JPH11295918A - Image forming method and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method by which image quality can be stably obtd. even in a low humidity or high humidity environment and which does not produce image defects with time. SOLUTION: In this method, the toner contains an inorg. fine powder and toner particles containing a binder resin, coloring agent and org. zirconium compd. The toner and the cleaning blade used have the following properties. The temp. (TT.C) at which the storage modulus and the loss modulus of the toner are equal to each other is present between 50 and 75 deg.C, the temp. (TT.P) at which the loss tangent of the toner is max. is present between 50 and 75 deg.C. The temp. at which the loss tangent of the cleaning blade is min. is present between 40 to 80 deg.C, and the temp. (TB.P) at which the loss tangent of the blade is max. is present between 70 and 130 deg.C. The difference between (TT.P) and (TB.P) ranges -40 to 20 deg.C. The ratio of the loss modulus of the toner to the loss modulus of the cleaning blade at (TT.C) ranges 5×10<2> to 5×10<4> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an image forming method and an image forming apparatus using a toner for visualizing a latent electrostatic image.

[0002]

2. Description of the Related Art As an electrophotographic method, US Pat.
Numerous methods are known as described in JP-B-97,691, JP-B-42-23910 and JP-B-43-24748. Generally, a photoconductive substance is used to form an electrostatic latent image on a photoreceptor by various means, and then the latent image is developed using toner, and if necessary, a toner image is formed on a transfer material such as paper. After the transfer, the toner image is fixed by heating, pressure, heating pressure or solvent vapor to obtain a toner image.

[0003] Toner must have a positive or negative charge, depending on the polarity of the electrostatic latent image to be developed.

In order to make the toner retain electric charge, it is possible to use the frictional charging property of the resin which is a component of the toner. However, in this method, the charging of the toner is not stable.
Density rises slowly and fog is easy. Therefore, a charge control agent is added to impart a desired triboelectric charge to the toner.

At present, as charge control agents known in the art, as triboelectric charge control agents, metal complex salts of monoazo dyes, metal complex salts such as hydroxycarboxylic acid, dicarboxylic acid and aromatic diol; Resins containing components are known. Nigrosine dyes, azine dyes, triphenylmethane dyes and pigments, quaternary ammonium salts, and polymers having quaternary ammonium salts in the side chain are known as positive friction charge control agents.

However, most of these charge control agents are colored and many cannot be used for color toners. Most of the colorless, white, or light-colored toners applicable to color toners have insufficient performance. They have drawbacks such as lack of uniformity of highlights and large fluctuations in image density in a durability test.

[0007] In addition, some charge control agents have the following disadvantages. It is difficult to balance image density and fog, it is difficult to obtain sufficient image density in a high-humidity environment, poor dispersibility in resin, adversely affects storage stability, fixability, and offset resistance.

Conventionally, metal complexes and metal salts of aromatic carboxylic acids have been disclosed in JP-A-53-127726 and JP-A-57-127726.
JP-A-111541, JP-A-57-124357, JP-A-57-104940, JP-A-61-6
No. 9073, JP-A-61-73963, JP-A-61-267058, JP-A-62-10515
No. 6, JP-A-62-145255, JP-A-62-145255
JP-A-2-163601, JP-A-63-208865, JP-A-3-276166, JP-A-4-84
Some proposals have been made, such as Japanese Patent Application Laid-Open No. 141 and JP-A-8-160668. However,
These publications are all excellent in terms of imparting triboelectric charging.However, with a simple developing device configuration, stable developability can be obtained regardless of environmental changes, aging, and use conditions. There are few things that can be done. Also, there are few high-speed machines that can provide stable developability even during long-term durability. Further, there are many cases in which there is an influence of other raw materials and restrictions on other raw materials occur. At present, none of the above items are satisfactory.

Further, during the step of obtaining the toner image, when the toner image is transferred from the photoreceptor to the transfer material,
Transfer residual toner exists. In order to quickly perform continuous copying, it is necessary to clean the residual toner on the photoconductor. If this cleaning is insufficient, it causes various image defects. As this cleaning means, magnetic brush cleaning, blade cleaning, or the like is used.

In the above-described cleaning method, in the magnetic brush cleaning method, the toner remaining on the photoreceptor is electrostatically adsorbed and collected on a carrier of a cleaning material. However, this method has problems such as toner scattering from the magnetic brush and poor cleaning which occur when the charge amount of the carrier of the cleaning material is reduced. As a method for solving these problems, Japanese Patent Application Laid-Open No. 5-88595 discloses a method for preventing toner scattering by changing the rotation speed of the cleaning roller itself according to the charged state of the cleaning material. However, this method cannot completely remove paper dust, ozone deposits, and the like generated or adhered on the photoreceptor.

Further, in the cleaning method using a blade, since the residual toner is directly scraped off from the surface of the photoreceptor, various problems such as filming, fusion of the toner, and scraping of the photoreceptor have occurred.

Further, the organic photoreceptor and the amorphous silicon photoreceptor cause a phenomenon of image deletion due to the influence of paper dust, ozone adhering substances and the like adhered to the surface of the photoreceptor, especially in a high temperature and high humidity environment. As a method for solving these problems, Japanese Patent Application Laid-Open No. Hei 2-110475 discloses a method using two kinds of inorganic fine powders for a toner using a metal-crosslinked styrene-acrylic resin. A method for removing ozone adducts and the like and improving toner scattering, image deletion, and image density reduction under high temperature and high humidity is disclosed. However, this method has a problem in image stability during continuous copying because the photoconductor itself is also shaved.

In recent years, the digitalization of copiers and the use of fine particles of toner have increased the number of functions of copiers, improved the quality of copied images, and taken measures against high temperature and humidity from the viewpoint of energy saving as an environmental measure. It is desired to eliminate the heater inside the photosensitive member (drum heater).

Further improvement of the method for removing the residual toner on the photoreceptor and removing paper dust, ozone adducts, etc. generated or adhered on the photoreceptor is required depending on the speed of copying and the material of the transfer paper. ing.

In JP-A-9-190125,
Using a blade having a rebound resilience at room temperature of 35 to 60%, containing inorganic particles on the surface of the organic photoreceptor, setting the surface roughness Rz of the photoreceptor to 0.05 to 1.0 μm, and applying a cleaning blade to the photoreceptor. A method is disclosed in which the cleaning blade is brought into contact with a counter and the cleaning blade is vibrated to 10 to 200 μm to perform cleaning. Although it is possible to improve the cleaning property under normal temperature and normal humidity by this method, there is a problem in achieving both the prevention of image deletion and the shaving of the photoreceptor under high temperature and high humidity.

That is, under the above-mentioned problems, in particular, under high temperature and high humidity, it has high charging ability, high image quality and high image density can be obtained, and in addition, poor cleaning, toner fusion, image deletion and the like occur. At present, no image forming method or apparatus has been realized.

[0017]

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

An object of the present invention is to provide an image forming method and an image forming apparatus which have high chargeability even under high temperature and high humidity, and which can obtain high image quality and high image density.

An object of the present invention is to provide an image forming method and an image forming apparatus which can stably obtain high image quality even when used under low humidity or under high humidity and do not cause image defects over time. To provide.

An object of the present invention is to provide an image forming method and an image forming apparatus capable of continuously obtaining an image faithful to a latent image even in long-term durability.

An object of the present invention is to provide an image forming method and an image forming apparatus which do not cause image deletion even under high temperature and high humidity.

SUMMARY OF THE INVENTION It is an object of the present invention to provide an image forming method and an image forming apparatus which do not cause photoreceptor scraping even when used in a high-speed copying machine and have excellent durability for many sheets.

An object of the present invention is to provide a high image quality even under high temperature and high humidity.
An object of the present invention is to provide an image forming method and an image forming apparatus capable of obtaining a high image density.

[0024]

According to the present invention, an electrostatic image formed on an electrostatic image carrier is developed using toner to form a toner image, and the formed toner image is formed as an electrostatic image. An image forming method including a step of transferring from a carrier to a transfer material via an intermediate transfer body or without the intermediate transfer body, and cleaning a transfer residual toner on the electrostatic image carrier using a cleaning blade; A toner having toner particles containing at least a binder resin, a colorant and an organic zirconium compound and inorganic fine powder, a) storage elastic modulus (G′T) and loss elastic modulus (G ″ T) of the toner. (TT.C) is equal to the temperature 5
B) a temperature (TT.P) at which the loss tangent (tan δTP) of the toner becomes a maximum exists at a temperature of 50 to 75 ° C, and c) a temperature at a temperature of 40 to 80 ° C. The storage elastic modulus (G′B) of the cleaning blade is 5 × 10 ^{5 to} 1 × 10 ⁷
D) The loss elastic modulus (G ″ B) of the cleaning blade at a temperature of 40 to 80 ° C. is 5 × 10 ^{3 to} 1 × 10 ^6.
E) The loss tangent of the cleaning blade (tan δB.
P) is a minimum temperature (TT.B) at a temperature of 40 to 8
0) f) Loss tangent (tan δB.
P) reaches a maximum (TB.P) at a temperature of 70 to 1
G) a temperature (TT.P) at which the loss tangent (tan δTP) of the toner is maximum, and a temperature (TB) at which the loss tangent (tan δBP) of the cleaning blade is maximum. .P)
(TT.P-TB.P) from -40 to 20 ° C. h) Loss modulus (G ″ T) of the toner at temperature (TT.C) and temperature (TT.C) (G "T) with the loss elastic modulus (G" BC) of the cleaning blade at
/ (G ″ BC) is in the range of 5 × 10 ^{2 to} 5 × 10 ⁴ .

Further, the present invention provides a developing means for developing an electrostatic image formed on an electrostatic image carrier using a toner to form a toner image, and a method for supporting the formed electrostatic image on the electrostatic image carrier. Having at least a transfer unit for transferring the toner from the image forming member to a transfer material via an intermediate transfer member or not, and a cleaning unit for cleaning the transfer residual toner on the electrostatic image carrier using a cleaning blade A toner having at least a binder resin, a colorant and an organic zirconium compound, and an inorganic fine powder, wherein: a) the storage elastic modulus (G′T) and the loss elasticity of the toner; The temperature (TT.C) at which the rate (G "T) becomes equal to the temperature 5
B) a temperature (TT.P) at which the loss tangent (tan δTP) of the toner becomes a maximum exists at a temperature of 50 to 75 ° C, and c) a temperature at a temperature of 40 to 80 ° C. The storage elastic modulus (G′B) of the cleaning blade is 5 × 10 ^{5 to} 1 × 10 ⁷
D) The loss elastic modulus (G ″ B) of the cleaning blade at a temperature of 40 to 80 ° C. is 5 × 10 ^{3 to} 1 × 10 ^6.
E) The loss tangent of the cleaning blade (tan δB.
P) is a minimum temperature (TT.B) at a temperature of 40 to 8
0) f) Loss tangent (tan δB.
P) reaches a maximum (TB.P) at a temperature of 70 to 1
G) a temperature (TT.P) at which the loss tangent (tan δTP) of the toner is maximum, and a temperature (TB) at which the loss tangent (tan δBP) of the cleaning blade is maximum. .P)
(TT.P-TB.P) from -40 to 20 ° C. h) Loss modulus (G ″ T) of the toner at temperature (TT.C) and temperature (TT.C) (G "T) with the loss elastic modulus (G" BC) of the cleaning blade at
/ (G ″ BC) is 5 × 10 ^{2 to} 5 × 10 ⁴ .

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION By using a zirconium complex compound or an aromatic carboxylate, the present inventors have obtained a high charge amount even in a high humidity environment while maintaining a good start-up. It was also found that a toner without excessive charging could be obtained.
Further, the organic zirconium compound of the present invention is preferable because it has excellent transparency and a clear color image can be obtained for a color toner. Further, the organic zirconium compound of the present invention contains 20% of hafnium element on the basis of zirconium element.
It may be contained at less than t%.

As the ligand, a zirconium complex or zirconium complex salt in which 2 to 4 aromatic diols, aromatic hydroxycarboxylic acids and aromatic polycarboxylic acids are chelated is preferable. In the case of a salt, those having 1 to 4 aromatic carboxylate ions, aromatic hydroxycarboxylic acid ions and aromatic polycarboxylic acid ions are preferable, and those having 2 to 3 aromatic carboxylate ions are more preferable. . Further, a complex, a complex salt having a different number of chelates, a complex having a different ligand, or a mixture of complex salts may be used. Also, a mixture of salts having different numbers of acid ions may be used.

Furthermore, it has been found that by combining this feature with a magnetic toner containing a magnetic material or by applying it to a one-component developing method, excellent developability can be obtained. That is, the organic zirconium compound of the present invention is a suitable negative charge control agent that satisfies these requirements for a magnetic toner or a one-component developing toner that requires a rapid rise in charge and a high charge amount with a small frictional charge opportunity. It is. As described above, it is suitably used for the toner used in the one-component developing method, and is most suitable for the toner used in the non-magnetic one-component developing method.

Further, in the present invention, when used together with a binder resin having an acid value, the polarity of water molecules can be used to greatly increase the effect of enhancing the charge.

The organic zirconium compound of the present invention is characterized by the fact that zirconium ions tend to take octa-coordinate and oxygen such as carboxyl group and hydroxyl group can easily coordinate.
The chance of coordinating a zirconium ion with a carboxyl group or the like increases. When a binder resin having an acid value such as a styrene-based resin having a carboxyl group as a functional group or a polyester-based resin is used as the binder resin, it can be easily blended into the binder resin, has excellent dispersibility, and falls off from toner particles. And uniform charging and stable charging durability can be obtained. Further, the influence on the transparency of the toner is reduced, which is preferable for expressing a vivid color for the color toner. In addition, since the polymer chain can be cross-linked through the coordination of the carboxyl group and the hydroxyl group of the binder resin to the zirconium ion, the binder resin can have a large rubber elasticity, and the releasability can be improved. Excellent, it is possible to effectively prevent the fixing member from being stained. In addition, kneading shear can be applied during melt-kneading during the production of the toner, the dispersion of the magnetic substance, the pigment and the dye can be improved, and a toner having high coloring power and clear color can be obtained.

The organic zirconium compound of the present invention is excellent in triboelectric charging ability and can obtain a high charge amount, so that it is a suitable charge control agent for a magnetic toner requiring a high charge amount. Furthermore, in addition to the good dispersibility of the organic zirconium compound itself, when a binder resin having an acid value is used, the dispersibility of the magnetic material is improved, so that durability and uniformity of charging can be obtained. .

Further, the present inventors have continued to study cleaning failure, toner fusion and image deletion under high temperature and high humidity, and found the following.

As a method of cleaning the residual toner on the photoreceptor, the generated or adhered paper dust, the ozone adduct, and the like, an electrostatic adsorption method using a magnetic brush, a scraping method using a cleaning blade, and the like are considered.

However, although the magnetic brush method is effective for cleaning residual toner, there is a problem in a method for cleaning paper dust, ozone adducts, etc. generated or adhered on the photoreceptor. In the scraping method using a cleaning blade, the effect obtained differs depending on the material of the blade used and the method of contacting the photosensitive member.

When a hard blade is brought into contact with the photoreceptor to remove residual toner on the photoreceptor, generated or adhered paper dust, ozone adducts, etc., the adhesion between the photoreceptor and the blade is hardly obtained, and the blade passes through. Cleaning failures are likely to occur due to such factors. If the contact pressure on the photoconductor is increased for the purpose of avoiding this phenomenon, problems such as scraping of the photoconductor and fusion of toner on the photoconductor occur.

Conversely, a soft blade is brought into contact with the photoreceptor, and the remaining toner on the photoreceptor and the generated or adhered paper powder,
When cleaning ozone adducts and the like, the adhesion between the photoconductor and the blade is enhanced, but cleaning failures occur due to chattering due to blade turning or the influence of vibration during rotation of the photoconductor. If the contact pressure on the photoreceptor is reduced for the purpose of avoiding this phenomenon, the original purpose is to clean the residual toner on the photoreceptor and the generated or adhered paper powder, ozone adducts, etc. Causes problems.

Further, a method of using a cleaning blade and a magnetic brush together for the purpose of achieving both the cleaning property and the polishing property has been considered. However, it is impossible to cope with the light weight and compactness of the copying machine itself, and the degree of freedom of setting. There is a problem such as the point that becomes narrow.

Further, for the material of the blade, the rebound resilience at normal temperature and normal humidity is defined, and the surface roughness of the organic photoreceptor surface layer is defined by containing an inorganic fine powder. A method has been considered in which the blade is brought into contact with a counter and the blade itself is vibrated to perform cleaning.However, even if it is effective for cleaning the residual toner on the photoreceptor, it is generated or adhered under high temperature and high humidity. There is a problem when cleaning paper dust, ozone adducts and the like that have been removed.

Furthermore, the method of adding a third component having a polishing effect to the toner as a cleaning aid has the effect of cleaning paper dust, ozone adducts, etc. generated or adhered on the photoreceptor. It does not satisfy all of shaving, developing property and cleaning property.

Therefore, the present inventors have considered the developing property and cleaning property of the toner particularly under high temperature and high humidity, and have examined in detail the problems in the cleaning. As a result, especially in a high-speed copying machine, the viscoelastic property of the cleaning blade is high. And that the viscoelastic properties of the toner have a close relationship. Furthermore, it has been found that in a blade and a toner satisfying the above conditions, the use of a composite oxide in the toner further enhances the present effect.

During continuous copying, the temperature of the cleaning blade in contact with the photoconductor rises due to friction with the photoconductor. This phenomenon becomes more remarkable depending on the environment in which the copying machine is installed. That is, the temperature rise under high temperature and high humidity becomes extremely severe, and in a high-speed copying machine, the temperature of the blade in contact with the photoreceptor becomes as high as 40 to 70 ° C.

Therefore, the present inventors measured the viscoelastic properties as temperature-dependent properties of various toners and blades, and developed the combination of these properties under high temperature and high humidity, and caused image deletion and photoreceptor shaving. Investigations were made focusing on the following, and the following was found.

When the developer contains the composite oxide (A) particles, which are inorganic fine powders represented by the following formula (1), the abrasion of paper powder and ozone adducts on the photoreceptor is improved.

[M ₁ ] _a [M ₂ ] _b O _c (1) (wherein, M ₁ represents a metal element selected from the group consisting of Sr, Mg, Zn, Co, Mn, Ca and Ce; M ₂ represents a metal element selected from Ti or Si, a is an integer of 1 to 9, b is an integer of 1 to 9, c is an integer of 3-9.)

The blocking of the toner in the developing device and the fusion to the photosensitive member can be prevented by setting the viscoelasticity of the toner and the blade within the following range.

When the toner is at a temperature of 50 to 75 ° C., a) there exists a temperature (TT.C) at which the storage elastic modulus (G′T) and the loss elastic modulus (G ″ T) become equal, and b) the loss tangent ( tanδT.P) is the maximum temperature (T
T. P) is present and the cleaning blade is c) at a temperature of 40 to 80 ° C., the storage elastic modulus (G′B) is
5 × 10 ^{5 to} 1 × 10 ⁷ Pa; d) At a temperature of 40 to 80 ° C., a loss elastic modulus (G ″ B) is
5 × a 10 ³ to 1 × 10 ⁶ Pa, e) at a temperature 40 to 80 ° C., the loss tangent (tanδB.
P) is at a minimum temperature (TT.B). F) At a temperature of 70 to 130 ° C., the loss tangent (tan δB.
P) exists at a temperature (TB.P) at which the toner and the cleaning blade have a loss tangent. G) The difference (TT.P−TB.P) is −40 to 20 ° C. H) the ratio of the loss elastic modulus (G "BC) of the cleaning blade at the temperature (TT.C) (G" T / G "BC);
Is 5 × 10 ^{2 to} 5 × 10 ⁴ .

Note that 1 Pa = 10 dyn / cm ² .

As described above, even when continuous copying is performed in a high-temperature and high-humidity environment using a high-speed copying machine, high image quality and high image density can be maintained, and residual toner on the photosensitive member and residual toner on the photosensitive member can be maintained. An organic zirconium compound is included as a charge control agent in order to prevent poor cleaning, image deletion, etc. by removing generated or adhered paper dust and ozone adducts. It is more important to define an organic zirconium compound as a charge controlling agent, and more preferably, to a composite oxide represented by the above formula (1) with respect to a toner in which the viscoelastic properties of the toner and the blade are specified. It is important to use things.

In the toner of the present invention, a temperature of 50 to 7
At 5 ° C., there is a temperature (T.TC) at which the storage elastic modulus (G′T) and the loss elastic modulus (G ′) become equal, and the loss tangent (tan)
δT. P) has a temperature (T.TP) at which the T.P. reaches a maximum. Preferably, the T.P. T
C and T.C. When TP is present, it is more preferable that T.P. TC and T.C. This is the case where the TP exists.

If the temperature is lower than 50.degree. TC and T.C.
The presence of TP is not preferable because a phenomenon called drum fusion, in which toner adheres to the electrophotographic photosensitive member during cleaning, may occur irrespective of the viscoelastic properties of the cleaning blade. T. When the temperature exceeds 75 ° C. TC and T.C. TP
When the toner is present, the toner may form a large scratch on the surface of the electrophotographic photosensitive member during cleaning regardless of the viscoelastic properties of the cleaning blade, which is not preferable.

In the present invention, the cleaning blade has a temperature of 40 to 80 ° C. and a storage elastic modulus (G′B) of 5 × 1.
0 ^{5 to} 1 × 10 ⁷ Pa, but preferably ⁷ × 10 ⁷ Pa
The pressure is 10 ^{5 to} 7 × 10 ⁶ Pa, and more preferably 1 × 10 ^{6 to} 5 × 10 ⁶ Pa. If G′B is less than 5 × 10 ⁵ Pa, a phenomenon called cleaning failure may occur in which the toner on the electrophotographic photosensitive member is not completely cleaned during cleaning regardless of the viscoelastic properties of the toner. There is not preferred. When G′B exceeds 1 × 10 ⁷ Pa, a phenomenon called drum abrasion in which the surface of the electrophotographic photosensitive member is significantly worn may occur, which is not preferable.

In the present invention, the cleaning blade has a temperature of 40 to 80 ° C. and a loss elastic modulus (G ″ B) of 5 × 1.
0 ^{3 to} 1 × 10 ⁶ Pa, but preferably 7 × 1 Pa
0 ^{3 to} 7 × 10 ⁵ Pa, and more preferably 1 × 10 ^{4 to} 5 × 10 ⁵ Pa. If G ″ B is less than 5 × 10 ³ Pa, the drum fusion phenomenon may occur during cleaning regardless of the viscoelastic properties of the toner.
0 ⁶ when Pa becomes greater is undesirable may phenomenon called cleaning failure occurs.

In the present invention, it is sufficient that the cleaning blade has a temperature (TT.B) at a temperature of 40 to 80 ° C. and a loss tangent (tan δBP) at a minimum. The tangent (tanδB.
P) at a temperature (TT.B) at which the loss tangent (t.
anδB. P) has a minimum temperature (TT.B).

If the temperature TT. At which (tan δBP) becomes a minimum, If B is less than 40 ° C., drum fusion may occur during cleaning regardless of the viscoelastic properties of the toner, which is not preferable. (TanδB.P) is the minimum temperature TT. When B exceeds 80 ° C., drum scraping may occur, which is not preferable.

In the present invention, the cleaning blade has a loss tangent (tan δBP) at a temperature of 70 to 130 ° C.
It is sufficient that there is a temperature (TB.P) at which the maximum value of TB. P is 75 to 120 ° C., and more preferably TB. P is 80-110 ° C
This is the case.

If the temperature TB. P <70 ° C. and temperature TB. When P exceeds 130 ° C., cleaning failure may occur, which is not preferable.

In the present invention, the difference (TT.P-TB.
P) may be −40 to 20 ° C., preferably −
30 to 10 ° C., and more preferably −2.
This is the case when the temperature is 0 to 5 ° C.

If the difference (TT.P-TB.P) is -40
When the temperature is lower than 20 ° C and the difference (TT.P-TB.P) is higher than 20 ° C, a sufficient removal effect from the drum cannot be obtained.
It is not preferable because drum fusion and cleaning failure may occur.

In the present invention, the ratio (G ″) of the loss elastic modulus of the toner and the cleaning blade at the temperature (TT.C) is used.
T / G ″ BC) may be 5 × 10 ^{2 to} 5 × 10 ⁴ Pa, preferably 7 × 10 ^{2 to} 3 × 10 ⁴ Pa, and more preferably 1 × 10 ³ Pa. To 1 × 10 ⁴
This is the case when it becomes Pa.

If the ratio (G "T / G" BC) is 5 × 1
When the ratio is less than 0 ² , drum scraping may occur, which is not preferable, and the ratio (G "T / G" BC) is 5 × 10 5
If it exceeds ⁴ , drum fusion may occur, which is not preferable.

Further, in the present invention, a more preferable constitution of the toner will be described in detail below.

The toner used in the present invention is characterized in that it contains a zirconium complex or a zirconium complex salt of an aromatic diol, an aromatic hydroxycarboxylic acid, or an aromatic polycarboxylic acid. Preferred are zirconium complexes or complex salts represented by the general formula (1).

[0063]

Embedded image In the general formula (1), Ar represents an aromatic residue, and an alkyl group, an aryl group, an aralkyl group,
Cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group,
It may have a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group, and a carbamoyl group.
X and Y represent -0- and -CO-O-, X and Y may be the same or different, and L is a neutral ligand, water,
C1 represents a monovalent cation, hydrogen, a monovalent metal ion, ammonium or alkylammonium;
2 represents a divalent cation, a divalent metal ion, n represents 2, 3, 4 and m represents 0, 2, 4. Aromatic carboxylic acids serving as ligands in each complex or complex salt,
The aromatic diols may be the same or different. Also, a mixture of complex compounds having different numbers of n and m may be used. Complexes in the binder resin, from the viewpoint of improving the dispersibility of the complex salt or improving the chargeability, as an aromatic residue, a benzene ring, a naphthalene ring, an anthracene ring,
A phenanthrene ring is preferable, a substituent is preferably an alkyl group, a carboxyl group, or a hydroxyl group, L is preferably water, and C1 is preferably hydrogen, sodium, potassium, ammonium, or alkylammonium.

Further preferred complexes or complex salts are zirconium complexes or salts represented by formulas (2), (3) and (4).

[0065]

Embedded image In the general formulas (2), (3) and (4), R represents hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group. A group, an aryloxycarbonyl group, an acyl group, a carboxyl group, a halogen, a nitro group, an amino group, or a carbamoyl group, which may be connected to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring. The ring may have a substituent R, and the substituent R may have 1 to 8 substituents, which may be the same or different,
C represents a monovalent cation, hydrogen, alkali metal, ammonium, or alkylammonium, 1 represents an integer of 1 to 8, n represents 2, 3, 4, m represents 0, 2, 4, The aromatic carboxylic acids and aromatic diols serving as ligands in the complex or complex salt may be the same or different. Also, a mixture of complex compounds having different numbers of n and m may be used. From the viewpoint of improving the dispersibility of the complex or complex salt in the binder resin or improving the chargeability,
As the substituent R, an alkyl group, an alkenyl group, a carboxyl group, or a hydroxyl group is preferable, and as C, hydrogen, sodium, potassium, ammonium, or alkylammonium is preferable. Particularly preferred are zirconium neutral complexes having no counter ion and in the case of n = 2 in the general formula, exhibiting excellent environmental stability, being excellent in dispersibility in a binder resin, and being excellent. Durability is obtained.

The zirconiwam complex or complex salt used in the present invention is a hexa- or octa-coordinate complex compound. Among the octa-coordinates, a dinuclear complex compound in which a ligand is bridged becomes a hexanuclear complex compound. There are coordination complex compounds. Representative structures of such complex compounds are represented by the following general chemical formulas (5) to (5).
(9) illustrates the structure. The following structures include those having no ligand L.

[0067]

Embedded image

[0068]

Embedded image One of the features is that the toner used in the present invention contains a zirconium salt of an aromatic carboxylic acid. Preferred are zirconium salts represented by the general formulas (10) and (11).

[0069]

Embedded image In the general formulas (10) and (11), Ar represents an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryl group as a substituent. A1 represents an aromatic residue which may have an oxycarbonyl group, an acyl group, a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group, or a carbamoyl group; ,
A2 represents a divalent anion, a sulfate ion, a hydrogen phosphate ion, and n represents 1,
Represents 2, 3, and 4. The aromatic carboxylic acids and aromatic diols that become acid ions in each metal salt may be the same or different. Further, a mixture of salts having different numbers of n may be used. From the viewpoint of improving the dispersibility or chargeability of the metal salt in the binder resin, the aromatic residue is preferably a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring, and the substituent is an alkyl group. A carboxyl group, a hydroxyl group and an acyloxy group are preferred, and in the general formula (10), n is preferably 4 and in the general formula (11), n is preferably 2.

Further preferred metal salts are those represented by the general formula (12):
It is a zirconium salt represented by (13).

[0071]

Embedded image In the general formulas (12) and (13), R represents hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group,
Represents a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, a carboxyl group, a halogen, a nitro group, an amino group, an amide group, or a carbamoyl group, and is connected to an aliphatic ring, an aromatic ring, or a heterocyclic ring May be formed, and in this case, the ring may have a substituent R. The substituent R may have 1 to 8 substituents, which may be the same or different, A1 represents a monovalent anion, a halogen ion, a hydroxyl ion, or a nitrate ion, A2 represents a divalent anion, a sulfate ion, a hydrogen phosphate ion, 1 represents an integer of 1 to 8, n represents 2, Represents 3 and 4. The aromatic carboxylic acids and aromatic diols that become acid ions in each metal salt may be the same or different. Further, a mixture of salts having different numbers of n may be used. As a substituent, an alkyl group, an alkenyl group, a carboxyl group, a hydroxyl group, or an acyloxy group is preferable as the substituent from the viewpoint of improving the dispersibility of the metal salt in the binder resin or improving the chargeability. In the general formula (12), n represents Four, general formula (13)
In this case, it is preferable that n is 2, excellent environmental stability is obtained, dispersibility in the binder resin is excellent, and excellent durability is obtained.

The organic zirconium compound of the present invention is obtained by dissolving a zirconium compound such as zirconium chloride chloride, zirconium sulfate, or organic acid zirconium in water, an alcohol, or an aqueous alcohol solution to obtain an aromatic carboxylic acid, an aromatic diol or an alkali metal salt thereof. Or an aromatic carboxylic acid, an aromatic diol and an alkali agent. These organic zirconium compounds are recrystallized with an alcohol aqueous solution or the like, and purified by washing with alcohol. In the case of a complex salt, a complex salt having various counter ions can be obtained by treating the product with a mineral acid, an alkali agent, or an amine agent. In the present invention, a zirconium complex salt having a plurality of counter ions such as hydrogen ions, alkali metal ions, and ammonium ions is also included.

Hereinafter, specific examples of the organic zirconium compound used in the present invention will be described. Although those which coordinate 2 to 4 water molecules are also included,
Here, the description of the water molecule is omitted. In addition, although the counter ions include those having a plurality of types, only the most common counter ions are described here.

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The method for incorporating the organic zirconium compound of the present invention into a toner includes a method of adding it inside the toner and a method of adding it externally. When added internally, the amount is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the binder resin. In the case of external addition, the amount is preferably 0.01 to 5 parts by weight, and particularly preferably mechanochemically fixed to the toner surface.

The compounds of the present invention can also be used in combination with known charge control agents as described in the prior art. For example, other organic metal complexes, metal salts, and chelate compounds include monoazo metal complexes, acetylacetone metal complexes, hydroxycarboxylic acid metal complexes, polycarboxylic acid metal complexes, and polyol metal complexes. Other examples include metal salts of carboxylic acids, carboxylic acid derivatives such as carboxylic acid anhydrides and esters, and condensates of aromatic compounds. Further, phenol derivatives such as bisphenols and calixarenes are also used.

Examples of the binder resin of the toner used in the present invention include vinyl resins, polyester resins, epoxy resins and the like. Among them, vinyl resins and polyester resins are more preferable in terms of chargeability and fixability.

Examples of the vinyl monomer include styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, etc. A styrene derivative;
Ethylene unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, propion Vinyl esters such as vinyl acrylate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and n-methacrylate
Octyl, dodecyl methacrylate, methacrylic acid (2
-Ethylhexyl), stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate,
Α-methylene aliphatic monocarboxylic acid esters such as diethylaminoethyl methacrylate; methyl acrylate,
Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic acid (2-ethylhexyl), stearyl acrylate, acrylic acid (2-chloroethyl), acrylic acid Acrylic esters such as phenyl; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole N-vinyl compounds such as N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide or methacrylic acid Conductor and the like. These vinyl monomers are used alone or as a mixture of two or more monomers.

Of these, a combination of monomers that results in a styrene-based copolymer and a styrene-acrylic copolymer is preferred.

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

Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene; examples of the diacrylate compound linked by an alkyl chain include:
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds Examples of the acrylate include methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate,
Tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and the above compounds in which the acrylate is replaced with methacrylate; including an aromatic group and an ether bond Examples of chain-linked diacrylate compounds include polyoxyethylene (2) -2,2
-Bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-
(Hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; polyester-type diacrylates include, for example, the trade name MANDA (Nippon Kayaku).

As the polyfunctional crosslinking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and those obtained by replacing the acrylate of the above compound with methacrylate; Triallyl cyanurate and triallyl trimellitate;

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

Among these crosslinkable monomers, those which are preferably used from the viewpoints of fixing property and anti-offset property to a binder resin include an aromatic divinyl compound (particularly divinylbenzene), a chain containing an aromatic group and an ether bond. Diacrylate compounds tied together.

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

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

The acid value of the vinyl resin is preferably from 1 to 1.
00 mg KOH / g, more preferably 3 to 70 mg KO
H / g is preferred. The glass transition temperature of the vinyl resin is preferably 45 to 80 ° C, more preferably 5 to 80 ° C.
5 to 70 ° C. and a number average molecular weight (Mn) of 2,500
~ 50,000, weight average molecular weight (Mw) of 10,000
It is preferably from 0 to 1,000,000.

As a method for synthesizing a binder resin comprising a vinyl polymer or a copolymer, polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. When a carboxylic acid monomer or an acid anhydride monomer is used, it is preferable to use a bulk polymerization method or a solution polymerization method due to the nature of the monomer.

As an example, the following method can be mentioned.
A vinyl copolymer can be obtained by a bulk polymerization method or a solution polymerization method using a monomer such as dicarboxylic acid, dicarboxylic anhydride or dicarboxylic acid monoester. In the solution polymerization method, a dicarboxylic acid or a dicarboxylic acid monoester unit can be partially dehydrated by devising the distillation conditions when the solvent is distilled off. Furthermore, the vinyl copolymer obtained by the bulk polymerization method or the solution polymerization method can be further dehydrated by heat treatment. The acid anhydride can also be partially esterified with a compound such as an alcohol.

Conversely, the vinyl copolymer thus obtained can be hydrolyzed to close the acid anhydride group to partially form a dicarboxylic acid.

On the other hand, using a dicarboxylic acid monoester monomer, a vinyl copolymer obtained by a suspension polymerization method or an emulsion polymerization method is dehydrated by heat treatment and ring opening by hydrolysis treatment to convert the dicarboxylic acid to a dicarboxylic acid. Can be obtained. By using a method of dissolving a vinyl copolymer obtained by a bulk polymerization method or a solution polymerization method in a monomer and then obtaining a vinyl polymer or a copolymer by a suspension polymerization method or an emulsion polymerization method, Part of the acid anhydride can be opened to obtain a dicarboxylic acid unit. At the time of polymerization, another resin may be mixed with the monomer, and the obtained resin can be esterified by acid treatment by heat treatment or by ring-opening alcohol treatment of the acid anhydride by treatment with weak alkaline water.

Since dicarboxylic acid and dicarboxylic anhydride monomers have strong alternating polymerizability, the following method is preferred for obtaining a vinyl copolymer in which functional groups such as anhydride and dicarboxylic acid are randomly dispersed. one of. This is a method in which a vinyl copolymer is obtained by a solution polymerization method using a dicarboxylic acid monoester monomer, and the vinyl copolymer is dissolved in the monomer to obtain a binder resin by a suspension polymerization method. In this method, the entire or dicarboxylic acid monoester moiety can be de-alcoholized and ring-closed and dehydrated depending on the processing conditions when the solvent is distilled off after the solution polymerization, and an acid anhydride can be obtained. At the time of suspension polymerization, the acid anhydride group is hydrolyzed and ring-opened to obtain a dicarboxylic acid.

In the acid anhydride formation of the polymer, the generation or disappearance of the acid anhydride can be confirmed because the infrared absorption of the carbonyl shifts to a higher wave number side than in the case of the acid or ester.

In the thus obtained binder resin, since the carboxyl group, anhydride group and dicarboxylic acid group are uniformly dispersed in the binder resin, it is possible to give the toner good chargeability.

As the binder resin, the following polyester resins are also preferable.

The polyester resin contained 45 to 55 of all components.
mol% is the alcohol component, 55 to 45 mol%
Is an acid component.

Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol represented by the formula (A) and derivatives thereof;

[0121]

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

Diols represented by the formula (B):

[0123]

Embedded image Examples include polyhydric alcohols such as glycerin, sorbit, and sorbitan.

Examples of the divalent carboxylic acid component containing 50 mol% or more of the total acid component include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; succinic acid, adipine Acid, sebacic acid, alkyldicarboxylic acids such as azelaic acid or anhydride thereof; and succinic acid or anhydride thereof further substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms; fumaric acid, maleic acid, citraconic acid,
Examples include unsaturated dicarboxylic acids such as itaconic acid and anhydrides thereof, and examples of the trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and anhydrides thereof.

The alcohol component of the polyester resin is particularly preferably a bisphenol derivative represented by the formula (A), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-dodecenyl succinic acid. Dicarboxylic acids such as acid or anhydride thereof, fumaric acid, maleic acid and maleic anhydride; and tricarboxylic acids of trimellitic acid or anhydride thereof. This is because a heat roller fixing toner using a polyester resin obtained from these acid component and alcohol component as a binder resin has good fixability and excellent offset resistance.

The acid value of the polyester resin is preferably 90
mgKOH / g or less, more preferably 50 mgKOH / g
g, and the OH value is preferably 50 mg KOH / g.
Or less, more preferably 30 mgKOH / g or less. This is because the environmental dependence of the charging characteristics of the toner increases as the number of terminal groups in the molecular chain increases.

The glass transition temperature of the polyester resin is preferably from 50 to 75 ° C., more preferably from 55 to 65 ° C., and the number average molecular weight (Mn) is preferably from 1,50.
0-50,000, more preferably 2,000-20,
000, and the weight average molecular weight (Mw) is preferably 6,000 to 100,000, more preferably 10,000.
It is preferably from 00 to 90,000.

[0128] As M ₁ is a composite oxide (A), magnesium, zinc, cobalt, manganese, strontium, calcium, cerium and the like. Examples of M ₂ include titanium and silica. In particular, strontium silicate [Sr], since the effects of the present invention can be further exhibited.
_a [Si] _{b Oc} and strontium titanate [Sr]
_a [Ti] _b O _c is preferred. More specifically, SrSi
O ₃ , Sr ₃ SiO ₅ , Sr ₂ SiO ₄ , SrSiO ₅ , Sr
₃ Si ₂ O ₇ and SrTiO ₃ , Sr ₂ TiO ₄ , Sr ₃ Ti ₂
O ₇ is mentioned, and among them, SrSiO ₃ and SrTiO ₃ are preferable.

The particles having a composite oxide used in the present invention are preferably produced by, for example, a sintering method, pulverized occasionally, and then subjected to air classification to use particles having a desired particle size distribution.

In the composite oxide of the present invention, 0.10 to 10 parts by weight, preferably 0.2 to 5.0 parts by weight of the fine particles having the composite oxide (A) is used based on 100 parts by weight of the toner particles.
It is good to use parts by weight. The particles containing the composite oxide have a weight average particle size of 0.1 to 5.0 μm, preferably 0.3 to 5.0 μm.
It is 3.0 μm, more preferably 0.5 to 2.5 μm.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co, Ni Or a metal such as Al, Co, Cu,
Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Alloys with metals such as d, Ca, Mn, Se, Ti, W, and V, and mixtures thereof, and the like.

Specifically, examples of the magnetic material include iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide ( Y ₃ Fe ₅
O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuFe)
₂ O ₄ ), lead iron oxide (PbFe ₁₂ —O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), and neodymium iron oxide (NdFe
₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like. The above-mentioned magnetic materials are used alone or in combination of two or more. Particularly preferred magnetic materials are fine powders of triiron tetroxide or gamma-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.05 to
At 2 μm, the magnetic properties at 795.8 kA / m applied are coercive force of 1.6 to 12.0 kA / m and saturation magnetization of 50 to 200 A
m ² / kg (preferably 50 to 100 Am ² / kg) and a remanent magnetization of ^{2 to 20} Am ² / kg are preferable.

The magnetic substance 1 was added to 100 parts by weight of the binder resin.
It is preferable to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

As the colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used. For example, as pigments, carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara,
Examples include phthalocyanine blue and indanthrene blue. These are used in an amount necessary to maintain the optical density of the fixed image, and are used in an amount of 0.1 to 100 parts by weight of the binder resin.
An addition amount of 20 parts by weight, preferably 0.2 to 10 parts by weight is good. A dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, and 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, per 100 parts by weight of the binder resin is good. .

In the present invention, if necessary, one or more release agents may be contained in the toner particles.

Examples of the release agent include aliphatic hydrocarbon waxes such as low molecular polyethylene, low molecular polypropylene, microcrystalline wax and paraffin wax; and aliphatic hydrocarbon wax oxides such as oxidized polyethylene wax; Or, a block copolymer thereof; waxes mainly containing a fatty acid ester such as carnauba wax, sasol wax and montanic acid ester wax; and a part or all of fatty acid esters such as deoxidized carnauba wax. And the like. In addition, palmitic acid, stearic acid,
Saturated fatty acids such as montanic acid or long-chain alkyl carboxylic acids having a longer-chain alkyl group; unsaturated fatty acids such as brandic acid, eleostearic acid, and vinaric acid; stearic alcohol, aralkyl alcohol, behenyl alcohol; Saturated alcohols such as carnaubavir alcohol, seryl alcohol, melisyl alcohol, or long-chain alkyl alcohols having a longer-chain alkyl group; polyhydric alcohols such as sorbitol; calcium stearate, calcium laurate, zinc stearate; Fatty acid metal salts such as magnesium stearate (commonly referred to as metal soaps); waxes obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid; And partial esters of fatty acids with polyhydric alcohols such as behenic acid monoglyceride, also, methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils.

The melting point of the release agent is preferably from 70 to 140.
° C, more preferably 80 to 135 ° C, and still more preferably 90 to 130 ° C. This is because if the melting point is too low, the toner has an adverse effect on the high-temperature offset resistance, and if it is too high, the toner has a bad effect on the low-temperature fixability.

The amount of the release agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the binder resin.

These release agents are usually added to the binder resin by dissolving the resin in a solvent, increasing the temperature of the resin solution, and adding and mixing while stirring, or by mixing at the time of kneading. it can.

[0141] Toner particles are used in terms of image density and resolution.
The weight average particle size is preferably 3 to 12 μm, and more preferably 3 to 9 μm.

A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner particles to increase the fluidity before and after the addition. For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet-process silica and dry-process silica, fine powder titanium oxide, fine powder alumina, a silane coupling agent thereof, Titanium coupling agents, treated silica surface-treated with silicone oil, and the like are available.

Preferred fluidity improvers are fine powders produced by vapor phase oxidation of silicon halides, and are so-called dry silica or fumed silica. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ + 4HC
l

In this production step, it is possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with the silicon halide. They are also included. The particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, fine silica powder in the range of 0.002 to 0.2 μm is used. .

Examples of commercially available fine silica powder produced by the vapor phase oxidation of silicon halides include those commercially available under the following trade names, for example.

AEROSIL (Nippon Aerosil) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N20 V15 WAC -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, a treated silica fine powder obtained by hydrophobizing silica fine powder generated by vapor-phase oxidation of the silicon halide compound is more preferable. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The hydrophobicity is given by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with the fine silica powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, Bromomethyldimethylchlorosilane,
α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, each having one to each of the terminal units. Examples include dimethylpolysiloxane containing a hydroxyl group bonded to Si. Further, a silicone oil such as dimethyl silicone oil may be used. These are used alone or as a mixture of two or more.

The fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 5 m ² / g or more.
Those with 0 m ² / g or more give good results. Toner 1
0.01 to 8 parts by weight of the fluidity improver based on 00 parts by weight,
Preferably, 0.1 to 4 parts by weight is used.

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

An example of an image forming apparatus that can carry out the image forming method of the present invention will be described with reference to FIGS. The surface of the electrostatic image carrier (photoconductor) 1 is charged to a negative or positive polarity by the primary charger 2 and an electrostatic image (for example, a digital latent image by image scanning) is formed by analog exposure or exposure 5 by laser light. And a magnetic blade 11 and a magnet 23 having magnetic poles N ₁ , N ₂ , S ₁ and S _2.
The electrostatic charge image is developed by the reversal development or the regular development with the magnetic toner 13 of the developing device 9 including the developing sleeve 4 including the developing sleeve 4. In the developing section, the conductive substrate 16 of the photoconductor 1
An alternating bias, a pulse bias, and / or a DC bias are applied by the bias applying unit 12 between the developing sleeve 4 and the developing sleeve 4. The magnetic toner image is transferred to a transfer material with or without an intermediate transfer member. When the transfer paper P is conveyed and arrives at the transfer section, the transfer charger 3 charges the transfer paper P with a positive or negative polarity from the back surface (the surface opposite to the photoreceptor side). The positive magnetic toner image or the positively charged magnetic toner image is electrostatically transferred onto the transfer paper P. After the charge is removed by the charge removing means 22, the transfer paper P separated from the photoreceptor 1 is heated and pressed and fixed on the toner image on the transfer paper P by the heating and pressing roller fixing device 7 including the heater 21.

The magnetic toner remaining on the photoreceptor 1 after the transfer step is removed by a cleaning means having a cleaning blade 8. After the cleaning, the photosensitive member 1 is neutralized by the erase exposure 6, and the process starting from the charging process by the primary charger 2 is repeated again.

Next, a method of measuring various physical property data measured in the following examples will be described below.

(1) Measurement of X-ray diffraction Apparatus used: X-ray diffractometer CN2013 [Rigaku Denki Co., Ltd.]: Powder sample molding machine PX-700 [manufactured by Thermonics Co., Ltd.]

The specimen to be measured is compression-pressed using the above molding apparatus. The molded sample is set on the X-ray diffractometer,
Measure under the following conditions. The structure is determined from the peak intensity and the 2θ angle of the obtained X-ray diffraction pattern. Target Filter Cu, Ni Voltage Current 32.5 kV, 15 mA Counter Se Time Constant 1 sec Divergence Slit 1 ° Receiving Slit 0.15 mm Scatter Slip 1 ° Angle 60 ° Angle 60 °

(2) Method for Quantifying Complex Oxide in Toner Apparatus used: X-ray fluorescence spectrometer 3080 (Rigaku Corporation): Sample press molding machine MAEKAWA Testing Machine (MFGCo., LTD)

Preparation of Calibration Curve A composite oxide for quantitative determination was mixed with the magnetic toner (X) at the following ratio (% by weight) using a coffee mill.
Make a sample for the calibration curve. 0%, 0.5%, 1.0
%, 2.0%, 3.0%, 5.0%, 10.0% The above seven samples are press-formed using a sample press-forming machine. The [M] Kα peak angle (a) in the composite oxide is determined from the 2θ table. The calibration curve sample is put into the fluorescent X-ray analyzer, and the sample chamber is evacuated and evacuated. The X-ray intensity of each sample is determined under the following conditions, and a calibration curve is created.

[Measurement Conditions] Measurement potential, voltage 50 kV-50 mA 2θ angle a Crystal plate LiF Measurement time 60 seconds

Quantitative Determination of Complex Oxide in Toner After forming a sample by the same method as described above, the X-ray intensity is determined under the same measurement conditions, and the amount added is calculated from the calibration curve.

(3) Measurement of Particle Size Distribution The particle size distribution can be measured by various methods. In the present invention, the measurement was carried out using a Coulter counter multisizer.

As a measuring device, a Coulter counter Multisizer II (manufactured by Coulter) was used, and an interface (manufactured by Nikkaki) for outputting the number distribution and volume distribution and a CX-1 personal computer (manufactured by Canon) were connected. As the electrolyte, a 1% NaCl aqueous solution is prepared using a special grade or primary grade sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and the measurement sample is further added to 2 to 20 ml.
Add mg. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and as an aperture, using the Coulter Counter Multisizer II,
The toner particle size is measured using a 100 μm aperture, and the inorganic fine powder particle size is measured using a 13 μm aperture. The volume and the number of the toner and the inorganic fine powder were measured, and the volume distribution and the number distribution were calculated. Then, the weight-based weight average diameter determined from the volume distribution is determined.

(4) Measurement of Acid Value in Vinyl Resin The qualitative and quantitative determination of the functional group in the binder resin was performed by infrared absorption spectrum, acid value measurement according to JIS K-0707, hydrolysis acid value measurement (total acid value measurement). Is applied as an example.

For example, in the case of infrared absorption, 1780 cm
The presence of an acid anhydride is confirmed because an absorption peak derived from the carbonyl of the anhydride near ^-1 appears.

In the present invention, the peak of the infrared absorption spectrum means a peak which is clearly recognized as a peak after 16 times of integration by FT-IR with a resolution of 4 cm ^-1 . F
As a model of T-IR, for example, FT-IR1600
(Manufactured by PerkinElmer).

Measurement of acid value according to JIS K-0070 (hereinafter referred to as J
IS acid value), the acid anhydride is about 50% of the theoretical value (the acid anhydride has an acid value as dicarboxylic acid).
% Is measured.

On the other hand, in the measurement of the total acid value (A), a value substantially as a theoretical value is measured. Therefore, the difference between the total acid value (A) and the JIS acid value is about 50% of the theoretical value, and the acid anhydride is measured as a dibasic acid. B) is required.

Total acid value (B) = [total acid value (A) −JIS acid value] × 2

Further, for example, when a maleic acid monoester is used as an acid component and a vinyl copolymer composition to be used as a binder resin is prepared by a solution polymerization method or a suspension polymerization method, a solution polymerization method is used. The total acid value (B) is measured by measuring the total acid value (A) of the JIS acid value of the produced vinyl copolymer, and the total acid value (B) and the vinyl used in the solution polymerization method are measured. The amount of acid anhydride generated in the polymerization step and the solvent removal step from the composition ratio of the system monomer (for example,
Mol%) is calculated. Further, the vinyl copolymer prepared by the solution polymerization method is dissolved in a monomer such as styrene and butyl acrylate to prepare a monomer composition, and the prepared monomer composition is subjected to suspension polymerization. At that time, a part of the acid anhydride group is opened. From the JIS acid value, total acid value (A), monomer composition ratio of the vinyl copolymer composition obtained by the suspension polymerization method and the added amount of the vinyl copolymer prepared by the solution polymerization method, binding is performed. The amount of dicarboxylic acid groups, acid anhydride groups, and dicarboxylic acid monoester groups in the vinyl copolymer composition used as the resin can be calculated.

The total acid value (A) of the binder resin is determined as follows. 30 g of dioxane in 2 ml of sample resin
And 10 ml of pyridine, 20 mg of dimethylaminopyridine and 3.5 ml of water are added thereto, and the mixture is refluxed for 4 hours while stirring. After cooling, 1 / 10N KOH
The acid value obtained by neutralization titration with a THF solution using phenolphthalein as an indicator is defined as the total acid value (A). Under the measurement conditions of the total acid value (A), the acid anhydride group is hydrolyzed to dicarboxylic acid, but the acrylate ester group, methacrylic ester group and dicarboxylic monoester group are not hydrolyzed.

The preparation of a 1 / 10N KOH / THF solution is performed as follows. 1.5 g of KOH is dissolved in about 3 ml of water, and 200 ml of THF and 30 ml of water are added thereto and stirred. If the solution has separated after standing, add a small amount of methanol,
If the solution is cloudy, add a small amount of water to make a uniform clear solution. The measured value of the KOH / THF solution is standardized with a 1 / 10N HCl standard solution.

The total acid value (A) of the binder resin is 2 to 100 m
gKOH / g, but the acid value of the vinyl copolymer containing an acid component in the binder resin is 10 according to JIS K-0070.
Preferably it is less than zero. When the acid value according to JIS K-0070 is 100 or more, the density of functional groups such as a carboxyl group and an acid anhydride group is high, and it is difficult to obtain a good charge balance. Problems tend to occur.

(5) Method of Measuring Acid Value of Polyester Resin The acid value is defined as the number of milligrams of potassium hydroxide required to neutralize the carboxyl group contained in 1 g of the resin. Therefore, the acid value indicates the number of terminal groups. The measuring method is as follows. Sample 2
10 to 10 g is weighed in a 200 to 300 ml Erlenmeyer flask, and a mixed solvent of methanol: toluene = 30: 70 (about 5: 5) is used.
Add 0 ml to dissolve the resin. If solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% bromthymol blue and phenol red, titration is performed with a previously standardized N / 10 potassium hydroxide-alcohol solution, and the acid value is determined from the consumption of the alcoholic potassium solution by the following calculation.

Acid value = KOH (ml number) × N × 56.1 /
Sample weight (N is a factor of N / 10KOH)

(6) Glass transition temperature Tg The Tg of the binder resin is measured using a differential thermal analyzer (DSC analyzer), DSC-7 (Perkin Elmer). The measurement sample is precisely weighed in an amount of 5 to 20 mg, preferably 10 mg.

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

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

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

(7) Measurement of toner charge amount (FIG. 3) After weighing the developer sampled from the developer carrying member of the developing device, a 500-mesh conductive material (which can be appropriately changed to a size that does not allow magnetic particles to pass) is provided at the bottom. A measurement sample is put in a metal measurement container 2 having a transparent screen 3 and a metal lid 4 is closed. At this time, the weight of the entire measurement container 2 is weighed and W1 (g)
And Next, in the suction device 1 (at least a portion in contact with the measurement container 2 is an insulator), the pressure of the vacuum gauge 5 is adjusted to 250 mmAq by adjusting the air volume control valve 6 by suctioning from the suction port 7. In this state, suction is sufficiently performed (about 2 minutes) to remove toner by suction. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor whose capacity is C
(ΜF). Further, the weight of the whole measurement container after suction is weighed to be W2 (g). This frictional charge amount T (mC / k
g) is calculated as follows:

T (mC / kg) = (C × V) / (W1-W2)

(8) Measurement of Viscoelastic Properties of Toner and Cleaning Blade) Measurement is performed using a viscoelasticity measuring device (rheometer) RDA-II (manufactured by Rheometrics). Measuring jig: parallel plate with diameter of 7.9 mm Measurement sample: toner heated and melted, diameter 8 mm, height 2
It is used by shaping into a disk-shaped sample of 5 to 5 mm. Fixing to a measuring jig is performed according to a conventional method.

The cleaning blade has a thickness of 1 to 5 mm
Punched out or cut out from a sheet-like sample having a diameter of about 8 mm. The fixing to the measuring jig is performed by using an instant adhesive or the like. Measurement frequency: 6.28 radians / second Measurement temperature: The temperature is raised from room temperature to 170 ° C. at a rate of 1 ° C. per minute.

(9) Melting point measurement of wax ASTM D3418-8 using a differential scanning calorimeter (DSC measuring apparatus) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min under normal temperature and normal humidity between 00 ° C.

In this heating process, an endothermic peak of a main peak in a temperature range of 30 to 200 ° C. is obtained.

(10) Measurement of DSC Curve of Toner In the same manner as the measurement of the melting point of the wax, the DSC curve in the process of raising the temperature of the toner is measured.

(11) Measurement of molecular weight distribution of wax Gel permeation chromatography (GPC) measuring apparatus: GPC150C (manufactured by Waters) Column: GMH-HT 30 cm 2 columns (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene ( (0.1% ionol added) Flow rate: 1.0 ml / min Sample: 0.45 ml of 0.15% sample injected The above conditions were measured, and the molecular weight of the sample was calculated by using a molecular weight calibration prepared using a monodisperse polystyrene standard sample. Use curves. Further, it is calculated by converting into polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula.

(12) Measurement of Molecular Weight Distribution of Binder Resin Raw Material or Binder Resin of Toner The molecular weight of a chromatogram by GPC is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was passed through the column at this temperature as a solvent at a flow rate of 1 ml per minute. When the sample is a binder resin material, a material obtained by passing the binder resin material through a roll mill (130 ° C., 15 minutes) is used. When the sample is a toner, 0.2 μm after dissolving the toner in THF
Filter with a filter and use the filtrate as a sample. The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight.
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. Examples of the standard polystyrene sample for preparing the calibration curve include, for example, Pressure Chemical Co. Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 10 ² ,
2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1
× 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 1
It is appropriate to use a sample of 0 ⁵ , 2 × 10 ⁶ and 4.48 × 10 ⁶ , and to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

In order to accurately measure a molecular weight region of 10 ³ to 2 × 10 ^6, a plurality of commercially available polystyrene gel columns may be used in combination.
μ-styragel 500, 10 ³ , 1
0 ⁴ 10 ⁵ of combinations and, shodex of Showa Denko Co., Ltd.
KA801,802,803,804,805,80
6,807 combinations are preferred.

[0193]

The present invention will be described below with reference to production examples and examples.

(Production Example 1 of Complex Oxide: Strontium Silicate) 1500 g of strontium carbonate and 600 g of silicon oxide
g was wet-mixed in a ball mill for 8 hours, filtered and dried, and the mixture was molded at a pressure of 5 kg / cm ^2.
Calcination was performed at 00 ° C. for 8 hours. This was mechanically pulverized to give a strontium silicate fine powder (M-
1) was obtained. Further, X obtained from (M-1)
Line diffraction was performed, and the composite oxide produced from the peak pattern of FIG. 6 was SrSiO ₃ (a = 1, b = 1, 1 in the formula (1)).
c = 3) and Sr ₂ SiO ₄ (a = 2, b =
1, c = 4).

(Production Example 2 of Composite Oxide: Strontium Titanate) 600 g of strontium carbonate and titanium oxide 3
20 g of the mixture was wet-mixed in a ball mill for 8 hours, followed by filtration and drying. The mixture was molded at a pressure of 5 kg / cm ² and calcined at 1100 ° C. for 8 hours. This is mechanically crushed,
A strontium titanate fine powder (M-2) having a weight average diameter of 1.7 μm was obtained.

(Production Example 3 of Composite Oxide: Cerium Oxide)
Combustion was performed at 1,300 ° C. for 10 hours in the presence of 1500 g of cerium carbonate and oxygen. This was mechanically pulverized to obtain cerium oxide fine powder (M-3) having a weight average diameter of 2.0 μm.

(Test blade) Blade A shown in Table 1
To K were prepared as blades for this study.

Viscoelastic data of blade B (data:
1) is attached as FIG.

[0199]

[Table 1]

[Production Example 1 of Toner] Binder resin (polyester resin) 100 parts by weight (Tg 60 ° C., acid value 20 mg KOH / g, hydroxyl value 30 mg KOH / g, molecular weight: Mn 3000, Mw 55000) Magnetic iron oxide 90 parts by weight (average particle diameter 0.15 [mu] m, the characteristics in 795.8 kA / m magnetic field Hc = 9.2kA / m, σs = 83Am 2 /kg,σr=11.5Am 2 / kg) · zirconium compound 14 2 parts by weight low Molecular weight polyethylene (release agent) 3 parts by weight (melting point 90 ° C)

After the above materials were mixed with a Henschel mixer, melt kneading was performed at 130 ° C. with a twin screw kneading extruder. After cooling the kneaded material, the mixture was coarsely pulverized by a cutter mill and finely pulverized using a jet stream. The particles were pulverized and classified using an air classifier to obtain magnetic toner particles (A) having a weight average diameter of 7.5 μm.

Hydrophobic silica (specific surface area: 200 m ² / g) was added to 100 parts by weight of the magnetic toner particles (a).
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed using a Henschel mixer, and the magnetic toner for evaluation (A
1).

[Toner Production Example 2] Binder resin (polyester resin) 100 parts by weight (Tg 60 ° C., acid value 20 mg KOH / g, hydroxyl value 30 mg KOH / g, molecular weight: Mn 3,000, Mw 55000) Magnetic iron oxide 90 parts by weight (average particle diameter 0.15 [mu] m, 795.8 kA / m characteristic at magnetic field Hc = 9.2kA / m, σs = 83Am 2 /kg,σr=11.5Am 2 / kg) · zirconium compound 15 2 parts by weight low Molecular weight polyethylene (release agent) 3 parts by weight (melting point 90 ° C)

A magnetic toner (a) having a weight average diameter of 7.6 μm was obtained in the same manner as in Toner Production Example 1 except that the zirconium compound in the toner material was changed.

Hydrophobic silica (specific surface area: 200 m ² / g) was added to 100 parts by weight of the magnetic toner particles (a).
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed by a Henschel mixer, and the magnetic toner for evaluation (a)
1).

[Toner Production Example 3] Binder resin (polyester resin) 100 parts by weight (Tg 72 ° C., acid value 13 mg KOH / g, hydroxyl value 23 mg KOH / g, molecular weight: Mn 7800, Mw 132000) Magnetic iron oxide 90 parts by weight (average particle diameter 0.15 [mu] m, the characteristics in 795.8 kA / m magnetic field Hc = 9.2kA / m, σs = 83Am 2 /kg,σr=11.5Am 2 / kg) · zirconium compound 14 2 parts by weight low Molecular weight polyethylene (release agent) 3 parts by weight (melting point 90 ° C)

A magnetic toner (C) having a weight average diameter of 7.6 μm was obtained in the same manner as in Production Example 1 of the toner except that the binder resin in the toner material was changed.

Hydrophobic silica (specific surface area: 200 m ² / g) was added to 100 parts by weight of the magnetic toner particles (c).
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed with a Henschel mixer, and the magnetic toner for evaluation (C)
1).

[Production Example 4 of Toner] Binder resin (polyester resin) 100 parts by weight (Tg 51 ° C., acid value 35 mg KOH / g, hydroxyl value 43 mg KOH / g, molecular weight: Mn 2300, Mw 49000) Magnetic iron oxide 90 parts by weight (average particle diameter 0.15 [mu] m, the characteristics in 795.8 kA / m magnetic field Hc = 9.2kA / m, σs = 83Am 2 /kg,σr=11.5Am 2 / kg) · zirconium compound 14 2 parts by weight low Molecular weight polyethylene (release agent) 3 parts by weight (melting point 90 ° C)

A magnetic toner (D) having a weight average diameter of 7.5 μm was obtained in the same manner as in Production Example 1 of the toner except that the binder resin in the toner material was changed.

Hydrophobic silica (specific surface area: 200 m ² / g) was added to 100 parts by weight of the magnetic toner particles (d).
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed with a Henschel mixer, and the magnetic toner for evaluation (A
1).

[Production Example 5 of Toner] Binder resin (vinyl resin) 100 parts by weight (Tg 62 ° C., acid value 17 mg KOH / g, molecular weight: Mn 37000, Mw 330 000) Magnetic iron oxide 90 parts by weight (average particle size) 0.15 [mu] m, 795.8 kA / m characteristic Hc = 9.2kA / m in a magnetic ^{field, σs = 83Am 2 /kg,σr=11.5Am 2 /} kg) · zirconium compound 14 2 parts by weight low molecular weight polyethylene (release 3 parts by weight (melting point 90 ° C)

A magnetic toner (e) having a weight average diameter of 7.3 μm was obtained in the same manner as in the above-mentioned toner production example 1 except that the binder resin in the toner material was changed.

Hydrophobic silica (specific surface area: 200 m ² / g) was added to 100 parts by weight of the magnetic toner particles (e).
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed with a Henschel mixer, and the magnetic toner for evaluation (e.g.
1).

[Production Example 6 of Toner] 100 parts by weight of binder resin (vinyl resin) (Tg 73 ° C., acid value 21 mg KOH / g, molecular weight: Mn 48000, Mw 370 000) 90 parts by weight of magnetic iron oxide (average particle diameter) 0.15 [mu] m, 795.8 kA / m characteristic Hc = 9.2kA / m in a magnetic ^{field, σs = 83Am 2 /kg,σr=11.5Am 2 /} kg) · zirconium compound 14 2 parts by weight low molecular weight polyethylene (release 3 parts by weight (melting point 90 ° C)

A magnetic toner (f) having a weight average diameter of 7.4 μm was obtained in the same manner as in Toner Production Example 1 except that the binder resin in the toner material was changed.

Hydrophobic silica (specific surface area: 200 m ² / g) was added to 100 parts by weight of the magnetic toner particles (f).
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed with a Henschel mixer, and the magnetic toner for evaluation (car
1).

[Production Example 7 of Toner] Binder resin (polyester resin) 100 parts by weight (Tg 60 ° C., acid value 20 mg KOH / g, hydroxyl value 30 mg KOH / g, molecular weight: Mn 3000, Mw 55000) Magnetic iron oxide 90 parts by weight (average particle diameter 0.15 [mu] m, the characteristics in 795.8 kA / m magnetic field Hc = 9.2kA / m, σs = 83Am 2 /kg,σr=11.5Am 2 / kg) · zirconium compound 14 2 parts by weight low Molecular weight polyethylene (release agent) 3 parts by weight (melting point 130 ° C)

A magnetic toner (g) having a weight average diameter of 7.4 μm was obtained in the same manner as in Toner Production Example 1 except that the binder resin in the toner material was changed.

Hydrophobic silica (specific surface area: 200 m ² / g) was added to 100 parts by weight of the magnetic toner particles (g).
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed with a Henschel mixer, and the magnetic toner for evaluation (Key
1).

[Production Example 8 of Toner] Binder resin (polyester resin) 100 parts by weight (Tg 60 ° C., acid value 20 mg KOH / g, hydroxyl value 30 mg KOH / g, molecular weight: Mn 3000, Mw 55000) Magnetic iron oxide 90 parts by weight (average particle diameter 0.15 [mu] m, 795.8 kA / m characteristic at magnetic field Hc = 9.2kA / m, σs = 83Am 2 /kg,σr=11.5Am 2 / kg) · zirconium compound 14 2 parts by weight of polypropylene (Release agent) 3 parts by weight (melting point 148 ° C)

A magnetic toner (h) having a weight average diameter of 7.4 μm was obtained in the same manner as in Toner Production Example 1 except that the binder resin in the toner material was changed.

Hydrophobic silica (specific surface area: 200 m ² / g) was added to 100 parts by weight of the magnetic toner particles (h).
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed with a Henschel mixer, and the magnetic toner (e.g.
1).

[Production Example 9 of Toner] Binder resin (polyester resin) 100 parts by weight (Tg 60 ° C., acid value 20 mg KOH / g, hydroxyl value 30 mg KOH / g, molecular weight: Mn 3000, Mw 55000) Magnetic iron oxide 90 parts by weight (average particle diameter 0.15 [mu] m, 795.8 kA / m characteristic at magnetic field Hc = 9.2kA / m, σs = 83Am 2 /kg,σr=11.5Am 2 / kg) · zirconium compound 14 2 parts by weight paraffin Wax (release agent) 3 parts by weight (melting point 75 ° C)

A magnetic toner (g) having a weight average diameter of 7.4 μm was obtained in the same manner as in Production Example 1 of the toner except that the binder resin in the toner material was changed.

Hydrophobic silica (specific surface area: 200 m ² / g) was added to 100 parts by weight of the magnetic toner particles (q).
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed with a Henschel mixer, and the magnetic toner for evaluation (case
1).

[Toner Production Example 10] Binder resin (polyester resin) 100 parts by weight (Tg 60 ° C., acid value 20 mg KOH / g, hydroxyl value 30 mg KOH / g, molecular weight: Mn 3000, Mw 55000) Magnetic iron oxide 90 parts by weight (average particle diameter 0.15 [mu] m, 795.8 kA / m characteristic at magnetic field Hc = 9.2kA / m, σs = 83Am 2 /kg,σr=11.5Am 2 / kg) · zirconium compound 14 2 parts by weight paraffin Wax (release agent) 3 parts by weight (melting point 66 ° C)

A magnetic toner (co) having a weight average diameter of 7.4 μm was obtained in the same manner as in Production Example 1 of the toner except that the binder resin in the toner material was changed.

Hydrophobic silica (specific surface area: 200 m ² / g) was added to 100 parts by weight of the magnetic toner particles (co).
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed with a Henschel mixer, and the magnetic toner for evaluation (Co
1).

[Toner Production Example 11] Weight average diameter 7.5
Using a magnetic toner (A) of μm, 1.0 part by weight of hydrophobic silica (specific surface area: 200 m ² / g) was externally mixed with 100 parts by weight of the magnetic toner particles (A) by a Henschel mixer. This was used as an evaluation magnetic toner (A-2).

[Toner Production Example 12] Weight average diameter 7.5
Using a magnetic toner (A) of μm, 1.0 part by weight of hydrophobic silica (specific surface area: 200 m ² / g) and a composite oxide (M-2) are used for 100 parts by weight of the magnetic toner particles (A).
3.0 parts by weight were externally added and mixed with a Henschel mixer to obtain a magnetic toner for evaluation (A-3).

[Toner Production Example 13] Weight average diameter 7.5
Using a magnetic toner (A) of μm, 1.0 part by weight of hydrophobic silica (specific surface area: 200 m ² / g) and a composite oxide (M-3) are used for 100 parts by weight of the magnetic toner particles (A).
3.0 parts by weight were externally added and mixed with a Henschel mixer to obtain a magnetic toner for evaluation (A-4).

[Comparative Toner Production Examples 1 to 4] The following compound 136 which is a zinc compound, an iron compound, an aluminum compound, and a chromium compound is used as the zirconium compound in the toner material.
Except having been changed to 139, a magnetic toner (t) having a weight average diameter of 7.6 μm
(T) was obtained.

The magnetic toner particles (T) to (T) 100
Hydrophobic silica (specific surface area: 200 m ² /
g) 3.0 parts by weight of the composite oxide (M-1) and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed by a Henschel mixer to obtain magnetic toners (T-1) to (T-1) for evaluation.

[0235]

Embedded image

(Measurement of Viscoelasticity of Toner) Magnetic Toner (A)
The viscoelasticity was measured with respect to (co) and (ta) to (te).

The results are shown in Table 2. The viscoelasticity measurement chart (data: 2) of (a) is attached as FIG.

[0238]

[Table 2]

<Evaluation-1> Canon copier NP608
5 Modified machine (removing the drum heater, adjusting development, drum, optics, paper transport system, etc. to increase copying speed by 12%) in a high-temperature and high-humidity room (temperature: 32.5 ° C, humidity: 8)
5%). At this time, B in Table 1 was brought into contact with the cleaning blade at a total pressure of 700 g against the drum.

Using the evaluation magnetic toner (A-1), continuous printing of 200,000 sheets was performed, and the image density, fog, image deletion and drum scraping amount were evaluated. As a result, from the initial stage of durability to the final 200,000 sheets, image density was high, stable, and image quality with high resolution without fog was obtained. Also, no image deletion occurred. Further, when the film thickness of the drum before and after the durability test was measured, the shaving amount was 9 mm. Detailed results are shown in Table 3.

The evaluation level of the image density was determined by the maximum image density during the endurance minus the image density at the end of 200,000 sheets.

The evaluation level of fog was judged by fog on a solid white image at the end of 200,000 sheets of endurance.

The fog measurement was performed by using a reflection measurement device R for fog measurement.
The reflectance of the solid white image and the unused paper is measured by EFLECTMETER (Tokyo Denshoku Co., Ltd.), and the difference between the two is regarded as fog. Unused paper reflectance-solid white reflectance = fogging% The evaluation level of image deletion was determined by measuring the area of an image missing portion.

The evaluation of the drum scraping amount was made based on the difference in film thickness (average of 10 points in the drum axis direction) between the pre-durability drum and the post-durability drum.

(Image Density Evaluation Level) A: Maximum Image Density-Image Density at End of Durability Less than 0.05 B: Maximum Image Density-Image Density at End of Durability 0.05 or More and Less Than 0.10 C: Maximum Image Density-Durability Finished image density 0.10 or more and less than 0.15 D: Maximum image density-Durable end image density 0.15 or more and less than 0.20 E: Maximum image density-Durable finished image density 0.20 or more and less than 0.30 F: Maximum image density-image density at the end of endurance 0.30 or more

(Fog evaluation level) A: Fog less than 0.1% B: Fog 0.1 or more and less than 0.5% C: Fog 0.5 or more and less than 1.0% D: Fog 1.0 or more and 1.5 % F: fog 1.5 or more and less than 2.0% F: fog 2.0% or more

[0247] (image deletion valuation) A: spot image area 0 cm ² B: less loss greater than the image area 0 cm ² 0.25 cm ² C: less than spot image area 0.25 or 2.0 cm ² D: spot image area 2 0.0 to less than 6.0 cm ² E: missing image area 6.0 to less than 10.0 cm ² F: missing image area 10.0 cm ² or more

(Drum abrasion amount evaluation level) A: Abrasion amount 0 to less than 10.0 ° B: Abrasion amount 10.0 to less than 25.0 ° C: Abrasion amount 25.0 to less than 50.0 ° D: Abrasion amount 50. 0 to less than 100.0 ° E: Shaved amount 100.0 to less than 150.0 ° F: Shaved amount 150.0 ° or more

<Evaluation-2 to 6> The same evaluation as Evaluation-1 was performed by changing the cleaning blade to C, D, F, G, H. The image density was high, stable, and a high-resolution image without fog was obtained. Further, the image deletion was at a level without any problem. Detailed results are shown in Table 3.

<Evaluation-7 to 11: Comparative Example> The same evaluation as Evaluation-1 was performed by changing the cleaning blade to A, E, I, J, and K. Image density is high and stable,
Image quality with high resolution was obtained at a level without fog. Furthermore, the image deletion was at a level without any problem.
For E, I, and K, cleaning failure occurred during the durability test, and for J, the drum fusion occurred during the durability test.
Detailed results are shown in Table 3.

<Evaluation-12 to 14> The same evaluation as Evaluation-1 was performed by changing the magnetic toner for evaluation to (A-2), (A-3) and (A-4). The image density was high and stable, and image quality with high resolution was obtained at a level at which fog was not a problem. Further, the image deletion was at a level without any problem.
Detailed results are shown in Table 3.

<Evaluation-15-18> The same evaluation as Evaluation-1 except that the magnetic toner for evaluation was changed to (A-1), (E-1), (C-1) and (K-1). Was done. The image density was high and stable, and image quality with high resolution was obtained at a level at which fog was not a problem. Further, the image deletion was at a level without any problem. Detailed results are shown in Table 3.

<Evaluations -19 to 23: Comparative Examples> The magnetic toners for evaluation were (C-1), (D-1), (F-1),
The same evaluation as Evaluation-1 was performed, changing to 1) and (Co-1). The image density and fogging were at a level without any problem, but (c-1), (ka-1) and (g-1) had a large amount of drum scraping, and streaks occurred in a halftone image. As for (D-1), drum fusion occurred during the durability. Detailed results are shown in Table 3.

<Evaluation-24 to 27: Comparative Example> The magnetic toners for evaluation were (T-1), (H-1), (T-1), and (T-1).
The evaluation was performed in the same manner as in Evaluation-1 except that the evaluation was changed to 1). Although there was no problem with respect to image deletion and drum abrasion, the image density decreased in the latter half of the durability test, and fog was worse. Detailed results are shown in Table 3.

<Evaluation-28> The following evaluations were carried out for the purpose of confirming that the toner is liable to be excessively charged, fog under a low humidity, a decrease in image density due to charge-up, a cleaning failure due to mismatching with a blade, and the like.

A modified copy machine NP6085 manufactured by Canon Inc. (removed the drum heater and adjusted all the development, drum, optics, paper transport system, etc. to increase the copy speed by 12%) in a room temperature and low humidity chamber (temperature: 23 ° C.) , Humidity: 5%).

At this time, B in Table 1 was brought into contact with the cleaning blade against the drum at a total pressure of 350 g.

Using the magnetic toner for evaluation (A-1), continuous printing of 200,000 sheets was performed, and the image density, fog and drum scraping amount were evaluated. The result is 20
Up to 10,000 sheets, the image density was high, stable, and high-definition image quality without fog was obtained. Further, when the film thickness of the drum before and after the durability test was measured, the shaving amount was 18 °. Detailed results are shown in Table 4.

<Evaluation -29 to 33> The same evaluation as Evaluation -28 was performed by changing the cleaning blade to C, D, F, G, and H. The image density was high, stable, and a high-resolution image without fog was obtained. Furthermore, drum scraping was at a level without any problem. Detailed results are shown in Table 4.

<Evaluation-34 to 38: Comparative Example> The cleaning blade was changed to A, E, I, J, and K, and evaluation-2.
The same evaluation as in Example 8 was performed. The image density was high and stable, and image quality with high resolution was obtained at a level at which fog was not a problem. For A, E, I, and K, cleaning failure occurred during the course of durability, and for J, an image defect occurred due to drum scraping during the course of durability. Detailed results are shown in Table 4.

<Evaluations -39 to 42> Evaluations similar to Evaluation -28 were made by changing the magnetic toners for evaluation to (A-1), (E-1), (C-1), and (K-1). Was done. The image density was high and stable, and image quality with high resolution was obtained at a level at which fog was not a problem. Furthermore, drum scraping was at a level without any problem. Detailed results are shown in Table 4.

<Evaluation-43 to 47: Comparative Example> The magnetic toners for evaluation were (C-1), (D-1), (F-1),
The same evaluation as in Evaluation -28 was performed, changing to 1) and (Co-1). The image density and fogging were at a level without any problem, but (c-1), (ka-1), and (g-1) had a large amount of drum scraping and caused streaks in a halftone image. Regarding (D-1), cleaning failure occurred during the durability. Detailed results are shown in Table 4.

<Evaluations -48 to 51: Comparative Examples> The magnetic toners for evaluation were (T-1), (H-1), (T-1) and (T-1).
The same evaluation as the evaluation -28 was performed, changing to 1). Although there was no problem with respect to image deletion and drum abrasion, the image density decreased in the latter half of the durability test, and fog was worse. Detailed results are shown in Table 4.

<Evaluation-52> The following evaluation was carried out to confirm the effect of the wax on the fixing area.

The fixing unit of the Canon NP6085 copier is removed, and an external drive and temperature controller are installed.

An unfixed image was formed using a magnetic toner (A-1) for evaluation using a Canon copier NP6085, and a fixing test was performed by changing the fixing temperature of the above fixing device. As a result, the lower limit temperature on the low temperature side was 130 ° C., and the upper limit temperature on the high temperature side was 230 ° C., confirming that the fixing region was wide. Detailed results are shown in Table 5.

The size of the fixing area was determined based on the following criteria.

(Fixing Area Evaluation Level) A: Higher temperature offset upper limit temperature-lower temperature fixing lower limit temperature 100 ° C. or more B: Higher temperature offset upper limit temperature—lower temperature fixing lower limit temperature 90 or more and less than 100 ° C. C: Higher temperature offset upper limit temperature -Lower temperature fixing lower limit temperature 80 or more and less than 90 ° C D: Higher temperature offset upper limit temperature -Lower temperature fixing lower limit temperature 70 or more and less than 80 ° C E: Higher temperature offset upper limit temperature-Low temperature fixing lower limit temperature 60 or more and less than 70 ° C F: High temperature Side offset upper limit temperature-Low temperature side fixing lower limit temperature 60 ° C or higher

<Evaluation-53 to 56> Evaluations similar to Evaluation-52 were made by changing the magnetic toners for evaluation to (G-1), (C-1), (G-1) and (K-1) Was done. Detailed results are shown in Table 5.

[0270]

[Table 3]

[0271]

[Table 4]

[0272]

[Table 5]

(Visco-elastic properties of toner and blade)
Table 6 shows the viscoelastic properties of the toner (A) and the blade used in this study.

[0274]

[Table 6]

[0275]

According to the present invention, since the toner and the cleaning blade used as described above have been improved, they have high chargeability even under high temperature and high humidity, and can obtain high image quality and high image density. Further, it is possible to provide an image forming method and an image forming apparatus that do not cause cleaning failure, toner fusion, and image deletion.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram illustrating an example of an image forming apparatus that can execute an image forming method of the present invention.

FIG. 2 is an enlarged view of a developing unit of the image forming apparatus shown in FIG.

FIG. 3 is a schematic diagram of an apparatus for measuring a triboelectric charge amount of a toner and an external additive.

FIG. 4 is a graph showing viscoelastic data of blade B.

FIG. 5 is a graph showing viscoelasticity data of the toner (A).

FIG. 6 is a graph showing an X-ray diffraction peak pattern of the composite oxide of Production Example 1.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Suction machine 2 Measurement container 3 Screen 4 Lid 5 Vacuum gauge 6 Air flow control valve 7 Suction port 8 Condenser 9 Electrometer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Tadashi Michigami, Canon Incorporated, 3-30-2 Shimomaruko, Ota-ku, Tokyo (72) Inventor Satoshi Matsunaga 3-30-2, Shimomaruko, Ota-ku, Tokyo Canon Inside the corporation

Claims (46)

[Claims] An electrostatic image formed on an electrostatic image carrier is developed using toner to form a toner image, and the formed toner image is transferred from the electrostatic image carrier to an intermediate transfer member. An image forming method comprising the steps of: transferring to a transfer material with or without intermediary, and cleaning the transfer residual toner on the electrostatic image carrier using a cleaning blade, wherein the toner comprises at least a binder resin, a colorant, A toner having toner particles containing an organic zirconium compound and inorganic fine powder, a) a temperature (TT.C) at which the storage elastic modulus (G′T) and the loss elastic modulus (G ″ T) of the toner are equal. ) But temperature 5
B) a temperature (TT.P) at which the loss tangent (tan δTP) of the toner becomes a maximum exists at a temperature of 50 to 75 ° C, and c) a temperature at a temperature of 40 to 80 ° C. The storage elastic modulus (G′B) of the cleaning blade is 5 × 10 ^{5 to} 1 × 10 ⁷
D) The loss elastic modulus (G ″ B) of the cleaning blade at a temperature of 40 to 80 ° C. is 5 × 10 ^{3 to} 1 × 10 ^6.
E) The loss tangent of the cleaning blade (tan δB.
P) is a minimum temperature (TT.B) at a temperature of 40 to 8
0) f) Loss tangent (tan δB.
P) reaches a maximum (TB.P) at a temperature of 70 to 1
G) a temperature (TT.P) at which the loss tangent (tan δTP) of the toner is maximum, and a temperature (TB) at which the loss tangent (tan δBP) of the cleaning blade is maximum. .P)
(TT.P-TB.P) from -40 to 20 ° C. h) Loss modulus (G ″ T) of the toner at temperature (TT.C) and temperature (TT.C) (G "T) with the loss elastic modulus (G" BC) of the cleaning blade at
/ (G ″ BC) is 5 × 10 ^{2 to} 5 × 10 ⁴ . 2. A zirconium complex compound in which the organic zirconium compound coordinates an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid as a ligand, or an aromatic carboxylate ion as an acid ion 2. The image forming method according to claim 1, wherein the zirconium carboxylate has an aromatic hydroxycarboxylate ion or an aromatic polycarboxylate ion. 3. The image forming method according to claim 1, wherein the inorganic fine powder has a composite oxide (A) particle represented by the following formula (1). [M ₁ ] _a [M ₂ ] _b O _c (1) (wherein, M ₁ represents a metal element selected from the group consisting of Sr, Mg, Zn, Co, Mn, Ca and Ce, and M ₂ represents A metal element selected from Ti or Si is shown, a represents an integer of 1 to 9, b represents an integer of 1 to 9, and c represents an integer of 3 to 9.) 4. The image forming method according to claim 3, wherein 0.10 to 10 parts by weight of the composite oxide (A) is externally added to 100 parts by weight of the toner particles. 5. The image forming method according to claim 3, wherein 0.20 to 5 parts by weight of the composite oxide (A) particles is externally added to 100 parts by weight of the toner particles. 6. The image forming method according to claim 3, wherein (M ₁ ) is Sr. 7. The image forming method according to claim 3, wherein (M ₂ ) is Ti. 8. The composite oxide (A) is strontium titanate (SrTiO ₃ ).
6. The image forming method according to any one of claims 1 to 5. 9. The image forming method according to claim 3, wherein (M ₂ ) is Si. 10. The image forming method according to claim 9, wherein the composite oxide (A) is strontium silicate (SrSiO ₃ ). 11. The composite oxide (A) particles are produced by a sintering method.
0. The image forming method according to any one of 0. 12. The composite oxide (A) particles have a weight average diameter of 0.1 to 5.0 μm.
12. The image forming method according to any one of claims 1 to 11. 13. The composite oxide (A) particles have a weight average diameter of 0.3 to 3.0 μm.
12. The image forming method according to any one of claims 1 to 11. 14. The composite oxide (A) particles have a weight average diameter of 0.5 to 2.5 μm.
12. The image forming method according to any one of claims 1 to 11. 15. The image forming method according to claim 1, wherein the toner particles contain a wax. 16. The wax is a differential scanning calorimeter (DS).
The melting point defined by the endothermic peak temperature at the time of temperature rise measured in C) is 70 to 140 ° C.
6. The image forming method according to 5. 17. The method according to claim 17, wherein the wax is a differential scanning calorimeter (DS).
The melting point defined by the endothermic peak temperature at the time of temperature rise measured in C) is 80 to 135 ° C.
6. The image forming method according to 5. 18. The method according to claim 18, wherein the wax is a differential scanning calorimeter (DS).
The melting point defined by the endothermic peak temperature at the time of temperature rise measured in C) is 90 to 130 ° C.
6. The image forming method according to 5. 19. The image forming method according to claim 1, wherein the colorant is a magnetic material. 20. The image forming method according to claim 1, wherein the toner particles have a larger weight average diameter than the composite oxide (A) particles. 21. The toner particles have a weight average diameter of 3 to 12.
The image forming method according to claim 20, wherein the thickness is μm. 22. The toner particles have a weight average diameter of 3 to 9 μm.
21. The image forming method according to claim 20, wherein m is m. 23. A cleaning blade comprising: a) a temperature of 40 to 80 ° C. and a storage elastic modulus (G′B) of 1;
× 10 ^{6 to} 5 × 10 ⁶ Pa; b) At a temperature of 40 to 80 ° C., a loss elastic modulus (G ″ B) of 1
The image forming method according to claim 1, wherein the pressure is from 10 ^{4 to} 5 × 10 ⁵ Pa. 24. Developing means for developing an electrostatic image formed on an electrostatic image carrier using toner to form a toner image, and intermediately transferring the formed toner image from the electrostatic image carrier. An image forming apparatus including at least a transfer unit for transferring to a transfer material with or without a body, and a cleaning unit for cleaning a transfer residual toner on the electrostatic image carrier using a cleaning blade; The toner has toner particles containing at least a binder resin, a colorant, and an organic zirconium compound, and inorganic fine powder. A) Storage elastic modulus (G′T) and loss elastic modulus (G ″) of the toner T) is equal to the temperature 5 (TT.C).
B) a temperature (TT.P) at which the loss tangent (tan δTP) of the toner becomes a maximum exists at a temperature of 50 to 75 ° C, and c) a temperature at a temperature of 40 to 80 ° C. The storage elastic modulus (G′B) of the cleaning blade is 5 × 10 ^{5 to} 1 × 10 ⁷
D) The loss elastic modulus (G ″ B) of the cleaning blade at a temperature of 40 to 80 ° C. is 5 × 10 ^{3 to} 1 × 10 ^6.
E) The loss tangent of the cleaning blade (tan δB.
P) is a minimum temperature (TT.B) at a temperature of 40 to 8
0) f) Loss tangent (tan δB.
P) reaches a maximum (TB.P) at a temperature of 70 to 1
G) a temperature (TT.P) at which the loss tangent (tan δTP) of the toner is maximum, and a temperature (TB) at which the loss tangent (tan δBP) of the cleaning blade is maximum. .P)
(TT.P-TB.P) from -40 to 20 ° C. h) Loss modulus (G ″ T) of the toner at temperature (TT.C) and temperature (TT.C) (G "T) with the loss elastic modulus (G" BC) of the cleaning blade at
/ (G ″ BC) is 5 × 10 ^{2 to} 5 × 10 ⁴ . 25. A zirconium complex compound in which the organic zirconium compound coordinates an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid as a ligand, or an aromatic carboxylate ion as an acid ion 25. The image forming apparatus according to claim 24, wherein the image forming apparatus is a zirconium carboxylate having an aromatic hydroxycarboxylic acid ion or an aromatic polycarboxylic acid ion. 26. The image forming apparatus according to claim 24, wherein the inorganic fine powder has a composite oxide (A) particle represented by the following formula (1). [M ₁ ] _a [M ₂ ] _b O _c (1) (wherein, M ₁ represents a metal element selected from the group consisting of Sr, Mg, Zn, Co, Mn, Ca and Ce, and M ₂ represents A metal element selected from Ti or Si is shown, a represents an integer of 1 to 9, b represents an integer of 1 to 9, and c represents an integer of 3 to 9.) 27. The image forming apparatus according to claim 26, wherein 0.10 to 10 parts by weight of the composite oxide (A) particles is externally added to 100 parts by weight of the toner particles. 28. The image forming apparatus according to claim 26, wherein 0.20 to 5 parts by weight of composite oxide (A) particles is externally added to 100 parts by weight of the toner particles. 29. The image forming apparatus according to claim 26, wherein (M ₁ ) is Sr. 30. The image forming apparatus according to claim 26, wherein (M ₂ ) is Ti. 31. The image forming apparatus according to claim 26, wherein the composite oxide (A) is strontium titanate (SrTiO ₃ ). 32. The image forming apparatus according to claim 26, wherein (M ₂ ) is Si. 33. The composite oxide (A) is strontium silicate (SrSiO ₃ ).
An image forming apparatus according to claim 1. 34. The image forming apparatus according to claim 26, wherein the composite oxide (A) particles are produced by a sintering method. 35. The composite oxide (A) particles have a weight average diameter of 0.1 to 5.0 μm.
An image forming apparatus according to any one of claims 6 to 34. 36. The composite oxide (A) particles have a weight average diameter of 0.3 to 3.0 μm.
An image forming apparatus according to any one of claims 6 to 34. 37. The composite oxide (A) particles have a weight average diameter of 0.5 to 2.5 μm.
An image forming apparatus according to any one of claims 6 to 34. 38. The image forming apparatus according to claim 24, wherein the toner particles contain wax. 39. The method according to claim 39, wherein the wax is a differential scanning calorimeter (DS).
The melting point defined by the endothermic peak temperature at the time of temperature rise measured in C) is 70 to 140 ° C.
9. The image forming apparatus according to 8. 40. A method in which the wax is a differential scanning calorimeter (DS).
The melting point defined by the endothermic peak temperature at the time of temperature rise measured in C) is 80 to 135 ° C.
9. The image forming apparatus according to 8. 41. The method according to claim 41, wherein the wax is a differential scanning calorimeter (DS).
The melting point defined by the endothermic peak temperature at the time of temperature rise measured in C) is 90 to 130 ° C.
9. The image forming apparatus according to 8. 42. The image forming apparatus according to claim 24, wherein the colorant is a magnetic material. 43. The image forming apparatus according to claim 24, wherein the toner particles have a larger weight average diameter than the composite oxide (A) particles. 44. The toner particles have a weight average diameter of 3 to 12.
44. The image forming apparatus according to claim 43, wherein the thickness is μm. 45. The toner particles have a weight average diameter of 3 to 9 μm.
The image forming apparatus according to claim 43, wherein m is m. 46. A cleaning blade comprising: a) a temperature of 40 to 80 ° C. and a storage elastic modulus (G′B) of 1;
× 10 ^{6 to} 5 × 10 ⁶ Pa; b) At a temperature of 40 to 80 ° C., a loss elastic modulus (G ″ B) of 1
The image forming apparatus according to any one of claims 24 to 45, wherein the pressure is from 10 ^{4 to} 5 10 ⁵ Pa.