge to the toner for a long period of time, and to obtain a high-definition image with high image density without toner scattering and image fogging. become.

The fluorine atom content on the surface of the carrier is measured by using an X-ray electron spectroscopic analyzer "ESCA-1000" (manufactured by Shimadzu Corporation).

A method of surface analysis by ESCA is disclosed in
No. 2-87157, the element number% of the measurement element existing on the surface of the material (here, the fluorine-containing resin coating the surface of the core material) is measured.

In the present invention, the element number% of the fluorine atom thus obtained is defined as the fluorine atom content rate (atomic%). Furthermore, specific measurement conditions and measurement elements are shown below. The element ratio is calculated from the obtained area intensity of each element. -ESCA measurement embodiment device: ESCA-1000 [manufactured by Shimadzu Corporation] Measuring elements: carbon (C1s), nitrogen (N1s), oxygen (O
1s), Fluorine (F1s), Silicon (2p) Iron (Fe2
p2 / 3), copper (Cu2p2 / 3), zinc (Zn2p2)
/ 3) The surface analyzer by ESCA is not particularly limited,
For example, ESCALAB210, ESCALAB200R (above produced by VG), ESCA-850, ESCA-1000 [above produced by Shimadzu Corporation], PHI560 (above produced by Philips) and the like can be mentioned.

The fluorine-based resin used in the present invention is not particularly limited as long as it has a fluorine atom content of 30 atom% or more on the carrier surface, and is not particularly limited. , Fluorinated methacrylate resin, copolymer of fluorinated methacrylate and methacrylic acid ester, fluorinated styrene resin,
Copolymer of fluorinated styrene and styrene, trifluoroethylene resin, tetrafluoroethylene (PTFE)
Examples thereof include resins, vinylidene fluoride (PVdF) resins, hexafluoropropylene (PHFP) resins, and copolymers of vinylidene fluoride and trifluoroethylene, tetrafluoroethylene or hexafluoropropylene.

Fluorine-based resins that can be used in the present invention are commercially available, and these commercially available NEOFRON VDF VP-850 (manufactured by Daikin Industries, Ltd.), FORAFLON 1000 VLD, KYNER.
450, KYNER 461, KYNER SL, KYNER
It is also possible to use ADS (above, manufactured by Elf Atchem).

Among these, the resin preferably used in the present invention is a fluorinated methacrylate resin or a fluorinated acrylate resin containing a repeating unit represented by the following formula 2, and a fluorinated methacrylate and a methacrylic acid ester or ethyl methacrylate. A polymer, a polyvinylidene fluoride resin (PVdF), a hexafluoropropylene resin, or a copolymer of vinylidene fluoride and hexafluoropropylene, and a more preferable resin is fluorine containing a repeating unit represented by the following formula 3. And a methacrylic acid resin, a copolymer of fluorinated methacrylate and methyl methacrylate or ethyl methacrylate, and a copolymer of vinylidene fluoride and hexafluoropropylene.

[0099]

[Chemical 14] [In the formula, R represents a hydrogen atom or a methyl group, and Rf represents an alkyl group substituted with a fluorine atom. ]

[0100]

[Chemical 15] [In the formula, Rf represents an alkyl group substituted with a fluorine atom. As the alkyl group in the alkyl group substituted with a fluorine atom represented by Rf, an alkyl group having 1 to 5 carbon atoms is preferable. Preferred Rf is an alkyl group substituted with 3 to 5 fluorine atoms. Specific examples of the fluorine atom-substituted alkyl group represented by Rf include -C
_{F 3, -CF 2 CF 2 H} , are -CF ₂ CF ₃ and the like.

These resins may be used alone or in combination of two or more kinds.

The above-mentioned fluororesin is preferably contained in an amount of 50 to 100% by weight based on the whole resin constituting the carrier. If it is less than 50% by weight, the property of imparting a positive charge to the toner is poor, and the stain resistance of the carrier surface is also poor, so that toner scattering and image fogging occur with long-term use.

If necessary, various additives such as a dispersion aid and a resistance control agent can be added to the carrier.

The carrier of the present invention can be manufactured by various conventionally known methods.

For example, a resin-coated magnetic carrier using magnetic material particles such as iron and ferrite as a core is prepared by dissolving a resin in an appropriate organic solvent to prepare a coating solution, and using this coating solution, a dipping method is used. After forming a coating layer on the surface of the magnetic material particles by a method such as a dry spray method or a fluidized bed method, a method generally called a wet method for producing by further applying heat or leaving it, or a resin coating layer It can be produced by a method generally called a dry method without using a solvent for formation.

The volume average particle diameter of the carrier is 30 to 15
It is preferably in the range of 0 μm.

The volume average particle size of the carrier is measured by using a laser diffraction particle size distribution measuring device "HELOS" (manufactured by JEOL Ltd.). The particles to be measured were dispersed by placing the particles to be measured, a surfactant and water (dispersion medium) in a 50 cc beaker and treating them with an ultrasonic homogenizer having an output of 150 W for 120 seconds.

The toner of the present invention can be used to visualize an electrostatic latent image in the commonly used electrophotographic method, electrostatic recording method, electrostatic printing method and the like. In electrophotography, for example, after an electrostatic latent image is formed on a photoconductor, the electrostatic latent image is visualized by a developer containing powdery toner in a developing device, and the obtained visible image The (toner image) is transferred to another transfer material such as transfer paper. The toner remaining on the photoconductor is cleaned, and the visible image formed on the transfer material is fixed. As the photoconductor, a generally known photoconductive photoconductor having a drum shape or a sheet shape can be used. For example, a selenium photoconductor, an amorphous silicon photoconductor, an organic photoconductor, and other conventionally known photoconductors. Although a body can be used, an amorphous silicon photoconductor or an organic photoconductor can be preferably used in consideration of durability and environmental compatibility of the photoconductor.

Then, using a plurality of toners of two or more colors,
There are roughly two types of image forming methods for forming an image by forming a toner image of an intermediate color on a recording material by performing color superposition and fixing the toner image.

One of the methods is to charge and expose a photoconductive photoconductor to form an electrostatic latent image, which is first formed.
After developing with toner, it is transferred to an intermediate transfer member, and then an electrostatic latent image is formed again on the photosensitive member by the second charging and exposure, and this is developed with the second toner, and the first image is transferred. When a color image is transferred to the intermediate transfer member holding the image and the color is further overlapped, this step is repeated a necessary number of times to form a color image on the intermediate transfer member, and then transferred and fixed on the transfer material. (This method is called a sequential transfer method.) Another method is charging on a photoconductive photoconductor,
Exposure is carried out to form an electrostatic latent image, which is then developed with a first toner, and subsequently a second electrostatic latent image is re-formed by a second charging and exposure, which is then developed with a second toner, When a toner image is formed by the first and second toners on the photoconductor and color superposition is further performed, this step is repeated as many times as necessary to form a color image on the photoconductor, and then transferred and fixed on the support. Is the way to do it. (This method is called a batch transfer method.) The batch transfer method is a preferable method because it does not require an intermediate transfer member and is advantageous for downsizing the apparatus.

FIG. 1 is an image in which a toner image of an intermediate color is formed on a recording material by performing color superposition using a plurality of toners of two or more colors of the present invention, and the toner image is fixed to form an image. FIG. 2 shows an example of an image forming apparatus using a sequential transfer method capable of performing the forming method, and FIG. 2 shows an example of an image forming apparatus also using the batch transfer method.

In FIG. 1 and FIG. 2, 1 is a charger, 2
Is a developing unit, 3 is a cleaning unit, 4 is a photoconductor drum, 5 is a transfer drum, 6 is a transport unit, 7 is a suction unit, 8 is a transfer unit, 9 is a peeler, 10 is a static eliminator, and 11 is an exposure unit. Shown respectively.

In FIG. 1, on the peripheral surface of the photosensitive drum 4 having an optical semiconductor that forms an electrostatic latent image on a conductive substrate,
The photoconductor drums 4 are brought into close proximity by corona discharge.
A charging unit 1 for applying electric charges to the surface, an exposure unit 11, a developing unit 2 in which a plurality of developing units each containing a single color developer are arranged, and a cleaning unit 3 for cleaning the toner remaining on the photosensitive drum 4 are sequentially arranged. Has been done. Also,
On the peripheral surface on the transfer drum 5 side, which is formed by sequentially forming a conductive elastic layer and an insulating layer on a conductive substrate, a transport unit 6 for supplying the transfer material to the transfer drum 5, a corona discharge, and the transfer material is transferred. An adsorption device 7 for electrostatically adsorbing on the surface of the drum 5, a transfer device 8 for transferring the toner image formed on the photoconductor drum 4 to a transfer material, a charge of the transfer drum 5 is removed, and the transfer material is separated from the transfer drum 5. A peeling device 9 for removing the charge and a static eliminator 10 for removing residual charges on the transfer material are sequentially arranged. The photosensitive drum 4 and the transfer drum 5 rotate in the direction of the arrow at the same peripheral speed.

Image formation by the sequential transfer method using a plurality of toners of two or more colors can be performed as follows.

The photoconductor drum 4 is uniformly charged by the charger 1. Next, the charged photosensitive drum 4 is subjected to the first image exposure by the exposure means 11, and the photosensitive drum 4 is exposed.
A first electrostatic latent image is formed on top. The formed first electrostatic image is developed by the first color developing device of the developing unit 2 to form a first color monochromatic toner image. The photosensitive drum 4 further rotates, and the first-color monochromatic toner image formed on the photosensitive drum 4 reaches the position of the transfer unit 8.

On the other hand, the transfer material supplied from the transport unit 6 is electrostatically adsorbed on the surface of the transfer drum 5 by the action of the adsorbing device 7 by corona discharge, and rotates to reach the position of the transfer device 8. At the position of the transfer device 8, the first color monochromatic toner image formed on the photosensitive drum 4 is transferred onto the transfer material by the transfer device 8.

The photoconductor drum 4 further rotates, the toner remaining on the photoconductor drum 4 is removed by the cleaning unit 3, and the photoconductor drum 4 is uniformly charged again by the charger 1 to be charged. The exposed photoconductor drum 4 is subjected to the second image exposure by the exposure unit 11, and the photoconductor drum 4 is exposed.
A second electrostatic latent image is formed on top. The formed second electrostatic image is developed by the second color developing device of the developing unit 2 to form a second color monochromatic toner image. The photoconductor drum 4 further rotates, and the second-color monochromatic toner image formed on the photoconductor drum 4 reaches the position of the transfer unit 8.

The transfer material on which the first-color monochromatic toner image has been transferred is further rotated together with the transfer drum 5, and the static eliminator 10 removes the electric charge remaining on the transfer material. When the transfer drum 5 further rotates and the transfer material reaches the position of the transfer device 8, the second color single color toner image formed on the photoconductor drum 4 is transferred onto the transfer material by the transfer device 8 and transferred. A first-color monochromatic toner image and a second-color monochromatic toner image are formed on the material.

By repeating the above steps, the third color monochromatic toner image and the fourth color monochromatic toner image can be formed on the transfer material.

After the required number of toner images are formed on the transfer material, the peeling device 9 removes the charges on the transfer drum 5, and the transfer material is separated from the transfer drum and discharged. A multicolor image is formed by fixing the discharged transfer material by a fixing device described later.

In FIG. 2, on the peripheral surface of the photosensitive drum 4 having an optical semiconductor that forms an electrostatic latent image on a conductive substrate,
The photoconductor drums 4 are brought into close proximity by corona discharge.
A charging unit 1 for applying electric charges to the surface, an exposure unit 11, a developing unit 2 in which a plurality of developing units each containing a monochromatic developer are arranged, and a cleaning unit 3 for cleaning the toner remaining on the photosensitive drum 4 are sequentially arranged. Has been done. Also,
Below the photoconductor drum 4, a belt conveyor and a transfer device 8 for transferring the toner image formed on the photoconductor drum 4 to a transfer material are arranged. The photoconductor drum 4 rotates in the direction of the arrow at a constant peripheral speed.

Image formation by the batch transfer method using a plurality of toners of two or more colors can be performed as follows.

The photoconductor drum 4 is uniformly charged by the charger 1. Next, the charged photosensitive drum 4 is subjected to the first image exposure by the exposure means 11, and the photosensitive drum 4 is exposed.
A first electrostatic latent image is formed on top. The formed first electrostatic image is developed by the first color developing device of the developing unit 2 to form a first color monochromatic toner image. The photoconductor drum 4 further rotates, the photoconductor drum 4 is uniformly charged again by the charger 1, and the photoconductor drum 4 is charged.
The second image exposure is performed by the exposure unit 11 to form a second electrostatic latent image on the photosensitive drum 4. The formed second electrostatic image is developed by the second color developing device of the developing unit 2 to form a second color monochromatic toner image.
By repeating the above steps, the third color monochromatic toner image and the fourth color monochromatic toner image can be formed on the photosensitive drum 4. As a result, the photosensitive drum 4
The required number of toner images can be formed on top.

In the above, the transfer unit 8 and the cleaning unit 3 are not operated until the desired number of exposures and developments are completed, and a plurality of toner images are formed on the photosensitive drum 4 without any trouble. can do.

The transfer material supplied from the transport unit 6 is
When the toner image formed on the photoconductor drum 4 is conveyed by the belt conveyer and reaches the lower part of the photoconductor drum 4, the toner image formed on the photoconductor drum 4 is transferred onto the transfer material by the transfer device 8 and discharged from the belt conveyer. A multicolor image is formed by fixing the discharged transfer material by a fixing device described later.

As a preferable fixing method for fixing the toner image on the transfer material, for example, a heat roller fixing method and a fixing method of heating and fixing via a fixing film material which moves in contact with a fixedly installed heating body (SURF). Fixing methods), but the toner of the present invention is suitable for fixing by these fixing methods.

The heat roller fixing method is a fixing method in which a transfer material carrying a toner image is passed between a rotating fixing roller and a pressure-bonding roller in pressure contact with the fixing roller to fix the toner image on the transfer material. Yes, specifically, on the surface tetrafluoroethylene, polytetrafluoroethylene-
Between an upper roller with a heat source inside a metal cylinder made of iron, aluminum, etc. coated with a material with excellent releasability such as perfluoroalkoxy vinyl ether copolymer, and a lower roller made of silicone rubber, etc. In this method, the transfer material is passed through so that the toner image contacts the upper roller, and the toner material is heated and fixed.

A linear heater is used as a heat source for the upper roller, and the surface temperature of the upper roller is heated to about 120 to 200 ° C. Upon fixing, pressure is applied between the upper roller and the lower roller to deform the lower roller and form a so-called nip. The formed nip width is preferably 1 mm to 10 mm, more preferably 1.5 mm to 7 mm. When the nip width is narrow, heat cannot be uniformly applied to the toner, and uneven fixing tends to occur. When the nip width is wide, melting of the resin is promoted and fixing offset becomes excessive. Prone to problems. For fixing, transfer material 40mm / se
It is preferable to move at a speed of c. to 400 mm / sec.

Further, as the heating element used in the latter SURF fixing method, a fixed linear heating element having a low heat capacity is used. The line-shaped heating element with low heat capacity has a thickness of 0.2 m.
m ~ 5.0mm, preferably 0.5mm ~ 3.5mm, width 10mm ~ 15mm, longitudinal length 240mm ~ 400mm alumina substrate 1.0mm ~ 2.5mm width applied to form an electrical resistor It is heated by energizing from both ends of the electric resistor. A pulse of 100 V and a cycle of 25 msec. Is used as the heating power source, and the amount of energy released is changed by changing the pulse width to control the heating temperature.

In the line-shaped heating element, when the surface temperature of the electric resistor detected by the temperature sensor is T ₁ , the surface temperature T ₂ of the fixing film material moving on the electric resistor is lower than T _1. Become. The surface temperature T ₁ of the electric resistor is preferably 120 ° C. to 220 ° C., and the surface temperature T ₂ of the fixing film material in contact with the electric resistor is 0.5 ° C. to 10 ° C. from the temperature of T _1.
It is preferably low. Further, the surface temperature T ₃ of the fixing film material at the position where the fixing film material is separated from the surface of the fixed toner is preferably almost equal to T ₂ .

The fixing film material has a thickness of 10 μm to 3 μm.
A 5 μm heat-resistant film, for example, a film made of polyester, polyperfluoroalkoxy vinyl ether, polyimide, polyester imide, and an endless film obtained by coating a release material layer made by adding a conductive material to a fluororesin such as Teflon to 5 μm to 15 μm is used. . The total thickness of the endless film is generally 15 μm to 50 μm. The endless film is driven by a driving roller and a driven roller, and is transported without wrinkles and twists.

For heating and fixing, a pressure roller arranged at a position facing the linear heating element is used. As the pressure roller, a roller having a rubber elastic layer having high releasability such as silicon rubber is used. The transfer material having a toner image is passed such that the toner image side is in contact with the endless film, is pressed by a pressure roller that rotates in pressure contact, and is heated and fixed by the heating body through the endless film. The pressure applied by the pressure roller is generally 2 kg to 30 kg in total pressure. Transfer material is 40mm / sec. ~ 400mm / se
It is preferable to move at the speed of c.

Further, instead of the above endless film, an end fixing film wound around a feeding shaft may be used, and the end film may be fixed while being wound around a winding shaft.
Further, instead of the endless film, a simple cylindrical one without a supporting roller such as a driving roller may be used.

In any of the fixing methods, it is possible to provide a mechanism for preventing the toner from adhering to the fixing device and a mechanism for cleaning the adhered toner. Examples of these mechanisms include a mechanism for supplying fluorine-based silicone oil to the upper roller or the fixing film, and a mechanism for cleaning the upper roller or the fixing film with a pad, roller, web, etc. impregnated with the fluorine-based silicone oil.

When an intermediate color is reproduced by color superposition,
A high toner adhesion amount is required as compared with the case of a conventional single color image. Conventional single-color image, for example, is at the black image, if there is usually 0.5mg / cm ² ~0.7mg / cm ² about the toner adhesion amount, relative to that obtained is 1.2 or sufficient image density, When reproducing intermediate colors by overlapping colors, 1.0 mg / cm ^{2 to} 2.0 mg should be added to ensure color vividness and image density.
A toner adhesion amount of / cm ² is required.

In order to stably obtain this high toner adhesion amount, the charge amount required for the toner is preferably 10 μC / g to 35 μC / g as the toner charge amount measured by the blow-off method or the like. If outside this area, problems such as not being able to obtain a sufficient toner adhesion amount or being an excessive adhesion amount will occur, and problems such as so-called fog and color mixing will occur on the white background portion. . With the toner of the present invention, it is possible to obtain a charge amount within a range that does not cause the above problems.

[0137]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, all “parts” indicate “parts by weight”. Example 1 << Production of Inorganic Fine Particles >> --Production of Inorganic Fine Particles 1-- 20 parts of the following silane coupling agent (S-1), a kinematic viscosity at 25 ° C. of 55 mm ² / sec, and a degree of polymerization of n = 50. 80 parts of dimethylpolysiloxane (A) having silanol groups at both ends was reacted in a 37% aqueous hydrochloric acid solution at 35 ° C. to give an ammonium functional group at the end with a kinematic viscosity of 50 mm ² / sec at 25 ° C. Organopolysiloxane having (A)
Got

[0138]

[Chemical 16] Next, 80 parts of silica fine particles (A) having a number average primary particle diameter of 7 nm were placed in a mixer, 5 parts of 25% aqueous ammonia was added to 25 ° C., and ammonium was added to the terminal synthesized above in the mixer. A solution prepared by dissolving 20 parts by weight of the organopolysiloxane (A) having a functional group in a mixed solvent of methanol / isopropanol (40/60) was sprayed.
Stir for minutes. After that, the solvent was removed at a set temperature of 130 ° C. under a nitrogen atmosphere in an air dryer to obtain inorganic fine particles 1 treated with an organopolysiloxane whose terminal was modified with an ammonium functional group.

-Production of Inorganic Fine Particles 2- In the production of inorganic fine particles 1, the kinematic viscosity at 25 ° C. was 110 mm ² / sec instead of dimethylpolysiloxane (A),
Synthesized in the same manner as the organopolysiloxane (A) except that dimethylpolysiloxane having a silanol group at both ends and a degree of polymerization of n = 100 was used, and the kinematic viscosity at 25 ° C. was 100 mm ² / sec. Inorganic fine particles 2 were obtained in the same manner except that the organopolysiloxane having an ammonium functional group was used instead of the organopolysiloxane (A).
Got

-Production of Inorganic Fine Particles 3- In the production of inorganic fine particles 1, the kinematic viscosity at 25 ° C. was 540 mm ² / sec instead of dimethylpolysiloxane (A).
Synthesized in the same manner as organopolysiloxane (A) except that dimethylpolysiloxane having a silanol group at both ends and having a degree of polymerization of n = 300 was used, and the kinematic viscosity at 25 ° C. was 500 mm ² / sec. Inorganic fine particles 3 were obtained in the same manner except that the organopolysiloxane having an ammonium functional group was used instead of the organopolysiloxane (A).
Got

—Production of Inorganic Fine Particles 4— In the production of the inorganic fine particles 1, the kinematic viscosity at 25 ° C. was 10 mm ² / sec instead of dimethylpolysiloxane (A),
Synthesized in the same manner as the organopolysiloxane (A) except that dimethylpolysiloxane having a silanol group at both ends and having a degree of polymerization of n = 10 was used, and the kinematic viscosity at 25 ° C. was 5 mm ² / sec. Inorganic fine particles 4 were obtained in the same manner except that the organopolysiloxane having an ammonium functional group was used instead of the organopolysiloxane (A).
Got

-Production of Inorganic Fine Particles 5- Inorganic fine particles 5 were obtained in the same manner as in the production of inorganic fine particles 1 except that silica fine particles having a number average primary particle diameter of 16 nm were used instead of silica fine particles (A). It was

-Production of Inorganic Fine Particles 6-Inorganic fine particles 6 were obtained in the same manner as in the production of inorganic fine particles 1 except that silica fine particles (A) were replaced with silica fine particles having a number average primary particle diameter of 100 nm. It was

In the production of the inorganic fine particles 1, at 25 ° C. in place of the dimethylpolysiloxane (A) -in the production of the inorganic fine particles 7-in the production of the inorganic fine particles 1, instead of the silane coupling agent (S-1), Silane coupling agent (S-
Organopolysiloxane (A) having a kinematic viscosity at 25 ° C. of 40 mm ² / sec and having an ammonium functional group at the end, which was synthesized in the same manner as organopolysiloxane (A) except that 2) was used, Inorganic fine particles 7 were obtained in the same manner except that they were used instead of

[0145]

[Chemical 17]

-Production of Inorganic Fine Particles 8- In the production of the inorganic fine particles 1, instead of the silane coupling agent (S-1), the following silane coupling agent (S-
3) except for using it was synthesized in the same manner as the organopolysiloxane (A), kinematic viscosity of 46 mm ² / s at 25 ° C., an organopolysiloxane having an ammonium functional group at the terminal, the organopolysiloxane (A Inorganic fine particles 8 were obtained in the same manner except that they were used instead of

[0147]

[Chemical 18]

-Production of Inorganic Fine Particles 9- In the production of the inorganic fine particles 1, the ratio of the silica fine particles (A) and the organopolysiloxane (A) to be used when the silica fine particles (A) is treated with the organopolysiloxane (A). , Silica fine particles (A) / organopolysiloxane (A) = 60/40
Got

-Production of Inorganic Fine Particles 10- In the production of the inorganic fine particles 1, the use ratio of the silica fine particles (A) and the organopolysiloxane (A) when the silica fine particles (A) is treated with the organopolysiloxane (A). Inorganic fine particles 1 in the same manner except that silica fine particles (A) / organopolysiloxane (A) = 97/3.
I got 0.

-Production of Inorganic Fine Particles 11-In the same manner as in the production of the inorganic fine particles 1, except that the silica fine particles (A) were replaced with alumina fine particles having a number average primary particle diameter of 20 nm and having hydroxyl groups on the surface, Inorganic fine particles 11 were obtained.

-Production of Inorganic Fine Particles 12-In the same manner as in the production of the inorganic fine particles 1, except that titanium oxide fine particles having a number average primary particle diameter of 50 nm and a hydroxyl group on the surface were used instead of the silica fine particles (A). Inorganic fine particles 12 were obtained.

-Production of Inorganic Fine Particles 13- In the production of the inorganic fine particles 1, instead of the organopolysiloxane (A), the kinematic viscosity at 25 ° C. was 55 mm ² / sec,
Inorganic fine particles 13 were obtained in the same manner except that dimethylpolysiloxane having a silanol group at both ends and a degree of polymerization n = 50 was used.

-Production of Inorganic Fine Particles 14- In the production of inorganic fine particles 1, instead of the organopolysiloxane (A), 15 parts of octyltrimethoxysilane and 25 parts of
Synthesized by reacting 85 parts of dimethylpolysiloxane having silanol groups at both ends with a kinematic viscosity of 55 mm ² / sec at ℃ at a polymerization degree of n = 50 in a 37% hydrochloric acid aqueous solution at 35 ° C. Inorganic fine particles 14 were obtained in the same manner except that an organopolysiloxane having a kinematic viscosity at 48 ° C. of 48 mm ² / sec and a terminal modified with octyltrimethoxysilane was used.

-Production of Inorganic Fine Particles 15- In the production of the inorganic fine particles 1, it was synthesized by subjecting dimethyldimethoxysilane and a silane coupling agent (S-3) to a copolycondensation reaction in place of the organopolysiloxane (A). , The kinematic viscosity at 25 ℃ is 52mm ² / sec,
Inorganic fine particles 15 were obtained in the same manner except that an organopolysiloxane having a degree of polymerization of n = 50 and having an ammonium functional group only in the side chain represented by the following formula was used.

[0155]

[Chemical 19]

Table 1 shows the contents of the composition of the inorganic fine particles 1 to 15, the degree of hydrophobicity, the bulk density and the triboelectric charge amount. In addition,
The number average primary particle diameter and the degree of hydrophobicity are obtained by the above-mentioned method, and the bulk density and the triboelectric charge amount are measured as follows.

<Bulk Density> This is a value measured according to ISO787 / 11 and is a value obtained by dividing the mass of the material by the volume after tapping.

<Frictional charge> A value measured by a blow-off method. 50 g of iron oxide powder (Type X-28, manufactured by Dowa Iron Mining Co., Ltd.) and 0.5 g of inorganic fine particles were put in a polyethylene bottle. The values are measured with TB-200 manufactured by Toshiba Chemical Co., Ltd. after stirring for 30 minutes with a ball mill (108 rpm type).

[0159]

[Table 1]

<< Manufacture of Toner >> Styrene-methyl methacrylate-butyl acrylate (65/25/10) copolymer 100 parts Carbon black (Black Pearls L, manufactured by Cabot) 10 parts Low molecular weight polypropylene (Viscole 660P, Sanyo Chemical ( Co., Ltd.) 4 parts After pre-mixing the above components with a stirring mixer, 2
Melt kneading with a shaft kneader, cool, pulverize with a jet mill, classify the pulverized product with a classifier,
Colored particles having a volume average particle size of 8.0 μm were produced.

Colored particles 100 produced as described above
1.0 part by weight of inorganic fine particles and zinc stearate
Toners 1 to 15 were manufactured by adding and mixing 0.1 part by weight. Table 2 shows the inorganic fine particles used.

<< Production of Developer >> 6 parts by weight of each of the toners described above is mixed with 94 parts by weight of a resin-coated carrier in which the surface of ferrite particles having a volume average particle diameter of 60 μm is coated with a silicone resin. Was prepared. Table 2 shows the toner used
Shown in.

[0163]

[Table 2]

<< Copy Test >> The electrostatic latent image formed on the organic photoconductor is developed with a developer to form a toner image,
After the toner image is transferred to the transfer material, the toner image is heated and fixed on the transfer material, and the toner remaining on the photoconductor is removed by using an electrostatic recording device. A copy was performed using the above developers 1 to 15 as the developers.

For heating and fixing, a SURF fixing device (film fixing device) using a line-shaped heating body, an endless film and a pressure roller was used. As the endless film, a polyimide film material having a thickness of 15 μm whose surface was coated with polytetrafluoroethyne in which a conductive substance was dispersed was used. A pad impregnated with polydimethylsiloxane was attached and used as a cleaning mechanism of the fixing device.

The fixing conditions are as follows.

Heating body temperature (T ₁ ) 180 ° C. Film material speed 250 mm / sec. Total pressure between heating body and pressure roll 15 kg Nip between pressure roller and film material 3 mm Normal temperature and normal humidity environment (environmental temperature 20 ° C., relative humidity) 50%) (NN environment) for copying 50,000 copies, and then high temperature and high humidity environment (environmental temperature 30 ° C, relative humidity 80%) (HH environment) 10
After copying 10,000 copies, the toner charge amount, maximum image density (Dmax), background fog (Fog), and the degree of toner scattering in the apparatus were evaluated. The results obtained are shown in Table 3.

When the toners 13 to 14 were used, the fog in the background portion and toner scattering in the apparatus occurred before the number of copying reached 50,000 copies, so the copying test was stopped at 30,000 copies. When toner 15 was used, the fog in the background portion and toner scattering in the apparatus occurred before the number of copies reached 150,000, so the copy test was stopped at 100,000 copies.

<< Evaluation of Toner Charge Amount >> The developer to be measured is carried on a rotatable cylindrical developer carrier having a magnetic pole fixed inside, and the developer carrier is for
Install phosphor bronze plates at a distance of 2.0 mm.

While rotating the developer carrier, between the developer carrier and the phosphor bronze plate, 800 V as a DC component, AC
A voltage of 2 kV (pp) is applied as a component to form an electric field between them, and the toner in the developer is moved to the phosphor bronze plate.

Toner electrostatically attached to the phosphor bronze plate is blown off using compressed air to separate it from the phosphor bronze plate.

At that time, the electric charge [Q (μC)] flowing in through the phosphor bronze plate was measured with an electrometer, and the weight of the phosphor bronze plate before and after the toner adhered was measured with an electronic balance. The weight [m (g)] of the toner adhered to was calculated, and the toner charge amount (μC / g) was calculated by the following formula and evaluated.

[0173]

[Equation 1]

<< Evaluation of Maximum Image Density (Dmax) >> The optical density on the copied image was measured using a Macbeth densitometer (RD-918 type).
Was measured using.

<< Evaluation of Fog in Background Part >> The optical density of the background part was measured using a Macbeth densitometer (RD-918 type). The average of the measured values at the five measurement locations is 0.1
In the above cases, it was determined that fogging of the background portion occurred.

<< Evaluation of Degree of Toner Scattering in Apparatus >> A double-sided tape was attached to three places on the upper wall of the image forming apparatus to perform copying, and the scattered toner was collected. After completion of copying, the double-sided tape was peeled off, and the number of adhered particles per 1 cm ² was calculated up to two decimal places from the SEM photograph image of the toner adhered to the double-sided tape. When the number of adhered particles per 1 cm ² exceeded 50.0, it was determined that toner scattering in the apparatus occurred.

[0177]

[Table 3]

As is clear from Table 3, toners 1 to 12
When the toner was used, the positive chargeability of the toner was remarkably good, and no fog at the image background portion or scattering of the toner in the apparatus was observed even after copying 150,000 copies. Also, the copy image obtained after copying 150,000 pies has a high image density, and
It was a high definition image.

The results show that the inorganic fine particles of the present invention have good positive charge imparting property and positive charge retaining property.

On the other hand, the toner 13 using the inorganic fine particles treated with the organopolysiloxane whose terminal is not modified with the organic group having the ammonium functional group, the terminal is modified with the organic group having no ammonium functional group. When the toner 14 using the inorganic fine particles treated with the above-mentioned organopolysiloxane is used, the positive charge imparting property of the inorganic fine particles is very small, and after the copying of 20,000 copies, the toner scattering in the apparatus increases. However, image fog occurred at the time of copying 30,000 copies.

Further, when the toner 15 using the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group only on the side chain is used, the inorganic fine particles have a certain degree of positive charge imparting property, but they are still insufficient. After copying 10,000 copies, toner scattering in the apparatus increased, and image fog occurred at the time of copying 100,000 copies.

Similar results were obtained when a heat roller fixing device was used for heat fixing. For heat roller fixing, as a heat roll fixing device, as a top roller, a surface made of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer was coated, and a cylindrical iron roller with a diameter of 30 mmφ with a heater built in the center was used. Used as the lower roller, the surface is tetrafluoroethylene-
A roller having a diameter of 30 mm and made of silicone rubber coated with a perfluoroalkyl ether copolymer was used. Further, as a cleaning mechanism, a pad impregnated with polydimethylsiloxane was attached and used.

For fixing, a linear pressure of 0.8 kg / cm, a nip width of 4.3 mm,
The printing linear velocity was set to 250 mm / sec.

<< Character dust test >> The electrostatic latent image formed on the organic photoconductor is developed with a developer to form a toner image, the toner image is transferred to a transfer material, and then the toner image is transferred. An electrostatic recording device capable of being heated and fixed on the surface of the photosensitive member and removing the toner remaining on the photoconductor by using a cleaning device is used.
5 was used for copying.

For heat fixing, the SUR used in the copy test was used.
The F fixing device (film fixing device) was used for fixing under the same fixing conditions.

Normal temperature and normal humidity environment (environmental temperature 20 ° C., relative humidity 50
%) To copy 50,000 character images, then
Copies 100,000 character images in a high-temperature and high-humidity environment (environmental temperature 30 ° C, relative humidity 80%), and starts 10,000 copies, 20,000 copies, 30,000 copies, 50,000 copies. , 8
At the time of 10,000 copies, at the time of 100,000 copies and at the time of 150,000 copies, the character dust rate shown below was calculated, and the degree of character dust of the fixed image was evaluated by the following. Table 4 shows the obtained results.
Shown in.

When toners 13 to 15 are used, 15
When the toners 13 and 14 are used, 30,000 copies are copied, and the toner 15 is used, 100,000 copies are copied, because the character dust is remarkably deteriorated before 10,000 copies are made. The evaluation was discontinued.

<Character Chile Rate> 6.0 points English letter “E”
After loading the fixed images of 2 types of characters of 7.0 and Japanese characters "Mori" into the image analyzer "SPICCA", the total fixed image area including the character part and the periphery of the outline (fixing The image area A) and the fixed image area of only the character portion (fixed image area B) are measured, and the character dust rate of each is calculated by the following formula, and the average value of both character dust rates is calculated, and the average character dust rate is calculated. And

[0189]

[Equation 2] When the average character dust rate exceeded 80%, it was determined that the character dust was significantly deteriorated.

[0190]

[Table 4]

As is clear from Table 4, toners 1 to 12
In the case of using, the positive chargeability of the toner was remarkably good, and the character dust ratio did not increase even after copying 150,000 times, and a high-definition image was always obtained.

The results show that the inorganic fine particles have good positive charge imparting property and positive charge retaining property.

On the other hand, the toner 13 using the inorganic fine particles treated with the organopolysiloxane whose terminal is not modified with the organic group having the ammonium functional group, the terminal is modified with the organic group having no ammonium functional group. When the toner 14 using the inorganic fine particles treated with the above-mentioned organopolysiloxane is used, the positive charge imparting property of the inorganic fine particles is very small, and the occurrence of the character dust is remarkable at the time of copying 20,000 copies. Became.

Further, when the toner 15 using the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group only on the side chain is used, the inorganic fine particles have a certain degree of positive charge imparting property, but they are still not sufficient. At the time when 80,000 copies were made, the occurrence of character dust became noticeable.

Similar results were obtained when the heat roller fixing shown in the copy test was used for the heat fixing. Example 2 << Production of Inorganic Fine Particles >> -Production of Inorganic Fine Particles 16- 20 parts of the following silane coupling agent (S-1), a kinematic viscosity at 25 ° C. of 55 mm ² / sec, and a degree of polymerization n = 50. 80 parts of dimethylpolysiloxane (A) having silanol groups at both ends was reacted in a 37% aqueous hydrochloric acid solution at 35 ° C. to give an ammonium functional group at the end with a kinematic viscosity of 50 mm ² / sec at 25 ° C. Organopolysiloxane having (A)
Got

[0196]

[Chemical 20] Then, the surface of silica fine particles (A) having a number average primary particle diameter of 7 nm was hydrophobized with dimethyldichlorosilane, and 80 parts of silica fine particles (B) having a hydrophobicity of 38% were put into a mixer. % After adding 5 parts of ammonia water to 25 ° C., the organopolysiloxane (A) having an ammonium functional group at the terminal synthesized in the above was prepared in a mixer.
20 parts by weight of methanol / isopropanol (40/60)
Spray the solution dissolved in the mixed solvent and stir for 20 minutes.
After that, the solvent was removed at a set temperature of 130 ° C. in a nitrogen atmosphere in an air dryer to obtain inorganic fine particles 16 treated with an organopolysiloxane whose end was modified with an ammonium functional group.

-Production of Inorganic Fine Particles 17- In the production of the inorganic fine particles 16, instead of dimethylpolysiloxane (A), the kinematic viscosity at 25 ° C. is 110 mm ² / sec and the degree of polymerization n = 100 is silanol at both ends. An organopolysiloxane having an ammonium functional group at the terminal and having a kinematic viscosity at 25 ° C. of 100 mm ² / sec, which was synthesized in the same manner as the organopolysiloxane (A) except that a dimethylpolysiloxane having a group was used, was prepared. Inorganic fine particles 17 were obtained in the same manner except that the polysiloxane (A) was used instead.

-Production of Inorganic Fine Particles 18-In the production of the inorganic fine particles 16, instead of dimethylpolysiloxane (A), the kinematic viscosity at 25 ° C. is 540 mm ² / sec, and the degree of polymerization n = 300 is silanol at both ends. An organopolysiloxane having an ammonium functional group at the end, which had a kinematic viscosity at 25 ° C. of 500 mm ² / sec and was synthesized in the same manner as the organopolysiloxane (A) except that a dimethylpolysiloxane having a group was used, was prepared. Inorganic fine particles 18 were obtained in the same manner except that the polysiloxane (A) was used instead.

-Production of Inorganic Fine Particles 19- In the production of the inorganic fine particles 16, instead of dimethylpolysiloxane (A), the kinematic viscosity at 25 ° C. is 10 mm ² / sec, and the degree of polymerization n = 10 is silanol at both ends. An organopolysiloxane having an ammonium functional group at the terminal and having a kinematic viscosity at 25 ° C. of 5 mm ² / sec, which was synthesized in the same manner as the organopolysiloxane (A) except that a dimethylpolysiloxane having a group was used, was prepared by Inorganic fine particles 19 were obtained in the same manner except that the polysiloxane (A) was used instead.

-Production of Inorganic Fine Particles 20- In the production of inorganic fine particles 16, the surface of silica fine particles having a number average primary particle diameter of 7 nm was treated with dimethyldichlorosilane in place of silica fine particles (B), and the degree of hydrophobicity was 30. %
Inorganic fine particles 20 were obtained in the same manner except that the silica fine particles were used.

-Production of Inorganic Fine Particles 21- In the production of inorganic fine particles 16, the surface of silica fine particles having a number average primary particle diameter of 7 nm was treated with dimethyldichlorosilane in place of silica fine particles (B), and the degree of hydrophobicity was 50. %
Inorganic fine particles 21 were obtained in the same manner except that the silica fine particles were used.

-Production of Inorganic Fine Particles 22- In the production of inorganic fine particles 16, the surface of silica fine particles having a number average primary particle diameter of 7 nm was treated with hexamethyldisilazane in place of silica fine particles (B). 62%
Inorganic fine particles 22 were obtained in the same manner except that the silica fine particles were used.

-Production of Inorganic Fine Particles 23- In the production of the inorganic fine particles 16, the surface of silica fine particles having a number average primary particle diameter of 7 nm was treated with octyltrimethoxysilane in place of the silica fine particles (B).
Inorganic fine particles 23 were obtained in the same manner except that silica fine particles of 56% were used.

-Production of Inorganic Fine Particles 24- In the production of inorganic fine particles 16, the surface of silica fine particles having a number average primary particle diameter of 16 nm was treated with dimethyldichlorosilane in place of silica fine particles (B), and the degree of hydrophobicity was 42. %
Inorganic fine particles 24 were obtained in the same manner except that the silica fine particles were used.

-Production of Inorganic Fine Particles 25- In the production of the inorganic fine particles 16, the surface of silica fine particles having a number average primary particle diameter of 16 nm was treated with hexamethyldisilazane in place of the silica fine particles (B). 70%
Inorganic fine particles 25 were obtained in the same manner except that the silica fine particles were used.

-Production of Inorganic Fine Particles 26-Inorganic fine particles 26 were obtained in the same manner as in the production of the inorganic fine particles 16 except that silica fine particles having a number average primary particle diameter of 100 nm were used instead of the silica fine particles (A). .

-Production of Inorganic Fine Particles 27- In the production of the inorganic fine particles 16, instead of the silane coupling agent (S-1), the following silane coupling agent (S-
Organopolysiloxane (A) having a kinematic viscosity at 25 ° C. of 40 mm ² / sec and having an ammonium functional group at the end, which was synthesized in the same manner as organopolysiloxane (A) except that 2) was used, Inorganic fine particles 27 were obtained in the same manner except that they were used instead of).

[0208]

[Chemical 21]

-Production of Inorganic Fine Particles 28- In the production of the inorganic fine particles 16, instead of the silane coupling agent (S-1), the following silane coupling agent (S-
3) except for using it was synthesized in the same manner as the organopolysiloxane (A), kinematic viscosity of 46 mm ² / s at 25 ° C., an organopolysiloxane having an ammonium functional group at the terminal, the organopolysiloxane (A Inorganic fine particles 28 were obtained in the same manner except that they were used instead of).

[0210]

[Chemical formula 22]

-Production of Inorganic Fine Particles 29- In the production of the inorganic fine particles 16, the use ratio of the silica fine particles (A) and the organopolysiloxane (A) when the silica fine particles (A) is treated with the organopolysiloxane (A). , Silica fine particles (A) / organopolysiloxane (A) = 60/40
Got 9.

-Production of Inorganic Fine Particles 30- In the production of the inorganic fine particles 16, the use ratio of the silica fine particles (A) and the organopolysiloxane (A) when the silica fine particles (A) is treated with the organopolysiloxane (A). , Silica fine particles (A) / organopolysiloxane (A) = 97/3
I got 0.

-Production of Inorganic Fine Particles 31- In the production of inorganic fine particles 16, the surface of alumina fine particles having a number average primary particle diameter of 20 nm was hydrophobized with hexamethyldisilazane in place of silica fine particles (B). Inorganic fine particles 31 were obtained in the same manner except that alumina fine particles having a hydrophobicity of 63% were used.

-Production of Inorganic Fine Particles 32- In the production of inorganic fine particles 16, the surface of titanium oxide fine particles having a number average primary particle diameter of 50 nm was hydrophobized with hexamethyldisilazane instead of the silica fine particles (B). Inorganic fine particles 32 were obtained in the same manner except that titanium oxide fine particles having a hydrophobicity of 66% were used.

-Production of Inorganic Fine Particles 33- In the production of the inorganic fine particles 16, instead of the organopolysiloxane (A), silanols at both ends having a kinematic viscosity at 25 ° C. of 55 mm ² / sec and a degree of polymerization of n = 50. Inorganic fine particles 33 were obtained in the same manner except that dimethylpolysiloxane having a group was used.

-Production of Inorganic Fine Particles 34- In the production of the inorganic fine particles 16, 15 parts of octyltrimethoxysilane instead of the organopolysiloxane (A),
Synthesized by reacting 85 parts of dimethylpolysiloxane having a silanol group at both ends with a kinematic viscosity of 55 mm ² / sec at 25 ° C. and a degree of polymerization of n = 50 in a 37% hydrochloric acid aqueous solution at 35 ° C., Inorganic fine particles 34 were obtained in the same manner except that organopolysiloxane having a kinematic viscosity at 25 ° C. of 48 mm ² / sec and a terminal modified with octyltrimethoxysilane was used.

-Production of Inorganic Fine Particles 35- In the production of inorganic fine particles 16, it was synthesized by subjecting dimethyldimethoxysilane and a silane coupling agent (S-3) to a copolycondensation reaction in place of the organopolysiloxane (A). Inorganic fine particles having a kinematic viscosity of 52 mm ² / sec at 25 ° C. and a degree of polymerization of n = 50, except that an organopolysiloxane having an ammonium functional group only on the side chain represented by the following formula is used. 35 was obtained.

[0218]

[Chemical formula 23]

Table 5 shows the contents of the constitution of the inorganic fine particles 16 to 35. Table 6 shows the hydrophobicity, bulk density and triboelectric charge of the inorganic fine particles 16-35. The number average primary particle diameter, the degree of hydrophobicity, the bulk density and the triboelectric charge amount are obtained by the above method.

[0220]

[Table 5]

[0221]

[Table 6]

<< Production of Toner >> Styrene-methyl methacrylate-butyl acrylate (65/25/10) copolymer 100 parts Carbon black (Black Pearls L, manufactured by Cabot) 10 parts Low molecular weight polypropylene (Viscor 660P, Sanyo Chemical ( Co., Ltd.) 4 parts After pre-mixing the above components with a stirring mixer, 2
Melt kneading with a shaft kneader, cool, pulverize with a jet mill, classify the pulverized product with a classifier,
Colored particles having a volume average particle size of 8.0 μm were produced.

Colored particles 100 produced as described above
1.0 part by weight of inorganic fine particles and zinc stearate
Toners 16 to 35 were manufactured by adding and mixing 0.1 part by weight of each. The inorganic fine particles used are shown in Table 7.

<< Production of Developer >> To 6 parts by weight of each of the toners described above, 94 parts by weight of a resin-coated carrier in which the surface of ferrite particles having a volume average particle diameter of 60 μm are coated with a silicone resin is mixed to prepare developers 16 to 35. Was prepared. The toner used is shown in Table 7.

[0225]

[Table 7]

<< Copy Test >> The electrostatic latent image formed on the organic photoreceptor is developed with a developer to form a toner image,
After the toner image is transferred to the transfer material, the toner image is heated and fixed on the transfer material, and the toner remaining on the photoconductor is removed by using an electrostatic recording device. , The above-mentioned developers 16 to 35 as the developer
Was duplicated using.

The heat fixing was carried out in the same manner as in Example 1 using a SURF fixing device.

High temperature and high humidity environment (environmental temperature 30 ° C, relative humidity 80
%) And then 50,000 copies in a low temperature and low humidity environment (environmental temperature of 10 ° C, relative humidity of 20%) is repeated twice to make a total of 200,000 copies. The toner charge amount, the maximum image density (Dmax), the background fog (Fog), and the degree of toner scattering in the apparatus were evaluated in the same manner as in Example 1. The obtained results are shown in Tables 8 and 9.

When the developers 33 to 35 are used, 20
Before copying 10,000 copies, toner scattering inside the device became noticeable and image fog also worsened significantly.
When the developers 33 and 34 are used, 30,000 copies are copied,
When the developer 35 was used, the evaluation was stopped when 100,000 copies were copied.

[0230]

[Table 8]

[0231]

[Table 9] As is clear from Tables 8 and 9, when the developers 16 to 32 are used, the positive chargeability of the toner is good, and the fluctuation of the charging characteristics due to the fluctuation of humidity can be reduced.
Even after making 10,000 copies, no fog on the image background or toner scattering in the apparatus was observed. The copied image obtained after copying 200,000 copies had high image density and high definition.

The results show that the inorganic fine particles of the present invention are excellent in positive charge imparting property and positive charge retaining property.

On the other hand, a developer 33 having a toner 33 using inorganic fine particles treated with an organopolysiloxane which is not modified with an organic group having an ammonium functional group at its end, and having a terminal having an ammonium functional group. When the developer 34 having the toner 34 using the inorganic fine particles treated with the organopolysiloxane modified with a non-organic group is used, the positive chargeability of the toner is not sufficient, and after copying at 20,000 pies, The toner scattering in the apparatus increased, and image fog occurred at the time of copying 30,000 copies.

Further, when the developer 35 having the toner 35 using the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group only in the side chain is used, the inorganic fine particles have a certain degree of positive charge imparting property, but are not yet present. Not enough, after the copying of 80,000 copies, the toner scattering in the apparatus increased, and the image fog occurred at the time of copying 100,000 copies.

Similar results were obtained when the heat roller fixing shown in Example 1 was used for the heat fixing.

<Character dust test> The above developers 16 to 35
Was used to conduct a character dust test in the same manner as in Example 1, and in the same manner as in Example 1, the average value of the character dust rate was calculated and evaluated. The results obtained are shown in Table 10.

[0237]

[Table 10]

As is apparent from Table 10, toners 1 to 1
When 7 is used, the positive chargeability of the toner is remarkably good,
Even if the copying was repeated ten thousand times, the character dust rate did not increase, and high-definition images were always obtained.

The results show that the inorganic fine particles have good positive charge imparting property and positive charge retaining property.

On the other hand, the developer 33 having the toner 33 using the inorganic fine particles treated with the organopolysiloxane which is not modified with the organic group having the ammonium functional group at the terminal, has the ammonium functional group at the terminal. When the developer 34 having the toner 34 using the inorganic fine particles treated with the organopolysiloxane modified with a non-organic group is used, the positive charge imparting property of the inorganic fine particles is small, and at the time of copying 20,000 copies. The occurrence of character dust became noticeable.

Further, when the developer 35 having the toner 35 using the inorganic fine particles treated with the organopolysiloxane having the ammonium functional group only in the side chain is used, the inorganic fine particles have a certain degree of positive charge imparting property. However, it is still not enough, and the occurrence of the character dust became remarkable at the time of copying 80,000.

The same results were obtained when the heat roller fixing shown in Example 1 was used for the heat fixing.

Example 3 <Production of Carrier> -Production of Carrier 1-Copolymer of the following fluorine atom-containing monomer (5FM) and methyl methacrylate (MMA) (monomer ratio 5FM /
A coating solution was prepared by dissolving 20 parts of MMA = 80/20) in 100 parts of a mixed solvent of acetone / methyl ethyl ketone [mixing ratio 1: 1 (volume)]. 200 parts of spherical magnetite particles having a volume average particle diameter of 60 μm were coated with this coating solution using a fluidized bed coating device to obtain a carrier 1. The content of fluorine atoms on the surface of carrier 1 was 38 atom%.

[0244]

[Chemical formula 24]

-Production of Carrier 2- 10 parts of a copolymer of vinylidene fluoride and hexafluoropropylene (monomer ratio: vinylidene fluoride / hexafluoropropylene = 80/20) and 10 parts of polymethylmethacrylate (Mw = 50,000) were prepared. A coating solution was prepared by dissolving in 100 parts of dimethylformamide. 200 parts of spherical magnetite particles having a volume average particle diameter of 60 μm were coated with this coating solution using a fluidized bed coating device to obtain carrier 2. The content of fluorine atoms on the surface of the carrier 2 was 94 atom%.

-Production of Carrier 3- Fluorine atom-containing monomer (5FM) represented by the above formula 9
And polymethylmethacrylate (MMA) copolymer (monomer ratio 5FM / MMA = 40/60) 20 parts 100 parts acetone / methyl ethyl ketone mixed solvent (mixing volume ratio 1:
A coating solution was prepared by dissolving in 1). 200 parts of spherical magnetite particles having a volume average particle diameter of 60 μm were coated with this coating solution using a fluidized bed coating device to obtain a carrier 3. The content of fluorine atoms on the surface of the carrier 3 was 22 atom%.

<< Manufacture of Developer >> According to the combinations shown in Table 11, 94 parts by weight of each carrier and 6 parts of the toner described in Example 2 were mixed to prepare developers 36 to 76.

[0248]

[Table 11]

<< Copy Test >> The electrostatic latent image formed on the organic photoreceptor is developed with a developer to form a toner image,
After the toner image is transferred to the transfer material, the toner image is heated and fixed on the transfer material, and the toner remaining on the photoconductor is removed by using an electrostatic recording device. , The above-mentioned developers 36 to 76 as the developer
Was duplicated using.

The heat fixing was carried out in the same manner as in Example 1 using a SURF fixing device.

High temperature and high humidity environment (environmental temperature 30 ° C, relative humidity 80
%) And then 50,000 copies in a low temperature and low humidity environment (environmental temperature of 10 ° C, relative humidity of 20%) is repeated twice to make a total of 200,000 copies. The toner charge amount, the maximum image density (Dmax), the background fog (Fog), and the degree of toner scattering in the apparatus were evaluated in the same manner as in Example 1. The obtained results are shown in Table 12, Table 13 and Table 14.

When using the developers 70 to 76, 20
Before copying 10,000 copies, the image fog in the background portion deteriorated, so the evaluation was terminated when the image fog worsened.

[0253]

[Table 12]

[0254]

[Table 13]

[0255]

[Table 14]

As is apparent from Tables 12, 13, and 14, when the developers 36 to 69 of the present invention are used, the positive chargeability of the toner is good, and the fluctuation of the charging characteristics due to the fluctuation of humidity is small. As a result, even if 200,000 copies were made, no fogging of the image background part or scattering of toner in the apparatus was observed. Further, the copied image obtained after copying 200,000 pies had high image density and high definition.

On the other hand, the developers 70 and 73 having the toner 33 using the inorganic fine particles treated with the organopolysiloxane which is not modified with the organic group having the ammonium functional group at the terminal, and the terminal having the ammonium functional group at the terminal are used. When the developers 71 and 74 having the toner 34 using the inorganic fine particles treated with the organopolysiloxane modified with an organic group which is not used, the positive charge imparting property of the inorganic fine particles is small and a copy of 20,000 copies is obtained. After the operation, the toner scattering in the apparatus increased, and the image fog occurred at the time of copying 30,000 copies.

Further, when the developers 72 and 75 having the toner 35 using the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group only in the side chain are used, the inorganic fine particles have a certain degree of positive charge imparting property. However, it is still not sufficient, and after copying 80,000 copies, toner scattering in the apparatus increased, and image fog occurred at the time of copying 100,000 copies.

When the toner 35 using the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group only in the side chain and the developer 76 having the carrier 3 are used, the inorganic fine particles have some positive charge imparting property. Since the resin constituting the carrier 3 has a fluorine atom content of less than 30 atom%, the carrier surface is contaminated with an increase in the number of actual images, and the positive charge is stably applied to the toner for a long period of time. In addition, since inorganic fine particles treated with an organopolysiloxane having an ammonium functional group only in the side chain are used as the inorganic fine particles, sufficient positive charge imparting property cannot be imparted, and thus 20,000 copies of After copying, the toner scattering inside the device increased, and the image fogging occurred when 30,000 copies were copied. It had occurred.

Similar results were obtained when the heat roller fixing shown in Example 1 was used for the heat fixing.

Example 4 << Production of Developer >> (1) Preparation of Black Developer 100 parts of polyester resin, 10 parts of carbon black and 3 parts of low molecular weight polypropylene were added, and the mixture was melted and kneaded. Colored particles having a particle size of 8.5 μm were obtained. Next, 1.0 part of each of the inorganic fine particles described in Example 2 was added to the colored particles to prepare a black toner.

A silicone carrier coated with this toner was mixed with a ferrite carrier (carrier A) having a volume average particle diameter of 35 μm and a saturation magnetization of 25 emu / g to give a toner density of 9
A black developer was prepared that was in weight percent.

(2) Preparation of yellow developer 10 parts of carbon black was used as C.I. I. Pigment Yellow 17
A yellow toner was prepared in the same manner as the above black developer except that the content was changed to 8 parts.

With respect to this toner, the volume average particle diameter is 35 μm.
A carrier prepared by coating ferrite having m and a saturation magnetization of 25 emu / g with a silicone resin was mixed to prepare a yellow developer having a toner concentration of 9% by weight.

(3) Preparation of magenta developer 10 parts of carbon black was used as C.I. I. Pigment Red 122
A magenta toner was produced in the same manner as the above black developer except that the content was changed to 8 parts.

This toner has a volume average particle size of 35 μm.
A magenta developer having a toner concentration of 9% by weight was prepared by mixing a carrier prepared by coating ferrite having m and a saturation magnetization of 25 emu / g with a silicone resin.

(4) Preparation of cyan developer 10 parts of carbon black was used as C.I. I. Pigment Blue 15:
A cyan toner was produced in the same manner as the above black developer except that the amount was changed to 33 parts.

With respect to this toner, the volume average particle diameter is 35 μm.
A carrier prepared by coating ferrite having m and a saturation magnetization of 25 emu / g with a silicone resin was mixed to prepare a cyan developer having a toner concentration of 9% by weight.

The black developer, the yellow developer, the magenta developer and the cyan developer obtained as described above were combined developers 77 to 99 as shown in Table 15.

In Table 15, black developer, yellow developer, magenta developer, and cyan developer used in combination represent the inorganic fine particles used in the preparation of the toner used to prepare each developer. Showed by.

[0271]

[Table 15]

<< Copy Test >> The electrostatic latent image formed on the photoconductor drum is subjected to the above-mentioned image forming conditions by the reversal development method while the developer is kept in non-contact with the photoconductor drum. Development of four colors is repeatedly performed using a developer composed of a combination of a black developer, a yellow developer, a magenta developer, and a cyan developer, and a toner image in which four color toners are superposed is formed on a photosensitive drum. An image formation in which the superposed toner images are collectively transferred to a transfer material by a transfer device of a batch transfer type, heat-fixed, and the toner remaining on the photoconductor is removed by a cleaning device. Copies were made using the device.

High temperature and high humidity environment (environmental temperature 30 ° C, relative humidity 80
%), And then 20,000 copies in a low temperature and low humidity environment (environmental temperature of 10 ° C, relative humidity of 20%) is repeated twice, and a total of 80,000 copies are tested. Then, the color difference of a total of three colors of red (R), green (G), and blue (B) in the copied image was evaluated.

Note that the color difference (ΔE * ab) of each superimposed image of blue (B), red (R), and green (G).
Represents a color difference (ΔE * ab) with respect to the chromaticity of these standard colors by presetting three standard colors of blue, red and green. Color difference (ΔE * ab)
The measurement was carried out with a color-difference meter CR-221 type (manufactured by Minolta Camera Co., Ltd.) using a D65 light source in a 2 ° field of view. In this measurement, when the color difference exceeded 7, it was judged that a problematic color shift had occurred.

The image forming conditions of the above image forming apparatus were as follows.

-Image forming conditions- As the photosensitive drum, an organic photosensitive member (OPC) having a diameter of 100 mm was used, the moving speed was 160 mm / sec., And the charging potential was + 700V. A 400 dpi LED was used as the exposure means, and the latent image potential was + 100V. The diameter of the developing sleeve of each developing unit is 2
0mm, the gap between the developing sleeve and the photosensitive drum is 0.5mm, the thickness of the developer layer on the sleeve is 0.3mm, and the moving speed of the developing sleeve is 320mm / sec. Development was carried out in the absence. At this time, a developing bias containing an AC component having a frequency of 8 kHz and Vp-p = 2.2 kV was applied.

The obtained results are shown in Table 16, Table 17, Table 18 and Table 19.

When the developers 94 to 99 are used, 8
Before the copying of 10,000 copies, the color difference of the superimposed image exceeded 7, so 10,000 copies were made when the developers 94 and 95 were used, and when the developers 96 to 99 were made. The evaluation was terminated when 20,000 copies were made.

[0279]

[Table 16]

[0280]

[Table 17]

[0281]

[Table 18]

[0282]

[Table 19]

As is clear from Table 16, Table 17, Table 18 and Table 19, the toner of the present invention is excellent in the positive charge imparting property and the positive charge retaining property of the inorganic fine particles, so that the toner is positively charged. In addition to being remarkably good, since the fluctuation of the charging characteristics due to the fluctuation of humidity can be made extremely small, when the developers 77 to 93 in which only the toner of the present invention is combined are used, Even when copying was performed 80,000 times under various environmental conditions, no decrease in single-color image density, no increase in color difference between superimposed images, and no occurrence of mixed-color images were observed, and good copied images could always be obtained. Further, the copied image obtained after copying 80,000 times was also a high-definition image with high image density.

On the other hand, in the case of the developer 94, since the yellow toner uses the inorganic fine particles 33 whose end is treated with the organopolysiloxane which is not modified with a substituent having an ammonium functional group, The inorganic fine particles have a small positive charge imparting property, and as a result, at the time of 10,000 copies, the yellow toner excessively develops due to the decrease in the charging property of the yellow toner, and the color difference between red and green increases.

Further, in the case of the developer 95, since the magenta toner uses the inorganic fine particles 34 which are modified with an organo group having an organic group having no ammonium functional group and treated with an organopolysiloxane, The positive charge imparting property of the fine particles was very small, and as a result, the magenta toner was overdeveloped due to the decrease in the charging property of the magenta toner at the time of 10,000 copies, and the color difference between red and blue was increased.

Further, in the case of the developer 96, since the cyan toner uses the inorganic fine particles 35 treated with the organopolysiloxane having an ammonium functional group only in the side chain, the positive charge imparting property of the inorganic fine particles is obtained. Is not sufficient, and as a result, over-development of the cyan toner occurs due to a decrease in the charging property of the cyan toner at the time of copying 20,000, and the color difference between green and blue increases.

Further, in the case of the developer 97, since the yellow toner uses the inorganic fine particles 35 treated with the organopolysiloxane having an ammonium functional group only in the side chain, a positive charge imparting property of the inorganic fine particles is obtained. Is not sufficient, and as a result, over-development of the yellow toner occurs due to a decrease in the charging property of the yellow toner at the time of copying 20,000, and the color difference between red and green increases.

Further, in the case of the developer 98, since the magenta toner uses the inorganic fine particles 35 treated with the organopolysiloxane having an ammonium functional group only in the side chain, the positive charge imparting property of the inorganic fine particles is obtained. Is not sufficient, and as a result, the magenta toner is overdeveloped at the time of 20,000 copies due to the decrease in the charging property of the magenta toner, and the color difference between red and blue is increased.

Further, in the case of the developer 99, since the inorganic fine particles 35 treated with the organopolysiloxane having an ammonium functional group only in the side chain are used in the black toner, the positive charge imparting property of the inorganic fine particles is obtained. Is not enough,
As a result, at the time of copying 20,000, the black toner is mixed in the superposed image portion of red, green and blue due to the toner scattering due to the deterioration of the chargeability of the cyan toner, and as a result, all the three colors of red, green and blue are mixed. The color difference of the image has increased.

[0290]

INDUSTRIAL APPLICABILITY The toner and the developer for developing an electrostatic charge image of the present invention are rapidly imparted with an appropriate amount of positive charge, and stably maintain an appropriate amount of positive charge for a long period of time. It is possible to form a high-definition image without toner scattering and image fogging in the apparatus and without image defects such as character dust. Also,
When a toner image of an intermediate color is formed on a recording material by performing color superposition using a plurality of toners of two or more colors, there is no color misregistration or color mixture in the superposed image, and a high-definition image with high image density is formed. Can be made.

[Brief description of drawings]

FIG. 1 is a diagram illustrating an image forming apparatus using a sequential transfer method.

FIG. 2 is a diagram for explaining an image forming apparatus using a batch transfer method.

[Explanation of sign]

1; charger 2; Development unit 3; Cleaning unit 4; photoconductor drum 5: Transfer drum 6; Transport unit 7; Adsorber 8: Transfer device 9; Peeler 10; Static eliminator 11: exposure means

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroko Furusawa, 2970 Ishikawa-cho, Hachioji-shi, Tokyo Konica stock company (72) Inventor Hiroshi Yamazaki 2970, Ishikawa-cho, Hachioji-shi, Tokyo Konica stock company (56) References Japanese Patent Laid-Open No. 1-114858 (JP, A) Japanese Patent Laid-Open No. 2-140758 (JP, A) Japanese Patent Laid-Open No. 4-294364 (JP, A) Japanese Patent Laid-Open No. 4-360153 (JP, A) Japanese Patent Laid-Open No. 2-217863 (JP , A) JP 2-130561 (JP, A) JP 4-67047 (JP, A) JP 63-46469 (JP, A) JP 64-66667 (JP, A) JP 62-229158 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/08-9/113

Claims (10)

(57) [Claims] 1. A toner obtained by adding inorganic fine particles treated with an organopolysiloxane having an ammonium functional group at a terminal represented by the following formula 1 to colored particles composed of at least a resin and a colorant. . [Chemical 1] [Wherein Y and Z are the number of substituted and unsubstituted carbon atoms, respectively]
1 to 8 represents an alkyl group or an aryl group. A and
B is a hydrogen atom, a substituted or unsubstituted C1-4 carbon atom, respectively.
Have one alkyl group or ammonium salt structure
Represents a group. However, at least one of A and B is
It is a group having an ammonium salt structure. n is an integer of 5 to 400
Represents a number. ] Wherein a plurality of toner two or more colors, serial to claim 1, characterized in that on the recording material by performing color superimposition is toner used to form an intermediate color of the toner image <br /> Listed toner. Inorganic fine particles treated with an organopolysiloxane having at 3. A terminal ammonium functional groups, the toner according to claim 1 or 2, characterized in that the inorganic fine particles treated with a hydrophobic treatment agent. 4. A toner and electrostatic image developer comprising a carrier according to any one of claims 1-3. 5. The carrier is a carrier in which the core surface having a fluorine atom content on the carrier surface of 30 atom% or more is coated with a fluororesin.
4. The developer for developing an electrostatic charge image according to item 4 . 6. The fluorinated resin is a fluorinated acrylate resin or fluorinated methacrylate resin containing a repeating unit represented by the following formula 2, vinylidene fluoride resin, hexafluoropropylene resin, or vinylidene fluoride and hexa. The developer for electrostatic image development according to claim 5, which is a fluoropropylene copolymer resin. [Chemical 2] [In the formula, R represents a hydrogen atom or a methyl group, and Rf represents an alkyl group substituted with a fluorine atom. ] 7. The fluororesin is a fluorinated methacrylate resin having 75% by weight or more of the repeating unit represented by the following formula 3, or a copolymer resin of vinylidene fluoride and hexafluoropropylene. Claims to
5. The developer for developing an electrostatic charge image according to 5 or 6 . [Chemical 3] [In the formula, Rf represents an alkyl group substituted with a fluorine atom. ] 8. A toner image of an intermediate color is formed on a recording material by superposing colors using a plurality of toners of two or more colors,
A color image forming method for forming an image by fixing the toner image, wherein the toner is used as a toner .
A color image forming method comprising using the toner according to any one of the claims. 9. The method according to any one of claims 1 to 3, which is provided between the rotating fixing roller and the pressure roller which is in pressure contact with the fixing roller.
5. A thermal fixing method comprising passing a recording material carrying a toner image as described in 1 above to fix the toner image on the recording material. 10. A movable film material is arranged between a fixedly arranged heating body and a pressure member that is pressed against and rotates against the heating body, and is arranged between the film material and the pressure member. Any one of claims 1 to 4 , so that the toner image is in contact with the film material.
5. A thermal fixing method comprising passing a recording material carrying a toner image as described in 1 above to fix the toner image on the recording material.