JP3308753B2 - Full-color image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic recording,
The present invention relates to a full-color image forming method for developing a full-color image by developing an electrostatic image in electrostatic printing or the like.

[0002]

2. Description of the Related Art In recent years, demands for higher definition and higher image quality of electrophotography have been increasing in the market, and in the technical field, attempts have been made to achieve high image quality and full color. In the case of full-color electrophotography, an image is formed by superimposing toners of three to four colors. However, if the toners of the respective colors are not developed in the same manner, color reproduction is poor or color unevenness occurs. . However, these colorings are performed by pigments and dyes, and these have a great influence on development. In a full-color image, the fixing property, color mixing property, and offset resistance at the time of fixing are important, and a binder resin suitable for the performance is selected. However, the effect on the developability of the binder resin is great. One of the effects is the influence of temperature and humidity on the charge amount, and there is an urgent need to develop a color toner having a stable charge amount even in a wide range of environments.

On the other hand, as a means for solving these problems, there is a method of adding various external additives to a toner. In particular, for the purpose of improving various image characteristics such as resolution, uniformity of density, fog, etc., it is widely used to add various fine powders in order to improve the chargeability and fluidity of the toner. I have.

[0004] Among the inorganic fine powders added for improving various toner properties, inorganic fine powders surface-treated with silicone oil, silicone varnish, and silane compounds are preferably used. Examples of inorganic fine powders treated with polysiloxanes are disclosed in
JP-A-9-200252, JP-A-61-277964, JP-A-1-114857, JP-A-2-10
9058, JP-A-2-197851, JP-A-3-130779, JP-A-4-204748, JP-A-5-34984, JP-A-5-289
391 publication. In these proposals, although the electrophotographic properties are certainly improved, the uniformity of the hydrophobicity is insufficient, and under high humidity, a sufficient amount of triboelectric charge cannot be obtained, so that the image density decreases and fog occurs. There was something.
In addition, sufficient release properties of the toner from the drum cannot be obtained, resulting in insufficient transferability, which may cause a decrease in transfer efficiency or omission during transfer, and there is no solution to achieve both. Was. Further, when applied to a full-color toner, it was not particularly strictly satisfactory.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a full-color image forming method which solves the above-mentioned problems.

That is, an object of the present invention is to provide a full-color image forming method capable of obtaining sufficient developability even under high humidity.

Another object of the present invention is to provide a full-color image forming method which is hardly affected by humidity and maintains sufficient developability even when left for a long time.

It is a further object of the present invention to provide a full-color image forming method which imparts releasability to toner, enhances transfer efficiency, and facilitates formation of beautiful pictorial full-color images.

Another object of the present invention is to provide a full-color image forming method which does not cause omission during transfer in a line image portion.

Another object of the present invention is to provide a full-color image forming method capable of obtaining good developability in a one-component developing method.

[0011]

SUMMARY OF THE INVENTION The present invention provides a full-color image in which a toner image formed on a latent image holding member is transferred onto a recording material, and the toner image on the recording material is fixed to form a full-color image. In the forming method, the full-color image forming method includes: (A) (i) forming a first toner image on a latent image holding member with a toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner; ,
Transferring the first toner image on the latent image carrier to a recording material on a transfer drum; (ii) toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner on the latent image carrier To form a second toner image and transfer the second toner image on the latent image holding member to a recording material on a transfer drum; (iii) cyan toner, magenta toner, yellow toner and Forming a third toner image with a toner selected from the group consisting of black toner, and transferring the third toner image on the latent image carrier to a recording material on a transfer drum; (iv) on the latent image carrier And a toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner.
Forming a toner image, and transferring the fourth toner image on the latent image holding member to a recording material on a transfer drum; fixing a plurality of toner images on the recording material to form a full-color image; B) (i) forming a first toner image on the latent image holding member using a toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner;
Transferring the first toner image on the latent image holding member to an intermediate transfer member;
(Ii) forming a second toner image on the latent image carrier with a toner selected from the group consisting of cyan toner, magenta toner, yellow toner and black toner, and forming the second toner image on the latent image carrier; Transferring to an intermediate transfer member;
(Iii) forming a third toner image on the latent image carrier with a toner selected from the group consisting of cyan toner, magenta toner, yellow toner and black toner, and forming the third toner image on the latent image carrier; Transferring to an intermediate transfer member;
(Iv) forming a fourth toner image on the latent image holding member with a toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner, and forming the fourth toner image on the latent image holding member; Transferring to an intermediate transfer member; transferring the first, second, third and fourth toner images on the intermediate transfer member to a recording material, and fixing a plurality of toner images on the recording material to form a full-color image; (C) (i) forming a first toner image on the latent image holding member with a toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner;
(Ii) forming a second toner image on the latent image holding member using a toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner;
(Iii) forming a third toner image on the latent image holding member using a toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner;
(Iv) forming a fourth toner image on the latent image carrier with a toner selected from the group consisting of cyan toner, magenta toner, yellow toner and black toner, and recording a plurality of toner images on the latent image carrier; (D) (i) a cyan toner, a magenta toner, and a yellow toner on the first latent image holding member by transferring to a recording material and fixing a plurality of toner images on the recording material to form a full-color image; A first toner image is formed with a toner selected from the group consisting of a black toner and a black toner, and the first toner image is transferred to a recording material.
Forming a second toner image on the latent image holding member with a toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner, transferring the second toner image to a recording material, and (iii) A) forming a third toner image on a third latent image holding member using a toner selected from the group consisting of cyan toner, magenta toner, yellow toner and black toner, and transferring the third toner image to a recording material; (Iv) cyan toner on the fourth latent image holding member,
A fourth toner image is formed with a toner selected from the group consisting of magenta toner, yellow toner, and black toner, the fourth toner image is transferred to a recording material, and a plurality of toner images on the recording material are fixed. A fixing step of forming a full-color image, wherein each color toner has toner particles having at least a binder resin and a colorant, and inorganic fine powder, and the inorganic fine powder has a part or all of hydrogen atoms. Is treated with a polysiloxane having an alkyl group or an aryl group as a substituent, which may be substituted with a fluorine atom, and a hydrogen polysiloxane having a methyl group and hydrogen,
In a full-color image forming method comprising alumina or titania in which the processing ratio of the polysiloxane to the hydrogen polysiloxane is 1: 4 to 4: 1, excellent developability and transferability can be obtained.

[0012]

The configuration of the present invention will be described in detail below.

The present invention provides an inorganic fine powder by treating an inorganic fine powder with a polysiloxane in which a hydrogen atom is partially or entirely substituted by a fluorine atom and having an alkyl group or an aryl group as a substituent. Treating inorganic fine powder with hydrogen polysiloxane having alkyl group, aryl group and hydrogen as a substituent, which gives mold releasability and lubricity and some or all of hydrogen atoms may be replaced by fluorine atoms Thereby, hydrophobicity and charge stability can be imparted to the inorganic fine powder, and the toner containing the treated inorganic fine powder can obtain excellent transferability and developability.

In the present invention, an alkyl group, in which a part or all of hydrogen atoms may be substituted by fluorine atoms,
The polysiloxane having an aryl group as a substituent means an alkyl group or an aryl group (partially another group) in which a substituent on silicon in a siloxane chain may have some or all of hydrogen atoms replaced with fluorine atoms. May have a substituent)
The term "polysiloxane" refers to an alkyl group, an aryl group, or another substituent in which the substituent on the terminal silicon may be partially or entirely hydrogen atom substituted with a fluorine atom. Among these substituents, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.

As the polysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane and dimethylpolysiloxane are preferred, and dimethylpolysiloxane is particularly preferred. Further, these polysiloxanes may have a cyclic structure or a branched structure. For example, polysiloxane represented by the following general formula 1 can be mentioned. A specific example is a polysiloxane represented by Formula 2.

[0017]

Embedded image

[In the formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R
₅ , R ₆ , R ₇ , and R ₈ each represent an alkyl group or an aryl group in which part or all of the hydrogen atoms may be substituted with fluorine atoms, and may be the same or different; The moiety may have another optional substituent. j is the sum of siloxy units satisfying the condition of the unit of j and represents an integer of 1 or more. In the formula 2, a part of the methyl group may have an arbitrary substituent. k is a sum of siloxy units satisfying the condition of the unit of k, and represents an integer of 1 or more. ]

These polysiloxanes are adsorbed on the surface of the inorganic fine powder, and depending on the conditions, some of the Si—O bonds may react with OH groups or other functional groups on the inorganic fine powder,
Part of the i-O-Si bond is oriented to the inorganic fine powder surface side,
The alkyl group and the aryl group are oriented toward the outside of the inorganic fine powder, and the hydrophobic treatment is performed. However, the necessary hydrophobicity cannot be obtained unless a sufficient baking treatment or the like is performed. Depending on the inorganic fine powder, the hydrophobicity is performed to some extent, but may not be sufficient. On the other hand, since two substituents and two siloxane bonds on silicon can be oriented, a lubricating effect and a releasing effect as polysiloxane can be exhibited. The toner containing the inorganic fine powder treated with such a polysiloxane is provided with a releasing property and a lubricating property, and can have a transfer property, a cleaning property and a non-staining property.
Since polysiloxane alone is insufficient in hydrophobization, charge leakage is large, sufficient chargeability cannot be obtained, and developability may be poor, particularly under high humidity.

In the present invention, an alkyl group, which may be partially or entirely substituted with a fluorine atom, may be substituted by a fluorine atom.
Hydrogenpolysiloxanes having an aryl group and hydrogen as substituents include an alkyl group, an aryl group and a hydrogen atom in which a substituent on silicon in the siloxane chain may be partially or entirely substituted with a fluorine atom. An alkyl group, an aryl group, a hydrogen atom or the like, in which a substituent on the terminal silicon may be partially or entirely substituted with a fluorine atom. Or, it refers to polysiloxane as another substituent. Among these substituents, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.

As the hydrogen polysiloxane, phenyl hydrogen polysiloxane, methyl hydrogen polysiloxane, and phenyl hydrogen methyl hydrogen polysiloxane are preferable, and methyl hydrogen polysiloxane is particularly preferable. These hydrogen polysiloxanes may have a cyclic structure or a branched structure. For example, a hydrogen polysiloxane represented by the following general formula 3 is given. A specific example is a hydrogen polysiloxane represented by Formula 4.

[0022]

Embedded image

[In the formula 3, R ₁ , R ₂ , R ₃ , R ₄ , R
₅ , R ₆ and R ₇ each represent an alkyl group, an aryl group or hydrogen in which a part or all of hydrogen atoms may be substituted by fluorine atoms, and may be the same or different; May have other optional substituents. m is a sum of siloxy units satisfying the condition of the unit of m and represents an integer of 1 or more. In Formula 4, a part of the methyl group may have an arbitrary substituent. n is the sum of siloxy units satisfying the condition of the unit of n and represents an integer of 1 or more. ]

These hydrogen polysiloxanes are adsorbed on the surface of the inorganic fine powder, easily baked, and
-H bonds react with OH groups and other functional groups on the inorganic fine powder or other Si-H bonds to form Si-O bonds,
Since the alkyl group and the aryl group are oriented toward the outside of the inorganic fine powder or have a two-dimensional or three-dimensional structure, sufficient hydrophobicity is achieved. On the other hand, since only one substituent on silicon can be oriented or has a two-dimensional or three-dimensional structure, the lubricating effect and releasing effect as polysiloxane are reduced. The toner containing the inorganic fine powder treated with such a hydrogen polysiloxane has sufficient hydrophobicity, has good triboelectricity, has excellent developability, and has good developability even under high humidity. Although the developability can be maintained, the release property and lubricity are insufficient with hydrogenpolysiloxane alone, and the effect on transferability, cleaning property and non-staining property is not so large.

The present invention is characterized in that it contains an inorganic fine powder treated with the polysiloxane and the hydrogen polysiloxane, so that the above-mentioned disadvantages can be compensated for and the advantages can be obtained. And transferability can be achieved at the same time, and more favorable results can be obtained than the effects obtained alone. That is, when the hydrogen polysiloxane is present at the same time, the polysiloxane can exert its function as a polysiloxane, so that the releasability and lubricity can be further improved. Further, when the polysiloxane is present at the same time, the hydrophobicity can be further increased without impairing the function as the polysiloxane due to the interaction with the hydrogen polysiloxane.

These polysiloxanes preferably have a viscosity at 25 ° C. of 1 to 2,000 mm ² / s. More preferably, it is 5 to 1,000 mm ² / s. If it is less than 1 mm ² / s, sufficient releasability and lubricity may not be obtained. If it exceeds 2,000 mm ² / s, it becomes difficult to uniformly treat inorganic fine powder, In some cases, and sufficient fluidity may not be obtained.

In the present invention, the following polysiloxanes may be used in combination. Examples of such polysiloxanes include reactive polysiloxanes such as amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, and heterofunctional group-modified; polyether-modified, methylstyryl-modified, and alkyl-modified. And non-reactive polysiloxanes such as fatty acid-modified, alkoxy-modified and fluorine-modified. Further, the treatment may be carried out in combination with other silane compounds, organic silicon compounds such as silicone varnish, organic aluminum compounds, organic titanium compounds and the like.

In the present invention, the treatment amount of each polysiloxane with respect to 100 parts by mass of the inorganic fine powder is from 1 to 4
It is preferably 0 parts by mass, more preferably 2 to 2 parts by mass.
30 parts by mass. When the amount is less than 1 part by mass, the respective treatment effects are not exhibited, and when the amount exceeds 40 parts by mass, aggregates are easily generated. Furthermore, the combined processing amount is 60
It is preferably at most 2 parts by mass, more preferably 2 to
It is 50 parts by mass, particularly preferably 4 to 40 parts by mass. 6
If the amount is more than 0 parts by mass, aggregates are generated and the treatment tends to be uneven. In addition, when other treating agents are used in combination, it is preferable that the treating amount is within the above-mentioned range.

The treatment ratio of the polysiloxane to the hydrogen polysiloxane is preferably 1: 4 to 4: 1, more preferably 1: 3 to 3: 1, and particularly preferably 1: 2. ２2: 1 is preferred. When the treatment is carried out at this ratio, uniformity of the surface treatment can be easily obtained, effective releasability, lubricity, and non-staining property can be easily obtained.

The inorganic fine powder used in the present invention includes:
Oxide, double oxide, metal oxide, metal, silicon compound, carbon, carbon compound, fullerene, boron compound, carbide,
Nitride, silicide, ceramics, and chalcogen compounds are used, preferably metal oxides. Among metal oxides, silica, alumina, titania and zirconia are particularly preferred. Further, alumina and titania, which have an appropriate charge saturation value and have stable chargeability depending on the environment, are particularly preferable.

The silica used in the present invention can be prepared by a dry method using vapor phase oxidation of a silicon halide (eg, thermal decomposition oxidation reaction in oxygen or hydrogen flame), or a method using sodium silicate, alkaline earth metal silicate, silicate, or the like. Acids, ammonia, salts,
Silica obtained by a wet method using decomposition with alkali salts is used, and an amorphous type is used. Also, by using together with a metal halide such as aluminum chloride, titanium chloride, germanium chloride, tin chloride, zirconium chloride, and lead chloride and a silicon halide, a fine powder of an oxide of silicon and another metal may be used. it can.

The titania used in the present invention is a sulfuric acid method,
Titania obtained by low-temperature oxidation (thermal decomposition, hydrolysis) of volatile titanium compounds such as titanium alkoxide, titanium halide, and titanium acetylacetonate is used as a chlorine method, and the crystal system is anatase type, rutile type, or a mixed crystal thereof. Either a mold or an amorphous material can be used.

Alumina used in the present invention may be a Bayer method, an improved Bayer method, an ethylene chlorhydrin method, a spark discharge method in water, an organic aluminum hydrolysis method, an aluminum alum pyrolysis method, an ammonium aluminum carbonate pyrolysis method, a chloride method. Alumina obtained by a flame decomposition method of aluminum is used. Α, β,
γ, δ, ξ, η, θ, κ, χ, ρ type, these mixed crystal types,
Any of amorphous is used, α, γ, δ,
Theta, mixed crystal type and amorphous type are preferably used.

The inorganic fine powder after treatment has an average particle size of 0.1.
It is preferably less than 1 μm, and if it is 0.1 μm or more, sufficient fluidity and uniform chargeability cannot be obtained, resulting in inferior developability and durability. Here, the average particle diameter is obtained by actually measuring the particle diameter of 400 arbitrary primary particles from a transmission electron microscope image of 100,000 times, and calculating the number average diameter. For the diameter, the major axis is measured, and when the major axis / minor axis ratio is 2 or more, the average value is measured and calculated.

Further, the inorganic fine powder of the present invention preferably has a methanol hydrophobicity of 50% or more, more preferably 55% or more, and particularly preferably 60% or more. 50
%, The hydrophobicity starts to be insufficient, and the lower the value is, the lower the moisture resistance becomes. As a result, the developing property under high humidity and the developing property due to standing are deteriorated with time.

The hydrophobicity of methanol was measured by placing 50 cm ³ of ion-exchanged water in a beaker of 200 cm ³ ,
g is weighed and put therein, and methanol is dripped with a burette while stirring, and the point at which the sample floating on the liquid surface completely disappears is defined as the end point, and the degree of hydrophobicity is determined from the following equation.

Degree of hydrophobicity (%) = ΔTitration (cm ³ ) /
[Titration (cm ³ ) +50 (cm ³ )]｝ × 100

Further, the water content of the inorganic fine powder is set to 3.
It is preferably 0% by mass or less, and good moisture resistance is obtained. When the water content is more than 3.0% by mass, the inorganic fine powder has high hygroscopicity, so that the developability under high humidity or after long-term storage becomes poor, and fogging or the like occurs. Further, the water content is more preferably 2.5% by mass or less, and particularly preferably 2.0% by mass or less.

In the present invention, the water content is measured using a fully automatic moisture measurement system AQS-624 (manufactured by Hiranuma Sangyo Co., Ltd.). As a sample, 1 g of a sample is prepared at 23 ° C. and 60% RH.
Using what was left for 12 hours in the above environment, about 0.2 g was accurately weighed (Ag) and measured. 20 samples
The mixture is heated at 0 ° C. to evaporate the adsorbed water.
The sample is titrated for 1 minute to determine the amount of adsorbed water (B μg) of the sample and the amount of water of reference (C μg). The water content is calculated by the following equation.

Water content (% by mass) = [(BC) / (A ×
1,000,000)] x 100

Other physical properties were determined by the BET one-point method.
15m^Two / G or more,
More preferably 20m^Two/ G, particularly preferably 2
5m^Two/ G or more. Specific surface area is 15m^Two/ G
In this case, the fluidity and the releasability become inferior, and the developability and the transfer
Adversely affect sex.

Further, it is preferable that a bulk density of 0.5 g / cm ³ or less, preferably further is 0.45 g / cm ³ or less, particularly preferably 0.4 g / cm ³
It is as follows. If the bulk density exceeds 0.5 g / cm ³ , the fluidity and the charging uniformity become poor, the developing property becomes non-uniform, and the density unevenness occurs.

The content of the inorganic fine powder of the present invention
The amount is preferably 0.2 to 5.0 parts by mass, more preferably 0.3 to 4.0 parts by mass, particularly preferably 0.4 to 3.5 parts by mass with respect to 00 parts by mass. 0.
When the amount is less than 2 parts by mass, the effect of the addition becomes small,
If the amount is more than 5.0 parts by mass, the chargeability tends to be environmentally dependent.

In the present invention, the specific surface area is measured by a flow type specific surface area automatic measuring device, Micromeritics Flowsorb I.
It is measured by I2300 type (manufactured by Shimadzu Corporation), and the measurement is performed after degassing the sample of 0.2 g at 70 ° C. for 30 minutes using a mixed gas flow of 30% by volume of nitrogen and 70% by volume of helium.

The bulk density is determined according to JIS K-5101.

Examples of the method for treating the inorganic fine powder particles with various treating agents include a method of treating in an aqueous medium, a method of treating in an organic solvent, and a method of treating in a gas phase.

In the method of treating in an aqueous medium, inorganic fine powder is dispersed so as to be primary particles, and in the case of a polysiloxane type treating agent, treatment is carried out using an emulsion. Process while disassembling.
In this treatment method, since the particles to be treated can be dispersed in an aqueous medium as they are without passing through a drying step after producing the particles to be treated, the particles are easily dispersed in the primary particles, but after treatment, the treated particles exhibit lipophilicity. Therefore, coalescence of particles starts, and an aggregate tends to be easily formed. When treating with several treatment agents, they may be added simultaneously or sequentially.

In the gas phase method, there is a method of treating the particles by dripping or spraying the treating agent while sufficiently agitating the particles to be treated mechanically or by a gas stream (this is referred to as "gas phase method 1"). ). At this time, the reactor was replaced with nitrogen,
It is also preferable to heat to 350 ° C. When the viscosity of the treatment agent is high, the treatment agent may be diluted with a solvent such as alcohol, ketone, or hydrocarbon. Ammonia, amine, alcohol, water and the like may be added in order to enhance the reactivity during the treatment. In this treatment method, since the reaction is carried out firmly, it is a preferable method in which high hydrophobicity and uniformity can be easily obtained.However, if the untreated particles are stirred strongly for a long time, the coalescence of the particles may occur or the treatment may occur. Care must be taken because non-uniformity is likely to occur. When treating with several kinds of treatment agents, they may be added simultaneously or sequentially.

As another method of the gas phase method, the treating agent is immediately (without being taken out) immediately after the particles to be treated are generated in the carrier gas by the gas phase method (chlorine method, low-temperature oxidation method, etc.). In some cases, there is a method of diluting with a solvent, vaporizing, atomizing, and treating the particles to be treated in a gas phase (this is referred to as “gas phase method 2”). In this method, in addition to the advantages of the gas phase method 1,
Since the treatment is performed before the particles to be treated are united, it is a preferable method that an aggregate is hardly formed.

The method of treating in an organic solvent is a method in which particles to be treated are dispersed in an organic solvent, treated with a treating agent, separated by filtration or the solvent is distilled off and then dried. In order to reduce agglomerates, it is also preferable to carry out a crushing treatment thereafter using a pin mill, a jet mill or the like. The drying step may be performed under standing or flowing, preferably at about 50 to 350 ° C., or under reduced pressure. As the organic solvent, hydrocarbon-based organic solvents such as toluene, xylene, hexane and isoper are preferably used. Stirring, shaking, crushing, mixing, and dispersing machines are used for the dispersion treatment. Among them, ceramics, agate,
A disperser using media such as balls and beads made of alumina, zirconia or the like is preferably used. For example,
Sand mill, Glen mill, Basket mill, Ball mill, Sand grinder, Visco mill, Paint shaker, Attritor, Dyno mill, Pearl mill, etc. As a particularly preferred treatment method, a method in which particles to be treated are dispersed in an organic solvent, and a treating agent is added from a paste and then applied to a disperser, a method for applying a treated particle paste of an organic solvent containing the treating agent to a disperser, There are a method in which a paste obtained by adding a treating agent and particles to be processed to an organic solvent is applied to a dispersing machine, and a method in which the treating agent is added while applying the paste to the dispersing machine. The method of treating in an organic solvent is a preferable method because the particles to be treated can be treated in a dispersed state, coalescence hardly occurs even after the treatment, and an aggregate is hardly generated. Further, when treating with several kinds of treating agents, they may be added simultaneously at the time of slurry preparation, may be added sequentially, or may be additionally added when applied to a dispersing machine. In addition, put it on a dispersing machine
Each time it is applied to a disperser, it may be added and mixed in advance in a slurry or added sequentially when it is applied to a disperser.

As the processing method, the above four methods can be used.
The treating agent may be treated at the same time, or may be treated in several steps in any order. When the processing is performed in a plurality of times, any combination of processing methods may be used.
When the treatment is performed in several stages, a method of treating with hydrogen polysiloxane and then treating with another polysiloxane is a preferable method since both advantages can be exhibited more.

Regardless of which process is used, the pulverization treatment using a pulverizer such as a pin mill, a hammer mill, or a jet mill after the treatment can also reduce the agglomerates and sufficiently exert the effect of the inorganic fine powder of the present invention. It is also preferred for

In the present invention, the following binder resins can be used as the binder resin for the toner.

For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene and their substituted products; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Copolymers: polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyol resin, polyurethane, polyamide resin, furan resin , Epoxy resin, xylene resin, polyvinyl butyral, terpene resin, cumarone indene resin, petroleum resin, and the like. Preferred binders include styrene copolymers, polyester resins, and epoxy resins, particularly polyester resins, epoxy resins, and polyol resins.

As comonomers for the styrene monomer of the styrene copolymer, for example, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, acrylic acid-
Monocarboxylic acids having a double bond such as 2-ethylhexyl, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide and the like, and substituted products thereof;
For example, dicarboxylic acids having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like;
Vinyl esters such as vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene, butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl methyl ether and vinyl Vinyl monomers such as ethyl ether, vinyl isobutyl ether and the like; and vinyl monomers such as one or two or more are used.

The styrene-based polymer or styrene-based copolymer may be cross-linked, or may be a mixed resin.

As a crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds may be mainly used. For example, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and the like; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate and the like; Divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone; and 3
Compounds having at least two vinyl groups are used alone or as a mixture.

Since the inorganic fine powder of the present invention is excellent in moisture resistance, it is suitably used for a toner containing a polyester resin, an epoxy resin, or a polyol resin, which is easily affected by humidity in chargeability. That is, the adverse effects of these resins can be compensated for and good developability under high humidity can be maintained. Polyester resins, polyol resins, and epoxy resins are preferably used because of their excellent fixability and, in particular, excellent color mixing properties in full-color toners. That is,
When the inorganic fine powder of the present invention is used with a toner containing a polyester resin, a polyol resin, or an epoxy resin as a binder resin component, fixability, developability under high humidity, and storage stability over time can be obtained. Further, in a color toner, excellent transferability and color mixing can be obtained, so that a beautiful pictorial image can be obtained.

For the above-mentioned reasons, styrene resins,
Mixtures of polyester resins, polyol resins and epoxy resins, as well as graft copolymers, block copolymers and mixtures of these resins are also preferably used.

The epoxy resin and the polyol resin used in the present invention are as follows. For example, as the skeleton, bisphenol A type, halogenated bisphenol A
Type, biphenyl type, saligenin type, sulfone type, long-chain bisphenol type, resorcinol type, bisphenol F
Type, tetrahydroxyphenylethane type, novolak type, alcohol type, polyglycol type, polyol type,
Glycerin triether type, polyolefin type, epoxidized soybean oil, alicyclic type and the like are used, and bisphenol type is preferably used. Furthermore, those obtained by reacting them with a curing agent, those obtained by reacting a terminal epoxy group with a compound having active hydrogen, those reacted with phenol / polyhydric phenols, amines / polyamines, Those reacted, those reacted with carboxylic acids, polybasic acids, acid anhydrides, ester derivatives, lactones,
Those reacted with a polyamide and those reacted with an oligomer having a carboxylic acid group are preferably used. Further, those obtained by reacting a hydroxyl group with a carboxylic acid, an acid anhydride, a lactone, or a lactam are particularly preferably used.

Examples of the active hydrogen-containing compound include the following. Examples of the phenols include phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol and the like, and examples of the dihydric phenols include bisphenol A, bisphenol F, bisphenol AD, bisphenol S and the like. No. As carboxylic acids, acetic acid, propionic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, oleic acid, margaric acid,
Arginic acid, linoleic acid, linolenic acid and the like can be mentioned.
Examples of the ester derivative include an alkyl ester of the above carboxylic acid. Among them, a lower alkyl ester is preferable, and a methyl ester, an ethyl ester and the like are particularly preferably used. As lactones, β-propiolactone, δ-valerolactone, ε-caprolactone, γ
-Butyrolactone, β-butyrolactone, γ-valerolactone and the like. As amines, methylamine,
Ethylamine, propylamine, isopropylamine,
Examples thereof include butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, laurylamine, and stearylamine.

The composition of the polyester resin used in the present invention is as follows.

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

[0064]

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(Wherein R is an ethylene or propylene group, x and y are each an integer of 0 or more, and
The average value of x + y is 0-10. )

Diols represented by the formula (B):

[0067]

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(Wherein R ′ is —CH ₂ CH ₂ — or

[0069]

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Examples of the divalent acid component include phthalic acid,
Benzenedicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides and lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides and lower alkyl esters; n- Alkenyl succinic acids or alkyl succinic acids such as dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides and lower alkyl esters thereof; fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acids such as itaconic acid or anhydrides, lower acids And dicarboxylic acids such as alkyl esters; and derivatives thereof.

It is preferable to use a trivalent or higher valent alcohol component and a trivalent or higher valent acid component, which also function as a crosslinking component, in order to improve durability.

The polyhydric alcohol component having three or more valences includes
For example, sorbitol, 1,2,6-hexanetriol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3
5-trihydroxybenzene and the like.

The trivalent or higher valent polycarboxylic acid component in the present invention includes, for example, trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid,
2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,2
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-
Octanetetracarboxylic acid, empol trimer acid, and anhydrides and lower alkyl esters thereof;

[0074]

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Wherein X is an alkylene group or alkenylene group having 30 or less carbon atoms which may have one or more side chains having 1 or more carbon atoms, etc., and anhydrides thereof. And polyvalent carboxylic acids such as lower alkyl esters and derivatives thereof.

The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%.
%, 60 to 40 mol% as an acid component, preferably 5%
It is preferably from 5 to 45 mol%.

The content of the trivalent or higher polyvalent component is preferably 1 to 60 mol% of all components.

Further, from the viewpoint of developability, fixability, durability and cleaning properties, styrene copolymers, polyester resins, polyol resins, epoxy resins, block copolymers thereof, graft copolymers or these resins Mixtures are preferred.

The styrene-based resin and the mixture with the styrene-based resin preferably have a peak in a region of 10 ⁵ or more in the molecular weight distribution measured by GPC, and more preferably in a region of 3 × 10 ^{3 to} 5 × 10 ^4. It is preferable to have a peak in terms of fixability and durability.

Such a resin component can be obtained, for example, by the following method.

By applying solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, block copolymerization, grafting and the like, a polymer (L) having a main peak in the molecular weight region of 3 × 10 ^{3 to} 5 × 10 ⁴ is obtained. A polymer having a main peak in a region of 10 ⁵ or more or a polymer (H) containing a gel component is formed. These components can be obtained by blending during melt kneading. The gel component can be partially or completely cut at the time of melt-kneading, becomes a THF-soluble component, and is measured by GPC as a component in a region of 10 ⁵ or more.

As a particularly preferred method, the polymer (L)
Alternatively, the polymer (H) is formed by solution polymerization, and when the polymerization is completed, the other is blended in a solvent, the other polymer is polymerized in the presence of one polymer, and the polymer (H) is suspended. A method in which a polymer (L) is formed by polymerization in the presence of the polymer, and a method in which the polymer (H) is blended in a solvent at the end of the solution polymerization; And a method in which the polymer (H) can be polymerized by suspension polymerization. By using these methods, a polymer in which a low molecular weight component and a high molecular weight component are uniformly mixed can be obtained.

Examples of the binder resin for the toner subjected to the pressure fixing method include low molecular weight polyethylene, low molecular weight polypropylene, ethylene-vinyl acetate copolymer, ethylene-
Acrylic ester copolymers, higher fatty acids, polyamide resins and polyester resins are mentioned. These can be used alone or as a mixture.

When a styrene copolymer is used as the binder resin, the following toners are preferred in order to obtain good fixing properties, blocking resistance and developability.

The molecular weight distribution of the toner by GPC (gel permeation chromatography) was 3 × 10
An area of ^{3 to} 5 × 10 ⁴ , preferably 3 × 10 ^{3 to} 3 × 10 ⁴
At least one peak (P ₁ ) exists in a region of 5 × 10 ³ to 2 × 10 ⁴ .
Good fixability, developability, and blocking resistance can be obtained. If it is less than 3 × 10 ³ , good blocking resistance cannot be obtained, and if it exceeds 5 × 10 ⁴ , good fixability cannot be obtained. Also, a region of 10 ⁵ or more, preferably 3 ×
10 ⁵ to 5 × 10 least one peak (P ₂₎ is present in ⁶ area of 10 ⁵ to 3 × 10 ⁵ to 2 × 10 ⁶ regions of
It is particularly preferred that there is a maximum peak in the above region,
Good high-temperature offset resistance, blocking resistance, and developability are obtained. The larger the peak molecular weight is, the stronger the high-temperature offset becomes. However, when a peak exists in a region of 5 × 10 ⁶ or more, there is no problem with a hot roll to which pressure can be applied. In addition, the elasticity increases and the fixing property is affected. Therefore,
In the case of heat fixing with a relatively low pressure used in a medium-to-low speed machine, a peak exists in a region of 3 × 10 ⁵ to 2 × 10 ⁶ , and this is preferably the maximum peak in a region of 10 ⁵ or more.

The component in the region of 10 ⁵ or less is 50% or more, preferably 60 to 90%, particularly preferably 65 to 8%.
5%. Within this range, good fixability and offset resistance can be obtained. If it is less than 50%, not only the sufficient fixing property cannot be obtained but also the pulverizability becomes inferior.
In addition, when it exceeds 90%, offset resistance,
It tends to be weak against blocking resistance.

When a polyester resin, epoxy resin or polyol resin is used, the molecular weight distribution of the toner by GPC is in the range of 3 × 10 ^{3 to} 2.0 × 10 ⁴ , preferably 4 × 10 ^{3 to} 1.7. × 10 ⁴ region, particularly preferably it is preferred that the main peak is present in the region of ^{5 × 10 3 ~1.5 × 10 4} . When used for a magnetic toner, at least one peak or shoulder exists in a region of 1.5 × 10 ⁴ or more or 5 × 10 ⁴ or more.
It is preferable that the area of 10 ⁴ or more is 5% or more.
It is also preferable that w / Mn is 10 or more.

When the molecular weight distribution is as described above, good developability, blocking resistance, fixing property, and offset resistance can be obtained.

When the main peak is less than 3 × 10 ³ , the blocking resistance and the developability are liable to decrease.
If the main peak exceeds 2.0 × 10 ⁴ , good fixability cannot be obtained. When a peak or shoulder exists in a region of 1.5 × 10 ⁴ or more, when a region of 5 × 10 ⁴ or more is 5% or more, or when Mw / Mn is 10 or more, good offset resistance is obtained. It is possible to obtain.

The binder resin used in the toner of the present invention preferably has a glass transition point (Tg) of 50 to 70 ° C. When Tg is lower than 50 ° C., the blocking resistance deteriorates. If the Tg exceeds 70 ° C., the fixability deteriorates.

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

That is, the column was stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent was flowed through the column at this temperature at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution was injected. Measure. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is used.
It is appropriate to use about a few standard polystyrene samples. An RI (refractive index) detector is used as the detector.
As the column, a plurality of commercially available polystyrene gel columns are preferably combined, and for example, showex GPC KF-801, 802, 80 manufactured by Showa Denko KK
3,804,805,806,807,800P or TSKgelG1000H (H
_{XL), G2000H (H XL)} , G3000H (H XL),
_{G4000H (H XL), G5000H (} H XL), G60
00H (H _XL ), G7000H (H _XL ), TSKgua
rdcolumn can be mentioned.

A sample is prepared as follows.

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

The method for measuring the glass transition point is described in ASTM D
Performed according to 3418-82. DS used in the present invention
The C curve is DS measured when the temperature is raised at a temperature rate of 10 ° C./min after the temperature has been raised and lowered once to obtain a pre-history.
Use the C curve. The definition is defined as follows.

Glass transition point (Tg) The temperature at the intersection of the DSC curve at the time of temperature rise and the line connecting the midpoint of the baseline before and after the specific heat change appears.

Further, in order to improve the releasability from the fixing member at the time of fixing and the fixing property, the following waxes may be contained in the toner.

Paraffin wax and its derivatives, montan wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, etc. Includes block copolymers and graft-modified products with vinyl monomers. In addition, alcohols, fatty acids, acid amides, esters, ketones, hardened castor oil and derivatives thereof, vegetable waxes, animal waxes, mineral waxes, petrolactam and the like can also be used.

Among these waxes, preferred are low-molecular-weight polyolefins obtained by radical polymerization of olefins under high pressure or polymerization using a Ziegler catalyst, and low-molecular-weight polyolefins obtained by thermal decomposition of by-products and high-molecular-weight polyolefins. A polyolefin, carbon monoxide, a distillation residue of a hydrocarbon obtained by using a catalyst from a synthesis gas consisting of hydrogen, or a wax obtained from a synthetic hydrocarbon obtained by hydrogenating these, and an antioxidant May be added. Or alcohol,
Fatty acids, acid amides, esters or montan derivatives. It is also preferable that impurities such as fatty acids have been removed in advance.

As the colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used. For example, pigments such as carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow,
There are Rhodamine Lake, Alizarin Lake, Bengala, Phthalocyanine Blue and Indanthrene Blue. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and preferably 0.1 to 100 parts by mass of the resin.
The addition amount is preferably 20 parts by mass, more preferably 0.2 to 10 parts by mass.

The dyes include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, and basic dyes and oil-soluble dyes are suitable. 0.1 to 20 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the binder resin.
The addition amount of 3 to 10 parts by mass is good.

Specific dyes include C.I. I. Direct red 1, 4; I. Acid Red 1; I.
Basic Red 1, 3b, 12; C.I. I. Modant red 3; I. Solvent Red 4, 52, 10
9; I. Direct blue 1, 2; acid blue 9, 15; basic blue 3, 5;

As the specific pigments, among the chromatic color pigments, organic pigments having high lipophilicity are preferable. Permanent red 4
R, Watching Red Calcium Salt, Brilliant Carmine 38, Fast Violet B, Methyl Violet Lake, Phthalocyanine Blue, Fast Sky Blue, Induslen Blue BC and the like.

Preferably, highly weather-resistant pigments such as polycondensed azo pigments, insoluble azo pigments, quinacridone pigments, isoindolinone pigments, perylene pigments, anthraquinone pigments, and copper phthalocyanine pigments are preferred.

Examples of the magenta coloring pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 20, 21, 22, 23, 30, 31, 3
2,37,38,39,40,41,48,49,5
0, 51, 52, 53, 54, 55, 57, 58, 6
0, 63, 64, 68, 81, 83, 87, 88, 8
9, 90, 112, 114, 122, 123, 163,
202, 206, 207, 209; I. Pigment Violet 19; I. Bad red 1,2,1
0, 13, 15, 23, 29, 35 and the like.

The yellow color pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 1
1,12,13,14,15,16,17,23,6
5,73,83,97,173,180; I. Bad Yellow 1, 3, 20 and the like.

Examples of the coloring pigment for cyan include C.I. I. Pigment Blue 2, 3, 14, 15, 16, 17;
I. Bad Blue 6; I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following general formula (C).

[0108]

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When used as a colorant for a full-color toner, the content thereof is preferably 15 parts by mass or less, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin due to the transparency of the OHP sheet. Parts by weight. Fifteen
When the amount exceeds the parts by mass, the reproducibility of the mixed colors red, green, and blue decreases, and the reproducibility of human skin color also decreases. If the amount is less than 0.5 parts by mass, it is difficult to obtain a desired coloring power, and it is difficult to obtain a high-quality image having a high image density.

As the black colorant, those obtained by mixing carbon black, a metal oxide exhibiting black, and a dye or pigment are preferably used. These colorants are used in an amount of 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the binder resin.

When a coloring agent having magnetism is used, it can also serve as a magnetic material and can be used as a magnetic toner. Magnetic powders as such coloring agents include iron oxides of magnetite, hematite and ferrite; metals such as iron, cobalt and nickel or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, Alloys of metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium and mixtures thereof are used, and oxides of metal ions such as Si, Al, and Mg on the surface or inside of magnetic iron oxide And those containing compounds such as hydrated oxides and hydroxides are preferably used. Particularly preferred is a magnetic iron oxide containing a silicon element,
It is preferable that the content is 0.1 to 3% by mass based on the magnetic powder. More preferably 0.15 to 3% by mass
And particularly preferably 0.2 to 2.0% by mass.

The shapes of the magnetic powder include hexahedron, octahedron,
Polyhedrons such as decahedron, dodecahedron, and tetrahedron, needles, scales, spheres, and irregular shapes are used.

[0113] As a BET specific surface area by nitrogen gas adsorption method of the magnetic ^{powder, 1m 2 / g~40m 2 / g} , more 2m
² / g to 30 m ² / g is preferable, and 3 m
Those having a ratio of ² / g to ²⁰ m ² / g are preferred.

The saturation magnetization of the magnetic powder is 796 kA /
m, a magnetic field of 5 to 200 Am ² / kg,
Those having a range of 150 Am ² / kg are preferred.

The residual magnetization of the magnetic powder was 796 kA /
m, a magnetic field of 1 to 100 Am ² / kg, and even 1 to 7
0Am ² / kg is preferred.

The average particle size of the magnetic powder is 2.0 μm
Hereinafter, preferably 0.03 to 1.0 μm, more preferably 0.05 to 0.6 μm, and still more preferably 0.1 to
0.4 μm is preferred.

The amount of the magnetic powder contained in the toner is 10 to 200 parts by mass per 100 parts by mass of the binder resin.
Preferably 20 to 170 parts by mass, particularly preferably 30 to 170 parts by mass.
It is 150 parts by mass.

The toner of the present invention is used as a one-component developer or a two-component developer by using the above colorants.

In order to provide the toner of the present invention with an appropriate charge amount, it is preferable to add the following charge control agent. can do.

The following substances control the toner to be positively charged.

Modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate;
Onium salts such as phosphonium salts, which are analogs thereof, and their lake pigments, triphenylmethane dyes and these lake pigments (as the lake-forming agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, Acid, lauric acid, gallic acid, ferricyanide, ferrocyanide), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin Diorganotin borates such as borate; guanidine compounds, imidazole compounds. These can be used alone or in combination of two or more. Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used. The general formula (D)

[0122]

Embedded image Monomer of a monomer represented by: styrene described above,
Copolymers with polymerizable monomers such as acrylates and methacrylates can be used as positive charge control agents. In this case, these charge control agents also act as (all or part of) the binder resin.

The following substances control the toner to be negatively charged.

For example, organic metal complexes and chelate compounds are effective, and examples thereof include monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

An azo metal complex represented by the following general formula (E) is preferred.

[0126]

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In particular, the central metal is preferably Fe or Cr, the substituent is preferably a halogen, an alkyl group or an anilide group, and the counter ion is preferably hydrogen, an alkali metal, ammonium or aliphatic ammonium.
Also, a mixture of complex salts having different counter ions is preferably used.

Alternatively, a basic organic acid metal complex represented by the following general formula (F) also gives negative chargeability and can be used in the present invention.

[0129]

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In particular, Fe, Cr, Si,
Zn and Al are preferable, and the substituent is preferably an alkyl group, an anilide group, an aryl group, or a halogen, and the counter ion is preferably hydrogen, ammonium, or aliphatic ammonium.

As a method for incorporating the charge control agent into the toner, there are a method of adding it inside the toner and a method of adding it externally. The use amount of these charge control agents is determined by the type of the binder resin, the presence or absence of other additives, the toner manufacturing method including the dispersion method, and is not limited to a specific one. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the binder resin. When adding externally, use resin 1
It is preferably 0.01 to 10 parts by mass with respect to 00 parts by mass, and particularly preferably mechanochemically fixed to the surface of the toner particles.

In producing the toner according to the present invention, the above-mentioned toner constituting materials are sufficiently mixed by a ball mill, a Henschel mixer, or another mixer.
It is preferable to knead well using a hot kneader such as a hot roll kneader or an extruder, cool and solidify the kneaded material, and then mechanically pulverize and classify the pulverized material to obtain a toner. Another method is to obtain a toner by dispersing the constituent materials in a binder resin solution and then spray-drying; emulsifying suspension by mixing a predetermined material with a monomer to form the binder resin. After that, there is a method for producing a toner by a polymerization method of polymerizing to obtain a toner. The toner according to the present invention may be a microcapsule toner composed of a core material and a shell material.

The toner of the present invention can be obtained by sufficiently mixing the above-mentioned toner with the inorganic fine powder characteristic of the present invention using a mixer such as a Henschel mixer.

Further, the following additives may be added as required.

The following inorganic powders can be added to improve developability and durability. Magnesium, zinc,
Metal oxides such as aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin, antimony; composite metal oxides such as calcium titanate, magnesium titanate, strontium titanate; calcium carbonate, magnesium carbonate, carbonate Metal salts such as aluminum; clay minerals such as kaolin; phosphate compounds such as apatite; silicon compounds such as silica, silicon carbide and silicon nitride; and carbon powders such as carbon black and graphite. Among them, zinc oxide, aluminum oxide, cobalt oxide, manganese dioxide, strontium titanate, magnesium titanate and the like are preferable.

For the same purpose, the following organic particles or composite particles can be added. Resin particles such as polyamide resin particles, silicone resin particles, silicone rubber particles, urethane particles, melamine-formaldehyde particles, acrylic resin particles; rubbers, waxes, fatty acid compounds, resins and the like and metals, metal oxides, salts, carbon black, etc. And composite particles composed of the above inorganic particles.

Further, the following lubricant powder can be added. Fluorine resins such as Teflon and polyvinylidene fluoride; fluorine compounds such as carbon fluoride; fatty acid metal salts such as zinc stearate; fatty acid derivatives such as fatty acids and fatty acid esters; molybdenum sulfide, amino acids and amino acid derivatives.

When the toner of the present invention is used as a two-component developer, it is used by mixing with a carrier, and the mixing ratio of the toner and the carrier is preferably 0.1 to 50% by mass as the toner concentration. Is 0.5 to 20% by mass, more preferably 3 to 10% by mass.

As the carrier core material, for example, surface oxidized or unoxidized iron, cobalt, nickel, copper, zinc, manganese, and chromium rare earth metals, alloys, compounds, oxides, and magnetic ferrites thereof are used. Among them, those containing 98% by mass or more of a ferrite carrier are preferably used. There are no particular restrictions on the carrier manufacturing method. A coated carrier in which the surface of a core material is coated with a resin or the like is particularly preferable. As a method of coating, a method of preparing a coating solution by dissolving or suspending a coating material such as a resin in a solvent, applying the coating solution to the surface of the carrier particles and attaching the coating solution to the surface of the carrier particles, simply coating the carrier particles A conventionally known method such as a method of dry mixing powder can be applied.

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

The blending amount is preferably such that the ratio of the fluorine-based resin, polyolefin-based resin or silicone-based resin to the total binder amount is 1.0 to 60% by mass, and particularly preferably 2.0 to 40% by mass. Content is 1.
If the amount is less than 0% by mass, the surface modification effect is not sufficient, and the toner spent is not effective. On the other hand, if it exceeds 60% by mass, it is difficult to uniformly disperse the two, so that a partial unevenness occurs in the volume resistance value and the charging characteristics deteriorate.

The fluororesin used as the binder resin for coating the carrier includes, for example, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, dichlorodifluoroethylene, tetrafluoroethylene, hexafluoropropylene and the like. And other monomers and a solvent-soluble copolymer.

Examples of the silicone resin used as the binder resin for coating the carrier include KR271, KR282, KR311, and KR25 manufactured by Shin-Etsu Silicone Co., Ltd.
5, KR155 (straight silicone varnish), KR
211, KR212, KR216, KR213, KR2
17, KR9218 (silicone varnish for modification), SA
-4, KR206, KR5206 (silicone alkyd varnish), ES1001, ES1001N, ES10
02T, ES1004 (silicone epoxy varnish),
KR9706 (silicone acrylic varnish), KR52
03, KR5221 (silicone polyester varnish)
And SR2100, SR2101, manufactured by Toray Silicone Co., Ltd.
SR2107, SR2110, SR2108, SR21
09, SR2400, SR2410, SR2411, S
H805, SH806A, SH840 and the like are used.

The amount of the above-mentioned materials may be determined as appropriate, but generally, the total amount is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the carrier.

The carrier has an average particle size of 20 to 100 μm,
Preferably 25 to 70 μm, more preferably 25 to 65
It is preferred to have μm.

A particularly preferred carrier is Cu-Z
n-Fe [composition weight ratio (5 to 20): (5 to 20):
(30-80)], the surface of which is coated with a fluorine resin, a styrene resin, a silicone resin, or a mixed resin thereof. For example, as a mixed resin, polyvinylidene fluoride and styrene-methyl methacrylate resin; polytetrafluoroethylene and styrene-methyl methacrylate resin;
90: 1 fluorine-based copolymer and styrene-based copolymer
A mixture having a weight ratio of 0 to 20:80, preferably 70:30 to 30:70 is used. 0.
A preferred carrier is a coated magnetic ferrite carrier having an average particle size of 70% by mass or more, in which the carrier particles are coated with 0.01 to 5% by mass, preferably 0.1 to 1% by mass, pass 250 mesh and turn on 350 mesh, in an amount of 70% by mass or more. No. As the fluorine-based copolymer, vinylidene fluoride-tetrafluoroethylene copolymer (1
0: 90-90: 10). Examples of the styrene-based copolymer are styrene-2-ethylhexyl acrylate copolymer (20: 80-80: 20) and styrene-2-ethylhexine acrylate-methyl methacrylate. Copolymers (20 to 60: 5 to 30:10 to 50) are exemplified.

The coated magnetic ferrite carrier having a sharp particle size distribution has effects of imparting a preferable triboelectric charge to the toner of the present invention and further improving electrophotographic characteristics.

When a two-component developer is prepared by mixing the toner of the present invention and a carrier, the mixing ratio is 1% by mass to 15% by mass, preferably 2% by mass to 13% by mass, as the toner concentration in the developer. Usually, good results are obtained when the content is in mass%. If the toner concentration is less than 1% by mass, the image density becomes low. If the toner concentration exceeds 15% by mass, fog and scattering inside the machine are increased, and the service life of the developer tends to be shortened.

In the charging / transferring step using the toner of the present invention, there are a system in which the latent image holding member using a corona charger is not in contact and a contact system using a roller, a blade or the like. Can be For efficient uniform charging, simplification, and low ozone generation, a contact type is preferably used. Among these, the toner of the present invention is of a contact type, and the effect is particularly remarkable.

Further, an example of an image forming method having the contact charging / transfer method will be described with reference to the schematic configuration diagram of FIG.

Reference numeral 101 denotes a rotating drum type electrostatic latent image holding member (hereinafter, referred to as a photosensitive member). The photosensitive member 101 includes a conductive base layer 101b made of aluminum or the like and a photoconductive layer 102a formed on the outer surface thereof. Is a basic constituent layer,
It is rotated at a predetermined peripheral speed (process speed) clockwise in the drawing.

Numerals 112 and 113 are cleaning members for cleaning the charging roller and the transfer roller.

Reference numeral 102 denotes a charging roller, which is basically composed of a central core bar 102b and a conductive elastic layer formed on the outer periphery thereof. The charging roller 102 is a photosensitive member 1
The photoconductor 101 is pressed against the surface 01 with a pressing force, and rotates following the rotation of the photoconductor 101. Reference numeral 103 denotes a charging bias current V ₂ for applying a voltage to the charging roller 102.
01 is charged to a predetermined polarity / potential. Next, an electrostatic charge image is formed by image exposure 104,
05 successively visualizes as a toner image.

A bias V ₁ is applied to the developing sleeve constituting the developing means 105 from the bias applying means 113. The toner image formed on the latent image holding member by the development is electrostatically transferred to the transfer material 108 by the contact transfer unit 106, and the toner image on the transfer material is heated and pressed by the heating and pressing unit 111.

The transfer bias V ₃ is applied to the contact transfer means 106.
Is applied.

In the image forming apparatus having such a contact charging / transfer method, the photosensitive member can be uniformly charged and sufficiently transferred with a relatively low bias voltage as compared with corona charging and corona transfer. It is excellent in miniaturizing the discharger itself and suppressing corona discharge products such as ozone.

As other means, there are a method using a charging blade shown in FIG. 2 and a method using a conductive brush. While these contact charging means have the effect of making high voltage unnecessary and reducing the generation of ozone,
Since the member is in direct contact with the photoreceptor, the adverse effect of toner fusion is likely to occur. Therefore, when used as a specific contact charging means, the toner of the present invention is optimal. The present invention does not limit the method and effect of the contact charging means to which the present invention is applied, and any method of charging a member by directly contacting the member with the photoreceptor is applicable to the present invention. It is possible.

Preferred process conditions when using a charging roller are as follows: the contact pressure of the roller is 0.5 to 50 kg.
/ M, when a voltage obtained by superimposing an AC voltage on a DC voltage is used, AC voltage = 0.5 to 5 kVpp, AC frequency = 5
0 to 5 kHz, DC voltage = ± 0.2 to ± 1.5 kV, and when DC voltage is used, DC voltage = ± 0.2 to ±
5 kV.

As the material of the charging roller and the charging blade, conductive rubber is preferable, and a release coating may be provided on the surface thereof. Nylon resin,
PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride) and the like are applicable.

In FIG. 1, reference numeral 106 denotes a transfer roller, which is basically composed of a central metal core 106b and a conductive elastic layer 106a forming the outer periphery thereof. The transfer roller 106 is pressed against the surface of the photoreceptor 101 with a pressing force, and is rotated at a constant speed or a difference between the peripheral speed and the peripheral speed of the photoreceptor 101. The transfer material 108 is conveyed between the photoconductor 101 and the transfer roller 106, and at the same time, a toner image on the photoconductor 101 is transferred by applying a bias having a polarity opposite to that of the toner to the transfer roller 106 from a transfer bias current 107. It is transferred to the front side of the material 108.

As the material of the transfer rotary member applicable to the present invention, the same material as that of the charging roller can be used. The preferable transfer process condition is that the contact pressure of the roller is 0.5 to 50 kg / kg. m, DC voltage ± 0.2
±± 10 kV.

Next, the transfer material 108 is conveyed to a fixing device 111 having a heating roller 111a having a built-in halogen heater and an elastic pressure roller 111b pressed against the heating roller 111a.
The toner image is fixed by passing through the gap. Further, a method of fixing with a heater via a film may be used. Further, pressure fixing may be performed using a developer used for pressure fixing. On the surface of the photoconductor 101 after the transfer of the toner image, adhered contaminants such as transfer residual toner are cleaned by a cleaning device equipped with an elastic cleaning blade pressed against the photoconductor 101 in the counter direction, and further, the charge is removed by the discharge exposure device 110. The image is repeatedly formed.

Examples of the contact-type transfer device include a transfer roller as shown in FIG. 3, a transfer belt and a transfer drum as shown in FIG.

FIG. 3 is a schematic side view of a main part of a typical image forming apparatus of this type. The illustrated apparatus is a cylindrical latent image extending in a direction perpendicular to the plane of the paper and rotating in the direction of arrow A. A holder (hereinafter, referred to as a photoreceptor) 301 and a conductive transfer roller 302 in contact with the holder are provided.

The transfer roller 302 is composed of a core metal 302a and a conductive elastic layer 302b. The conductive elastic layer 302b is made of urethane or ethylene-containing conductive material such as carbon dispersed therein.
It is made of an elastic material having a volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm, such as a propylene-diene terpolymer (EPDM). A bias is applied to the core metal 302a by a constant voltage power supply 308. The bias condition is ± 0.2
±± 10 kV is preferred.

FIG. 4 shows the present invention applied to a transfer belt. The transfer belt 409 is supported and driven by the conductive roller 410. Normally, the pressure of the transfer device is
Alternatively, the pressing is performed by pressing the end bearing of the cored bar of 410.

The contact pressure of the charger with the photosensitive member is 0.1 kg / m or more (preferably 0.1 kg / m) as a linear pressure.
Up to 30 kg / m, particularly preferably 0.3 to 10 kg / m
m).

The linear pressure is calculated by the following equation. (Linear pressure) [kg / m] = (total pressure applied to transfer member)
[Kg] ÷ (length contacted) [m]

When the contact pressure is less than 0.1 kg / m, transfer failure of the transfer member due to insufficient transfer current and insufficient transfer current occur, which is not preferable. The toner of the present invention has a remarkable effect particularly on transferability and omission during transfer in a system in which the transfer roller rotates at the same speed as the photosensitive member.

When using a charging roller and a charging blade,
The toner of the present invention has excellent releasability and lubricity, does not contaminate these members, and does not cause an abnormal image due to uneven charging. Even if it adheres, it is easily detached, so that the photoreceptor is not damaged or cut off more than necessary.

Further, since the releasability from the photoreceptor is excellent, the transferability is excellent, the transfer efficiency can be improved, and the phenomenon of omission during transfer can be prevented. The effect is particularly remarkable in a contact transfer system such as a transfer roller, a transfer belt, and a transfer drum.

Further, since the transferability is excellent, good transferability can be obtained even when the transfer current and the transfer voltage are reduced, so that the photosensitive member is less damaged and the life can be extended.

Further, in the present invention, it is possible to make it difficult for toner particles to directly adhere to the surface of the contact charging member, the surface of the contact transfer member, and the surface of the photoreceptor, and to improve the releasability of the toner particles from those surfaces to fix the toner. Even if the toner particles adhere to the surface of the contact charging member, the surface of the contact transfer member, and the surface of the photoreceptor, the toner adhering position is determined by the lubricity and releasability of the toner particles. When the cleaning member abuts on the contact charging member and the contact transfer member, it always moves between or between the member and the photoconductor, and does not stay at the same position, so that the toner particles are not fixed. Due to the releasability, the cleaning property of the toner particles adhered to the contact charging member surface and the contact transfer member surface is sufficiently improved.

As the cleaning method, blade cleaning is preferable. Blade cleaning is performed by using urethane rubber, silicone rubber, or elastic resin as a blade, or by holding a chip-shaped resin at the tip of a blade made of metal or the like in the forward or reverse direction with respect to the moving direction of the photoconductor. It is known as abutted or pressed. Preferably, the blade is pressed against the moving direction of the photoreceptor in the opposite direction. At this time, the contact pressure of the blade against the photoconductor is preferably 0.5 kg / m or more as a linear pressure, more preferably 1 to 5 kg / m. Further, a mag brush cleaning method, a fur brush cleaning method, a roller cleaning method, or the like may be combined with the blade cleaning method.

Since the toner of the present invention can obtain a suitable friction and is excellent in releasability and lubricity, it not only shows good cleaning properties by blade cleaning but also makes it possible to bring the blade into contact with the photoreceptor. It is hard to be scratched and hard to cut. On the other hand, fusion, filming, and the like hardly occur.

In the developing step, the toner of the present invention is
A one-component developing method such as a magnetic one-component developing method or a non-magnetic one-component developing method, or a two-component developing method including a toner and a carrier is used.

The toner of the present invention is rapidly charged, has a stable chargeability, and is uniformly charged. Therefore, the toner is excellent in transportability of the toner in the developing device, and is charged even when the surface area of the frictional charging member is small. Rise quickly, and the charge amount is quickly made uniform. Therefore, in the image forming method for developing the latent image on the electrostatic latent image holding member with the one-component toner on the toner holding member carrying the one-component toner, the layer thickness of the one-component toner on the toner holding member is reduced. The toner is preferably used in an image forming method using a developing method having a regulating member for regulating the toner. Particularly, a magnetic force cannot be expected, it is difficult to supply the toner onto the toner carrier, and the effect is extremely large in a non-magnetic one-component developing method having a small frictional charging ability.

That is, the toner of the present invention can obtain excellent developability, durability and environmental stability even in a one-component developing method, and can provide a clear image with high density without fog.
There is no fogging or lowering of the density even when left under high humidity or during durability. Further, a uniform solid and halftone image is obtained, the gradation is smoothly reproduced, and a graphic image with a beautiful gradation is obtained.

Further, the toner of the present invention hardly fuses.
Since the supply to the regulating portion is smooth, sufficient toner can be supplied for toner consumption, friction can be reduced, and torque can be reduced. Therefore, the regulating member is also preferably used in an image forming method in which the regulating member is thinned by pressing the elastic member. .

The magnetic one-component developing method of the above-described developing method will be described with reference to FIG.

In FIG. 5, the substantially right half peripheral surface of the developing sleeve 90 is always in contact with the toner reservoir in the toner container 91, and the toner near the developing sleeve surface is brought into contact with the developing sleeve surface by the magnetic generating means 92 in the sleeve. Adhered and held by magnetic and / or electrostatic forces. Developing sleeve 90 is advice service as thin magnetic toner T ₁ of the respective portions substantially uniform thickness in the process of magnetic toner layer when driven rotating the sleeve surface passes the position of the doctor blade 93. The magnetic toner is charged mainly by frictional contact between the sleeve surface caused by the rotation of the developing sleeve 90 and the magnetic toner in the toner reservoir near the sleeve, and the magnetic toner thin layer surface on the developing sleeve 90 is rotated by the rotation of the developing sleeve. The latent image holding member 94 rotates to the side of the latent image holding member 94 and passes through the developing area A, which is the closest part between the latent image holding member 94 and the developing sleeve 90. During this passage, the magnetic toner of the magnetic toner thin layer on the side of the developing sleeve 90 flies by the DC and AC electric fields generated by the DC and AC voltages applied between the latent image holding member 94 and the developing sleeve 90, and the latent image on the developing area A It reciprocates between the surface of the image carrier 94 and the surface of the developing sleeve 90 (gap α). Finally the toner image T ₂ are sequentially formed by selectively transition adhere according to the potential pattern of the latent image on the surface of the magnetic toner a latent image holding member 94 side of the developing sleeve 90 side.

The surface of the developing sleeve, in which the magnetic toner has been selectively consumed after passing through the developing area A, is re-rotated into the toner reservoir of the hopper 91 to be resupplied with the magnetic toner, and is developed to the developing area A. magnetic thin toner layer T ₁ side of the sleeve 90 is transported, repeatedly developing process is performed.

The doctor blade used in the present invention comprises:
A metal blade or a magnetic blade (for example, 93 shown in FIG. 5) disposed at a constant gap from the sleeve is used.

Instead of the doctor blade, a rigid roller or sleeve made of metal, resin, ceramic, or the like may be used as the toner thinning regulating member, or a magnet generating means may be provided inside.

In the magnetic one-component developing method and the non-magnetic one-component developing method, an elastic blade which comes into contact with the sleeve surface with an elastic force is used as a doctor blade. An elastic roller may be used instead of the doctor blade as the toner thinning regulating member. The toner of the present invention is particularly preferably used in a developing method in which the regulating member comes into contact with the toner carrier with elasticity to form a thin toner layer.

As the elastic blade and the elastic roller, rubber elastic bodies such as silicone rubber, urethane rubber and NBR; synthetic resin elastic bodies such as polyethylene terephthalate; metal elastic bodies such as stainless steel and steel can be used. Further, even a complex thereof can be used. Preferably, a rubber elastic body is good.

The material of the elastic blade and the elastic roller greatly affects the charging of the toner on the toner carrier.
Therefore, an organic substance or an inorganic substance may be added to the elastic body, may be melt-mixed, or may be dispersed. For example, metal oxides, metal powders, ceramics, carbon allotropes,
Examples include whiskers, inorganic fibers, dyes, pigments, and surfactants. Further, a rubber, synthetic resin, or metal elastic body may be used in which a substance such as resin, rubber, metal oxide, or metal is applied to the sleeve contact portion for controlling the charging property of the toner. When durability is required for the elastic body and the toner carrier, it is preferable that a resin or rubber is stuck to the metal elastic body so as to contact the sleeve contact portion.

When the toner is negatively chargeable, urethane rubber, urethane resin, polyamide, nylon, and those which are easily charged to a positive polarity are preferable. When the toner is positively chargeable, urethane rubber, urethane resin, silicone rubber, silicone resin, polyester resin, fluorine-based resin (for example, Teflon resin), polyimide resin, and those which are easily charged to negative polarity are preferable. The sleeve contact part is resin,
In the case of a molded article such as rubber, metal oxides such as silica, alumina, titania, tin oxide, zirconia, and zinc oxide, carbon black, and a charge generally used for toner are used to adjust the chargeability of the toner. It is also preferable to include a control agent and the like.

The base on the upper side of the elastic blade is fixed and held on the developer container side, and the lower side is bent in the forward or reverse direction of the developing sleeve against the elasticity of the blade, and the inner side of the blade is (In the case of the opposite direction, the outer surface side) is brought into contact with the sleeve surface with moderate elastic pressure. FIG. 6 shows an example of the image forming apparatus. According to such an apparatus, a thin and dense toner layer can be obtained more stably with respect to environmental fluctuations. Although the reason is not always clear, the toner particles are forcibly rubbed against the sleeve surface by the elastic blade as compared with a device in which a commonly used metal blade is mounted at a certain distance from the sleeve. It is presumed that the charging is always performed in the same state regardless of the change in the behavior due to the change.

On the other hand, the toner tends to be excessively charged and the toner on the sleeve and the blade is easily fused. However, the toner of the present invention is preferably used because its triboelectric chargeability is stable.

In the case of the magnetic one-component developing method, the contact pressure between the blade and the sleeve is 0.1 kg / m or more, preferably 0.3 to 25 kg, as the linear pressure in the sleeve generatrix direction.
/ M, more preferably 0.5 to 12 kg / m is effective. If the contact pressure is less than 0.1 kg / m, it becomes difficult to apply the toner uniformly, and the charge amount distribution of the toner becomes broad, causing fogging and scattering. The contact pressure is 2
If it exceeds 5 kg / m, a large pressure is applied to the developer,
Since the developer deteriorates, it is not preferable that the developer aggregates. Further, a large torque is required to drive the developer carrier, which is not preferable.

The gap α between the latent image carrier and the toner carrier is
For example, the thickness is set to 50 to 500 μm, and when a magnetic blade is used as the doctor blade, the gap between the magnetic blade and the toner carrier is preferably set to 50 to 400 μm.

The layer thickness of the magnetic toner layer on the toner carrier is
It is most preferable that the gap is smaller than the gap α between the latent image holding member and the toner carrying member. The layer thickness of the toner layer may be regulated.

Further, the sleeve is set at 10
It is rotated at a peripheral speed of 0 to 200%. The alternating bias voltage is 0.1 kV or more in peak to peak, preferably 0.2 to 3.0 kV, more preferably 0.3 to 2.0 k.
V is good. The alternating bias frequency is 1.0 to
It is used at 5.0 kHz, preferably 1.0 to 3.0 kHz, and more preferably 1.5 to 3.0 kHz. As the alternating bias waveform, a waveform such as a rectangular wave, a sine wave, a sawtooth wave, and a triangular wave can be applied. Also, asymmetrical AC biases having different positive and reverse voltages and times can be used. It is also preferable to superimpose a DC bias.

In the present invention, the sleeve is made of a material such as metal or ceramics. Aluminum or SUS is preferable from the viewpoint of charging property to the toner. The sleeve can be used as it is drawn or cut.However, in order to control the toner transportability and triboelectricity, the sleeve is polished, roughened in the circumferential or longitudinal direction, or blasted. , Coating and the like are performed. In the present invention, blast treatment may be performed, and shaped particles and irregular shaped particles are used as a blasting agent, and they may be used alone or in combination, and may be used as a blasting agent.

As the irregular shaped particles, arbitrary abrasives can be used.

As the regular shaped particles, for example, various hard spheres made of metal such as stainless steel, aluminum, steel, nickel, and brass having a specific particle size or various hard spheres such as ceramic, plastic, and glass beads can be used. it can. As the shaped particles, spherical or spheroidal particles having substantially a curved surface and a ratio of major axis / minor axis of 1 to 2 (preferably 1 to 1.5, more preferably 1 to 1.2) Is preferred. Therefore, it is preferable that the diameter (or long diameter) of the fixed particles used in the blasting process on the surface of the developing sleeve is 20 to 250 μm. In the case of repeated striking, the regular blast particles are preferably larger than the irregular blast particles, particularly preferably 1 to 20 times, more preferably 1.5 to 9 times.

When performing the overstrike treatment with the regular particles, it is preferable that at least one of the treatment time and the collision force of the treated particles is made smaller than that of the irregular particle blast.

As the developing sleeve, those having a coating layer containing conductive fine particles formed on the surface of the sleeve are also preferable. The conductive fine particles are preferably carbon fine particles, or carbon fine particles and crystalline graphite, or crystalline graphite.

The crystalline graphite used in the present invention is roughly classified into natural graphite and artificial graphite. Artificial graphite is obtained by solidifying pitch coke with tar pitch or the like, firing it at about 1,200 ° C, and then putting it into a graphitization furnace.
By processing at a high temperature of about 2,300 ° C., carbon crystals grow and change to graphite. Natural graphite is produced from underground, completely graphitized by natural geothermal heat and underground high pressure for a long time. Since these graphites have various excellent properties, they have wide industrial applications. Graphite is a dark gray or black glossy, very soft, lubricating crystalline mineral that is used in pencils and other materials and has heat resistance and chemical stability, so it can be used as a powder in lubricants, fire-resistant materials, electrical materials, etc. It is used in the form of solids and paints. The crystal structure includes hexagonal and other rhombohedral, and has a complete layer structure. Regarding electrical properties, free electrons exist between carbon and carbon bonds, and are good conductors of electricity. The graphite used in the present invention may be either natural or artificial.

Further, the graphite used in the present invention preferably has a particle size of 0.5 μm to 20 μm.

The polymer material forming the coating layer is, for example, styrene resin, vinyl resin, polyether sulfone resin, polycarbonate resin, polyphenylene oxide resin, polyamide resin, fluororesin, cellulose resin, acrylic resin. Thermosetting resin such as resin, epoxy resin, polyester resin, alkyd resin, phenol resin, melamine resin, polyurethane resin, urea resin, silicone resin, polyimide resin, etc. it can. Among them, those having excellent releasability such as silicone resin and fluorine resin, or those having excellent mechanical properties such as polyether sulfone, polycarbonate, polyphenylene oxide, polyamide, phenol resin, polyester, polyurethane and styrene resin are more preferable. preferable.

The conductive amorphous carbon is generally defined as “an aggregate of crystallites formed by burning or thermally decomposing a compound containing a hydrocarbon or carbon in an insufficient air supply”. . In particular, it is excellent in electric conductivity, and is widely used because it can be filled with a polymer material to impart conductivity, or a certain degree of conductivity can be obtained by controlling the amount of addition. The particle diameter of the conductive amorphous carbon used in the present invention is preferably from 10 mμ to 80 mμ, more preferably from 15 mμ to 40 mμ.

Next, an example of a developing method in the case of performing non-magnetic one-component development using the toner of the present invention will be described, but the invention is not necessarily limited thereto. FIG. 7 shows an apparatus for developing an electrostatic image formed on a latent image holding member. 70
Reference numeral 8 denotes a latent image holding member, and a latent image is formed by an electrophotographic process unit or an electrostatic recording unit (not shown). 709
Denotes a developing sleeve, which is formed of a non-magnetic sleeve made of aluminum or stainless steel.

As the developing sleeve, a rough tube of aluminum or stainless steel may be used as it is, but preferably the surface is uniformly roughened by spraying glass beads or the like, mirror-finished, or coated with a resin or the like. Those are good, and are the same as those used in the magnetic one-component developing method.

The toner 700 is stored in the hopper 701, and is supplied onto the developer carrier by the supply roller 702. The supply roller is made of a foam material such as polyurethane foam, and rotates in a forward or reverse direction at a relative speed other than 0 with respect to the toner carrier, and together with the toner supply, the developed toner (undeveloped) on the toner carrier. Toner). The toner supplied on the toner carrier is uniformly and thinly applied by the toner application blade 703.

The contact pressure between the toner application blade and the toner carrier is 0.3 to 2 as a linear pressure in the sleeve generatrix direction.
5 kg / m, preferably 0.5 to 12 kg / m is effective. If the contact pressure is less than 0.3 kg / m, it becomes difficult to apply the toner uniformly, and the charge amount distribution of the toner becomes broad, causing fogging and scattering. If the contact pressure exceeds 25 kg / m, a large pressure is applied to the toner, and the toner is deteriorated. Further, a large torque is required to drive the toner carrier, which is not preferable. That is, by adjusting the contact pressure to 0.3 to 25 kg / m, the aggregation of the toner of the present invention can be effectively loosened, and the charge amount of the toner can be instantaneously increased. Become.

The toner thinning regulating member is similar to that used in the magnetic one-component developing method. The elastic blade and the elastic roller are preferably made of a material of a triboelectric series suitable for charging the toner to a desired polarity, and are similar to those used in the magnetic one-component developing method. In the present invention, silicone rubber, urethane rubber, styrene-butadiene rubber and the like are preferred. In addition, polyamide,
Polyimide, nylon, melamine, melamine cross-linked nylon, phenolic resin, fluororesin, silicone resin,
An organic resin layer such as a polyester resin, a urethane resin, and a styrene resin may be provided. Also, conductive rubber, conductive resin, etc. are used.Fillers such as metal oxides, carbon black, inorganic whiskers, inorganic fibers, etc. and charge control agents are used in the rubber of the blade according to those used in the magnetic one-component developing method. It is preferable because it imparts appropriate conductivity and charge imparting properties such as being dispersed in a resin, and can appropriately charge the toner.

In the system proposed in the present invention in which a thin layer of toner is coated on a developing sleeve by a blade, the thickness of the toner layer on the developing sleeve is set to a value between the developing sleeve and the developing sleeve in order to obtain a sufficient image density. It is preferable that the gap length is smaller than the length of the opposing gap with the image carrier, and an alternating electric field is applied to this gap. That is, by applying an alternating electric field or a developing bias in which a DC electric field is superimposed on the alternating electric field between the developing sleeve 709 and the latent image holder 708 by the bias power supply 704 shown in FIG. The movement of the toner upward can be facilitated, and a higher quality image can be obtained. These conditions also conform to the magnetic one-component developing method.

The toner of the present invention has good releasability and excellent transferability. Therefore, in the image forming method for transferring the toner image formed on the latent image holding member to a recording material or an intermediate transfer member, the recording material is used. It is preferably used in an image forming method in which toner images on a plurality of latent image holders are multiplex-transferred onto an upper or intermediate transfer member.

In an image forming method for transferring a toner image formed on a latent image holding member or an intermediate transfer member to a recording material, a plurality of toner images are formed on the latent image holding member or the intermediate transfer member. It is also preferably used in an image forming method for transferring the multiple toner images collectively to a recording material.

Further, since the toner of the present invention is excellent in non-aggregation property and uniform charging property, a minute latent image can be faithfully reproduced, and a digital latent image can be beautifully developed. In particular, in full-color images, the reproduction of highlights and the reproduction of minute color differences are excellent, and the texture is full and smooth.
Since a fresh and pictorial full-color image can be obtained, a graphic image and a line character image can also be obtained beautifully, and it can be suitably used for digital full-color copying machines and printers.

The above-mentioned multiple transfer method will be described with reference to FIG. 8 by taking a full-color electrophotographic method as an example.

The electrostatic latent image formed on the photosensitive drum 1 by an appropriate means is transferred to the rotary developing unit 2 rotating in the direction of the arrow.
Is visualized by the developer having the first color toner and the carrier in the developing device 2-1 attached to the printer. The color toner image on the photosensitive drum is transferred by the transfer charger 8 to the transfer material S held on the transfer drum 6 by the gripper 7.

As the transfer charger, a corona charger or a contact charger is used. When a corona charger is used as the transfer charger 8, a voltage of -10 kV to +10 kV is applied.
The transfer current is from -500 μA to +500 μA. A holding member is stretched over the outer peripheral surface of the transfer drum 6, and the holding member is formed of a film-like dielectric sheet such as a polyvinylidene fluoride resin film or polyethylene terephthalate. For example, a sheet having a thickness of 100 μm to 200 μm and a volume resistance of 10 ¹² to 10 ¹⁴ Ω · cm is used.

Next, the rotary developing unit rotates as the second color, and the developing device 2-2 faces the photosensitive drum 1. Then, the toner image is developed by a developer having a second color toner and a carrier in the developing device 2-2, and this color toner image is also transferred onto the same transfer material as above.

Further, the third color and the fourth color are performed in the same manner.
As described above, the transfer drum 6 is rotated a predetermined number of times while holding the transfer material, and the toner images of a predetermined number of colors are multiplex-transferred. It is preferable that the transfer current for electrostatic transfer be increased in the order of first color <second color <third color <fourth color in order to reduce transfer residual toner remaining on the photosensitive drum.

On the other hand, it is not preferable to increase the transfer current because the transferred image is disturbed. However, since the toner of the present invention has excellent transferability, the second, third, and fourth colors during multiple transfer can be firmly transferred. Therefore, an image of any color is properly formed, and a sharp multicolor image can be obtained. Further, in a full-color image, a beautiful image excellent in color reproduction can be obtained. Moreover, since it is not necessary to increase the transfer current so much, it is possible to reduce the disturbance of the image in the transfer step. When the transfer material is separated from the transfer drum 6, the charge is removed by the separation charger 9. However, if the transfer current is large, the electrostatic attraction of the transfer material to the transfer drum increases, and the current at the time of separation does not increase. And cannot be separated. Then, since the polarity is opposite to the transfer current, the toner image is disturbed and the toner is scattered from the transfer material, and the inside of the image forming apparatus is stained. Since the toner of the present invention is easy to transfer, it is not necessary to increase the separation current, and the separation can be facilitated.
As a result, it is possible to prevent the image from being disturbed at the time of separation and toner scattering. Therefore, the toner of the present invention is preferably used in an image forming method for forming a multicolor image and a full-color image having a multiple transfer process.

The transfer material subjected to the multiple transfer is separated from the transfer drum 6 by a separation charger 9, and the heating and pressing roller fixing device 1 having a web impregnated with silicone oil is used.
The image is fixed at 0 and is added and mixed at the time of fixing to form a full-color copy image.

The replenishing toner supplied to the developing units 2-1 to 2-4 is supplied from a replenishing hopper provided for each color to the center of the rotary developing unit 2 via a toner transport cable by a fixed amount based on a replenishing signal. And is sent to each developing device.

The above-described multiple development batch transfer method will be described with reference to FIG. 9 using a full-color electrophotographic printer as an example.

The electrostatic latent image formed on the photosensitive drum 21 by the charger 22 and the exposure unit 23 using laser light is
4, 25, 26, and 27 sequentially develop and visualize the toner. In the development process, a non-contact development method is preferably used. According to the non-contact developing method, the developer layer in the developing device does not rub against the surface of the image forming body.
In the subsequent and subsequent development steps, development can be performed without disturbing the image formed in the preceding development step. In the order of development, in the case of multiple colors, it is preferable to develop a color other than black, starting with a color having high lightness and high saturation. In the case of full color, it is preferable to develop in the order of yellow, then magenta or cyan, then the remaining magenta or cyan, and finally black.

A multicolor multiplex image formed on the photosensitive drum,
The full-color image is transferred to the transfer material S by the transfer roller 29. In the transfer step, an electrostatic transfer method is preferably used, and a corona discharge and a contact transfer method are used. In this method, a transfer charger for generating corona discharge via a transfer material is arranged so as to face an image, and a corona discharge is applied from the back surface of the transfer material to electrostatically transfer. The other is a method in which a transfer roller or a transfer belt is brought into contact with an image forming body via a transfer material to apply a bias to the roller, or to perform electrostatic transfer from the back surface of the belt. By this electrostatic transfer method, the multicolor toner image carried on the surface of the image forming body is collectively transferred to the transfer material. In such a batch transfer method, since the amount of toner to be transferred is large, the remaining amount of transfer is large, transfer unevenness is likely to occur, and color unevenness is likely to occur in a full-color image.

However, the toner of the present invention is excellent in transferability, and all colors are properly formed in a multicolor image. In a full-color image, a beautiful image with excellent color reproducibility can be obtained. Further, since the transfer efficiency is good even at a low current, it is possible to reduce disturbance of the image at the time of transfer. Further, the separation is facilitated, so that the disturbance toner scattering of the image at the time of separation can be reduced. Also, since it has excellent release properties, it exhibits good transferability even in the contact transfer means. Therefore, the toner of the present invention is also preferably used in an image forming method having a multiple development batch transfer step.

The transfer material on which the multicolor toner images are collectively transferred is
The image is separated from the photosensitive drum 21 and fixed by the heat roller fixing device 32 to form a multicolor image.

Further, an image forming method using the intermediate transfer member will be described with reference to FIG. A charging roller 42 that rotates in contact with the photosensitive drum 41 has a surface potential on the photosensitive drum 41 and forms a latent image by an exposure unit 43. The latent image is developed by the developing units 44, 45, 46, 47 to form a toner image. The toner image is multiplex-transferred on the intermediate transfer member 48 for each color, and a multiplex toner image is formed. The intermediate transfer member 48 is in the form of a drum and has a holding member stretched on the outer peripheral surface, and a conductive member such as carbon black, zinc oxide, tin oxide, silicon carbide, titanium oxide, etc. is sufficiently coated on the base material. A material having a dispersed elastic layer (for example, nitrile butadiene rubber) is used. Further, a belt-shaped intermediate transfer member may be used. The hardness of the intermediate transfer member is 10
It is preferable that the transfer member is formed of an elastic layer having a hardness of about 50 degrees (JIS K-6301) or, in the case of a transfer belt, a support member having an elastic layer having this hardness at a transfer portion to a transfer material. From the photosensitive drum 41 to the intermediate transfer member 48
The transfer to the toner image is performed by applying a bias to the core metal 55 of the intermediate transfer member 48 from the power supply 49 to obtain a transfer current. Corona discharge or roller charging from the back of the holding member or belt may be used. The toner image on the intermediate transfer body 48 is collectively transferred onto the transfer material S by the transfer means 51. As the transfer unit, a contact electrostatic transfer unit using a corona charger, a transfer roller, or a transfer belt is used. Such an image forming method is preferably used because the effects of the above two methods can be obtained.

An image forming method in which images of a plurality of colors are formed in an image forming section, and the images are sequentially superimposed and transferred on the same transfer material will be described with reference to FIG.

A multicolor electrophotographic color electrophotographic apparatus for obtaining a color image includes a plurality of image forming units, and each image forming unit forms a visible image (toner image) having a different color. There is an image forming method in which the toner images are sequentially superimposed and transferred onto the same transfer material.

In this image forming method, for example, FIG.
There is a configuration shown in FIG. Here, the first, second,
Third and fourth image forming units P _a , P _b , P _c , and P _d are arranged side by side, and the image forming units are respectively dedicated image carriers,
It is provided with a so-called photosensitive drum 61 _a, 61 _b, 61 _c and 61 _d.

[0230] photosensitive drum 61 _a to 61 _d is a latent image forming unit 62 _a on the outer peripheral side, 62 _b, 62 _c and 62 _d, the developing unit 63 _a, 63 _b, 63 _c and 63 _d, transferring discharge section 6
4 _a, 64 _b, 64 _c and 64 _d, and the cleaning unit 65 _a, 65 _b, 65 _c and 65 _d are disposed.

[0231] In this structure, first, the original image by the latent image forming unit 62 _a, for example, a yellow component color latent image is formed on the photosensitive drum 61 _a of the first image forming portion P _a. Latent image is a visible image with a developer having a yellow toner of the developing unit 63 _a, at the transfer portion 64 _a, is transferred to the transfer material S.

[0232] On the other hand, while the yellow image as described above is transferred to the transfer material S, the second image forming unit P _b in a magenta component color latent image is formed on the photosensitive drum 61 _b, followed by development It is visible image with a developer having a magenta toner in parts 63 _b. This visible image (magenta toner image)
, When the transfer material S that transfer of the first image forming portion P _a of the is finished it is carried to the transfer section 64 _b, are transferred to overlap the position of the transfer material S.

Hereinafter, the third and fourth steps are performed in the same manner as described above.
The cyan and black images are formed by the image forming units P _c and P _d of the same transfer material.
The black color is superimposed and transferred. When such an image forming process is completed, the transfer material S is transferred to the fixing unit 67.
To fix the image on the transfer material. Thus, a multicolor image is obtained on the transfer material S. On the other hand, each of the photosensitive drums 61 _a , 61 _b , 61 _c and 61 _d to which the transfer has been completed is a cleaning unit 65 _a , 65 _b , 65 _c and 65.
_The residual toner is removed by _d, and is provided for the subsequent formation of the next latent image.

In the above-described image forming apparatus, the transfer belt 68 is used to transfer the transfer material S.
In 1, the transfer material 6 is conveyed from right to left, in the conveying process, the image forming section P _a, P _b, the transfer unit 64 _a in the P _c and P _d, 64 _b, 64 _c and 64 _d And is transcribed.

In this image forming method, a conveyance belt using a mesh of tetron fiber as a conveyance means for conveying a transfer material, a polyethylene terephthalate resin, a polyimide resin, a urethane resin, from the viewpoint of ease of processing and durability. For example, a conveyor belt using a thin dielectric sheet is used.

[0236] When the transfer material S passes through the fourth image forming portion P _d, AC voltage is applied to the static eliminator 69, the transfer material S is neutralization, is separated from the belt 68 and then placed into a fixing device 67, the image The toner is fixed and discharged from the discharge port 70.

In this image forming method, each image forming section is provided with an independent image carrier, and the transfer material is sequentially sent to the transfer section of each image carrier by a belt-type conveying means. It may be configured as follows.

In this image forming method, the image forming section is provided with an image carrier common to the image forming section, and the transfer material is repeatedly sent to the transfer section of the image carrier by a drum type conveying means. You may comprise so that transfer of each color may be received.

However, since the transport belt has a high volume resistance, the transport belt does not have the same structure as the color image forming apparatus.
In the process of repeating the transfer several times, the transport belt increases the charge amount. For this reason, uniform transfer cannot be maintained unless the transfer current is sequentially increased for each transfer.

Since the toner of the present invention has excellent transferability,
Even if the charging of the conveying means increases each time the transfer is repeated, the transferability of the toner in each transfer can be made uniform with the same transfer current, and a high-quality high-quality image can be obtained.

[0241]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples. Explained from the constituent materials of the toner used in the present invention,
First, the inorganic fine powder will be described.

Examples of Production of Treated Inorganic Fine Powder Table 1 shows the fine particles to be treated used in the examples.

[0243]

[Table 1]

The processing method was as follows.

In a container of an organic solvent method (solvent method) , 1 kg of toluene and 200 g of fine powder particles to be treated are put into a vessel, and stirred by a mixer to form a slurry. With stirring. This slurry was applied to a sand mill using zirconia balls as a medium for 30 minutes.

The slurry was taken out of the sand mill, and
After removing toluene under reduced pressure at a temperature of 200 ° C., the mixture was dried at 200 to 300 ° C. for 2 hours while stirring in a stainless steel container. The powder obtained here was subjected to crushing treatment with a hammer mill to obtain a treated inorganic fine powder.

Gas phase method 1 (gas 1 method) 20 g of fine powder particles to be treated were placed in a closed high-speed stirring mixer, and purged with nitrogen. The treatment agent is diluted with an appropriate amount of n-hexane, if necessary, and sprayed with gentle stirring. Further, 180 g of particles to be treated are added, and at the same time, the remaining amount of the treatment agent is sprayed, and the addition is completed. Thereafter, the mixture was stirred at room temperature for 10 minutes, and then heated while stirring at a high speed for 200 to 300 minutes.
The temperature was raised to ° C. and the mixture was stirred for 1 hour. The temperature was returned to room temperature while stirring, and the powder was taken out of the mixer and crushed by a hammer mill to obtain a treated inorganic fine powder.

Gas phase method 2 (gas 2 method) A volatile titanium compound (for example, titanium tetraisopropoxide) was vaporized in an evaporator at 200 ° C. under a nitrogen atmosphere. Water is vaporized in an evaporator under a nitrogen atmosphere, and 500
It was introduced into a heater heated to ° C. The vaporized titanium compound and heated steam were introduced into a reactor heated to 250 ° C. and hydrolyzed to obtain titanium oxide particles. Here, the prescribed amount of the treatment agent was vaporized in a nitrogen atmosphere in an evaporator heated to 200 ° C. or atomized in a nitrogen atmosphere at 200 ° C. and introduced into a reaction vessel. The introduction into the reactor was conducted so as to be mixed with the treating agent after the titanium oxide was formed. The above operation was performed under a nitrogen stream, and the treated particles were collected with a filter.

The production method and formulation of the treated inorganic fine powder used in the examples are shown in Table 2, and the physical properties are shown in Table 3. The processing amount of the processing agent / diluent is part by mass with respect to 100 parts by mass of the fine powder particles to be processed.

[0250]

[Table 2]

[0251]

[Table 3]

Production Examples of Binder Resin Polyester Resin 1 Terephthalic acid 6.0 mol n-Dodecenyl succinic anhydride 3.0 mol Bisphenol A propylene oxide 2.2 mol adduct 10.0 mol Trimellitic anhydride 0.7 mol Dibutyltin oxide 0 .1g

The above compound was placed in a reactor, and a thermometer, a stir bar, a condenser, and a nitrogen inlet tube were attached. After the atmosphere was replaced with nitrogen, the temperature was gradually increased while stirring, and the reaction was carried out at 180 ° C. for 5 hours. Then, the temperature was raised to 200 ° C., and the pressure was reduced (15 h).
Pa), and the mixture was reacted for 4 hours to be dehydrated and condensed, and the reaction was completed to obtain a polyester resin 1. This polyester resin has a peak molecular weight of 10,700 and a glass transition point of 63 ° C.
Met.

Polyester resin 2 Terephthalic acid 9.5 mol Bisphenol A ethylene oxide 2.2 mol adduct 5.0 mol Cyclohexanedimethanol 5.0 mol Dibutyltin oxide 1.0 g

The above compound was placed in a reactor, and a thermometer, a stir bar, a condenser, and a nitrogen inlet tube were attached. After the atmosphere was replaced with nitrogen, the temperature was gradually increased while stirring, and the reaction was carried out at 240 ° C. for 6 hours. Was. Next, the mixture was reacted under reduced pressure (15 hPa) for 2 hours for dehydration and condensation, and the reaction was terminated to obtain a polyester resin 2.

This polyester resin had a peak molecular weight of 9,100 and a glass transition point of 62 ° C.

Epoxy resin 3 Bisphenol A type liquid epoxy resin 2000 g (Epoxy equivalent of a condensate of bisphenol A and epichlorohydrin, 188, viscosity 13,000 mPa · s / 25 ° C.) Bisphenol A 937 g p-cumylphenol 559 g xylene 400 g

The above compound was placed in a reactor, and a thermometer, a stir bar, a condenser, and a nitrogen inlet tube were attached thereto. After the atmosphere was replaced with nitrogen, the temperature was gradually raised to 70 ° C. with stirring. Add 64 g of 5N aqueous solution, and add
Then, xylene and water were distilled off under reduced pressure to release the reduced pressure, and the reaction was carried out for 6 hours. 184 g of ε-caprolactone was added thereto and reacted for 6 hours to obtain a modified epoxy polyol resin (Epoxy resin 3).

This polyol resin has a peak molecular weight of 7,
600 and a glass transition point of 60 ° C.

Styrene resin 4 Styrene 1600 g Butyl acrylate 400 g 2,2-Bis (4,4-di-t-butylperoxycyclohexyl) propane 4 g

From the above compounds, polymer A was obtained by a suspension polymerization method.

Styrene 2550 g Butyl acrylate 450 g Di-t-butyl peroxide 60 g

From the above compounds, a polymer B was obtained by a solution polymerization method using xylene as a solvent.
The solutions were mixed at a mass ratio of 5:75 to obtain a styrene resin 4. This styrenic resin has peak molecular weights of 9,400 and 720,000 and a glass transition point of 6
It was 0 ° C.

Production Example of Classified Product (Toner Particles) Classified Product 1 100 parts by weight of polyester resin 1 Copper phthalocyanine phthalimide derivative pigment 5 parts by mass Chromium di-t-butylsalicylate complex 4 parts by mass

After the above raw materials were premixed with a Henschel mixer, they were melted and kneaded with a twin screw extruder set at 130 ° C. After cooling the kneaded material, finely pulverized by a pulverizer using a jet stream, and classified using an air classifier,
Classified cyan product with a weight average diameter of 8 μm (cyan toner particles)
1 was obtained.

The pigment was C.I. I. Pigment Re
d122 5 parts by mass, C.I. I. Pigment Ye
magenta classified product (magenta toner particles) 1, yellow classified product (yellow toner particles) 1, black classified product (black toner particles) 1 in the same manner except that 3.5 parts by mass of low 17 and 5 parts by mass of carbon black were used. I got

Classified product 2 100 parts by mass of polyester resin 2 C.I. I. Pigment Blue 15: 3 5 parts by mass Chromium di-t-butylsalicylate complex 4 parts by mass

After the above raw materials were premixed with a Henschel mixer, they were melted and kneaded with a twin screw extruder set at 130 ° C. After cooling the kneaded material, finely pulverized by a pulverizer using a jet stream, and classified using an air classifier,
Classified cyan product with a weight average diameter of 8 μm (cyan toner particles)
2 was obtained.

The pigment was C.I. I. Pigment Re
d 57: 15 parts by mass, C.I. I. Pigment Ye
magenta classified product (magenta toner particles) 2, yellow classified product (yellow toner particles) 2, black classified product (black toner particles) 2 except that 3.5 parts by mass of low 17 and 5 parts by mass of carbon black were used. I got

Classified product 3 100 parts by mass of epoxy resin 3 C.I. I. Pigment Blue 15: 3 5 parts by mass Chromium di-t-butylsalicylate complex 4 parts by mass

After the above raw materials were premixed with a Henschel mixer, they were melted and kneaded with a twin screw extruder set at 130 ° C. After cooling the kneaded material, finely pulverized by a pulverizer using a jet stream, and classified using an air classifier,
8 μm weight average diameter cyan classified product (cyan toner particles) 3
I got

The pigment was C.I. I. Pigment Re
d122 5 parts by mass, C.I. I. Pigment Ye
Magenta classified product (magenta toner particles) 3, yellow classified product (yellow toner particles) 3, and black classified product (black toner particles) 3 were obtained in the same manner except that 5 parts by mass of low 83 and 5 parts by mass of carbon black were used. Was.

Classified product 4 Styrene resin 4 100 parts by mass Copper phthalocyanine phthalimide derivative pigment 5 parts by mass Quaternary ammonium salt 1 part by mass Low molecular weight ethylene propylene copolymer 3 parts by mass

After the above raw materials were premixed with a Henschel mixer, they were melted and kneaded with a twin screw extruder set at 130 ° C. After cooling the kneaded material, finely pulverized by a pulverizer using a jet stream, and classified using an air classifier,
Weight average diameter 8 μm cyan classified product (cyan toner particles) 4
I got

The pigment was C.I. I. Pigment Re
d 57: 15 parts by mass, C.I. I. Pigment Y
Magenta classified product (magenta toner particles) 4, yellow classified product (yellow toner particles) 4, and black classified product (black toner particles) 4 were obtained in the same manner except that 5 parts by mass of Yellow 97 and 5 parts by mass of carbon black were used. Was.

Classified product 5 Styrene resin 4 100 parts by weight Magnetite (magnetic iron oxide) 80 parts by weight Chromium di-t-butylsalicylate complex 2 parts by weight Low molecular weight ethylene propylene copolymer 3 parts by weight

After the above raw materials were premixed with a Henschel mixer, they were melted and kneaded with a twin screw extruder set at 130 ° C. After cooling the kneaded material, finely pulverized by a pulverizer using a jet stream, and classified using an air classifier,
A black-classified product (black toner particles) 5 having a weight average diameter of 8 μm was obtained.

Production Example of Toner and Developer To 100 parts by mass of the classified product (toner particles), the composition shown in Table 4 was sufficiently stirred with a Henschel mixer, and the inorganic fine powder of the present invention was externally added and mixed. I got

When used as a one-component toner, the developer was used as it was, and when used as a two-component toner, the following developer was used.

The cyan toner 1, the magenta toner 1, the yellow toner 1, and the black toner 1 were mixed with a Cu—Zn—Fe ferrite carrier coated with a silicone resin at 0.45% by mass so as to have a toner concentration of 5% by mass. A developer was used.

The cyan toner 11, the magenta toner 2, the yellow toner 2, and the black toner 2 were prepared by mixing a styrene-butyl methacrylate copolymer (mass ratio 80:20) with 0.3.
5% by mass and a Cu-Zn-Fe-based ferrite carrier coated with 0.15% by mass of a silicone resin were mixed with a toner so as to have a toner concentration of 7% by mass to obtain a developer.

The cyan toner 12, the magenta toner 3, the yellow toner 3, and the black toner 3 each contain 2.5 parts of a styrene-methyl methacrylate copolymer (mass ratio 65:35).
The mixture was mixed with a Cu-Fe-based ferrite carrier coated at a concentration of 7% by mass so as to have a toner concentration of 7% by mass to obtain a developer.

[0283]

[Table 4]

Reference Example 1 A commercially available digital full-color electrophotographic copying machine (color laser copier 550) having the structure shown in FIG.
5,000 print endurance tests were conducted at 23 ° C. and 60% RH. At this time, the developing device was modified so as to perform one-component development. Specifically, a doctor blade is attached to an elastic plate of a phosphor bronze plate having a thickness of 150 μm with urethane rubber having a thickness of 1 mm, and a surface having a thickness of 20 μm
Was replaced with an elastic blade provided with a nylon resin layer, and was placed so as to contact the sleeve at a linear pressure of 4 kg / m. Also, using a urethane foam rubber roller as the supply roller,
The developing sleeve was changed to one in which the magnet was removed from the inside and the sleeve surface was blasted with # 600 glass beads. A charging roller is used as a contact charging member for primary charging, and a basic structure includes a core metal at the center and a conductive elastic layer whose outer periphery is formed of epichlorohydrin rubber containing carbon black. The charging roller is pressed against the photosensitive drum surface with a pressing force of a linear pressure of 4 kg / m, and rotates following the rotation of the photosensitive drum. Further, the charging roller is in contact with a felt pad as a cleaning member.

The density was measured by using a Macbeth densitometer RD918 type (manufactured by Macbeth) to measure the reflection density using an SPI filter, and measuring a 5 mm circle image to obtain the image density.

The fog on the image was measured using a reflection densitometer (Reflectometer Model TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.).
The reflection average density of the transfer material before image formation is assumed to be Dr, and Ds-
The fog was evaluated using Dr as the fog amount. When this value is 1% or less, fogging is at a very good level. When it is 1.5% or less, an image having substantially good fog is obtained. When it is 2% or less, there is no practical problem.

The transfer efficiency is determined from the change in the Macbeth density of the toner image before and after the transfer on the photosensitive drum when the transfer current is 275 μA. The Macbeth density of the image after fixing on the transfer paper is 1.
When the transfer rate reaches 5, the image polyester film before and after the transfer on the photosensitive drum is transferred with an adhesive tape, and each and the tape alone are stuck to transfer paper, and Macbeth density measurement is performed. When the density before transfer is D _a , the density after transfer is D _b , and the density of the tape alone is D _c , the transfer efficiency is defined by the following equation.

Transfer efficiency = ｛[(D _a −D _c ) − (D _b −
D _c )] / (D _a −D _c )｝ × 100

That is, the higher the value, the higher the transfer efficiency and the better the transferability.

The transfer latitude is determined by forming a 16-gradation image and fixing the transferred image obtained by changing the transfer current. The range of the transfer current in which an image of all gradations is obtained with a transfer unevenness, roughness, and an image with good sparseness is obtained. That is, if the transferability is excellent, the transfer is performed properly even with a low transfer current, and an image having a firm image density without transfer unevenness and a gradation can be obtained. In addition, since the toner having excellent transferability does not require an excessively high transfer current, an image having a rough surface and good clarity can be obtained. That is, a toner having a good transfer property and having a wide range from a low transfer current value to a transfer upper limit is excellent in transferability and has a wide transfer latitude. That is, if the transfer latitude is wide, the application range of the transfer material and the image forming environment is widened, and the transfer control of the image forming apparatus can be made easy.

[0291] With regard to the blank portion in the transfer, the blank portion in the character portion was visually determined. A: There is almost no hollow. B: There is a slight void. C: There is a void, but there is no practical problem. D: The void is conspicuous and practically impossible.

The gradation was determined by visually observing a 16-gradation image. A: 16 gradations can be confirmed, the halftone portion has no roughness, and the highlight portion is reproduced properly. B:
Although 16 gradations can be confirmed, a slight roughness is observed in the halftone portion. C: Highlight portion reproduction is getting worse, but there is no practical problem. D: 14 gradations or more could not be confirmed, and practically impossible.

Table 5 shows the fog on the 5,000th sheet, image density, omission during transfer in the line portion, gradation, transfer efficiency at the time of 1,000 sheets, and transfer latitude at the initial stage of the test.

Table 6 shows image defects due to contamination and scratches on the photosensitive member, image defects due to contamination of the charging roller, and poor cleaning at 5,000 sheets.

An image defect due to contamination was determined as follows. A: There is no image defect at all. B: A spot-like or streak-like pattern due to dirt is slightly generated. C: A spot-like or streak-like pattern due to dirt appears or density unevenness occurs, but there is no practical problem. D: The influence of dirt and scratches is great, fusing, filming, etc. occur, many images other than the latent image appear on the image, and uneven density and uneven charging occur, disturbing the image. I have.

Further, a printing durability test was performed in an environment of 30 ° C. and 80% RH. The test was started after the developing device and the toner for replenishment were applied to the test environment for one week, and 5,000 sheets were printed. Initial, 5,000th sheet fog, image density,
Table 7 shows omissions during transfer, gradation, image defects due to contamination and scratches on the photoreceptor, image defects due to contamination of the charging roller, and poor cleaning.

As shown in Tables 5 to 7, the cyan toner 1 of the present invention has a high image density, no fog, no dropout in the line portion, excellent gradation, and no image defects due to contamination and scratches. A clear cyan image was obtained. In addition, the transfer efficiency was good, and the toner had a wide transfer latitude.

Reference Examples 2 to 8 Cyan toners 2, 3, 6, 7, 8, 9, and 10 were used in Reference Example 1.
Tables 5 to 7 show the results of the same evaluation.

Comparative Example 1 Tables 5 to 7 show the results of the same evaluation as in Reference Example 1 for cyan toner 4. Although there was no problem with the hollow portion of the character portion and the transfer latitude, the initial fog was particularly poor under high humidity.

Comparative Example 2 The same evaluation as in Reference Example 1 was performed on the cyan toner 5 and the results are shown in Tables 5 to 7. Although there was no problem with the developability, it was inferior in the hollow portion of the character portion and the transfer latitude.

[0301] Example 1 Cyan Toner 1, Magenta Toner 1, Yellow Toner 1, a black toner 1 remodeled digital full-color electrophotographic copying machine used in Reference Example 1 (Color Laser Copier 55
0, manufactured by Canon Inc.), and a full-color copying test of 2,000 sheets was conducted at 23 ° C. and 60% RH. As a result, a beautiful pictorial image excellent in color reproduction and gradation and without color unevenness was obtained, and the color difference of the image during transfer was hardly observed. The fog was 1.1% or less at the worst value of the four colors superposed, and there was no problem during the running.

Further, a copy test was performed in an environment of 30 ° C. and 80% RH. 2,000 copies were made after the developing device and toner for replenishment were allowed to adjust to the test environment for one week. As a result, a beautiful full-color image was obtained, and the fog was 1.2% or less at the worst value when four colors were superimposed, and there was no problem at the initial stage.

Example 2 Cyan Toner 1, Magenta Toner 1, Yellow Toner 1
The developer and black toner 5 prepared from the above were transferred to a commercially available digital full-color electrophotographic copying machine (Color Laser Copier 550, manufactured by Canon Inc.) at 23 ° C. and 60%
2,000 full color copy tests were conducted under RH. At this time, the doctor blade of the black developing device was modified (to a magnetic cut type), and modified so that development and transfer could be performed from black. For cyan, magenta, and yellow, the two-component developing device was used as it was. As a result, a beautiful pictorial image excellent in color reproduction and gradation and without color unevenness was obtained, and almost no color difference was observed in the image being copied. The fog was 1.4% or less at the worst value when four colors were overlapped, and there was no problem during the running.

Further, a copy test was performed in an environment of 30 ° C. and 80% RH. 2,000 copies were made after the developing device and toner for replenishment were allowed to adjust to the test environment for one week. As a result, a beautiful full-color image was obtained, and the fog was 1.7% or less at the worst value when four colors were superimposed, and there was no problem at the initial stage.

Example 3 A commercially available digital full-color electrophotographic copying machine (Pretail 550 Co., Ltd.) using a transfer belt as an intermediate transfer member was prepared by using a developer prepared from cyan toner 11, magenta toner 2, yellow toner 2, and black toner 2. (Ricoh Co., Ltd.), and a full-color copying test was performed on 2,000 sheets at 23 ° C. and 60% RH. As a result, a beautiful full-color image excellent in color reproduction and without color unevenness was obtained, and almost no color difference was observed in the image being copied. The worst value of fogging of four sheets was 1.3% or less, and there was no problem.

Further, a copy test was performed in an environment of 30 ° C. and 80% RH. 2,000 copies were made after the developing device and toner for replenishment were allowed to adjust to the test environment for one week. As a result, a beautiful full-color image was obtained, and the fog was 1.6% or less at the worst value when four colors were superimposed, and there was no problem at the initial stage.

Example 4 A commercially available digital full-color electrophotographic copying machine (U-Bix 9028 Konica Corporation) of a multi-developing batch transfer system using a developer prepared from cyan toner 12, magenta toner 3, yellow toner 3, and black toner 3 Made)
A full-color copying test was performed on 2,000 sheets at 23 ° C. and 60% RH. As a result, a beautiful full-color image excellent in color reproduction and without color unevenness was obtained, and almost no color difference was observed in the image being copied. The worst value of fogging of four sheets was 1.0% or less, and there was no problem.

Further, a copy test was performed in an environment of 30 ° C. and 80% RH. 2,000 copies were made after the developing device and toner for replenishment were allowed to adjust to the test environment for one week. As a result, a beautiful full-color image was obtained, and the fog was 1.3% or less at the worst value when four colors were superimposed, and there was no problem at the initial stage.

Example 5 A digital full-color electrophotographic copying machine using the cyan toner 13, the magenta toner 4, the yellow toner 4, and the black toner 4 in Example 1 was used to print 2,000 sheets at 23 ° C. and 60% RH. A full color copy test was performed. However, the photosensitive drum is replaced with a positively charged α-Si photosensitive drum,
The elastic blade was changed to a stainless steel elastic plate with silicone rubber attached, and the power supply for primary charging, developing bias, transfer charging, and separation charging was modified so that image formation of positively chargeable toner could be performed.

As a result, a full-color image excellent in gradation and without color unevenness was obtained, and almost no color difference was observed in the image being copied. The worst value of fogging of four sheets was 1.4% or less, and there was no problem.

Further, a copy test was performed in an environment of 30 ° C. and 80% RH. 2,000 copies were made after the developing device and toner for replenishment were allowed to adjust to the test environment for one week. As a result, a good full-color image was obtained, and the fog was 1.9% or less at the worst value of four colors superimposed, and there was no problem at the initial stage.

Reference Examples 9 to 13 Commercially available electrophotographic copying machine NP-6016 (manufactured by Canon Inc.)
A bias power supply was modified so that reversal development of contact charging means, contact transfer means, elastic tip doctor blade, and urethane rubber blade cleaner was performed. Using this copier, black toner 5 to 9
Endurance copy test of 20,000 sheets at 23 ° C, 60% RH
And at 30 ° C. and 80% RH. Tables 8 and 9 show the results. Image density, fogging, filming, cleaning, transfer unevenness, charge unevenness, scratches on the photoreceptor, and contamination of the charging roller and the transfer roller were evaluated. The transfer omission was evaluated by using 200 g / m ² thick paper as the transfer material. The evaluation criteria are as follows.

(Scratch on Photoconductor) A: No scratch appears on the image. B: There is a scratch appearing in the halftone portion. C: There is a flaw appearing in a normal image.

(Surface condition of each member) A: No toner adhesion / contamination at all. B: Almost no sticking or contamination of toner. C: Toner is slightly adhered or contaminated. D: Toner sticking and contamination.

[0315]

[Table 5]

[0316]

[Table 6]

[0317]

[Table 7]

[0318]

[Table 8]

[0319]

[Table 9]

[0320]

Since the toner of the present invention contains an inorganic fine powder treated with a specific polysiloxane, it has excellent moisture resistance, mold release properties and chargeability, and has good developability, transferability and durability. Image forming method using a toner having excellent stability and storage stability.

That is, this is an image forming method capable of obtaining sufficient developability even under high humidity or long-term storage. further,
This is an image forming method with good transfer efficiency, a wide transfer latitude, and a beautiful pictorial full-color image can be easily obtained.

Further, there is provided an image forming method for suppressing omission during transfer in a line image portion and a character portion.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an image forming step used in the image forming method of the present invention.

FIG. 2 is a schematic view showing a primary charging step used in the image forming method of the present invention.

FIG. 3 is a schematic view illustrating a transfer step used in the image forming method of the present invention.

FIG. 4 is a schematic view showing a transfer step used in the image forming method of the present invention.

FIG. 5 is a schematic view showing a developing step used in the image forming method of the present invention.

FIG. 6 is a schematic view showing a developing step used in the image forming method of the present invention.

FIG. 7 is a schematic view showing a developing step used in the image forming method of the present invention.

FIG. 8 is a schematic view showing an image forming step used in the image forming method of the present invention.

FIG. 9 is a schematic view illustrating an image forming step used in the image forming method of the present invention.

FIG. 10 is a schematic view showing an image forming step used in the image forming method of the present invention.

FIG. 11 is a schematic view illustrating an image forming step used in the image forming method of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 photosensitive drum 2 developing unit 2-1, 2, 3, 4 developing device 3 exposure means 4 charger 5 holding member 6 transfer drum 7 gripper 8 transfer charger 9 separation charger 10 paper feed roller 11 separation claw 21 photosensitive drum 22 Charger 23 Exposure unit 24, 25, 26, 27 Developing device 28 Cleaner 29 Transfer roller 31 Static eliminator 32 Fixing device 41 Photosensitive drum 42 Charging roller 43 Exposure means 44, 45, 46, 47 Developing device 48 Intermediate transfer body 49 Power supply 50 Holding member 51 Transfer roller 53 Photosensitive drum cleaner 54 Intermediate transfer material cleaner 55 Core metal Pa, b, c, d Image forming unit 61-a, b, c, d Photosensitive drum 62-a, b, c, d Latent image formation Unit 63-a, b, c, d Developing unit 64-a, b, c, d Transfer discharge unit 65-a, b, c, d Cleaning unit 66- , B, c, d Charging device 67 Fixing device 68 Conveying belt 69 Separation and static eliminator 70 Outlet 71, 72 Adsorption charger 73-a, b, c, d Separation and static elimination discharge unit 90, 96 Developing sleeve 91 Hopper 92 Magnetic generation Means 93, 97 Doctor blade 94, 95 Latent image holder 101 Latent image holder (photoconductor, photosensitive drum) 101a Photoconductive layer 101b Conductive base layer 102 Charging roller 102a Conductive elastic layer 102b Core bar 103 Charging bias power supply 104 Image Exposure 105 Developing means 106 Transfer means 107 Transfer bias power supply 108 Transfer material 109 Cleaning device 110 Static elimination exposure device 111 Fixing device 112, 113 Cleaning member 114 Development bias power supply 201 Latent image holder 202 Charging blade 203 Metal support member 204 Conductive rubber 205 Releasability table Layer 206 Charging bias power supply 301 Latent image holder (photoconductor, photosensitive drum) 302 Transfer roller 302a Conductive elastic layer 302b Core bar 308 Transfer bias power supply 401 Latent image holder (photoconductor, photosensitive drum) 408 Transfer bias power supply 409 Transport Belt 410 Transfer roller 700 Toner 701 Hopper 702 Supply roller 703 Doctor blade 704 Power supply 708 Latent image holder 709 Developing sleeve S Transfer material

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI G03G 15/08 503 G03G 15/08 504B 504 9/08 361 507 15/08 507L (72) Inventor Hiroaki Kawakami 3-chome 30-2 Canon Inc. (56) References JP-A-6-313982 (JP, A) JP-A-5-45926 (JP, A) JP-A-5-94037 (JP, A) JP-A-5-139748 (JP, A) JP-A-6-19186 (JP, A) JP-A-5-127416 (JP, A) JP-A-5-2284 (JP, A) JP-A-4-274442 (JP JP, A) JP-A-3-294864 (JP, A) JP-A-6-11887 (JP, A) JP-A-4-107478 (JP, A) JP-A-5-88412 (JP, A) JP Hei 5-249742 (JP, A) JP-A-6-51554 (JP, A) Open flat 8-202080 (JP, A) JP flat 4-204748 (JP, A) JP flat 5-34984 (JP, A) (58 ) investigated the field (Int.Cl. ^7, DB name) G03G 9 / 08

Claims (3)

(57) [Claims] 1. A toner image formed on a latent image holding member is recorded.
Transfer to recording material, fix toner image on recording material, full color
In the full-color image forming method for forming an image , (A) (i) cyan toner, magenta toner on the latent image holding member
Glue consisting of toner, yellow toner and black toner
Forming a first toner image with toner selected from the group
Recording material on transfer drum for transferring first toner image on latent image carrier
(Ii) cyan toner and magenta on the latent image carrier
Toner, yellow toner and black toner.
Forms the second toner image with the toner selected from the group
Forming the second toner image on the latent image holding member on the transfer drum.
(Iii) cyan toner on the latent image holding member
ー, magenta toner, yellow toner and black toner
Toner with toner selected from the group consisting of
Forming an image and transferring the third toner image on the latent image holding member.
(Iv) shearing on the latent image holding member
Toner, magenta toner, yellow toner and black toner
4th with toner selected from the group consisting of Kutner
To form a fourth toner image on the latent image holding member.
Transfer to recording material on transfer drum; multiple toners on recording material
Fixing step, (B) (i) cyan toner on the latent image holding member to form a full color image by fixing the over image, Mazentato
Glue consisting of toner, yellow toner and black toner
Forming a first toner image with toner selected from the group
Transferring the first toner image on the latent image holding member to an intermediate transfer member;
(Ii) cyan toner and magenta toner on the latent image holding member
Glue consisting of yellow toner and black toner
Forming a second toner image with the toner selected from the
Transferring the second toner image on the image carrier to an intermediate transfer member;
(Iii) cyan toner and magenta toner on the latent image carrier
Glue consisting of yellow toner and black toner
Forming a third toner image with the toner selected from the
Transferring the third toner image on the image carrier to an intermediate transfer member;
(Iv) cyan toner and magenta toner on the latent image carrier
Glue consisting of yellow toner and black toner
Forming a fourth toner image with the toner selected from the
Transferring the fourth toner image on the image carrier to the intermediate transfer member;
The first, second, third and fourth toner images on the intermediary transfer member are used as recording materials.
Transfer, fix multiple toner images on the recording material,
A fixing step of forming an image, (C) (i) cyan toner and magenta toner on the latent image holding member.
Glue consisting of toner, yellow toner and black toner
Forming a first toner image with toner selected from the group
(Ii) cyan toner and magenta toner on the latent image holding member
Glue consisting of yellow toner and black toner
Forming a second toner image with the toner selected from the
(Iii) cyan toner and magenta toner on the latent image carrier
Glue consisting of yellow toner and black toner
Forming a third toner image with the toner selected from the
(Iv) cyan toner and magenta toner on the latent image carrier
Glue consisting of yellow toner and black toner
Forming a fourth toner image with the toner selected from the
Transfers multiple toner images on the image carrier to a recording material,
Fix multiple toner images on top to form a full-color image
That the fixing step, or, (D) (i) cyan toner to the first latent image holding member, Mazets
Toner, yellow toner and black toner.
Forms the first toner image with the toner selected from the group
And transferring the first toner image to a recording material.
Toner, magenta toner and yellow toner on the latent image carrier
Selected from the group consisting of low toner and black toner
A second toner image is formed with the selected toner, and a second toner image is formed.
The image is transferred to a recording material, and (iii) on the third latent image holding member.
And cyan toner, magenta toner, yellow toner and
Toner selected from the group consisting of black toner
To form a third toner image, and use the third toner image as a recording material.
(Iv) cyan toner on the fourth latent image holding member,
Magenta toner, yellow toner and black toner
Fourth toner image with toner selected from the group consisting of
Is formed, the fourth toner image is transferred to the recording material, and
Fusing multiple toner images to form a full-color image
Fixing step, wherein each color toner has at least a binder resin and a colorant.
And the toner particles have an inorganic fine powder, the inorganic fine powder, some or all of the hydrogen atoms may be substituted by a fluorine atom, a polysiloxane alkyl group, an aryl group and a substituted group, Treated with a hydrogenpolysiloxane having a methyl group and hydrogen ,
Treatment of polysiloxane and hydrogen polysiloxane
A full-color image forming method , comprising alumina or titania having a ratio of 1: 4 to 4: 1 . 2. The polysiloxane has the following formula (1): Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R
₈ represents an alkyl group or an aryl group in which some or all of the hydrogen atoms may be substituted by fluorine atoms, each of which may be the same or different, and some other arbitrary substituents May be provided. j is the sum of siloxy units satisfying the condition of the unit of j and represents an integer of 1 or more. Wherein the hydrogen polysiloxane is represented by the following formula (4): [In the formula, n represents an integer of 1 or more. The full-color image formation according to claim 1, wherein the methyl hydrogen polysiloxane is represented by the following formula:
How . 3. The polysiloxane is represented by the following formula (2): [In the formula, k represents an integer of 1 or more. Full-color image forming method according to claim 1 or 2, characterized in that a dimethylpolysiloxane represented by].