JP2001013727A - Color toner, color image forming method usign the color toner and device unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color toner excellent in anti-offsetting property in spite of the oilless state and capable of low temperature fixation. SOLUTION: This color toner contains a bonding resin and a wax. The bonding resin has at least a nonlinear polyester resin (A) and a linear polyester resin (B) mixed in a weight ratio of 25:75 to 75:25. When the content of polycarboxylic acid monomer units having >=3 COOH groups in the bonding resin is represented by Xa (mol%) and the content of polycarboxylic acid monomer units having a 5-30C saturated or unsaturated aliphatic hydrocarbon group and/or polyol monomer units is represented by Ya (mol%), the nonlinear polyester resin A satisfies 0.5<Xa<15, 5<Ya<30 and 1<=Ya/Xa<=10. The linear polyester resin B does not contain a polycarboxylic acid monomer unit having >=3 COOH groups and a polyol monomer unit having >=3 OH groups. The maximum endothermic peak of the wax measured with a differential scanning calorimeter(DSC) is at 60-135 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color toner used in an electrophotographic method, an image forming method for visualizing an electrostatic latent image or a color toner used in a toner jet method. The present invention relates to a color image forming method used and an apparatus unit detachably attached to an image forming apparatus main body.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Application Laid-Open Publication No. Sho. 43-24748, and the like. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. After forming the latent image with toner, the latent image is developed into a visible image, and if necessary, the toner is transferred to a transfer material such as paper. The toner is fixed to obtain a copy, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

In recent years, such copying apparatuses have become smaller and smaller.
Lighter weight, higher speed, and higher reliability have been strictly pursued. In addition, it has begun to be used not only as a copy machine for office work for simply copying an original manuscript, but also for copying a high-resolution image such as a digital printer or graphic design as a computer output.

[0004] Further, with the spread of computer equipment for personal users, full-color video communication has become widespread as a video information transmission mechanism.

[0005] Under such circumstances, full-color printing is rapidly progressing also in printers and copiers as one of output devices, and color images are becoming more familiar to general users.

For this reason, higher definition and higher image quality have been demanded as full-color image quality, and as a result, the performance required for toner has also become higher.

The most important performance required for toner in a digital full-color printer and full-color copying of a high-definition image is a fixing performance.

Various methods and apparatuses have been developed for the fixing step, but the most common method at present is a pressure heating method using a heat roller.

In the pressure heating method using a heating roller, the toner image surface of a sheet to be fixed is brought into contact with the surface of a heat roller having a surface formed of a material (silicone rubber or fluororesin) having releasability from the toner under pressure. The fixing is carried out by allowing the sheet to pass therethrough. According to this method, since the surface of the heat roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. Can be. However, in the above method, since the surface of the heat roller and the toner image come into contact with each other under pressure in a molten state, a part of the toner image adheres to and transfers to the surface of the fixing roller, thereby fouling the next sheet to be fixed ( Offset phenomenon). Preventing toner from adhering to the surface of the heat fixing roller is one of the essential conditions of the heat roller fixing method.

In the case of full color, color reproduction is generally performed using three color toners of yellow, magenta, and cyan, or four color toners obtained by adding a black toner thereto. A multicolor image must be fixed on paper or a sheet to be fixed such as an overhead projector sheet (OHT), and color reproduction and transparency of the OHT image must be satisfied. Therefore, it is required that the toner layer be sufficiently melted and the image surface be smoothed. In order to achieve both image smoothness and offset prevention, it is necessary to provide a means for supplying oil such as silicone oil to the fixing roll and uniformly covering the roller, and these are means for designing a small and inexpensive system. It is an inhibitory factor.

As a method for imparting good fixability and offset resistance to the toner itself, JP-A-52-3304, JP-A-52-3305, and JP-A-57-525 are known.
No. 74, JP-A-61-138259, JP-A-56-87051, JP-A-63-188158, JP-A-63-113558 and JP-A-8-118.
JP-A-030036 discloses a technique for incorporating waxes into a toner.

[0012] Waxes are used to improve the anti-offset property of toner and the fixability at low temperatures, and a large number of copiers, printers, and the like are commercially available as electrophotographic devices that achieve oil-less fixing. ing. However, as a high-quality full-color electrophotographic apparatus that requires a pictorial full-color image, an image is given an appropriate gloss and an overhead projector sheet (OHT) is used.
It is insufficient in satisfying the above color reproduction and transparency.

Further, these waxes deteriorate the anti-blocking property, or deteriorate in developability when exposed to heat due to an increase in temperature of a copying machine or the like. Or worse. Furthermore, these waxes are hard to be uniformly dispersed in the toner, and the loose or unevenly distributed wax tends to have an adverse effect on developability and durability, and sufficient release properties cannot be obtained with an added amount that does not affect the wax. In addition, it is essential to use a release agent such as oil on the fixing device side.

As a method for imparting good fixability and offset resistance as a toner binder, Japanese Patent Application Laid-Open No.
JP-A-7-12334, JP-A-57-37353 and JP-A-57-208559 disclose an etherified bisphenol monomer, a dicarboxylic acid monomer and a trihydric or higher polyhydric alcohol monomer. There has been proposed a toner containing, as a binder, a polyester composed of a non-linear copolymer obtained from a monomer component containing a polymer and / or a trivalent or higher polyvalent carboxylic acid monomer. This technique is to convert a polyester comprising an etherified bisphenol monomer and a dicarboxylic acid monomer into a large amount containing a trihydric or higher polyhydric alcohol monomer and / or a trivalent or higher polyhydric carboxylic acid monomer. The toner has an anti-offset property by containing a polyester obtained by crosslinking by a monomer component as a binder. However, when these toners are used for full-color image formation, they have a high softening point, a good low-temperature fixation is difficult, and a sharp Due to the difficulty, the color mixing and color reproducibility due to the superposition of full-color toners using the polyester are not sufficient.

JP-A-57-109825, JP-A-62-78568, JP-A-62-78569, JP-B-63-57785, and JP-A-59-2
No. 9256 discloses an etherified bisphenol monomer, a dicarboxylic acid monomer introduced with a long-chain aliphatic hydrocarbon or other dicarboxylic acid monomer, and a trihydric or higher polyhydric alcohol monomer and / or Or a non-linear copolymer obtained from a monomer component containing a trivalent or higher polycarboxylic acid monomer, wherein the side chain has a saturated or unsaturated aliphatic carbon having 3 to 22 carbon atoms. Although a toner containing a polyester having a hydrogen group as a binder is disclosed, these polyester resins are mainly intended for high-speed fixing toner, and the viscoelastic properties of the resin are completely different from those of the above-mentioned viscosity-oriented polyester. Conversely, the elasticity is enhanced and the hot offset to the roller is significantly reduced.
Then, at the time of fixing, the pressure and heating of the heat roller are increased as much as possible, and the toner is pressed between the fibers of the transfer paper in a semi-molten state to perform pressure and heat fixing to achieve the object. is there. Therefore, it is almost impossible to obtain a smooth surface by melting a toner layer necessary for a color image to form a continuous film, and the fixed toner is present in the form of particles on transfer paper, and the obtained color image is dull. It is a strange thing and the saturation is low. In an OHT image, light is scattered and diffused on the surface of the toner particles, hardly transmits light, and becomes practically unusable.

JP-B-55-6895 and JP-A-56-6995
As described in JP-A-98202, there is a method of suppressing the offset phenomenon by increasing the width of the molecular weight distribution of the binder resin. However, in general, the degree of polymerization of the resin is increased, and the fixing temperature used must be set higher. .

Further, as described in JP-B-57-493, JP-A-50-44836, and JP-A-57-37353, the offset phenomenon is caused by making the resin non-linear or cross-linked. Method for suppressing odor;
JP-A-213858, JP-A-1-295269,
JP-A-1-36061, JP-A-1-302267
Japanese Patent Application Laid-Open No. HEI 3-96964 discloses a method for improving the offset phenomenon by crosslinking a polyester resin with metal ions.

As a method for improving the offset resistance of the toner, a toner using a covalently crosslinked resin or a branched resin using a polyfunctional monomer or a polyfunctional initiator called a crosslinked polymer (Japanese Patent Laid-Open No. 3-203746). And JP-A-4-24648) and toners using an ion-bonding crosslinked polymer in which a metal oxide and a polymer are strongly bonded (JP-A-61-213858, JP-A-6-175395). Described in Japanese Unexamined Patent Publication (KOKAI) No. 2000-222). In both cases, although the offset resistance is improved, the inherent fixability of the binder resin is reduced, and since the entanglement of the polymer molecules is strong, the resin component due to cross-linking typified by tetrahydrofuran insolubles binds the colorant and the charge control agent. It is difficult to disperse the resin in the resin and is not suitable for a full-color toner. Further, the pulverizability of the kneaded toner during the production of the toner is also reduced.

Further, Japanese Patent Application Laid-Open No. 63-225244 discloses
JP-A-63-225246 discloses a toner containing two types of non-linear polyesters for the purpose of improving low-temperature fixing property, high-temperature offset resistance, and blocking resistance. Also, JP-A-60-214368, JP-A-2-082267, JP-A-2-158747, JP-A-4-338973, and JP-A-7-26.
JP-A-1459 and JP-A-8-101530 propose a method of blending two kinds of polyesters having different physical properties to improve the fixing property and the offset resistance of the toner, but are insufficient for full-color fixing. Things,
Although the amount of the release agent such as silicone oil applied to the fixing roller is reduced, it is indispensable, and a complete oilless full-color toner has not yet been obtained.

Further, Japanese Patent Application Laid-Open No. 3-188468 discloses that
The polyester resin as a binder in the toner particles has the following conditions (A) to (C); (A) when the acid value of the polyester resin is Av and the hydroxyl value is OHv,
Av is 20 to 35 (KOHmg / g), Av / OHv =
In the range of 1.0 to 1.5, (B) the tetrahydrofuran-insoluble content is 10% or less, and (C) the molecular weight distribution of tetrahydrofuran-soluble component by gel permeation chromatography (GPC), The ratio of the weight average molecular weight Mw to the number average molecular weight Mn is Mw / M
n ≧ 10, number average molecular weight 3,000 to 8,000
Has at least one peak (low-molecular-side peak) in the region of No., one peak or shoulder (high-molecular-side peak) in the region of number-average molecular weight of 100,000 to 600,000, and A toner that satisfies that the peak region is present at 5 to 15% has been proposed. However,
The polyester disclosed in JP-A-3-188468 has an acid value as high as 20 (KOH mg / g) or more, and contains a soft segment component but has a large amount of polycarboxylic acid.
Since the proportion of the crosslinking component is high (the THF insoluble content is 2% or more in the examples), full-color fixability (gloss control and offset resistance) is not satisfied.

Further, Japanese Patent Application Laid-Open No. 7-234537 discloses that
Proposed are a toner containing a polyester resin having a soft segment having 5 to 30 carbon atoms as a main component and a wax having a specified thermal property, and a toner using a mixture of a non-linear polyester resin and a linear polyester resin satisfying the same. Have been. However, although the polyester disclosed in JP-A-7-234537 contains a soft segment component, the amount of the trivalent or higher polyvalent monomer component relative to the soft segment component is large. ) Is not satisfied.

As described above, while satisfying the color reproducibility of a pictorial full-color image having an appropriate gloss and the color reproducibility and transparency on an overhead projector sheet (OHT), good low-temperature fixing performance, As a color toner which is excellent in offset resistance and can be used for oil-less fixing, there remains a problem to be improved in addition to the image characteristics described below.

Further, in order to meet demands for energy saving, suppression of curl after fixing of a transfer material, improvement of toner storability, etc., a full-color image can be obtained while exhibiting excellent offset resistance by oilless fixing at a lower temperature. However, it suppresses irregular reflection by toner particles as much as possible, has moderate gloss and luster, has transparency that does not hinder the toner layer of different color under the toner layer, and has color reproducibility up to high chroma color tone There is a demand for excellent color toners.

On the other hand, due to the recent miniaturization and compactness of copiers and printers, the temperature inside the developing machine tends to rise,
It is desired that the toner has higher storage stability at high temperatures than ever before, and furthermore, for high-quality image output, a toner that sufficiently satisfies both stable developing property and good transfer property at the same time is desired.

In order to obtain stable developability and good transferability, it is essential to control the charge of the toner particles. In order to make the toner retain electric charge, it is possible to use the frictional charging property of the resin, which is a component of the toner.However, in this method, since the charging of the toner is not stable, the rise of the density is slow,
Easy to fog. Therefore, a charge control agent is added to impart a desired triboelectric charge to the toner.

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

However, depending on the charge control agent, it is difficult to balance image density and fog, it is difficult to obtain sufficient image density in a high humidity environment, poor dispersibility in resin, storage stability, fixability and anti-offset properties. It has disadvantages such as adversely affecting the properties. Conventionally, metal complexes and metal salts of aromatic carboxylic acids have been disclosed in JP-A-53-127726, JP-A-57-111541, and JP-A-57-12435.
No. 7, JP-A-57-104940, JP-A-57-104940
1-69073, JP-A-61-73693, JP-A-61-267058, JP-A-62-1
05156, JP-A-62-145255,
JP-A-62-163061, JP-A-63-208
Some proposals have been made, such as Japanese Patent Application Laid-Open No. 865, Japanese Patent Application Laid-Open No. 3-276166, Japanese Patent Application Laid-Open No. 4-84141, and Japanese Patent Application Laid-Open No. 8-160668. However, those proposed in these publications are all excellent from the viewpoint of triboelectric charging,
In particular, when applied to full-color toners, there are few simple developing device configurations that can achieve stable developability regardless of environmental fluctuations, aging, and use conditions. Further, it has been difficult to achieve both the fixing performance required for the color toner and the stable developing property as described above.

[0028]

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

That is, an object of the present invention is to provide a color toner which is excellent in offset resistance and can be fixed at a low temperature and can be fixed by using only a small amount of fixing oil and without using fixing oil. It is in.

Another object of the present invention is to set a low fixing temperature and use a small amount of fixing oil, or even by oilless fixing, to obtain a full-color image having moderate gloss and gloss, It is an object of the present invention to provide a color toner and a color image forming method which are excellent in (color developability) and excellent in color reproducibility up to a high color tone.

Another object of the present invention is to provide a color toner which has no stickiness of oil on a recording material, especially on an overhead projector sheet (OHT), and satisfies color reproduction and transparency.

Further, an object of the present invention is to eliminate uneven gloss,
An object of the present invention is to provide a color toner and a color image forming method capable of obtaining a stable image quality with no change in gloss even by repeated use.

Another object of the present invention is to provide a simple oil applying mechanism or not having an oil applying mechanism.
An object of the present invention is to provide an apparatus unit having a low-cost color image forming apparatus.

It is a further object of the present invention to provide an apparatus unit having a color image forming apparatus which does not require replenishment of fixing oil and has a small number of consumable parts in a fixing unit, thereby reducing running costs.

It is a further object of the present invention to provide a color toner which can provide high image quality even when used under low humidity or high humidity and does not cause image defects over time, and a color toner using the color toner. An object of the present invention is to provide an image forming method and an apparatus unit having a color image forming apparatus using the color toner.

[0036]

According to the present invention, there is provided a color toner comprising at least a binder resin, a wax, an organometallic compound and a colorant, wherein the binder resin is a polyvalent carboxylic acid monomer having at least three or more valences. Unit and 5 to 3 carbon atoms
A polyvalent carboxylic acid monomer unit having a saturated or unsaturated aliphatic hydrocarbon group of 0 and / or a polyhydric alcohol monomer unit, wherein the trivalent or higher polyvalent carboxylic acid in the binder resin is contained. When the content of the acid monomer unit is Xa mol
%, A polyvalent carboxylic acid monomer unit having a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms, and / or
Or, the content of the polyhydric alcohol monomer unit is
ol%, a non-linear polyester resin A satisfying the following condition: 0.5 <Xa <155 5 <Ya <302 2 ≦ Ya / Xa ≦ 10, and a trivalent or higher polyvalent carboxylic acid monomer A non-linear polyester resin A having at least a linear polyester resin B containing no units and a trihydric or higher polyhydric alcohol monomer unit.
And the linear weight of the polyester resin B is 25/75.
And the maximum endothermic peak of the wax measured by a differential scanning calorimeter (DSC) is 60 to 135.
° C.

The present invention further relates to an aromatic compound, wherein the organometallic compound has zirconium as a metal element and is selected from the group consisting of aromatic diols, aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids. The present invention relates to a color toner characterized in that the group III compound is an organic zirconium compound which is coordinated and / or bound. A charging step of charging the latent image holder; a latent image forming step of forming an electrostatic latent image on the charged latent image holder; a developing step of developing the electrostatic latent image with toner to form a toner image; Transferring the transferred toner image onto a recording material with or without an intermediate transfer member; and bringing a fixing member into contact with the surface of the toner image transferred onto the recording material, and applying heat to the toner image. And a fixing step of fixing the toner image on the recording material by applying pressure to the recording material, wherein the developing step comprises a color having at least a binder resin, a wax, an organometallic compound and a colorant. A step of using a toner, wherein the binder resin comprises at least a trivalent or higher polyvalent carboxylic acid monomer unit and a polyvalent carboxylic acid having a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms. acid Mer units and / or polyhydric contain alcohol monomer units, the content of the trivalent or higher polycarboxylic acid monomer units in the binder resin X
a mol%, and the content of the polyvalent carboxylic acid monomer unit and / or polyhydric alcohol monomer unit having a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms was defined as Ya mol%. A non-linear polyester resin A satisfying the following conditions: 0.5 <Xa <155 5 <Ya <302 2 ≦ Ya / Xa ≦ 10; a trivalent or higher polyvalent carboxylic acid monomer unit; It has at least the linear polyester resin B containing no polyhydric alcohol monomer unit, and the mixing weight ratio of the non-linear polyester resin A and the linear polyester resin B is 25/75 to
75/25, and a step of developing an electrostatic latent image using a color toner having a maximum endothermic peak measured by a differential scanning calorimeter (DSC) at 60 to 135 ° C. to form a toner image. The present invention relates to a characteristic color image forming method.

Further, the present invention provides at least a toner for developing an electrostatic latent image, a toner container for holding the toner, and a toner container for holding the toner held in the toner container and transporting the toner to a development area. A toner carrier, and a toner layer thickness regulating member for regulating a layer thickness of the toner carried on the toner carrier; the toner comprises at least a binder resin, a wax, an organometallic compound, and a colorant; Wherein the binder resin has at least a trivalent or higher polyvalent carboxylic acid monomer unit, and has 5 to 3 carbon atoms.
A polyvalent carboxylic acid monomer unit having a saturated or unsaturated aliphatic hydrocarbon group of 0 and / or a polyhydric alcohol monomer unit, wherein the trivalent or higher polyvalent carboxylic acid in the binder resin is contained. When the content of the acid monomer unit is Xa mol
%, A polyvalent carboxylic acid monomer unit having a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms, and / or
Or, the content of the polyhydric alcohol monomer unit is
ol%, a non-linear polyester resin A satisfying the following condition: 0.5 <Xa <155 5 <Ya <302 2 ≦ Ya / Xa ≦ 10, and a trivalent or higher polyvalent carboxylic acid monomer Unit and at least a linear polyester resin B containing no trivalent or higher polyhydric alcohol monomer unit, and the mixing weight ratio of the non-linear polyester resin A and the linear polyester resin B is 25/75 to
The present invention relates to an apparatus unit detachably attached to a color image forming apparatus main body, which is 75/25 and has a maximum endothermic peak measured by a differential scanning calorimeter (DSC) at 60 to 135 ° C.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is based on the results of intensive studies on various resin systems and waxes for the purpose of oil-less full-color fixing. As a result, in a specific configuration, oil-less fixing (fixing roller non-winding performance, offset resistance), It has been found that the image gloss control and the OHT transparency are all satisfied, and that the fixing temperature can be set lower.

That is, in a color toner having at least a binder resin, a wax, an organometallic compound and a colorant, the binder resin is composed of at least a trivalent or higher polyvalent carboxylic acid monomer unit and 5 to 30 carbon atoms. A polyvalent carboxylic acid monomer unit and / or a polyhydric alcohol monomer unit having a saturated or unsaturated aliphatic hydrocarbon group, and When the content of the monomer unit is Xa mol% and the number of carbon atoms is 5
When the content of the polyvalent carboxylic acid monomer unit and / or polyhydric alcohol monomer unit having from 30 to 30 saturated or unsaturated aliphatic hydrocarbon groups is defined as Ya mol%, the following condition 0.5 < Non-linear polyester resin A satisfying the following condition: Xa <155 <Ya <302 2 ≦ Ya / Xa ≦ 10; trivalent or higher polyvalent carboxylic acid monomer unit and trivalent or higher polyhydric alcohol monomer Non-linear polyester resin A having at least a linear polyester resin B containing no units
And the linear weight of the polyester resin B is 25/75.
And the maximum endothermic peak of the wax measured by a differential scanning calorimeter (DSC) is 60 to 135.
Attained by a color toner which is characterized in that the temperature is in the range of .degree.

In general, it is known that an organometallic compound binds to a terminal polar group of a polyester to form a metal crosslink.

As a technique for controlling the degree of metal cross-linking in a polymer, the present inventors have proposed a polycarboxylic acid monomer unit having a saturated or unsaturated aliphatic hydrocarbon group having at least 5 to 30 carbon atoms. And / or a polyhydric alcohol monomer unit, a polyester resin having a trivalent or higher polyvalent carboxylic acid monomer unit as a constituent monomer unit, a toner containing an organometallic compound, and a wax, a three-dimensional structure against a metal crosslinking reaction. Polyvalent carboxylic acid monomer unit and / or polyhydric alcohol monomer unit having a hindered saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms (soft segment component)
And a non-linear polyester resin having a limited content and ratio of a trivalent or higher polyvalent carboxylic acid monomer unit having a high reaction probability of metal crosslinking, and a metal crosslinking property with an organometallic compound which is relatively low, The use of a linear polyester resin that enhances the sharp melt property and a wax having a maximum endothermic peak at 60 to 135 ° C. measured by a differential scanning calorimeter (DSC) achieves both gloss control and offset resistance required for full-color fixing. And found it important.

That is, a trivalent or higher polyvalent carboxylic acid monomer unit and a polyvalent carboxylic acid monomer unit having a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms and / or a polyhydric alcohol By defining the content of monomer units (soft segment components) and their ratios, a linear polyester resin having a relatively low metal crosslinking property with an organometallic compound and enhancing the sharp melt property of the toner is blended at a predetermined ratio. The present inventors have found that by adding a polyester resin having a controlled metal crosslink density and a specific wax to the polyester resin, the oil-less color fixability can be remarkably improved.

In the present invention, the non-linear polyester resin A is 3
The content of the polyvalent carboxylic acid monomer unit having a valency of not less than 0.
When the amount is less than 5 mol%, the non-offset region becomes narrow because the crosslinking reaction with the organometallic compound does not proceed. Further, the content of the trivalent or higher polyvalent carboxylic acid monomer unit is 3 mol.
%, It is difficult to obtain a sufficiently large non-offset area, and when forming a color image on both sides,
At the time of fixing the second side, the smoothness of the image is deteriorated, resulting in a color image with low gloss, or offset occurs.
Therefore, it is more preferable that the content of the trivalent or higher polyvalent carboxylic acid monomer unit of the non-linear polyester resin A is 3 mol% or higher.

On the other hand, when the content of the trivalent or higher polyvalent carboxylic acid monomer unit exceeds 15 mol%, the non-offset region is widened by the crosslinking reaction with the organometallic compound, but the fixability is impaired and the sharp melt is not obtained. Even when the linear polyester resin B is blended as a binder resin, the gloss required for a color image is reduced, and the OHT permeability is also deteriorated. In order to further improve the fixability and obtain bright and excellent color reproducibility on the OHP projected image up to the light-colored portion on the OHT, the content of the trivalent or more polyvalent carboxylic acid monomer unit should be 10 mol% or less. Is more preferred.

When the content of the soft segment component in the non-linear polyester resin of the present invention is less than 5 mol%, the effect of steric hindrance on the metal crosslinking reaction of the soft segment component is not sufficient, and The metal crosslinking reaction with the organometallic compound is easy to proceed.
Even if the content of the polyvalent carboxylic acid monomer unit or organometallic compound having a valency or higher is reduced, the crosslink density of the metal crosslink increases, and the high molecular weight component generated by the metal crosslink becomes less flexible in heat. Therefore, fixability is impaired, gloss required for a color image is reduced, and OH
T permeability also deteriorates. Conversely, if the content of the soft segment component exceeds 30 mol%, steric hindrance to the metal crosslinking reaction exerted by the soft segment component becomes excessive, and the metal crosslinking reaction between the polyester resin and the organometallic compound does not proceed, and the non-offset region Becomes narrow.

Furthermore, the content Xa of the trivalent or higher polyvalent carboxylic acid monomer unit in the non-linear polyester resin A
mol% and the content of the soft segment component Ya mo
If the 1% ratio (Ya / Xa) is less than 2, the crosslinking reaction with the organometallic compound is further promoted, and the non-offset region is widened, but the fixability is impaired, and the gloss required for the color image decreases, OHT permeability also deteriorates. The ratio (Ya /
When Xa) is more than 10, the crosslinking property is reduced due to steric hindrance to the metal crosslinking reaction of the soft segment component,
The non-offset area becomes narrow.

Further, in the present invention, it is possible to mix the non-linear polyester resin A with the linear polyester resin B having a sharp melt property in a weight ratio of 25/75 to 75/25, thereby lowering the fixing temperature. It is necessary to achieve both gloss control and offset resistance required for full-color fixing. Non-linear polyester resin A
When the mixing weight ratio of the resin and the linear polyester resin B is smaller than 25/75, the offset resistance as a total binder resin is not sufficient, and when the mixing weight ratio exceeds 75/25, a lower fixing ratio is obtained. It is difficult to satisfy the full-color fixing at the temperature setting, and increasing the fixing temperature setting not only increases the power consumption, but also causes a decrease in the fluidity and blocking of the toner in the image forming apparatus, and a This leads to various adverse effects such as shortening the service life and increasing the curl of the obtained image transfer material.

Further, the wax used in the present invention is selected by a differential scanning method in order to select a wax melting property that more closely matches the melting behavior of the binder resin and to achieve oilless full-color fixing at a lower fixing temperature setting. It is necessary that the maximum endothermic peak measured by a calorimeter (DSC) is at 60 to 135 ° C. When the maximum endothermic peak of the wax measured by a differential scanning calorimeter (DSC) is less than 60 ° C., the storage stability and durability of the color toner are deteriorated. The releasability of the toner is not exhibited.

In the present invention, the content of the organometallic compound in the toner is 0.2 to 10% by weight, and the trivalent or higher polyvalent carboxylic acid monomer unit in the binder resin is used. It is preferable that the total content Xc mol% and the content Z% by weight of the organometallic compound in the toner satisfy the following formula.

2 ≦ Xc × Z ≦ 50

When the content of the organometallic compound in the toner is less than 0.2% by weight, the crosslinking reaction does not proceed and the non-offset region becomes narrow. When the content exceeds 10% by weight, the crosslinking reaction is further accelerated. Although the non-offset area expands, the fixability is impaired, the gloss required for the color image is reduced, and the OHT transmittance is also deteriorated.

The content Xam of the trivalent or higher polyvalent carboxylic acid monomer unit in the non-linear polyester resin A
ol% and the content of the organometallic compound in the toner Z wt%
When the product (Xc × Z) is less than 2, the crosslinkability decreases and the non-offset region becomes narrow. (Xc × Z) is 50
When the value exceeds, the cross-linking reaction is further accelerated and the non-offset region is widened, but the fixability is impaired, the gloss required for the color image is reduced, and the OHT permeability is also deteriorated. That is, in addition to limiting the content and the content ratio of the soft segment and the trivalent or higher polyvalent carboxylic acid monomer unit, the trivalent or higher polyvalent having a high content of the organometallic compound and a high reaction probability of metal crosslinking. By using a polyester resin in which the content ratio of the carboxylic acid monomer unit to the whole organic resin compound in the binder resin component is limited, gloss control required in full-color fixing and offset resistance can be achieved in a more preferable form. Presenting.

In the toner of the present invention, the maximum endothermic peak of the wax measured by a differential scanning calorimeter (DSC) is 6%.
It is necessary to contain wax at 0 to 135 ° C. To further enhance the releasability of a color toner that starts melting at a lower temperature, a differential scanning calorimeter (DS)
C) It is more preferable that the maximum endothermic peak measured is in the range of 60 to 120 ° C.

Examples of these waxes include, among the following waxes, those having a maximum endothermic peak at 60 ° C. or more and 135 ° C. or less in differential thermal analysis.

Examples of the wax used in the toner of the present invention include petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax and petrolactam, montan wax and its derivatives, hydrocarbon waxes and their derivatives by the Fischer-Tropsch method,
Polyolefin wax represented by polyethylene and its derivatives, natural wax such as carnauba wax and candelilla wax and its derivatives, etc. The derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Among the fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, etc. It has a temperature of not less than 135 ° C and not less than 135 ° C.

Among these, the compound having a maximum endothermic peak at 60 ° C. or more and 135 ° C. or less in differential thermal analysis is preferably polyolefin, a hydrocarbon wax by the Fischer-Tropsch method, or a petroleum wax. Preferably, hydrocarbon wax and polyethylene wax are used.

Further, in the present invention, the GP
The ratio Mw / Mn of the number average molecular weight (Mn) to the weight average molecular weight (Mw) in the C molecular weight distribution is preferably from 1.0 to 2.0. The maximum endothermic peak in the differential thermal analysis of the wax that more closely matches the melting behavior of the binder resin defined in the present invention, by limiting the molecular weight distribution of the wax component so as to show sharper melting at that temperature. In addition, low-temperature fixability can be imparted in oil-less full-color fixing, and OHT transparency can be further enhanced while satisfying offset resistance performance. When the ratio Mw / Mn of the number average molecular weight (Mn) to the weight average molecular weight (Mw) in the GPC molecular weight distribution of the wax exceeds 2.0, the releasability of the color toner of the present invention that starts melting at a low temperature is low. It is not efficient. In order to obtain sufficient releasability, the amount of wax added must be increased.
Not only impairs HT transparency, but also makes it difficult to uniformly disperse the wax in the polyester resin, which is a binder resin, causing deterioration of blocking resistance and deterioration of developability.

Further, the content ratio of wax is preferably 0.3 to 4.5% by weight based on the toner.
If the wax content is less than 0.3% by weight, the releasing effect is not sufficient, and if the wax content exceeds 4.5% by weight, as described above, O
HT transparency is impaired, blocking resistance deteriorates, and developability deteriorates. Therefore, in the color toner of the present invention, the addition amount of the wax is preferably as small as possible within a range where a sufficient releasing effect can be obtained, and the addition amount is more preferably 3% by weight or less. Further, other waxes may be used in combination as long as they do not adversely affect.

Further, the wax in the present invention is preferably one having a small polarity or a non-polar one. As the polarity of the wax is smaller, the offset resistance can be improved with a small amount of addition, which is advantageous in increasing the transparency of a color image having high chroma and excellent color reproducibility and a color image on an OHT. When a polyester resin is mainly used as the binder resin as in the present invention, it is considered that a wax having a small polarity has poor dispersibility in the binder resin. However, according to the study of the present inventors, if a large amount of a wax having a small polarity is added to the polyester resin, the dispersibility of the wax in the binder resin becomes poor, and the development characteristics and the toner fluidity decrease. However, when about 4.5% by weight of the wax is added, the wax exists in the binder resin of the present invention with a fine dispersion diameter, and there is no adverse effect such as a decrease in developing characteristics and a decrease in toner fluidity. Was found to be able to be increased. In order to further enhance the transparency and color reproducibility of the color image on the OHT, the amount of the wax added is more preferably 3% by weight or less. That is, when a polyester resin is mainly used as the binder resin as in the present invention, a wax having a maximum endothermic peak in the differential thermal analysis at 60 ° C. or more and 135 ° C. or less is a polyolefin having a small polarity or a non-polarity. Alternatively, a hydrocarbon wax or a petroleum wax according to the Fischer-Tropsch method is more preferred, and a hydrocarbon wax or a polyethylene wax is particularly preferred.

Further, the wax used in the present invention is DSC
Onset temperature at the time of temperature rise in the curve is 55 to 105 ° C.
Is preferred. By using such a wax, a toner having excellent blocking resistance and fixability can be obtained.

When the on-set temperature is lower than 55 ° C., the toner particles undergo a plastic change at a relatively low temperature, so that the blocking resistance is poor, and the developing property is liable to deteriorate with increasing temperature. On the other hand, when the temperature exceeds 105 ° C., the rate of plastic change by heating becomes slow, and the low-temperature offset resistance and the fixing property become poor.

Further, the wax used in the present invention has a number average molecular weight (Mn) of 200 to 2,000 and a weight average molecular weight (Mw) of 200 to 2500 (more preferably Mn30).
0-1000, Mw 300-1200) and M
It is preferable that w / Mn is 2 or less.

By having the molecular weight in the above range, the toner can have preferable thermal characteristics. That is, when the molecular weight is smaller than the above range, the composition is susceptible to thermal effects excessively, and the blocking resistance and the developability are deteriorated. When the molecular weight is larger than the above range, heat from the outside cannot be used effectively, and it is difficult to obtain excellent fixing properties and offset resistance. When Mw / Mn is more than 2, the melting behavior is not sharp due to heat because of a wide molecular weight distribution, and the fixing temperature range in which good color reproducibility (color mixing of toner in the fixing step) can be obtained is obtained. It becomes difficult to obtain a region that satisfies both good fixability and offset resistance.

The maximum endothermic peak temperature and the onset temperature in the DSC curve of the wax used in the present invention can be obtained from the DSC curve measured by a differential scanning calorimeter. For example, DSC-7 manufactured by PerkinElmer can be used as the measuring device.

The measuring method is as described in ASTM D3418-82.
Perform according to. The DSC curve used in the present invention is obtained by taking a pre-history by raising the temperature once, and then measuring the temperature by 10 ° C./min.
After the temperature is lowered in the range of 30 to 160 ° C., the DSC curve measured when the temperature is raised is used.

The molecular weight of the wax used in the present invention can be measured by the following method.

(GPC measurement conditions) Apparatus: GPC-150C (Waters) Column: GMH-HT 30 cm double (manufactured by Tosoh Corporation) Temperature: 135 ° C Solvent: o-dichlorobenzene (0.1% ionol added) Flow rate: 1. 0 ml / min sample: Inject 0.4 ml of 0.15% sample under the above conditions, and calculate the molecular weight of the sample by using a molecular weight calibration curve created by a monodisperse polyester standard sample. Further, it is calculated by converting to polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula.

Further, in the present invention, the binder resin component of the color toner preferably contains a THF-soluble component and a THF-insoluble component of 0% by weight or more and less than 5.0% by weight. In the GPC molecular weight distribution, the component content (M1) of less than 10,000 is 45 to 65%, the component content of 10,000 to 50,000 (M2) is 25 to 50%, and 50,000 to 50,000.
The component content (M3) is 2 to 20%, the component content exceeding 500,000 (M4) is 0.1 to 10%, and M1>
It is preferable to satisfy the relationship of M2>M3> M4.

When the toner binder resin contains 5.0% by weight or more of a THF-insoluble component as a gel component, the presence of a gel that does not melt at a low temperature increases the viscosity of the system and reduces the low-temperature fixability required for a color toner. Not only does it worsen, but also when a sharp melt component that melts at the low temperature required for color toners is included, the toner surface viscosity at the time of fixing is increased despite the increase in internal viscosity due to the difference in melting temperature. The offset width is also low. Further, when a large amount of the THF-insoluble matter is contained, the smoothness of the obtained color image is also adversely affected, and the image tends to be low in gloss or not uniform. In order to stably obtain an image having a uniform gloss, the THF-insoluble content of the toner binder resin is more preferably less than 2.0% by weight.

In the GPC molecular weight distribution of the THF-soluble component, the component content (M1) of less than 10,000 was 45 to 65%,
Component content (M2) of 10,000 to 50,000 25 to 50%, 50,000 to
Component content (M3) of 500,000 is 2 to 20%, component content of over 500,000 (M4) is 0.1 to 10%, components of 50,000 or less are 80% or more of the whole, and M1>M2> M
When the relationship of 3> M4 is not satisfied, the low-temperature fixability, gloss, OHT transparency and offset resistance required for the color toner are not compatible.

In the present invention, the linear polyester resin B used in combination with the non-linear polyester resin A is used.
Has a number average molecular weight (Mn) of 2,000 to 8,000, a weight average molecular weight (Mw) of 8,000 to 30,000, a number average molecular weight (Mn) and a weight average molecular weight (Mw)
Is preferably 2 to 3.5. If the molecular weight is less than the lower limit, the viscosity at the time of fusing is greatly reduced with respect to the non-linear polyester resin A used as a mixture, thereby lowering the offset resistance. If the molecular weight exceeds the upper limit, the linear polyester resin B And the effect of lowering the fixing temperature cannot be obtained. Further, Mw / Mn is preferably as small as possible in order to obtain a sharp melt property. When Mw / Mn exceeds 3.5, the sharp melt property decreases, and the linear polyester resin B is mixed to lower the fixing temperature. The effect of lowering is small.

In the present invention, the binder resin (the whole polymer component of the toner composition) and the TH of the linear polyester resin B
The GPC molecular weight distribution of the F-insoluble portion and the THF-soluble portion was measured according to the following method.

(Measurement of THF Insoluble Content of Toner) The THF insoluble content of the present invention indicates "weight ratio of polymer component insoluble in THF solvent in toner" calculated by Soxhlet extraction method. That is, the toner samples 1.
0 g was weighed (W1 g), placed in a thimble filter paper (for example, No. 86R made by Toyo Roshi Kabushiki Kaisha), subjected to a Soxhlet extractor, extracted with 200 ml of THF as a solvent for 12 hours, and the soluble matter extracted by the solvent was evaporated. Later, 1
After vacuum drying at 00 ° C. overnight, the amount of the resin component soluble in THF is weighed (W2 g). When measuring the THF-insoluble content of the toner, the weight other than the resin component such as a pigment is calculated by (W3 g).
Is obtained from the following equation.

[0075]

(Equation 1)

(Measurement of Molecular Weight Distribution of THF Soluble Content of Toner) The TH of the toner sample subjected to the Soxhlet extraction described above was measured.
The F-soluble matter and THF are mixed at a concentration ratio of 5 to 25 mg / 5 ml, allowed to stand at room temperature for several hours, shaken sufficiently, and then allowed to stand overnight. Thereafter, a sample processing filter (pore size: 0.4 to 0.5 μm, for example, Mishoridisk H-25-2 manufactured by Tosoh Corporation, Exiclodisk 25CR)
What has passed through (German Science Japan Co., Ltd.) is used as a measurement sample.

In the GPC measuring apparatus, the entanglement is stabilized in a heat chamber at 40 ° C., and THF at a temperature of 1 ml / min. , And about 100 ml of a THF sample solution is injected for measurement. When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As the standard polystyrene samples for calibration curve prepared, for example, Tosoh Corporation or Showa Denko Co., Ltd. molecular weight of 10 ² -
It is appropriate to use about 10 ^{7 and} to use at least about 10 standard polystyrene samples. An IR (refractive index) detector is used as the detector. As a column,
It is preferable to combine several commercially available polystyrene gel columns, and Shodex GPC K manufactured by Showa Denko KK
F-801, 802, 803, 804, 805, 80
A combination of 6,807,800P is preferred. GPC
In the measurement of, on both sides of the polymer, the measurement was started from the starting point of the chromatogram rising from the baseline to the low molecular weight side and the molecular weight of about 400 was taken as the molecular weight calculation range. The measuring device used was GPC-150C (Waters).

Further, the acid value of the binder resin (the whole polymer component of the toner composition) used in the present invention is 2 mgKOH /
g to 20 mgKOH / g is preferred. When the acid value of the binder resin is less than 2 mgKOH / g, the development stability and the durability stabilizing effect due to the interaction with the organometallic compound cannot be sufficiently exhibited, or the wax is poorly dispersed due to the poor dispersion of the organometallic compound. , The deterioration of low-temperature fixability is observed. On the other hand, when it exceeds 20 mgKOH / g, the hygroscopicity becomes strong, the image density tends to decrease, and the fog tends to increase.

In the present invention, the acid value of the entire polymer component of the toner composition is determined by the following method.

(Measurement of acid value) The basic operation is JIS K-0.
070.

1) The sample is used after removing additives other than the polymer component in advance, or the acid value and content of the component other than the polymer are determined in advance. 0.5-2.0 (g) of crushed sample
Is precisely weighed to obtain the weight W (g) of the polymer component.

2) A sample was placed in a 300 ml beaker, and a mixed solution of toluene / ethanol (4/1) 150
(Ml) and dissolve.

3) Titration with a methanol solution of 0.1 N KOH using a potentiometric titrator (for example,
Potentiometric titrator AT-400 (w
automatic titration using an AWP-410 motorized burette. )

4) At this time, the used amount S (m
1), and at the same time, a blank is measured, and the amount of the KOH solution used at this time is defined as B (ml).

5) Calculate the acid value according to the following equation. f is KO
H factor.

Acid value (mgKOH / g) = ((S−B) ×
f × 5.61) / W

The preferred composition of the polyester resin used in the present invention is described below.

The non-linear polyester resin A used in the present invention comprises 3 to 15 mol% of all the components of polyvalent carboxylic acid monomer units having 3 or more valences, and has 5 to 30 carbon atoms. 5 to 30 mol of a polycarboxylic acid monomer unit and / or a polyhydric alcohol monomer unit (soft segment component) having an aliphatic hydrocarbon group of
%, And the others consist of a divalent acid component and a divalent alcohol component. The linear polyester resin B used in the present invention comprises a divalent acid component and a divalent alcohol component.

The trivalent or higher polyvalent carboxylic acid monomer unit as a component of the polyester resin used in the present invention includes 1,2,4-benzenetricarboxylic acid,
1,3,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-
Hexanetricarboxylic acid, tetra (methylenecarboxy) methane, 1,3-dicarboxyl-2-methyl-2
Polycarboxylic acids such as -methylenecarboxypropane and 1,2,7,8-octanetetracarboxylic acid, and acid anhydrides or lower alkyl esters thereof.

The monomer unit serving as a soft segment as a component of the non-linear polyester resin A used in the present invention has a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms. A monomer unit having a saturated or unsaturated aliphatic hydrocarbon group which is a polyvalent carboxylic acid monomer unit and / or a polyhydric alcohol monomer unit and is introduced by being branched into the skeleton of the polyester resin. Preferably, there is. The soft segment component is preferably one having a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms in any of divalent and trivalent or higher monomers constituting the polyester resin. More preferably, it is a monomer of a substituted aliphatic dicarboxylic acid and / or an aliphatic diol substituted with a soft segment.

Examples of the aliphatic dicarboxylic acid monomer unit substituted with a soft segment include an alkyl group or an alkenyl group having 5 to 30 carbon atoms (eg, n-dodecenyl group, isododecenyl group, n-dodecyl group, isododecyl group, or isooctyl). Alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, and their anhydrides, and dodecenylsuccinic acid, octylsuccinic acid, and anhydrides thereof.

The aliphatic diol monomer unit substituted with a soft segment may have 5 to 30 carbon atoms.
Ethylene glycol, 1,3-propylene diol, tetramethyl glycol, 1,4-butylene diol, 1,5-pentyl diol, etc. substituted with an alkyl group or an alkenyl group, and n-dodecenyl Ethylene glycol, n-dodecenyl triethylene glycol and the like are preferably used.

Further, the divalent acid component of the polyester resin used in the present invention includes phthalic acid, terephthalic acid,
Isophthalic acid, benzenedicarboxylic acids such as phthalic anhydride or anhydrides or lower alkyl esters thereof; succinic acid, adipic acid, sebacic acid, alkyldicarboxylic acids such as azelaic acid or anhydrides or lower alkyl esters thereof; fumaric acid, Unsaturated dicarboxylic acids such as maleic acid, citraconic acid, and itaconic acid, or anhydrides or lower alkyl esters thereof, and the like.

The dihydric alcohol component includes ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5- Pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,
3-hexanediol, hydrogenated bisphenol A, bisphenol represented by the formula (a) and derivatives thereof;

[0095]

Embedded image (In the formula, 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 to 10.) Further, diols represented by the formula (b);

[0096]

Embedded image Wherein R ′ is an ethylene or propylene group, and x ′
And y ′ are each an integer of 0 or more, and x ′ +
The average value of y ′ is 0 to 10. And the like.

Of these, it is preferable to use at least propoxylated and / or ethoxylated etherified bisphenol.

Further, as the trivalent or higher alcohol component usable in the present invention, for example, sorbitol, 1,2,3,3
6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-menthatriol, glycerin, 2-methylpropanetriol, 2-
Methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.

The organometallic compounds used in the present invention include:
For example, organometallic complexes, metal salts, chelate compounds,
Examples thereof include a monoazo metal complex, an acetylacetone metal complex, a salicylate metal complex, an alkylsalicylate metal complex, a dialkylsalicylic acid metal complex, a metal complex of offsinaphthoic acid, a metal complex of hydroxycarboxylic acid, and a metal salt of polycarboxylic acid. Examples of the metal elements constituting the complex organometallic complex, metal salt, and chelate compound include chromium, iron, zinc, aluminum, and zirconium. In the case of a black toner, it can be used regardless of color or color. The color toner is preferably a colorless or light color toner that does not affect the color tone of the toner.

In the present invention, as the metal element of the organometallic compound, aluminum or zirconium is preferable because it has stability in crosslinking property with the polyester resin of the present invention and can easily control viscoelasticity.

The present inventors use a zirconium compound, particularly a zirconium complex compound or an aromatic carboxylate of zirconium, in combination with the binder resin composition of the present invention as the organometallic compound used in the present invention. As a result, it is possible to obtain a toner that is excellent in low-temperature fixability, maintains a good rise in toner charging, and has a relatively stable charge amount with respect to environmental changes from a high humidity environment to a low humidity environment. Was found.

The organic zirconium compound of the present invention has an opportunity to coordinate a zirconium ion with a carboxyl group, a hydroxyl group, or the like because zirconium ions are easily coordinated with octa and oxygen such as a carboxyl group or a hydroxyl group is easily coordinated. Increase. Therefore, the familiarity of the organic zirconium compound into the binder resin is good, and the property excellent in dispersibility,
By using the polyester resin having the configuration of the present invention, it is possible to prevent the toner particles from falling off from the toner particles, and to obtain uniform charging and stable charging.

Further, the polymer chain can be more effectively cross-linked through the coordination of carboxyl groups and hydroxyl groups to zirconium ions in the polyester resin of the present invention whose metal cross-linking property is controlled. It is easy to control rubber elasticity and viscosity, which are the objectives. Further, it is excellent in releasing property, can effectively prevent the fixing member from being stained, and can achieve full-color oil-less fixing.

Further, the organic zirconium compound usable in the present invention is improved in dispersion of other materials (pigments, dyes, waxes, etc.) in the polyester resin of the present invention, whereby uniform charge and durability of charge can be obtained. Stability is obtained.
In addition, the effect on the transparency of the toner is reduced, which is preferable for expressing a vivid color for the color toner.

The content of the organic zirconium compound is 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
More preferably, it is used in the range of 0.5 to 6 parts by weight, and it can be used in combination with a known charge control agent as described in the related art.

In the present invention, the object of the present invention can be more highly achieved by a toner containing a zirconium complex or a zirconium complex salt of an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid as an organometallic compound. is there.

The zirconium compound preferably used as the organometallic compound of the present invention is a zirconium complex or a zirconium complex in which 2 to 4 aromatic diols, aromatic hydroxycarboxylic acids, or aromatic polycarboxylic acids are chelated. More preferably, it is a zirconium complex salt. In the case of a salt, those having 1 to 4 aromatic carboxylic acid ions, aromatic hydroxy carboxylic acid ions and aromatic polycarboxylic acid ions are preferable, and those having 2 to 3 aromatic carboxylic acid ions are more preferable. Further, complexes and complex salts having different numbers of chelate formation or complexes and complex salts having different ligands may be used. Further, a mixture of salts having different numbers of acid ions may be used.

The zirconium compound preferably used as the organometallic compound in the present invention is a zirconium complex or a zirconium complex salt which coordinates an aromatic diol, an aromatic hydroxycarboxylic acid or an aromatic polycarboxylic acid as a ligand. And more preferably a zirconium complex or a zirconium complex salt represented by the general formula (1).

[0109]

Embedded image In the general formula (1), Ar represents an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group,
Having an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group, and a carbamoyl group. You may. X and Y represent -0- and -CO-O-, X and Y may be the same or different, L represents a neutral ligand,
Represents water, alcohol, ammonia, alkylamine, pyridine, C1 represents a monovalent cation, hydrogen, a monovalent metal ion, ammonium, alkylammonium, C2 represents a divalent cation, a divalent metal ion,
n represents 2, 3, and 4, and m represents 0, 2, and 4. The aromatic carboxylic acids and aromatic diols serving as ligands in each complex or complex salt may be the same or different. Also, a mixture of complex compounds having different numbers of n and m may be used. From the viewpoint of improving the dispersibility of the complex or complex salt in the binder resin or improving the chargeability, the aromatic residue is preferably a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring, and the substituent is an alkyl group. , A carboxyl group and a hydroxyl group are preferable, L is preferably water, and C1 is preferably hydrogen, sodium, potassium, ammonium or alkylammonium.

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

[0111]

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

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

[0113]

Embedded image

[0114]

Embedded image Preferred zirconium salts of aromatic carboxylic acids used in the present invention are represented by general formulas (10) and (11).

[0115]

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

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

[0117]

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

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

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

[0120]

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As the coloring agent used in the present invention, conventionally known coloring agents can be used.

For example, as a cyan colorant used for a cyan toner, a copper phthalocyanine compound and its derivative, an anthraquinone compound, a basic dye lake compound and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15:
4, 60, 62, 66, etc. can be suitably used.

Examples of the magenta colorant used in the magenta toner include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Can be Specifically, C.I. I. Pigment Red 2, 3,
5, 6, 7, 23, 48; 2, 48; 3, 48; 4, 5
7; 1, 81; 1, 122, 144, 146, 166,
169, 177, 184, 185, 202, 206, 2
20, 221 and 254 are preferred.

As the yellow colorant used in the yellow toner, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 1
3, 14, 15, 17, 62, 74, 83, 93, 9
4, 95, 109, 110, 111, 128, 129,
147, 168, etc. are preferred.

As the black colorant used for the black toner, carbon black, a magnetic substance, and a black color tone using the above-described cyan / magenta / yellow colorant can be used.

These colorants can be used alone or as a mixture or in the form of a solid solution. In the present invention, the colorant includes hue angle, saturation, lightness, weather resistance, OHP transparency,
It is selected from the viewpoint of dispersibility in the toner. The colorant is preferably added in an amount of 1 to 20 parts by weight based on 100 parts by weight of the resin component.

Among the chromatic colorants, the cyan toner may contain a copper phthalocyanine organic pigment, the magenta toner may contain a quinacridone organic pigment, and the yellow toner may contain a diarylide organic pigment. It is particularly preferable that it is contained in that good chargeability, fluidity and spectral reflection characteristics of the toner can be obtained.

Examples of the copper phthalocyanine organic pigment include:
C. I. Pigment Blue 15; 15: 1; 15: 2;
15: 3; 15: 4. Further, a phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the formula (C) is exemplified. A copper phthalocyanine pigment having another substituent may be used.

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The content is 0.1 to 12 parts by weight, preferably 0.1 to 12 parts by weight, based on 100 parts by weight of the binder resin.
5 to 10 parts by weight, more preferably 1 to 8 parts by weight.
If the amount exceeds 12 parts by weight, the saturation and lightness of the cyan toner decrease, and the color reproducibility decreases.

Examples of quinacridone organic pigments include C.I.
I. Pigment Red 122 is preferred, and C.I. I. Pigment Red 192, 202, 206, 207, 209
Is also preferred. Further, C.I. I. Pigment Violet 1
9 is also preferred. C. I. Pigment Red 122 as a base pigment may be used in combination with other coloring agents. Examples of the pigment used at that time include C.I. I. Pigment Red 1,
2,3,4,5,6,7,8,9,10,11,12,
13,14,15,16,17,18,19,21,2
2,23,30,31,32,37,38,39,4
0, 41, 48, 49, 50, 51, 52, 53, 5
4,55,57,58,60,63,64,68,8
1,83,87,88,89,90,112,114,
123,146,150,163,184,185,2
38; I. Pigment Violet 19; I.
Butt Red 1,2,10,13,15,23,29,
35 and the like. A dye such as a xanthene dye may be partially used in combination.

The content is 0.1 to 15 parts by weight, preferably 1 to 12 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the binder resin. Even when used in combination with another dye / pigment, the other dye / pigment is preferably 50 parts by weight or less, more preferably 25 parts by weight or less, based on 100 parts by weight of the quinacridone-based pigment.

Examples of diarylide organic pigments include C.I.
I. Pigment Yellow 12, 13, 14, 17, 8
1,106,113 are preferred, and C.I. I. Pigment Yellow 55, 63, 83, 87, 90, 11
4,121,124,126,127,136,15
2,170,171,172,174,176,188
It may be.

Further, C.I. I. Pigment Yellow 1
2,13,14,17,81 may be used as a base pigment in combination with other yellow colorants, or may be used in combination with a yellow dye.

The content is 0.1 to 12 parts by weight, preferably 0.5 to 1 part by weight, per 100 parts by weight of the binder resin.
0 parts by weight, more preferably 1 to 8 parts by weight.

In the case where a magnetic material is used as the black colorant, unlike other colorants, it is 20 to 200 parts by weight, particularly preferably 40 to 1 part by weight, per 100 parts by weight of the resin component.
It is preferable to add 50 parts by weight.

Examples of the magnetic substance include iron oxides such as magnetite, maghematite, and ferrite; metals such as iron, cobalt, and nickel;
Cobalt, copper, lead, magnesium, manganese, selenium,
Alloys of metals such as titanium, tungsten, and vanadium and mixtures thereof are used, and those containing a non-ferrous element on the surface or inside of the magnetic material are preferable.

As these magnetic materials, magnetic iron oxides such as magnetite, maghemite and ferrite containing different elements and mixtures thereof are preferably used. Among them, lithium,
Beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, titanium, zirconium,
Tin, lead, zinc, calcium, barium, scandium,
Selected from vanadium, chromium, manganese, cobalt, copper, nickel, gallium, cadmium, indium, silver, palladium, gold, mercury, platinum, tungsten, molybdenum, niobium, osmium, strontium, yttrium, technetium, ruthenium, rhodium, bismuth Magnetic iron oxide containing at least one or more elements is preferable. In particular, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, and the fourth transition metal element are preferred elements. These elements may be taken into the iron oxide crystal lattice, may be taken into the iron oxide as an oxide, or may be present as an oxide or hydroxide on the surface. It is a preferred embodiment that it is contained as an oxide.

These magnetic materials have a uniform particle size distribution.
In combination with the dispersibility in the binder resin, the chargeability of the toner can be stabilized. In recent years, the toner particle diameter has been reduced, and even when the weight average particle diameter is 10 μm or less, the uniformity of charging is promoted, the cohesiveness of the toner is reduced, the image density is improved, and the fog is improved. The performance is improved. In particular, the effect is remarkable in a toner having a weight average particle diameter of 6.0 μm or less, and an extremely high-definition image can be obtained. It is preferable that the weight average particle size is 2.5 μm or more, since sufficient image density can be obtained.

The content of these different elements is preferably 0.05 to 10% by weight based on the iron element of the magnetic iron oxide. The content is more preferably 0.1 to 7% by weight, particularly preferably 0.2 to 5% by weight, further preferably 0.3 to 4% by weight. If the content is less than 0.05% by weight, the effect of containing these elements cannot be obtained, and good dispersibility and uniform charging cannot be obtained. On the other hand, when the content is more than 10% by weight, the release of electric charge is increased and insufficient charging is caused, so that the image density may be lowered or fog may be increased.

Regarding the content distribution of the different elements in these magnetic materials, it is preferable that the one that is present more in the vicinity of the surface of the magnetic material. For example, the ratio (B / A) × 100 of the content B of the different element present in the iron oxide dissolution rate of iron oxide up to 20% by weight and the total content A of the different element in the magnetic iron oxide is 40.
% Is preferable. Further, it is preferably from 40 to 80%, particularly preferably from 60 to 80%. By increasing the surface abundance, the dispersion effect and the electric diffusion effect can be further improved. The amount contained in the toner is 20 to 200 parts by weight based on 100 parts by weight of the resin component.
It is more preferably 40 to 150 parts by weight, particularly preferably 100 parts by weight of the resin component.

The magnetic iron oxide used in the magnetic toner of the present invention may be treated with a silane coupling agent, a titanium coupling agent, titanate, aminosilane or the like.

The amount of the element in the magnetic iron oxide of the present invention is determined by the fluorescent X
Ray analyzer SYSTEM3080 (Rigaku Denki Kogyo Co., Ltd.)
And X-ray fluorescence analysis according to JIS K0119 X-ray fluorescence analysis standard. Regarding the element distribution, the amount of the element while dissolving hydrochloric acid was measured and quantified by plasma emission spectroscopy (ICP), and the dissolution rate was determined from the concentration of each element at the time of each dissolution with respect to the concentration of each element at the time of total dissolution.

The binder resin used in the toner of the present invention is:
In addition to the polyester resin in the present invention, it can be used in combination with other resins to such an extent that the present invention is not adversely affected.

For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester 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, polyurethane, polyamide resin, furan resin, epoxy resin , Xylene resin, polyvinyl butyral, terpene resin, cumarone indene resin, petroleum resin and the like can be used. Preferred binder materials include styrene copolymers.

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

The resin composition of the present invention has a glass transition temperature (Tg) of from 45 to 75 ° C., preferably from 50 to 70 ° C., from the viewpoint of storage stability. The toner is likely to deteriorate, and offset is likely to occur during fixing. On the other hand, when Tg exceeds 75 ° C., the fixability tends to decrease.

It is preferable that inorganic fine powder or hydrophobic inorganic fine powder is mixed in the toner of the present invention. For example, it is more preferable to add and use silica fine powder, alumina fine powder, and titanium oxide fine powder.

The fine silica powder used in the present invention includes both a so-called dry method produced by vapor phase oxidation of a silicon halide and a so-called fumed silica and a so-called wet silica produced from water glass or the like. Can be used, but dry silica which has few silanol groups on the surface and inside and has no production residue is preferable.

The silica fine powder used in the present invention is preferably subjected to a hydrophobic treatment. The hydrophobizing treatment is applied by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with the silica fine powder. A preferred method is to treat the dry silica fine powder produced by the vapor phase oxidation of the silicon halide compound with a silane coupling agent or simultaneously with the silane coupling agent and an organic silicon compound such as silicone oil. Is mentioned.

Examples of the silane coupling agent used for the hydrophobizing treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, and allylphenyl. Dichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane,
Chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldi Siloxane and 1,3-diphenyltetramethyldisiloxane.

Examples of the organosilicon compound include silicone oil. Preferred silicone oils are those having a viscosity of about 30 to 1,000 centistokes at 25 ° C., such as dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. Silicone oil and the like are preferred.

The silicone oil treatment may be carried out, for example, by mixing silica fine powder treated with a silane coupling agent and silicone oil directly using a mixer such as a Henschel mixer, or using a silica A method of injecting oil may be used. Alternatively, it may be prepared by dissolving or dispersing a silicone oil in an appropriate solvent, mixing with a base silica fine powder, and removing the solvent.

If necessary, an external additive other than the above-mentioned inorganic fine powder may be added to the toner of the present invention.

For example, a charge auxiliary agent, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent for fixing a hot roll,
These are resin fine particles and inorganic fine particles that function as a lubricant, an abrasive and the like.

For example, lubricants such as Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride are preferable, and polyvinylidene fluoride is particularly preferable. Alternatively, a polishing agent such as cerium oxide, silicon carbide, and strontium titanate, among which strontium titanate is preferable. Alternatively, for example, a fluidity-imparting agent such as titanium oxide or aluminum oxide, particularly a hydrophobic agent is preferable. A small amount of a caking preventing agent, a conductivity imparting agent such as carbon black, zinc oxide, antimony oxide, tin oxide and the like, and white and black fine particles of opposite polarity can also be used as a developing improver.

The amount of the inorganic fine powder or the hydrophobic inorganic fine powder mixed with the toner is 0.1 to 100 parts by weight of the toner.
It is preferable to use 5 parts by weight (preferably 0.1 to 3 parts by weight).

In order to produce the toner according to the present invention, the above-mentioned toner constituting materials are sufficiently mixed by a mixer such as a ball mill or a Henschel mixer, and then a hot roll kneader or an extruder may be used. After kneading and solidifying by cooling, a method of obtaining a toner by mechanical pulverization and classification is preferable, and the toner according to the present invention can be produced.

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

The image forming method of the present invention includes a charging step of charging a latent image carrier; a latent image forming step of forming an electrostatic latent image on the charged latent image carrier; developing the electrostatic latent image with toner Developing step of forming a toner image by transfer; transferring the developed toner image onto a recording material with or without an intermediate transfer member; and fixing to the surface of the toner image transferred on the recording material. Fixing the toner image on the recording material by contacting the members and applying heat and pressure to the toner image; and the developing step includes:
A step of using a color toner having at least a binder resin, a wax, an organometallic compound, and a colorant, wherein the binder resin comprises at least a trivalent or higher polyvalent carboxylic acid monomer unit and 5 to 30 carbon atoms. A polyvalent carboxylic acid monomer unit and / or a polyhydric alcohol monomer unit having a saturated or unsaturated aliphatic hydrocarbon group, and When the content of the monomer unit is Xa mol%, the content of the polyvalent carboxylic acid monomer unit and / or polyhydric alcohol monomer unit having a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms is determined. Assuming that the content is Ya mol%, a non-linear polyester resin A satisfying the following conditions: 0.5 <Xa <155 5 <Ya <302 2 ≦ Ya / Xa ≦ 10; It is composed of a linear polyester resin B containing no monomer unit and no trivalent or higher polyhydric alcohol monomer unit, and the mixing weight ratio of the non-linear polyester resin A and the linear polyester resin B is 25/75 to 75. / 2
Developing a latent electrostatic image using a specific color toner of the present invention having a maximum endothermic peak measured by a differential scanning calorimeter (DSC) of 60 to 135 ° C. to form a toner image It is characterized by being.

Various methods and apparatuses have been developed for the fixing step of fixing the toner image on the recording material by applying heat and pressure to the toner image. This is a compression heating method using a heat roller. Conventionally, in a fixing method in which a fixing member is brought into contact with the surface of a toner image transferred onto a recording material such as a heat roller, and heat and pressure are applied to the toner image, the toner image is fixed on the recording material. Since the surface of the fixing member and the toner image come into contact with each other under pressure in a molten state, a part of the toner image may adhere to and transfer to the surface of the fixing member, thereby fouling the next sheet to be fixed (offset phenomenon).

Further, using three color toners of three primary colors, yellow, magenta and cyan, or four color toners obtained by adding black toner to each other, the respective color toners are heated and fixed in a superimposed manner. In the color image forming method for performing full-color color reproduction, a multicolor image must be fixed on paper or a sheet to be fixed such as an overhead projector sheet (OHT), and the color reproduction and the transparency of the OHT image must be satisfied. Therefore, it is required that the toner layer on the sheet to be fixed be sufficiently melted and the image surface be smoothed. Therefore, it is required to achieve both smoothness of an image and prevention of offset.

On the other hand, the present invention achieves both smoothness of an image and prevention of offset by applying a specific color toner having excellent releasability and color mixing with the fixing member in the present invention.

In the present invention, in the fixing step, the coating amount of fixing oil supplied from the fixing member to the fixing surface of the toner image of the recording material per unit area of the recording material is 0 to 1 × 10 ⁻⁷ g.
/ Cm ² is preferably a step of fixing a toner image on a recording material.

In order to achieve both image smoothness and prevention of offset, means for supplying a fixing oil such as silicone oil to a fixing member as a release agent and uniformly covering the roller is widely used. As means for regulating the amount of fixing oil (for example, silicone oil) supplied from the fixing member to the fixing surface of the toner image on the recording material per unit area of the recording material, the web, pad, roller, or the like is impregnated with the oil and supplied. A form is possible, and a fixing member (for example, a silicone rubber roller) impregnated with oil is also possible.

However, when the fixing oil is applied and / or supplied, the sheet to be fixed has a sticky feeling due to the fixing oil,
There is a problem in that the obtained color image is dim, and the obtained image quality (eg, glossiness, oily stickiness, etc.) tends to fluctuate due to the difference in the supply amount of the release agent between the initial stage and after long-term use. In order to make the supply amount of the mold agent constant, a complicated application and / or supply mechanism of the mold release agent is required. When applying a trace amount of release agent as in the present invention by a simple means, uneven application of oil is likely to occur, and uneven adhesion of oil on the obtained image greatly reduces image quality. The application mechanism of the fixing oil or the replenishment of the oil is an obstacle to miniaturization, inexpensive equipment, low running cost, and the like.

On the other hand, by applying the fixing oil supplied from the fixing member to the fixing surface of the recording material on the toner image of the recording material per unit area of the recording material, from 0 to 1 × 10 ⁻⁷ g / cm ² , It is possible to suppress the brightness of the image. By applying the specific color toner according to the present invention, it is possible to achieve both the smoothness of the image and the prevention of the offset while suppressing the blur of the image.

Preferably, in order to suppress the unevenness of gloss due to the fixing oil of the color image, the amount of the fixing oil supplied from the fixing member to the fixing surface of the toner image of the recording material per unit area of the recording material is zero. ~ 3 × 10 ^-8 g / cm ²
And more preferably 0 to 1 × 10 ⁻⁸ g /
cm ² is good.

Further, in the present invention, the fixing step is preferably a step of fixing the toner image on the recording material without supplying fixing oil from the fixing member to the recording material.

One of the objects of the present invention is complete oil-less fixing, that is, no fixing oil such as silicone oil is applied (the amount of fixing oil present on the surface where the fixing member contacts the toner image on the transfer material is substantially reduced). 0 g / cm ² ), it is possible to reduce the size and cost of the color image forming apparatus, and the color image quality does not change due to repeated use or a change in the supply amount of the fixing oil over time. By applying the specific color toner in the present invention, even in complete oil-less fixing, a color image showing moderate and stable gloss with excellent smoothness of an image can be obtained with a small-sized, low-cost apparatus while preventing offset. It is possible to obtain.

Next, the fixing step in the image forming method of the present invention will be described with reference to FIG.

In the fixing step in the image forming method of the present invention, the toner image is recorded by bringing a fixing member into contact with the surface of the toner image formed on the recording material and applying heat and pressure to the toner image. The toner is fixed on a material, and the above-described specific toner in the present invention is used as a toner for forming the toner image.

For example, the unfixed toner image transferred onto the recording material is introduced into a heat-pressure fixing device having a heating roller 153 and a pressure roller 154 shown in FIG.

The mechanical structure of the fixing device is as follows.
It is preferable to use an elastic roller as the fixing roller 153 on the side where the toner image 161 on 60 directly contacts. That is, when the fixing roller has elasticity, the fixing roller surface itself deforms and presses against the unevenness of the unfixed toner image surface, so that the toner image is uniformly heated,
Pressurization becomes possible, which is more effective in making the gloss uniform.

The image forming method of the present invention includes a step of fixing the color toner images of a plurality of colors superimposed on the recording material 160 by a fixing member that performs contact heating and pressurization. When the toner image 161 is fixed, the recording material 16 is transferred from a fixing roller 153 serving as a fixing member.
The amount of silicone oil supplied to the fixing surface of the 0 toner image 161 per unit area of the recording material is 0 to 1 × 10
^-7 g / cm ² , preferably 0 to 3 × 10 ^-8 g / cm ² ,
More preferably, no silicone oil is applied (0 g /
cm ² ) is good.

Further, if necessary, the separation claw 15 between the recording material 160 and the fixing roller 153 or the pressure roller 154 may be used.
9 is provided in the fixing device.

As a form of applying silicone oil to the fixing member of the present invention, a simple form in which a web or a pad is impregnated with silicone oil and supplied is possible. Further, a fixing member such as a silicone rubber roller impregnated with oil in advance may be used.

The fixing temperature is preferably in the range of about 140 to 180 ° C., and the pressing force is preferably in the range of about 20 to 60 kgf.

In the present invention, a plurality of constituent members constituting the image forming apparatus used in the above description of the image forming method can be unitized and detachably attached to the main body of the image forming apparatus. Units can be configured.

The apparatus unit of the present invention includes a toner for developing an electrostatic latent image, a toner container for holding the toner, the toner held in the toner container, and transporting the toner to a development area. And a toner layer thickness regulating member for regulating the layer thickness of the toner carried on the toner carrier, and is detachably attached to the image forming apparatus main body. The toner of the present invention described above is used as the toner.

As such a device unit, for example, the developing device 170 shown in FIG. 7 and the developing device 18 shown in FIG.
0.

When the developing device 170 shown in FIG. 7 is used as an apparatus unit, a developing container 171 as a toner container,
In addition to a one-component developer 176 as a toner, a developing sleeve 172 as a toner carrier, and an elastic blade 174 as a toner layer thickness regulating member, the developer sleeve 17
Supply roller 17 for supplying one-component developer onto
3 may be configured as a unit.

When the developing device 180 shown in FIG. 8 is used as an apparatus unit, a developing container 181 as a toner container,
In addition to a one-component developer 188 as a toner, an elastic roller 182 as a toner carrier, and an elastic blade 186 as a toner layer thickness regulating member, the elastic roller 18
Supply roller 18 for supplying one-component developer onto
5 and a stirring member 187 for stirring the one-component developer 188 in the developing container 181 may be formed as a unit.

Further, the developing device 170 shown in FIG. 7 or the developing device 180 shown in FIG. 8 is replaced with the developing means 17a, 17b, 17c and 17 of the full-color image forming apparatus shown in FIG.
In the case of using each of d, the developing unit 17a as a device unit and the photosensitive drum 19a as a latent image holding member can be unitized to form a device unit, and this device unit is detachably attached to the image forming apparatus main body. can do. Similarly, the developing means 17b and the photosensitive drum 19b
And the developing unit 17c and the photosensitive drum 19c, and the developing unit 17d and the photosensitive drum 19d are unitized to form an apparatus unit.

In this case, it is possible to constitute a device unit in which a cleaning unit 18a is added in addition to the developing unit 17a and the photosensitive drum 19a.

The image forming method and the image forming apparatus of the present invention will be described in detail.

In the image forming method of the present invention, a charging step of charging a latent image holding member; a latent image forming step of forming an electrostatic latent image on the charged latent image holding member; and developing the electrostatic latent image with toner Developing step of forming a toner image by transfer; transferring the developed toner image onto a recording material with or without an intermediate transfer member; and fixing to the surface of the toner image transferred on the recording material. Fixing the toner image onto the recording material by contacting the members and applying heat and pressure to the toner image, and the present invention as described above as a toner used in the developing process. The specific toner inside is used.

In the charging step, a non-contact charging member for charging the surface of the latent image carrier in a non-contact manner, such as a corona charger, and a contacting member for the surface of the latent image carrier, such as a blade, a roller, or a brush, are used. Any charging member such as a contact charging member that performs charging by charging, a charging member such as a blade or a roller, and a proximity charging member that performs charging by bringing the charging member close to (less than 1 mm) the surface of the latent image carrier can be used. It is preferable to use a contact charging member or a proximity charging member because the occurrence of charging can be reduced.

In contact charging, a charging member as a charge supply member such as a roller type, a blade type, a brush type, and a magnetic brush type is brought into contact with the photoreceptor, and a predetermined charging bias is applied to the contact charging member. The body surface is uniformly charged to a predetermined polarity and potential. As compared with the charging process using a corona charger, the power supply can be made lower in voltage, and the advantages such as low generation of ozone and low power can be obtained. Among them, a roller charging method using a conductive roller (charging roller) as a contact charging member is particularly preferably used from the viewpoint of charging stability.

Specifically, since charging is performed by discharging from the charging member to the member to be charged, charging is started by applying a voltage equal to or higher than a certain threshold voltage. For example, when a charging roller is pressed against an organic photoconductor, the surface potential of the photoconductor starts to increase when a voltage of about 640 V or more is applied, and thereafter, the applied voltage is reduced. On the other hand, the photoreceptor surface potential linearly increases at an inclination of 1. Since then
This threshold voltage is defined as a discharge start voltage (charging start voltage) Vth (a voltage value applied to the contact charging member when a DC voltage is applied to the contact charging member to start charging the image carrier as the member to be charged) ).

The method of charging by applying only the DC voltage to the contact charging member in this manner is called a "DC charging method".

However, in the DC charging system, the resistance value of the contact charging member fluctuates due to environmental fluctuations and the like, and the discharge starting voltage Vth fluctuates when the film thickness changes due to the shaving of the photoreceptor. Was difficult to obtain a desired value.

Therefore, as disclosed in JP-A-63-149669, in order to further uniform the charging,
A DC voltage corresponding to a desired charged body surface potential V is 2 × V
A voltage (alternating voltage, pulsating voltage, oscillating voltage; voltage whose voltage value changes periodically with time) on which an AC voltage component (AC voltage component) having a peak-to-peak voltage equal to or greater than th is applied to the contact charging member. The “AC charging method” is used.
This is for the purpose of the leveling effect of the potential by the AC voltage, and the potential of the member to be charged converges to the potential V, which is the center of the peak of the AC voltage, without being affected by disturbances such as the environment. This is an excellent method as a contact charging method.

Here, as the waveform of the AC voltage, a sine wave, a rectangular wave, a triangular wave, or the like can be used as appropriate. Alternatively, a rectangular wave formed by periodically turning on / off a DC power supply may be used. As described above, a bias whose voltage value periodically changes can be used as the waveform of the AC voltage.

A charge injection layer (charging layer) is provided on the surface of an image carrier as a member to be charged, and charges are directly injected into the charge injection layer by a contact charging member to which a voltage is applied, so that the surface of the image carrier has a predetermined surface. There is also an injection charging method of charging to a polarity and a potential, which is also a category of contact charging.

In the proximity charging, the charging member does not necessarily come into contact with the surface of the charged object,
The present invention utilizes the fact that the member to be charged can be charged even in a non-contact and close arrangement, as long as a dischargeable region determined by the gap voltage and the Paschen curve is assured.

In the proximity charging, the charging member is disposed so as to be opposed to the surface of the member to be charged in a non-contact manner with a small gap of about several tens to several hundreds μm, and a DC voltage or a DC + AC voltage is applied to the charging member. By doing so, the surface of the member to be charged is uniformly charged to a predetermined polarity and potential.

As compared with the charging process using the corona charger, the proximity charging also achieves a lower voltage of the power supply, generates less ozone, and has a non-contact charging member with the charging member. It has the advantage of not damaging.

Examples of the latent image carrier include an electrophotographic photosensitive member and an electrostatic recording dielectric having a photoconductive insulating material layer such as amorphous selenium, cadmium sulfide, zinc oxide, an organic photoconductor, and amorphous silicon. , A photosensitive drum or a photosensitive belt. Of these,
As the latent image carrier, a photosensitive member having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

The organic photosensitive layer may be a single layer type in which the photosensitive layer contains a charge generating substance and a substance having charge transporting ability in the same layer, or a functional separation type in which the charge transporting layer and the charge generating layer are components. It may be a photosensitive layer. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated on a conductive substrate in this order is one of preferred examples.

One preferred embodiment of the image carrier used in the present invention will be described below.

Examples of the conductive substrate include metals such as aluminum and stainless steel; plastics having a coating layer of an aluminum alloy or indium oxide-tin oxide alloy; paper, plastic impregnated with conductive particles, plastics having a conductive polymer, etc. Are used. That is, the conductive material may be formed into a drum shape or a film shape such as a belt as it is, or may be processed as a paint or by vapor deposition, etching, plasma treatment, or the like.

On these conductive substrates, the adhesion of the photosensitive layer is improved, the coating properties are improved, the substrate is protected, defects on the substrate are covered,
An undercoat layer may be provided for the purpose of improving the charge injection property from the substrate and protecting the photosensitive layer against electrical breakdown. The undercoat layer is polyvinyl alcohol, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, phenol resin, casein, polyamide, copolymerized nylon, glue,
It is formed of a material such as gelatin, polyurethane, and aluminum oxide. The film thickness is usually 0.1 to 10 μm,
More preferably, the thickness is 0.1 to 3 μm.

The charge generation layer may be made of an organic compound such as an azo pigment, a phthalocyanine pigment, an indigo pigment, a perylene pigment, a polycyclic quinone pigment, a squarylium dye, a pyrylium salt, a thiopyrylium salt, or a triphenylmethane dye. A charge generating substance formed of an inorganic substance such as crystalline silicon is dispersed in an appropriate binder, and is formed by coating or vapor deposition. As the binder, a wide range of binder resins can be selected. For example, a polycarbonate resin, a polyester resin, a polyvinyl butyral resin, a polystyrene resin, an acrylic resin, a methacryl resin, a phenol resin, a silicone resin, an epoxy resin, a vinyl acetate resin and the like can be mentioned. The amount of the binder contained in the charge generation layer is 80% by weight or less, preferably 0 to 40% by weight. The thickness of the charge generation layer is 5 μm or less, particularly 0.05 μm.
２2 μm is preferred.

The charge transport layer has a function of receiving charge carriers from the charge generation layer in the presence of charges and transporting them. The charge transporting layer is formed by dissolving a charge transporting substance in a solvent together with a binder resin if necessary, and applying the solution. The film thickness is generally 5 to 40 μm. As the charge transport material, biphenylene,
Anthracene, pyrene, polycyclic aromatic compounds having a structure such as phenanthrene, indole, carbazole, oxadiazole, nitrogen-containing cyclic compounds such as pyrazoline,
Hydrazone compounds, styryl compounds, amorphous silicon, and the like.

As the binder resin for dispersing these charge transporting substances, polycarbonate resin, polyester resin,
Resins such as polymethacrylate, polystyrene resin, acrylic resin and polyamide resin; organic photoconductive polymers such as poly-N-vinylcarbazole and polyvinylanthracene;

In another embodiment of the organic photoreceptor used in the method of the present invention, a photosensitive layer containing the above-mentioned charge generating substance and a substance having a charge transport property in the same layer is formed on a conductive substrate. And the like.

A protective layer may be provided as a surface layer. Examples of the resin of the protective layer include a polyester resin, a polycarbonate resin, an acrylic resin, an epoxy resin, a phenol resin, and a resin obtained by curing these resins with a curing agent. These are used alone or in combination of two or more.

The conductive fine particles in the resin of the protective layer may be dispersed. Examples of the conductive fine particles include metals and metal oxides. Preferably, there are ultrafine particles formed of zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin oxide-coated titanium oxide, tin-coated indium oxide, antimony-coated tin oxide, and zirconium oxide. Even if these are used alone,
A mixture of more than one species may be used. Generally, when particles are dispersed in the protective layer, it is preferable that the particle diameter of the particles is smaller than the wavelength of the incident light in order to prevent scattering of the incident light by the dispersed particles. The particle size of the conductive particles or insulating particles dispersed in the protective layer is preferably 0.5 μm or less. The content in the protective layer is 2 to the total weight of the protective layer.
90% by weight is preferable, and 5 to 80% by weight is more preferable. The thickness of the protective layer is preferably from 0.1 to 10 μm,
~ 7 µm is more preferred.

The coating of the surface layer can be performed by spray coating, beam coating or permeation coating of the resin dispersion.

It is also preferable to impart releasability to the surface layer, and this effect can improve the transfer efficiency of the toner. When the surface of the latent image carrier is mainly composed of a polymer binder, for example, when a protective film mainly composed of a resin is provided on an inorganic photoreceptor such as selenium or amorphous silicon, or when a function-separated organic photosensitive material is used. When a charge transport layer of the body has a surface layer composed of a charge transport agent and a resin,
It is particularly effective when a protective layer is further provided thereon.

As means for imparting release properties to the surface layer,
A) Use a resin having a low surface energy for the resin constituting the film itself. B) Add an additive that imparts water repellency and lipophilicity. C) Disperse the material having high release properties into powder. To be included. As an example of a), it can be achieved by introducing a fluorine-containing group and a silicon-containing group into the structure of the resin. As (b), a surfactant may be used as an additive. As (c), a powder of a compound containing a fluorine atom (for example, ethylene tetrafluoride, polyvinylidene fluoride, carbon fluoride, etc.) may be mentioned. Among them, polytetrafluoroethylene is particularly preferable. Particularly, dispersion of a releasable powder such as a fluororesin in the outermost surface layer is preferable.

In order to include these powders on the surface, a layer in which the powders are dispersed in a binder resin is provided on the outermost surface of the image bearing member, or an organic solvent originally composed mainly of a resin. In the case of an image carrier, the powder may be dispersed in the uppermost layer without providing a new surface layer.

The amount of the powder added to the surface layer is 1 to 60% by weight, more preferably 2 to 50% by weight, based on the total weight of the surface layer.
Is preferred. When the amount is less than 1% by weight, the transfer efficiency is not improved, and when the amount is more than 60% by weight, the strength of the film is reduced, and the amount of light incident on the image carrier is undesirably reduced. The particle size of the powder is 1 μm from the viewpoint of image quality.
m, more preferably 0.5 μm or less. 1 μm
If it is larger, the line breaks due to scattering of incident light.

Further, having a charge injection layer as a surface layer is also a preferred embodiment of the image forming method of the present invention.

The volume resistance of the charge injection layer is set to 1 × 10 ⁸ to 1 × 10 ⁸ so that sufficient chargeability and image deletion do not occur.
It is preferably ¹⁵ Ωcm, more preferably 1 × 10 ¹⁰ to 1 × 10 ¹⁵ from the viewpoint of image deletion.
Ωcm, considering the environmental fluctuation of volume resistance value, etc.
It is desirable to use one having a volume resistivity of 1 × 10 ¹⁰ to 1 × 10 ¹⁴ Ωcm. Cause smeared images for charge in a high-humidity environment is not held on the surface direction is less than 1 × 10 ⁸ Ωcm, can not be sufficiently injected and hold the charge from the charging member exceeds 1 × 10 ¹⁵ Ωcm, defective charging Tends to occur. By providing such a functional layer on the surface of the photoreceptor, it plays a role of retaining the charged electric charge injected from the charging member, and also plays a role of releasing this electric charge to the photoreceptor base during light exposure, thereby reducing the residual potential. . By using such a photoreceptor and a contact charging member for injection charging, the charging start voltage Vth is small, and the charging potential of the photoreceptor is charged to almost 90% or more of the voltage applied to the charging member. Becomes possible.

For example, the absolute value of the charging member is 100 to 20.
When a DC voltage of 00 V is applied, the charging potential of the electrophotographic photosensitive member having the charge injection layer can be set to 80% or more, and more preferably 90% or more of the applied voltage. On the other hand, the charging potential of the photoreceptor obtained by the charging using the conventional discharge is almost 0 V when the applied voltage is equal to or lower than the discharge starting voltage, and the charging potential is less than 50% of the applied voltage even with the DC voltage of 1000 V. Only potential was obtained.

The charge injection layer is an inorganic layer such as a metal deposition film,
Alternatively, it is composed of a conductive fine particle dispersion layer or the like in which conductive fine particles are dispersed in a binder resin, and the deposited film is deposited, and the conductive fine particle dispersed film is formed by dip coating, spray coating, roll coating, and beam coating. It is formed by applying by an appropriate application method such as a construction method. In addition, a resin formed by mixing or copolymerizing a resin having high light transmittance and ionic conductivity with an insulating binder, or a resin having a medium resistance and photoconductive resin alone may be used. In the case of the conductive fine particle dispersed film, the amount of the conductive fine particles to be added is 2 to 250 parts by weight, and more preferably 2 to 250 parts by weight based on 100 parts by weight of the binder resin.
Preferably, it is 190 parts by weight. If the amount is less than 2 parts by weight, it becomes difficult to obtain a desired volume resistance value.
When the amount exceeds 0 parts by weight, the film strength is reduced, the charge injection layer is easily scraped off, and the life of the photoconductor tends to be shortened.
This is because image defects due to the flow of the latent image potential are likely to occur.

Examples of the binder resin for the charge injection layer include a polyester resin, a polycarbonate resin, an acrylic resin, an epoxy resin, a phenol resin, and a resin obtained by curing these resins with a curing agent. These are used alone or in combination of two or more. In addition, the binder resin of the charge injection layer can be the same as the binder resin of the lower layer, but in this case, the coating surface of the charge transport layer may be disturbed at the time of coating the charge injection layer. Therefore, it is necessary to particularly select a coating method. Further, when the photosensitive layer is made of amorphous silicon, the charge injection layer is preferably made of SiC.

When a large amount of conductive fine particles are dispersed, it is preferable to disperse the conductive fine particles and the like in a reactive monomer or a reactive oligomer, apply them to a photoreceptor, and then cure them with light or heat.

The conductive fine particles dispersed in the binder resin of the charge injection layer include metals and metal oxides.
Preferably, there are ultrafine particles such as zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin oxide-coated titanium oxide, tin-coated indium oxide, antimony-coated tin oxide, and zirconium oxide.
These may be used alone or as a mixture of two or more. The particle size of the conductive particles or insulating particles dispersed in the charge injection layer is preferably 0.5 μm or less.

Further, it is also preferable that the charge injection layer contains a lubricating powder. The reason is that the friction between the photoreceptor and the injection charging member during charging is reduced, so the charging nip expands,
This is because the charging characteristics are improved. In particular, as the lubricating powder, it is more preferable to use a fluorine resin, a silicone resin, or a polyolefin resin having a low critical surface tension. More preferably, tetrafluoroethylene resin (PTF
E) is used. In this case, the amount of the lubricating powder added is
The amount is preferably 2 to 50 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the binder resin. If the amount is less than 2 parts by weight, the amount of the lubricating powder is not sufficient, so that the charging characteristics are not sufficiently improved. If the amount exceeds 50 parts by weight, the resolution of the image and the sensitivity of the photoreceptor are greatly reduced. It is.

The charge injection layer preferably has a thickness of 0.1 to 10 μm, more preferably 1 to 7 μm. When the film thickness is less than 0.1 μm, resistance to minute scratches is lost, and as a result, an image defect due to poor injection occurs. When the film thickness exceeds 10 μm, the image is easily disturbed due to diffusion of injected charges.

Here, the method for measuring the volume resistance of the charge injection layer is as follows. A charge injection layer is formed on a polyethylene terephthalate (PET) film having a conductive film deposited on its surface, and the charge injection layer is measured using a volume resistance measurement device (Hewlett Packard). Company 4
140B pAMATER) and a voltage of 100 V is applied in an environment of 23 ° C. and 65% for measurement.

In the case of a photoreceptor having no charge injection layer, the charge must be efficiently injected into a small number of trap points, so that the resistance value of the charging member must be 1 × 10 ³ Ω or less. If the resistance value of the member becomes 1 × 10 ⁴ Ωcm or less, an excessive leakage current flows from the contact charging member to a flaw or a pinhole generated on the surface of the photoreceptor. Good charge injection charging could not be performed due to enlarging and energizing destruction of the charging member. On the other hand, when the charge injection layer is provided, the area where the charge can be held on the surface of the photoreceptor increases, so that good charging can be performed even if a charging member having a higher resistance value is used. That is, while using a medium-resistance contact charging member, a structure in which a charge injection layer for assisting charge injection to the photoconductor is provided on the surface of the photoconductor as a means for improving charge injection charging efficiency to the photoconductor is preferable. It is necessary to perform injection charging.

It is considered that the essential charging mechanism of the injection charging is that the charge is injected from the surface of the charging member to the charge injection layer when the surface of the charging member comes into contact with the charge injection layer on the surface of the photoreceptor.
Therefore, the characteristics required for the charging member are to have a sufficient density on the surface of the charge injection layer and an appropriate resistance to the movement of charges.

A medium-resistance contact charging member for injecting electric charge to the surface of a photoreceptor having a medium-resistance surface resistance. Preferably, the charge is not injected to the trapping potential of the surface material of the photoreceptor. The conductive fine particles in the charge injection layer in which conductive fine particles are dispersed in a light-transmitting and insulating binder resin are charged with electric charge to perform charging.

Specifically, it is based on the theory of charging a small capacitor having a charge transport layer as a dielectric, an aluminum support and conductive fine particles in the charge injection layer as both electrode plates with a contact charging member. It is. At this time, the conductive fine particles are electrically independent of each other and form a kind of minute float electrode. For this reason, macroscopically, the photoconductor surface appears to be charged and charged to a uniform potential,
Actually, the situation is such that countless minute charged conductive fine particles cover the surface of the photoreceptor. For this reason,
Even when image exposure is performed, each conductive fine particle is electrically independent, so that an electrostatic latent image can be held.

Therefore, by substituting the trap level, which was present in the conventional photoreceptor surface, though small in amount, with the conductive fine particles, the charge injection property and the charge retention property are improved.

The resistance value of the charging member in the injection charging is 1 × 10 ⁴ from the injection charging property and the above-described pinhole leak resistance.
It is preferably about 1 × 10 ⁷ Ωcm.

Although the shape of the injection charging member may be a blade shape or a brush shape, it is considered that a rotatable roller shape, a belt shape, and a brush roller shape (brush roll) are advantageous in appropriately setting the peripheral speed difference. Can be

The roller-shaped contact charging member is disclosed in, for example, Japanese Patent Application Laid-Open No. 1-211799. Metals such as iron, copper and stainless steel, carbon-dispersed resin, metal Alternatively, a metal oxide-dispersed resin or the like can be used. The elastic roller has a configuration in which an elastic layer, a conductive layer, and a resistance layer are provided on a conductive substrate. The roller elastic layer includes chloroprene rubber, isoprene rubber, EPDM rubber, polyurethane rubber, epoxy rubber, and butyl rubber. Such as rubber or sponge, styrene-butadiene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester thermoplastic elastomer, ethylene-vinyl acetate thermoplastic elastomer such as thermoplastic elastomer can be formed. , Volume resistivity is 10 ⁷ Ωcm
Hereinafter, it is desirably 10 ⁶ Ωcm or less. For example, a metal-deposited film, a conductive particle-dispersed resin, a conductive resin, and the like are used. Specific examples of the metal-deposited film include a deposited film of aluminum, indium, nickel, copper, iron, and the like. Examples of the dispersed resin include those in which conductive particles such as carbon, aluminum, nickel, and titanium oxide are dispersed in a resin such as urethane, polyester, and vinyl acetate-vinyl chloride copolymer polymethyl methacrylate. Examples of the conductive resin include quaternary ammonium salt-containing polymethyl methacrylate, polyvinylaniline, polyvinylpyrrole, polydiacetylene, and polyethyleneimine. The resistance layer is, for example, a layer having a volume resistivity of 10 < ⁶ > to 10 < ¹² > [Omega] cm, and a semiconductive resin, a conductive particle dispersed insulating resin, or the like can be used. As the semiconductive resin, resins such as ethyl cellulose, nitrocellulose, methoxymethylated nylon, ethoxymethylated nylon, copolymerized nylon, polyvinyl hydrin, and casein are used. Examples of the conductive particle-dispersed resin include a small amount of conductive particles such as carbon, aluminum, indium oxide, and titanium oxide in an insulating resin such as urethane, polyester, vinyl acetate-vinyl chloride copolymer, and polymethyl methacrylate. Dispersed materials are exemplified.

It is preferable that the contact charging member moves with a peripheral speed difference relative to the photosensitive member. By making the moving speed of the peripheral surface of the contact charging member different from the moving speed of the surface of the photoreceptor, while maintaining the charging stability for a long period of time, maintaining the long life of the photoreceptor, and maintaining the long life of the charging roller Can be achieved at the same time, and high stabilization of charging and a long life of the image forming system can be achieved. That is, the toner tends to adhere to the surface of the contact charging member, and the adhered toner tends to inhibit the charging. By making the surface moving speed of the photoconductor different from the surface moving speed of the contact charging member, the surface of the same photoconductor is made different. On the other hand, it is possible to supply substantially more contact charging member surfaces, so that the effect of preventing charging is obtained. In other words, when the toner comes to the charged portion, the toner having a small adhesive force with the photoreceptor moves toward the charging member due to the electric field, and the resistance of the charging member surface locally changes.
This effectively eliminates the problem that the discharge path is cut off, making it difficult for a potential to be applied to the surface of the photoreceptor, resulting in poor charging.

In the latent image forming step, known means such as a laser and an LED are used as an image exposing means. In view of recent demands for high resolution and high image quality, a means capable of exposing a smaller spot diameter is preferable, and a laser is particularly preferably used in terms of power.

In the developing step, as a developing means for developing an electrostatic latent image, a one-component developing method using a one-component developer consisting of toner alone and a two-component developer consisting of toner and carrier are used. The two-component developing system used can be used.

When a magnetic toner in which a magnetic substance is contained in a toner is used as a one-component developing method, the magnetic toner is transported and charged by using the magnetic binding force of a magnet built in a developing sleeve, and the toner is developed. There is a way. Further, when a non-magnetic toner containing no magnetic material is used as a one-component developer, a blade member, a roller member, a brush member, or the like is used, and the non-magnetic toner is forcibly brought into pressure contact with the developing sleeve. There is a method in which a non-magnetic toner is frictionally charged, and the toner is adhered on a developing sleeve to be conveyed and developed.

In the two-component developing method, a two-component developer composed of a toner and a carrier is circulated and conveyed on a developer carrier, and the latent image is held in a latent image holding body and a developing area of the developer carrier opposed thereto. The latent image held on the image holding member is developed with a two-component developer on the developer holding member.

In the transfer step, a corona charger, a transfer roller, a transfer blade or a transfer belt is used as the transfer means.

In the transfer step, in addition to directly transferring the toner image formed on the latent image holding member onto a recording material such as paper or an OHT sheet, an intermediate transfer member is used to transfer the toner image onto the latent image holding member. The toner image formed on the intermediate transfer member may be primarily transferred onto the intermediate transfer member, and the toner image transferred onto the intermediate transfer member may be secondarily transferred from the intermediate transfer member onto a recording material.

The image forming method of the present invention comprises a first charging step of charging a latent image holding member; a first latent image forming step of forming an electrostatic latent image on a charged latent image holding member; Developing a latent image with a first toner to form a first toner image;
A first transfer step of transferring the developed first toner image onto the intermediate transfer member; a second charging step of charging the latent image holder; and an electrostatic latent image on the charged latent image holder. A second latent image forming step of forming an image; a second developing step of developing the electrostatic latent image with a second toner to form a second toner image; A second transfer step of transferring the toner image onto the intermediate transfer member onto which the toner image has been transferred;
A third charging step of charging the latent image holder; a third latent image forming step of forming an electrostatic latent image on the charged latent image holder; developing the electrostatic latent image with a third toner A third developing step of forming a third toner image; a third transfer of transferring the developed third toner image onto an intermediate transfer member on which the first toner image and the second toner image have been transferred. A fourth charging step of charging the latent image holding member; a fourth latent image forming step of forming an electrostatic latent image on the charged latent image holding member; developing the electrostatic latent image with a fourth toner Developing step of forming a fourth toner image by performing a first toner image, a second toner image, and a third toner image on the developed fourth toner image A fourth transfer step of transferring the first toner image onto the intermediate transfer member;
A batch transfer step of batch-transferring a multicolor toner image having a second toner image, a third toner image, and a fourth toner image onto a recording material at once; Fixing the multicolor toner image to the recording material by bringing a fixing member into contact with the surface of the formed multicolor toner image and applying heat and pressure to the multicolor toner image. In the forming method, the first toner is a color toner selected from the group consisting of a cyan toner, a magenta toner, a yellow toner, and a black toner, and the second toner is a color toner selected as the first toner. The third toner is a color toner selected from the remaining group excluding the toner,
And the color toner selected from the remaining groups excluding the color toner selected as the second toner and the color toner selected as the second toner, and the fourth toner is the color toner selected as the first toner. , Second
It is preferable that the color image forming method is a color toner that is the remaining color toner except for the color toner selected as the third toner and the color toner selected as the third toner.

An image forming method for simultaneously transferring a multi-toner image onto a recording material using the above-described intermediate transfer member and fixing the multi-toner image on the recording material will be described with reference to FIG.

A surface potential is provided on the photosensitive drum 3 by the charging roller 2 which rotates while being in contact with the photosensitive drum 3 as a latent image holding member, and an electrostatic latent image is formed by the exposure means 1. The electrostatic latent image is sequentially developed by the first developing device 4, the second developing device 5, the third developing device 6, and the fourth developing device 7 to form toner images, respectively. The image is multiplex-transferred to form a multi-toner image. The intermediate transfer member 11 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 or titanium oxide is sufficiently dispersed on the base material. A layer having an elastic layer (for example, nitrile butadiene rubber) is preferably used. A belt-shaped intermediate transfer member may be used. The intermediate transfer member has an elastic layer having a hardness of 10 to 50 degrees (JIS K-6301). In the case of a transfer belt, the intermediate transfer member has an elastic layer having this hardness at a transfer portion to a transfer material (recording material). It is preferable that the support member is constituted by a support member. In the transfer from the photoconductor drum 3 to the intermediate transfer member 11, a transfer current is obtained by applying a bias from the power source 13 onto the metal core 9 of the intermediate transfer member 11, thereby transferring the toner image. Corona discharge or roller charging from the back surface of the holding member or the belt may be used. The multiple toner image on the intermediate transfer member 11 is transferred to the transfer charging unit 1
4 is collectively transferred onto the recording material S. As the transfer charging unit, an electrostatic transfer unit using a corona charger, a transfer roller, or a transfer belt is preferably used.

In the image forming method of the present invention, a first charging step of charging the latent image holding member; a first latent image forming step of forming an electrostatic latent image on the charged latent image holding member; A first development step of developing the electrostatic latent image with a first toner to form a first toner image; a second step of transferring the developed first toner image onto a recording material without passing through an intermediate transfer member 1 transfer process;
A second charging step of charging the latent image holding member; a second latent image forming step of forming an electrostatic latent image on the charged latent image holding member; developing the electrostatic latent image with a second toner A second developing step of forming a second toner image; a second transferring step of transferring the developed second toner image onto a recording material onto which the first toner image has been transferred; A third charging step of charging; a third charging step of forming an electrostatic latent image on the charged latent image holding member
Forming a third toner image by developing the electrostatic latent image with a third toner; forming the third toner image into a first toner image and a third toner image; A third transfer step of transferring the toner image onto a recording material onto which the toner image of No. 2 has been transferred; a fourth charging step of charging the latent image holding member; a third forming step of forming an electrostatic latent image on the charged latent image holding member 4 latent image forming step; a fourth developing step of developing the electrostatic latent image with a fourth toner to form a fourth toner image;
A fourth transfer step of transferring the first toner image, the second toner image, and the third toner image onto a recording material on which the first toner image, the second toner image, and the third toner image have been transferred; the first toner sequentially transferred onto the recording material An image, a second toner image, a third toner image, and a fixing member contacting the surface of the multicolor toner image having the fourth toner image, and applying heat and pressure to the multicolor toner image, A fixing step of fixing the multicolor toner image to the recording material.
Is a color toner selected from the group consisting of a cyan toner, a magenta toner, a yellow toner, and a black toner, and the second toner is a color toner selected from the remaining groups excluding the color toner selected as the first toner. The third toner is a color toner selected from the remaining groups excluding the color toner selected as the first toner and the color toner selected as the second toner, The fourth toner is a color toner selected from the group consisting of the color toner selected as the first toner, the color toner selected as the second toner, and the remaining color toner excluding the color toner selected as the third toner. Preferably, the method is a method.

An example of an image forming method for fixing a multi-toner image sequentially transferred onto a recording material without passing through the intermediate transfer member on the recording material will be described with reference to FIG.

Here, first, second, third and fourth image forming units 29 _a , 29 _b , 29 _c and 29 _d are arranged side by side, and each image forming unit is provided with a dedicated electrostatic latent. image holding member, which comprises a so-called photosensitive drum 19 _a, 19 _b, 19 _c and 19 _d.

[0269] photosensitive drum 19 _a to 19 _d latent image forming means on the outer peripheral side 23 _a, 23 _b, 23 _c and 23 _d, the developing unit 17 _a, 17 _b, 17 _c and 17 _d, transferring discharge section 2
_4a , _24b , _24c and _24d , and cleaning units _18a , _18b , _18c and _18d are arranged.

[0270] In this structure, first, the original image by the latent image forming means 23 _a, for example, a yellow component color latent image is formed on the photosensitive drum 19 _a of the first image forming unit 29 _a. Latent image is a visible image with a developer having a yellow toner of the developing means 17 _a, at the transfer portion 24 _a,
The image is transferred to the recording material S.

[0271] While the yellow image as described above is transferred onto the recording material S, the latent image of the second image forming unit 29 _b in the magenta component color is formed on the photosensitive drum 19 _b, followed by developing means 17 _A visible image is formed with the developer having the magenta toner _b . This visible image (magenta toner image)
When the recording material S transfer in the first image forming portion 29 _a of the is finished is carried to the transfer section 24 _b, are transferred to overlap the position of the recording material S.

Hereinafter, the third and fourth steps are performed in the same manner as described above.
The image forming section 29 _c, cyan by 29 _d, the image formation of black color is performed, in the same recording material S, it is to transfer overlaid cyan, and black colors. When such an image forming process is completed, the recording material S is conveyed to the fixing unit 22, and the image on the recording material S is fixed. Thus, a multicolor image is obtained on the recording material S.
Each of the photosensitive drums 19 _a , 19 _b , 19 _c, and 19 _d , on which the transfer has been completed, is a cleaning unit 18 _a , 18 _b , 18 _c, and 1
8 the residual toner is removed by _d, is subjected to subsequent next latent image formation is performed.

In the image forming apparatus described above, the transport belt 25 is used to transport the recording material S.
, The recording material S is conveyed from the right side to the left side, and in the conveyance process, the transfer sections 24 _a , 24 _b , 24 _c and 24 _{c in the} image forming sections 29 _a , 29 _b , 29 _c and 29 _d .
Pass _d and receive transcription.

In this image forming method, a transport belt using a mesh of Tetron (registered trademark) fiber as a transport means for transporting the recording material and a polyethylene terephthalate resin, a polyimide resin, A transport belt using a thin dielectric sheet such as a urethane resin is preferably used.

[0275] When the recording material S passes through the fourth image forming unit 29 _d, AC voltage is applied to the static eliminator 20, the recording material S is discharged, is separated from the belt 25, thereafter, the fixing device 22
And the image is fixed, and is discharged from the discharge port 26.

FIG. 1 is a schematic view of still another image forming apparatus capable of performing the image forming method of the present invention.

A first image forming unit Pa, a second image forming unit Pb, a third image forming unit Pc, and a fourth image forming unit Pd are provided in the main body of the image forming apparatus.
Images of different colors are formed on the recording material through the processes of latent image, development, and transfer.

The structure of each image forming unit provided in the image forming apparatus will be described by taking the first image forming unit Pa as an example.

The first image forming unit Pa has an electrophotographic photosensitive drum 61a of 30φ as a latent image holding member, and the photosensitive drum 61a is rotated in the direction of arrow a. Reference numeral 62a denotes a primary charger as a charging means, which uses a magnetic brush charger supported on a 16φ sleeve so as to be in contact with the photosensitive drum 61a. 67a is
This is an exposure device as a latent image forming unit for forming an electrostatic latent image on the photosensitive drum 61a whose surface is uniformly charged by the primary charger 62a. Reference numeral 63a denotes a developing device as a developing unit for developing a latent image formed on the photosensitive drum 61a to form a color toner image, and holds a color toner. Reference numeral 64a denotes a transfer blade as transfer means for transferring the color toner image formed on the surface of the photosensitive drum 61a to the surface of the recording material conveyed by the belt-shaped recording material carrier 68. The transfer blade 64a is a recording material carrier 68
And a transfer bias can be applied by contacting the back surface.

In the first image forming unit Pa, the photosensitive drum 61 is charged at the charging section by the primary charger 62a.
After the photosensitive member a is uniformly primary charged, an electrostatic latent image is formed on the photosensitive member by the exposure device 67a, and the developing device 63a develops the electrostatic latent image in a developing section using color toner. A transfer bias is applied from a transfer blade 64a which abuts the back side of a belt-shaped recording material carrier 68 which carries and conveys the recording material at a first transfer portion (contact position between the photosensitive member and the recording material). Then, the image is transferred onto the surface of the recording material.

The first image forming unit Pa comes into contact with the surface of the photosensitive drum, and a cleaning member for removing transfer residual toner from the surface of the photosensitive drum is provided between the transfer section and the charging section and between the transfer section and the charging section. The developing and cleaning system is not provided between the developing unit and the developing unit, and the developing unit also serves to clean the transfer residual toner present on the photoconductor.

The present image forming apparatus has the same configuration as the above-described first image forming unit Pa, and includes the second image forming unit Pb and the third image forming unit Pb having different colors of the color toner held in the developing device. An image forming unit Pc and a fourth image forming unit Pd are provided side by side. For example, yellow toner is used for the first image forming unit Pa, magenta toner is used for the second image forming unit Pb, cyan toner is used for the third image forming unit Pc, and black toner is used for the fourth image forming unit Pd. The transfer of each color toner onto the recording material is sequentially performed at the transfer section of each image forming unit. In this step, while the registration is being performed, the color toners are superimposed on the same recording material by one movement of the recording material, and when the recording is completed, the recording material is separated from the recording material carrier 68 by the separation charger 69. The sheet is sent to the fixing device 70 by a conveying means such as a conveying belt, and the final full-color image is obtained by a single fixing.

The fixing device 70 has a pair of 40φ fixing roller 71 and a 30φ pressing roller 72.
Has heating means 75 and 76 inside. 73
Is a web for removing dirt on the fixing roller. In the case of the present invention, the web mechanism 73 may be omitted.

The unfixed color toner image transferred onto the recording material passes through a pressure contact portion between the fixing roller 71 and the pressure roller 72 of the fixing device 70, and is applied to the recording material by the action of heat and pressure. Is established.

In FIG. 1, the recording material carrier 68 is an endless belt-like member, which is moved in the direction of arrow e by a driving roller 80. 7
9 is a transfer belt cleaning device, 81 is a belt driven roller, and 82 is a belt static eliminator. 8
Reference numeral 3 denotes a pair of registration rollers for conveying the recording material in the recording material holder to the recording material carrier 68.

As the transfer means, contact transfer in which a transfer bias can be directly applied by contacting the back surface of a recording material support such as a roller-shaped transfer roller instead of the transfer blade contacting the back surface of the recording material support. Means can be used.

Further, instead of the above-described contact transfer means, a transfer bias is applied by applying a transfer bias from a corona charger arranged in a non-contact manner on the back side of a generally used recording material carrier. It is also possible to use contact transfer means.

However, it is more preferable to use the contact transfer means in that the amount of ozone generated when the transfer bias is applied can be controlled.

An image forming method for forming a full-color image according to still another embodiment will be described with reference to FIG.

The electrostatic latent image formed on the photosensitive drum 33 by an appropriate means is supplied to a developing unit 36 as a developing means attached to a rotary developing unit 39 which rotates in the direction of the arrow. Visualized by a two-component developer having a carrier. The color toner image on the photosensitive drum 33 is transferred by the transfer charger 44 to the recording material S held on the transfer drum 48 by the gripper 47.

As the transfer charger 44, a corona charger or a contact charger is used. When a corona charger is used as the transfer charger 44, a voltage of -10 kV to +10 kV is applied, and the transfer current is-. 500 μA to +500 μA. A holding member is stretched on the outer peripheral surface of the transfer drum 48,
The holding member is formed of a film-like dielectric sheet such as a polyvinylidene fluoride resin film or polyethylene terephthalate. For example, a thickness of 100 μm to 20 μm
A sheet having a thickness of 0 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 35 faces the photosensitive drum 33. Then, the image is developed by a developer having a second color toner and a carrier in the developing device 35, and this color toner image is also transferred onto the same recording material as above.

Further, the third color and the fourth color are performed in the same manner.
In this manner, the transfer drum 48 rotates a predetermined number of times while holding the recording material, and the toner image of a predetermined number of colors is 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.

The recording material S on which multiple transfer has been performed is separated
5, the toner is separated from the transfer drum 48, and is fixed by a heating / pressing roller fixing device 32 (or a fixing device without a web mechanism) having a web impregnated with silicone oil or not impregnated with oil. By mixing, a full-color copy image is obtained.

The replenishment toner supplied to the developing units 34 to 37 is supplied from a replenishing hopper provided for each color by a fixed amount based on a replenishment signal via a toner transport cable to a toner replenishing cylinder at the center of the rotary developing unit. And sent to each developing device.

The multiple development batch transfer method will be described with reference to FIG. 5 taking a full-color electrophotographic printer as an example.

The electrostatic latent image formed on the photosensitive drum 103 by the charging unit 102 and the exposure unit 101 using laser light is developed by the developing units 104, 105, 106, and 107, and is visualized. In the development process, a non-contact development method is preferably used. According to the non-contact developing method, since the developer layer in the developing device does not rub the surface of the image forming body, the developing is performed without disturbing the image formed in the preceding developing step in the second and subsequent developing steps. be able to. 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.

The multicolor multiplex image and the full-color image formed on the photosensitive drum 103 are transferred to the recording material S by the transfer charger 109. In the transfer step, an electrostatic transfer method is preferably used, and a corona discharge or contact transfer method is used. The corona discharge transfer method is a method in which a transfer charger 109 for generating a corona discharge via the recording material S is disposed so as to face the image, and a corona discharge is applied from the back surface of the recording material S to electrostatically transfer the image. is there. The contact transfer method is a method in which a transfer roller or a transfer belt is brought into contact with an image forming body via a recording material S to apply a bias to the roller, or is transferred electrostatically from the back surface of the belt. By this electrostatic transfer method, the multicolor toner image carried on the surface of the photosensitive drum 103 is collectively transferred to the recording material S.

Recording material S on which multicolor toner images are collectively transferred
Is separated from the photosensitive drum 103 by the heat roller fixing device 1
The image is fixed at 12 to form a multicolor image.

Next, the structure of a developing device usable in the present invention will be described in detail with reference to the drawings.

In the present invention, a contact development method in which a developer carried on a developer carrier is brought into contact with the surface of a photoreceptor in a development area to perform development, and a development method in which a developer carrier is carried on the surface of a photoreceptor in a development area Any of the non-contact developing methods in which the developing agent is developed by flying from a developer carrying member set at a distance such that the photoconductor and the developer layer are not in contact with each other can be used.

As the contact developing method, there are a developing method using a two-component developer having a toner and a carrier (FIG. 6) and a developing method using a one-component developer (FIG. 8).

As a contact two-component developing method, a two-component developer obtained by mixing a toner and a magnetic carrier is used, for example, as shown in FIG.
The development can be performed using a developing device 120 as shown in FIG.

The developing device 120 includes a two-component developer 128.
, A developing sleeve 121 as a developer carrying member for carrying the two-component developer 128 contained in the developing container 126 and transporting the developer to the developing area;
A developing blade 127 as a developer layer thickness regulating unit for regulating the thickness of the toner layer formed on the developing sleeve 121 is provided.

The developing sleeve 121 has a magnet 123 inside a non-magnetic sleeve base 122.

The inside of the developing container 126 is divided into a developing chamber (first chamber) R ₁ and a stirring chamber (second chamber) R ₂ by a partition 130, and the toner is separated above the stirring chamber R _{2 by} the partition 130. storage chamber R ₃ is formed. Developing room R ₁ and stirring room R ₂
A developer 128 is accommodated in the toner storage chamber R.
₃ contains a supply toner (non-magnetic toner) 129. Incidentally, the supply port 131 provided in the toner storage chamber R _3, replenishing toner 129 quantities commensurate with the toner consumed through the supply port 131 is dropped replenished into the stirring chamber R _2.

[0307] A conveying screw 124 in the developing chamber R ₁ provided, the developer 128 in the developing chamber R ₁ by the driving rotation of the conveying screw 124 is conveyed toward the longitudinal direction of the developing sleeve 121 . Similarly, in the stirring chamber R ₂ is provided conveying screw 125 by the rotation of the conveying screw 125, a toner that has fallen into the stirring chamber R ₂ from the supply port 131 for conveying in the longitudinal direction of the developing sleeve 121.

The developer 128 is a two-component developer having a non-magnetic toner and a magnetic carrier.

Examples of the carrier used in the two-component developer include, for example, surface-oxidized or unoxidized iron, nickel, and the like.
Magnetic particles selected from the group consisting of magnetic metals such as copper, zinc, cobalt, manganese, chromium and rare earths, their magnetic alloys, their magnetic oxides and their magnetic ferrites.

Further, a binder type carrier in which magnetic powder is dispersed in a resin can also be used.

As the carrier, it is preferable to use a coated carrier obtained by coating the surface of the carrier core of the magnetic particles with a coating material. In this coated carrier, the method of coating the surface of the carrier core with a coating material includes a method of dissolving or suspending the coating material in a solvent, applying the coating material, and attaching the coating material to the carrier core, or a method of simply mixing in a powder state. Applicable.

Examples of the coating material for the carrier core include polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. No. These are suitably used alone or in combination.

The processing amount of the above materials may be determined as appropriate, but is generally 0.1 to 30% by weight based on the total amount of the carrier.
(Preferably 0.5 to 20% by weight).

The carrier used in the present invention has an average particle size of preferably 10 to 100 μm, more preferably 20 to 100 μm.
The thickness is preferably 70 μm.

When the average particle diameter of the carrier is less than 10 μm, packing of the two-component developer is strengthened, the mixing property between the toner and the carrier is reduced, the charging property of the toner is hardly stabilized, and the carrier Adhesion to the surface of the photosensitive drum is likely to occur.

When the average particle diameter of the carrier exceeds 100 μm, the chance of contact with the toner is reduced, and therefore, the toner having a low charge amount is mixed and fog is easily generated. Further, since the toner tends to be scattered, it is necessary to set the toner concentration in the two-component developer at a low level, and an image having a high image density may not be formed.

As a particularly preferred carrier, the surface of a magnetic core particle such as a magnetic ferrite core particle is coated with a resin such as a silicone resin, a fluorine resin, a styrene resin, an acrylic resin and a methacrylate resin, preferably from 0.01 to 0.01%. 5% by weight, more preferably 0.1 to 1% by weight
A magnetic carrier containing 70% by weight or more of carrier particles of 250 mesh pass and 400 mesh on and having a particle size distribution adjusted to have the above average particle size.

When the magnetic coated carrier has a sharp particle size distribution, favorable triboelectrification is obtained with respect to the color toner of the present invention, and there is an effect of improving electrophotographic characteristics.

When a two-component developer is prepared by mixing a color toner and a carrier, the mixing ratio is 2 to 15% by weight, preferably 3 to 13% by weight, as the toner concentration in the developer. %, More preferably 4% by weight to 10%
Good results are usually obtained with a percentage by weight. If the toner concentration is less than 2% by weight, the image density tends to be low.
The service life of the developer tends to be short.

The magnetic characteristics of the carrier are affected by the magnet roller built in the developing sleeve, and greatly affect the developing characteristics and transportability of the developer.

In the present invention, on a developing sleeve having a built-in magnet roller, the magnet roller is fixed and the developing sleeve is rotated alone, and a carrier composed of magnetic particles and a two-component developer composed of an insulating color toner are used. When the electrostatic roller is circulated and transported on the developing sleeve and develops the electrostatic latent image held on the surface of the electrostatic latent image holding member with the nuclear two-component developer, the magnet roller has a pole configuration having repulsive poles, And the saturation magnetization of the carrier is 20 to 70 Am ² /
When the weight is kg, the uniformity and the gradation reproducibility of the image in color copying are excellent, which is preferable.

The carrier has a saturation magnetization of 70 Am ² / kg
If it exceeds (with respect to the applied magnetic field of 3000 Oersteds), the brush-like spikes composed of the carrier and the toner on the developing sleeve facing the electrostatic latent image on the photoreceptor during development are tightly tightened. , And the gradation and the reproduction of the halftone are deteriorated. On the other hand, when it is less than 20 Am ² / kg, it becomes difficult to hold the toner and the carrier on the developing sleeve satisfactorily, and the problem that the adhesion of the carrier and the suppression of the scattering of the toner are deteriorated easily occurs.

An opening is provided in a portion of the developing container 126 close to the photosensitive drum 119, and the developing sleeve 121 is discharged to the outside from the opening, and a gap is provided between the developing sleeve 121 and the photosensitive drum 119. Is provided. A bias applying unit 132 for applying a bias is arranged on the developing sleeve 121 made of a non-magnetic material.

A magnet roller as a magnetic field generating means fixed to the sleeve base 122, ie, a magnet 123,
As described above, the developing magnetic pole S ₁ , the magnetic pole N ₃ located downstream of the developing magnetic pole S ₁ , the magnetic pole N ₂ for transporting the developer 128,
S ₂ and N ₁ . The magnet 123 is provided on the sleeve base 122 so that the developing magnetic pole S ₁ is opposed to the photosensitive drum 119.
Is located within. The developing magnetic pole S ₁ is the developing sleeve 1
A magnetic field is formed near the developing unit between the photoconductor 21 and the photoconductor drum 119, and the magnetic field forms a magnetic brush.

The regulating blade 127, which is disposed above the developing sleeve 121 and regulates the layer thickness of the developer 128 on the developing sleeve 121, is made of a non-magnetic material such as aluminum or SUS316. The distance A between the end of the non-magnetic blade 127 and the surface of the developing sleeve 121 is 300 to 100.
0 μm, preferably 400 to 900 μm. If this distance is smaller than 300 μm, the magnetic carrier is clogged during this time, and the developer layer tends to be uneven, and the developer required for good development cannot be applied, and the density of the developed image is low and uneven. There is a problem that only can be obtained. In order to prevent non-uniform application (so-called blade jam) due to unnecessary particles mixed in the developer,
400 μm or more is preferred. If the thickness is larger than 1000 μm, the amount of the developer applied on the developing sleeve 121 increases, so that a predetermined thickness of the developer layer cannot be regulated. As a result, the adhesion of the magnetic carrier particles to the photosensitive drum 119 increases, and the developer circulates. There is a problem that the development regulation by the non-magnetic developing blade 127 is weakened, and toner tribo is insufficient and fogging is likely to occur.

In the development of the two-component developing device 120, the toner and the magnetic carrier are used while applying an alternating electric field.
It is preferable that the development is performed in a state in which the magnetic brush latent image carrier (for example, the photosensitive drum) 119 is in contact with the magnetic brush. The distance (S-D distance) B between the developer carrier (developing sleeve) 121 and the photosensitive drum 119 is 100 to 10
The thickness of 00 μm is favorable in preventing carrier adhesion and improving dot reproducibility. If it is smaller than 100 μm, the supply of the developer tends to be insufficient and the image density is lowered. If it is larger than 1000 μm, the magnetic force lines from the magnet S ₁ are widened and the density of the magnetic brush is reduced, resulting in poor dot reproducibility or poor carrier performance. The binding force is weakened and carrier adhesion is likely to occur.

The voltage between the peaks of the alternating electric field is 500 to 50.
00V is preferable, the frequency is 500 to 10000 Hz,
The frequency is preferably 500 to 3000 Hz, and can be appropriately selected and used for each process. In this case, a triangular wave, a rectangular wave, a sine wave, or a waveform having a changed duty ratio can be used as the waveform. If the applied voltage is lower than 500 V, it is difficult to obtain a sufficient image density, and it may not be possible to satisfactorily collect the fog toner in the non-image area. If the voltage exceeds 5000 V, the electrostatic image may be disturbed via the magnetic brush, which may cause deterioration in image quality.

By using a two-component developer having a well-charged toner, the fog removal voltage (Vback)
And the primary charge of the photoconductor can be reduced, so that the life of the photoconductor can be extended. Vbac
k is preferably 150 V or less, more preferably 100 V or less, depending on the developing system.

As the contrast potential, 200 V to 500 V is preferably used so that a sufficient image density can be obtained.

If the frequency is lower than 500 Hz, although it depends on the process speed, charge injection into the carrier occurs, so that the image quality may be degraded by carrier adhesion or disturbing the latent image. If the frequency exceeds 10,000 Hz, the toner cannot follow the electric field, and the image quality is likely to deteriorate.

In order to achieve sufficient image density, excellent dot reproducibility, and development without carrier adhesion, the contact width (developing nip C) of the magnetic brush on the developing sleeve 121 with the photosensitive drum 119 is preferably set. 3 to 8 mm. If the developing nip C is smaller than 3 mm, it is difficult to sufficiently satisfy a sufficient image density and dot reproducibility. If the developing nip C is larger than 8 mm, packing of a developer occurs and the operation of the machine is stopped, or the carrier adheres. It is difficult to sufficiently suppress this. As a method of adjusting the developing nip, the nip width is appropriately adjusted by adjusting the distance A between the developer regulating member 127 and the developing sleeve 121 or adjusting the distance B between the developing sleeve 121 and the photosensitive drum 119.

Incidentally, the transfer residual toner on the photoreceptor is collected at the time of development by the magnetic brush composed of the toner and the carrier of the developing device.

As a contact one-component developing method, it is possible to develop using a non-magnetic toner, for example, using a developing device 180 as shown in FIG.

The developing device 180 includes a developing container 18 containing a one-component developer 188 having a magnetic or non-magnetic toner.
1. One-component developer 18 stored in developing container 181
Developer carrying member 1 for carrying and transporting the developing agent 8 to a developing area
82, a supply roller 185 for supplying the developer onto the developer carrier, and an elastic blade 18 as a developer layer thickness regulating member for regulating the thickness of the developer layer on the developer carrier
6. It has a stirring member 187 for stirring the developer 188 in the developing container 181.

As the developer carrier 182, it is preferable to use an elastic roller having an elastic layer 184 formed on a roller base 183 by an elastic member such as rubber or resin such as foamed silicone rubber.

The elastic roller 182 is pressed against the surface of a photosensitive drum 189 serving as a latent image holding member, and electrostatically formed on the photosensitive member by a one-component developer 188 applied to the surface of the elastic roller. While developing the latent image, an unnecessary one-component developer 188 existing on the photoconductor after transfer is collected.

In the contact one-component developing method, the developer carrying member is substantially in contact with the surface of the photosensitive member. This means that the developer carrier is in contact with the photoconductor when the one-component developer is removed from the developer carrier. At this time, an image having no edge effect can be obtained by an electric field acting between the photoconductor and the developer carrier via the developer, and at the same time, cleaning is performed. There is a need to have an electric potential between the surface of the elastic roller or the vicinity of the surface as a developer carrier and an electric field between the surface of the photosensitive member and the surface of the elastic roller.
For this reason, it is also possible to use a method in which the elastic rubber of the elastic roller is resistance-controlled in the medium resistance region to keep the electric field while preventing conduction with the photoreceptor surface, or a thin dielectric layer is provided on the surface layer of the conductive roller. . Further, a configuration in which a conductive layer is provided on a surface of the conductive roller which is in contact with the surface of the photoreceptor with a conductive resin sleeve having a surface in contact with the surface of the photoreceptor covered with an insulating material, or a surface of the insulating roller which is not in contact with the photoreceptor. It is possible.

The elastic roller carrying the one-component developer may rotate in the same direction as the photosensitive drum or in the opposite direction. When the rotation is in the same direction, it is preferable that the peripheral speed ratio is greater than 100% with respect to the peripheral speed of the photosensitive drum. If it is less than 100%, problems tend to occur in image quality such as poor line clarity. As the peripheral speed ratio increases, the amount of the developer supplied to the development site increases, and the frequency of desorption of the developer from the electrostatic latent image increases.
An unnecessary portion of the developer is scraped off, and the necessary portion is repeatedly supplied with the developer, whereby an image faithful to the electrostatic latent image is obtained. More preferably, the peripheral speed ratio is 100
% Or more is good.

The developer layer thickness regulating member 186 is not limited to an elastic blade, but may be an elastic roller, as long as it is in pressure contact with the surface of the developer carrier 182 by elastic force.

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.

In the case of the elastic blade, 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. In this state, the inner surface of the blade (the outer surface in the case of the opposite direction) is brought into contact with the sleeve surface with moderate elastic pressure.

The supply roller 185 is made of a foam material such as polyurethane foam, and rotates at a relative speed other than 0 in the forward or reverse direction with respect to the developer carrier.
Along with the supply of the one-component developer, the developer after development (undeveloped developer) on the developer carrier is also stripped off.

When the electrostatic latent image on the photosensitive member is developed with a one-component developer on the developer bearing member in the developing area, a direct and / or alternating current is applied between the developer bearing member and the photosensitive drum. It is preferred to apply a developing bias of to develop.

Next, the non-contact developing system will be described.

As a non-contact developing method, there is a developing method using a one-component magnetic developer having a non-magnetic toner.

Here, a developing method using a one-component non-magnetic developer having a non-magnetic toner will be described with reference to a schematic configuration diagram shown in FIG.

The developing device 170 includes a developing container 17 containing a non-magnetic one-component developer 176 having a non-magnetic toner.
1. A developer carrier 172 for carrying the one-component non-magnetic developer 176 contained in the developing container 171 and transporting it to the development area, and supplying the one-component non-magnetic developer on the developer carrier Roller 173 for controlling the thickness, the elastic blade 174 as a developer layer thickness regulating member for regulating the thickness of the developer layer on the developer carrier, and the one-component non-magnetic developer 176 in the developing container 171 are stirred. Stirring member 175 for the purpose.

Reference numeral 169 denotes an electrostatic latent image holding member, and a latent image is formed by an electrophotographic process means or an electrostatic recording means (not shown). Reference numeral 172 denotes a developing sleeve as a developer carrier, which is made 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,
A mirror-finished one or a resin-coated one is preferred.

The one-component non-magnetic developer 176 is used in the developing container 1
The developer is supplied to the developer carrier 172 by a supply roller 173. Supply roller 173
Is made of foam material such as polyurethane foam,
The developer carrier is rotated in a forward or reverse direction at a relative speed other than 0, and the developer is supplied and the developer (undeveloped developer) on the developer carrier 172 after the development is peeled off. ing. The one-component non-magnetic developer supplied onto the developer carrier 172 is uniformly and thinly applied by an elastic blade 174 as a developer layer thickness regulating member.

The contact pressure between the elastic coating blade and the developer carrier is 0.3 to 2 as a linear pressure in the developing sleeve generatrix direction.
5 kg / m, preferably 0.5 to 12 kg / m is effective. When the contact pressure is less than 0.3 kg / m, it is difficult to uniformly apply the one-component non-magnetic developer, and the charge amount distribution of the one-component non-magnetic developer becomes broad, which causes fogging and scattering. When the contact pressure exceeds 25 kg / m, a large pressure is applied to the one-component non-magnetic developer, and the one-component non-magnetic developer is deteriorated. Absent. Further, a large torque is required to drive the developer carrier, which is not preferable. That is, by adjusting the contact pressure to 0.3 to 25 kg / m, it becomes possible to effectively loosen the aggregation of the one-component non-magnetic developer using the toner of the present invention. It is possible to instantly raise the charge amount of the non-magnetic developer.

As the developer layer thickness regulating member, an elastic blade or an elastic roller can be used, and it is preferable to use a material of a triboelectric series suitable for charging the developer to a desired polarity.

In the present invention, silicone rubber, urethane rubber and styrene butadiene rubber are preferred. Furthermore, polyamide, polyimide, nylon, melamine, melamine cross-linked nylon, phenolic resin, fluororesin,
An organic resin layer such as a silicone resin, a polyester resin, a urethane resin, and a styrene resin may be provided. Uses conductive rubber and conductive resin, and further disperses fillers and charge control agents such as metal oxides, carbon black, inorganic whiskers, and inorganic fibers in the rubber and resin of the blade to achieve appropriate conductivity and charging. It is preferable because it gives imparting properties and can appropriately charge the one-component non-magnetic developer.

In this non-magnetic one-component developing method, in a system in which a one-component non-magnetic developer is thinly coated on the developing sleeve by a blade, the one-component non-magnetic developer on the developing sleeve is required to obtain a sufficient image density. It is preferable that the thickness of the non-magnetic developer layer is made smaller than the opposing gap length β between the developing sleeve and the latent image holding member, 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 172 and the latent image holder 169 by the bias power supply 177 shown in FIG. The transfer of the one-component non-magnetic developer to the non-magnetic developer can be facilitated, and a higher quality image can be obtained.

[0355]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. However, this does not limit the embodiment of the present invention at all. Parts in the examples are parts by weight.

As resins used in the examples, polyester resins having the monomer compositions shown in Table 1 were synthesized by a dehydration condensation method, and non-linear polyester resins A1 to A11 having dodecenyl groups introduced into the resin skeleton by branching. When,
Linear polyester resins B1 and B2 having the compositions shown in Table 2 and the molecular weights shown in Table 3 were obtained.

<Example 1>-60 parts by weight of non-linear polyester resin A-1 (described in Table 1)-40 parts by weight of linear polyester resin B-1 (described in Tables 2 and 3)-Copper phthalocyanine pigment 4 parts by weight (CI Pigment Blue 15: 3) 1.5 parts by weight of polyethylene wax (mp = 106 ° C., Mn = 670, Mw / Mn = 1.35) 5 parts by weight of zirconium compound (14) After premixing the ingredients with a Henschel mixer,
The mixture was melt-kneaded by a twin-screw kneading extruder set at a temperature of ° C. Since the viscosity of the kneaded material gradually increased during the melt-kneading, it was confirmed that new crosslinks were formed.

The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, and then pulverized by a fine pulverizer using a jet stream, and the obtained finely pulverized powder was subjected to a multi-division classifier utilizing the Coanda effect. To obtain toner particles A having a weight average particle diameter of 6.4 μm. Table 4 shows the formulation and physical properties.

Hydrophobic hydrophobic fine silica powder having a methanol wettability of 80% and a BET specific surface area of 120 m ² / g (100 parts by weight of hexamethyldisilazane per 100 parts by weight of toner particles A)
1.2 parts by weight and 10 parts by weight of dimethyl silicone)
The toner A was prepared by externally adding and mixing parts by weight.

To 6.0 parts by weight of the cyan toner A, styrene-methyl methacrylate (copolymer weight ratio: 6 parts by weight) was used.
5:35) was mixed with about 0.35% by weight of a Cu—Zn—Fe-based ferrite carrier having an average particle diameter of 45 μm so that the total weight was 100 parts by weight to obtain a two-component developer. The toner concentration in the two-component developer was 6.0% by weight.

A fixing device without a fixing oil supply mechanism (fixing speed 130 mm / sec., Fixing roller diameter Φ40 mm, pressure roller diameter Φ40 mm, fixing / pressure roller surface layer PFA [perfluoroalkoxyethylene] 20 μm, Nip width 8mm, total pressure 40kg
In f), the fixing property and the anti-offset property were evaluated without fixing oil on the surface of the fixing / pressure roller.

As a result, the fixing start point was as low as 110 ° C.
The non-offset width is also large. Further, there was a region where the gloss was 10 or more, which was important for the full-color toner, and the gloss could be controlled. In addition, an image is placed on the OHT
The mode is 170 ° C., 40 mm / sec. A fixing test was performed at a fixing speed of. This color image was projected on an overhead projector (OHP) and evaluated. The obtained image was excellent in transparency without offset, without uneven brightness, and excellent in color reproducibility up to a light halftone color tone.

Further, using a commercially available full-color copying machine (Color Leather Copier 800, manufactured by Canon Inc.) with a fixing device modified to the above-mentioned fixing device without an oil application mechanism, the environment of 15 ° C. and 10% RH was used. A print test of 10,000 sheets was performed in an environment of 30 ° C. and 80% RH. The developability (image density) and fog after printing 10,000 sheets were evaluated. The durability density transition and fog suppression were good. Table 5 shows the evaluation results.

<Examples 2 to 5 and Comparative Examples 1 to 5> In place of the non-linear polyester resin A-1 used in Example 1,
Toners B to J were prepared in the same manner as in Example 1 except that the non-linear polyester resins A-2 to A-5 and the non-linear polyester resins A-7 to A-11 for comparison described in Table 1 were used. Table 5 shows the results of the same test.

<Examples 6 to 8 and Comparative Examples 6 to 7> The non-linear polyester resin A-6 shown in Table 1 was used in place of the non-linear polyester resin A-1 used in Example 1, and The toners K to O were prepared in the same manner as in Example 1 except that the nonlinear polyester resin B-2 shown in Tables 2 and 3 was used instead of the polyester resin B-1 and the formulation was as shown in Table 4. Table 5 shows the results of the same test. However, the organometallic compound was changed from the zirconium compound (14) of Example 1 to a zirconium compound (27).

<Examples 9 to 14 and Comparative Example 8> Toners P to W were prepared in the same manner as in Example 1 using the formulations shown in Table 4, and the same test was conducted. The results are shown in Table 5. However, for toner Q, the cyan pigment of Example 1 was changed to 5 parts by weight of carbon black. In the toners P and Q, the following compounds (13), which are zinc compounds and chromium compounds as organometallic compounds,
6) to (137) were used. However, coordinated water molecules are omitted.

[0367]

Embedded image

The toner evaluation method and evaluation criteria in the examples of the present invention will be described below.

(1) Developability In an environment of 30 ° C. and 80% RH, evaluation was performed by maintaining image density at the end of printing out 10,000 sheets on ordinary paper for copying machines (75 g / m ² ). The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth Co., Ltd.).
The relative density of the white background portion of the 00 to the printout image was measured. A: 1.40 or more B: 1.30 or more and less than 1.40 C: 1.20 or more and less than 1.30 D: less than 1.20

(2) Fog The fog was measured by measuring the whiteness of a white background portion of 10,000 printout images on ordinary paper for copying machines (75 g / m ² ) in an environment of 23 ° C. and 5% RH. (Manufactured by Tokyo Denshoku Co., Ltd.), and the fog density (%) was calculated and evaluated from the difference between the whiteness and the whiteness of the transfer paper. A: Very good (less than 1.0%) B: Good (more than 1.0% and less than 2.0%) C: Normal (more than 2.0% and less than 3.0%) D: Bad (3.0%) that's all)

(3) Fixing Property and Gloss Fixing property was determined by measuring the amount of toner applied to a fixed image by 0.6 g / cm ^2.
A solid image is applied, a load of 50 g / cm ² is applied to the image, and the fixed image is rubbed with soft thin paper. The temperature at which the reduction rate (%) of the image density before and after the rubbing becomes 20% or less is determined. Evaluation was made as a fixing start temperature.

Similarly, the offset resistance is determined by setting the amount of toner applied to the fixed image to a solid image of 0.6 g / cm ² , and setting the temperature at which contamination (transfer of toner) of the fixing roller at the time of fixing starts to the offset temperature on the high temperature side. evaluated.

The glossiness (gloss) of the same fixed image was measured using a handy gloss meter gloss meter PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.) under the condition of a light incident angle of 75 °.

The fixing temperature condition is from 110 ° C. to 5 ° C.
Each time, up to 200 ° C.

(4) Endurance Offset The endurance offset was determined by printing out a sample image having an image area ratio of about 5% at a fixing temperature of 190 ° C.
The degree of dirt on one image was evaluated by observing the surface of the fixing / pressure roller after 3000 sheets. A: There is no image or roller. Practical: B: Not on the image but slightly on the roller but with traces of toner. : Practical acceptable C: Five images with slight toner traces on the back of the image, and slight toner traces on the roller. Impractical D: The frequency of occurrence of offset on the image / roller is high. ; Not practical E: wrapped around the fixing device and not durable. : Not practical

(5) OHT Image Transparency The OHT image transparency was evaluated by setting the image on the OHT in the OHT mode at 170 ° C. and 40 mm / sec. The color image was projected on an overhead projector (OHP) and evaluated.

With respect to the color reproducibility of the OHT image on the OHT image, the evaluation of the color reproduction of a light color (halftone) portion is more severe. This is because the toner particles on the OHT image before fixing exist in isolation, and the individual toner particles must be completely melted to form a color. A: The obtained image is excellent in transparency without offset, without uneven brightness, and excellent in color reproducibility. Practical: good: although there is some unevenness in brightness, there is no practical problem. Δ: There is uneven brightness and poor color reproduction. Unusable; ×: Transparency is remarkably inferior, and color is hardly reproduced. ;
Impractical

[0378]

[Table 1]

[0379]

[Table 2]

[0380]

[Table 3]

[0381]

[Table 4]

[0382]

[Table 5]

[0383]

According to the present invention, it is possible to obtain a color toner which is excellent in offset resistance and can be fixed at a lower temperature, which can perform fixing without using a fixing oil. Further, even by oilless fixing in which the fixing temperature is set low, a full-color image having appropriate glossiness and luster and excellent color reproducibility up to a high chroma color tone can be obtained. Further, it is possible to obtain a color toner which has no stickiness of oil on an over head projector sheet (OHT) and which satisfies color reproduction and transparency. Further, it is possible to form a vivid color with high transparency up to a halftone without offset on the OHT, and to reproduce brightly and vividly a light color portion in the projected image of the OHT. In addition, high image quality can be obtained even when used under low humidity or when used under high humidity, and a color toner that does not cause image defects over time can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a suitable image forming apparatus capable of performing an image forming method of the present invention.

FIG. 2 is a schematic diagram illustrating another example of an image forming apparatus capable of performing the image forming method of the present invention.

FIG. 3 is a schematic diagram illustrating another example of an image forming apparatus capable of performing the image forming method of the present invention.

FIG. 4 is a schematic diagram illustrating another example of an image forming apparatus capable of performing the image forming method of the present invention.

FIG. 5 is a schematic diagram illustrating another example of an image forming apparatus that can perform the image forming method of the present invention.

FIG. 6 is a schematic view of an image forming apparatus using a two-component developer.

FIG. 7 is a schematic diagram of a developing device using a non-contact one-component developing method.

FIG. 8 is a schematic diagram of a developing device according to a contact one-component developing method.

FIG. 9 is a schematic diagram of a heat roll fixing device as an example of a heating and pressing fixing device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Exposure means 2 Charging roller 3 Photosensitive drum 4 Developing device 5 Developing device 6 Developing device 7 Developing device 8 Photosensitive drum cleaner 9 Core metal 10 Holding member 11 Intermediate transfer body 12 Intermediate transfer body cleaner 13 Power supply 14 Transfer charger 15 Separation and static eliminator DESCRIPTION OF SYMBOLS 16 Charger 17 Developing device 18 Photosensitive drum cleaner 19 Photosensitive drum 20 Separation static eliminator 22 Fixing device 23 Latent image forming part 24 Transfer discharge part 25 Conveyor belt 26 Discharge part 27 Adsorption charger 28 Separation static elimination discharge part 29 Image forming part 31 Exposure Means 32 Fixing device 33 Photosensitive drum 34 Developing device 35 Developing device 36 Developing device 37 Developing device 38 Photosensitive drum cleaner 39 Rotary developing unit 40 Transfer drum unit 44 Transfer charger 45 Separator charger 46 Charger 47 Gripper 48 Transfer drum 49 Separating claw 60a Transfer bias applying means ( 61a Photoconductor drum 62a Primary charger 63a Developing device 64a Transfer blade 65a Toner hopper 66a Supply roller 67a Exposure device 68 Recording material carrier 69 Separation charger 70 Fixing device 71 Fixing roller 72 Pressure roller 73 Webs 75, 76 Heating means 78 Temperature detecting means 79 Transfer belt cleaning device 80 Driving roller 81 Belt driven roller 82 Belt neutralizer 83 Registration roller 84 Feeding roller 101 Exposure means 102 Charging means 103 Photosensitive drum 104 Developing device 105 Developing device 106 Developing device Device 107 Developing Device 108 Photosensitive Drum Cleaner 109 Transfer Charging Device 110 Separation Static eliminator 111 Static eliminator 112 Fixing device 119 Photoconductor drum 120 Developing device 121 Developing sleeve (developer carrier) 122 Sleeve base 123 magnet 124 transport screw 125 transport screw 126 developing container 127 developing blade 128 two-component developer 129 toner for replenishment 130 partition 131 refilling port 169 electrostatic latent image holder (photosensitive drum) 170 developing device 171 developing container 172 developing sleeve ( (Developer carrier) 173 Developer supply roller 174 Elastic blade (developing blade) 175 Stirring member 176 One-component non-magnetic developer 180 Developing device 181 Developing container 182 Developing sleeve (Developer carrier) 183 Roller base 184 Elastic layer 185 Developing Agent supply roller 186 Elastic blade (developing blade) 187 Stirring member 188 One-component developer 189 Photoconductor drum

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuki Karaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Hiroshi Yuza 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon F term (reference) 2H005 AA01 AA06 AA21 CA08 CA13 CA14 CA25 DA02 EA03 EA06 EA07 EA10 FB01 2H030 AA03 AD01 BB23 BB24 BB34

Claims (64)

[Claims] 1. A color toner comprising at least a binder resin, a wax, an organometallic compound and a colorant, wherein the binder resin comprises at least a trivalent or higher polyvalent carboxylic acid monomer unit and a carbon number of 5 to 30. A polyvalent carboxylic acid monomer unit and / or a polyhydric alcohol monomer unit having a saturated or unsaturated aliphatic hydrocarbon group, and When the content of the monomer unit is Xa mol%, the carbon number is 5 to 30.
When the content of the polycarboxylic acid monomer unit having a saturated or unsaturated aliphatic hydrocarbon group and / or the polyhydric alcohol monomer unit is defined as Ya mol%, the following condition: 0.5 <Xa < Non-linear polyester resin A satisfying 155 <Ya <302 2 ≦ Ya / Xa ≦ 10, a trivalent or higher polyvalent carboxylic acid monomer unit and a trivalent or higher polyhydric alcohol monomer unit A non-contained linear polyester resin B, at least a mixed weight ratio of the non-linear polyester resin A and the linear polyester resin B of 25/75 to 75/25, and a differential scanning calorimeter of the wax. (DSC) A color toner having a maximum endothermic peak measured at 60 to 135 ° C. 2. The content of the organometallic compound in the toner is from 0.2 to 10% by weight, and the total content of trivalent or higher polyvalent carboxylic acid monomer units in the binder resin is Xc
2. The color toner according to claim 1, wherein, when the content of the organometallic compound in the toner is Z wt%, the following condition 2 ≦ Xc × Z ≦ 50 is satisfied. 3. 3. The organic metal compound has zirconium as a metal element, and an aromatic compound selected from the group consisting of aromatic diols, aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids. The color toner according to claim 1, wherein the color toner is a coordinated and / or bound organic zirconium compound. 4. The organic metal compound has aluminum as a metal element, and an aromatic compound selected from the group consisting of aromatic diols, aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids is provided. The color toner according to claim 1, wherein the color toner is a coordinated and / or bound organoaluminum compound. 5. A differential scanning calorimeter (DSC) for the wax.
The color toner according to any one of claims 1 to 4, wherein the maximum endothermic peak measured is in the range of 60 to 120C. 6. A ratio M between the number average molecular weight (Mn) and the weight average molecular weight (Mw) in the GPC molecular weight distribution of the wax.
The color toner according to any one of claims 1 to 5, wherein w / Mn is 1.0 to 2.0. 7. The wax according to claim 1, wherein the wax has a number average molecular weight (Mn) of 200 to 2,000 and a weight average molecular weight (Mw) of 200 to 2500 in a GPC molecular weight distribution. 2. The color toner according to 1. 8. The color toner according to claim 1, wherein the content ratio by weight of the wax is 0.3 to 4.5% by weight based on the toner. 9. The color toner according to claim 1, wherein the wax is a hydrocarbon wax. 10. The color toner according to claim 1, wherein the wax is a polyethylene wax. 11. The non-linear polyester resin A, which is a component constituting the binder resin, is obtained by introducing a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms into the skeleton of the polyester resin. The color toner according to any one of claims 1 to 10, wherein: 12. The non-linear polyester resin A, which is a component constituting the binder resin, comprises an aliphatic dicarboxylic acid and an aliphatic dicarboxylic acid substituted with a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms. 12. The color toner according to claim 1, wherein the color toner is obtained by using at least one monomer unit of a diol. 13. A linear polyester resin B which is a component constituting the binder resin has a number-average molecular weight (Mn) in a GPC molecular weight distribution of a THF-soluble component of 2,000 to 800.
0 and a weight average molecular weight (Mw) of 8000 to 300
13. The color toner according to claim 1, wherein the ratio Mw / Mn of the number average molecular weight (Mn) to the weight average molecular weight (Mw) is 2 to 3.5. 14. The toner according to claim 14, wherein the resin component has an acid value of 2 mgK.
The color toner according to any one of claims 1 to 13, wherein the color toner is OH / g to 20 mgKOH / g. 15. The color toner according to claim 1, wherein the resin component of the toner contains a THF-insoluble content of 0 to less than 5.0% by weight. 16. The resin component of the toner has a component content (M1) of less than 10,000 to 45 to 65% and a component content of 10,000 to 50,000 (M1) in a GPC molecular weight distribution of a THF-soluble component.
2) 25 to 50%, 50,000 to 500,000 component content (M3)
2-20%, component content exceeding 500,000 (M4) 0.1
16. The color toner according to claim 1, wherein the color toner satisfies the relationship of M1>M2>M3> M4. 17. The toner according to claim 1, wherein the toner is a cyan toner containing a cyan colorant for forming a full-color image by combining at least a cyan toner, a magenta toner, and a yellow toner.
6. The color toner according to any one of 6. 18. The toner according to claim 1, wherein the toner is a magenta toner containing a magenta colorant for forming a full-color image by combining at least a cyan toner, a magenta toner and a yellow toner. A color toner as described in Crab. 19. The toner according to claim 1, wherein the toner is a yellow toner containing a yellow colorant for forming a full-color image by combining at least a cyan toner, a magenta toner, and a yellow toner. A color toner as described in Crab. 20. The toner according to claim 1, wherein the toner is a black toner containing a black colorant for forming a full-color image by combining at least a cyan toner, a magenta toner, a yellow toner, and a black toner. 16. The color toner according to any one of items 16. 21. A charging step of charging the latent image holding member; a latent image forming step of forming an electrostatic latent image on the charged latent image holding member;
A developing step of developing the electrostatic latent image with toner to form a toner image; a transferring step of transferring the developed toner image onto a recording material with or without an intermediate transfer member; and A fixing step of bringing the fixing member into contact with the surface of the transferred toner image and applying heat and pressure to the toner image to fix the toner image on the recording material. The developing step is a step of using a color toner having at least a binder resin, a wax, an organometallic compound and a colorant, wherein the binder resin comprises at least a trivalent or higher polyvalent carboxylic acid monomer unit, A polyvalent carboxylic acid monomer unit having a saturated or unsaturated aliphatic hydrocarbon group of several to 30 and / or a polyhydric alcohol monomer unit; The content of the polyhydric carboxylic acid monomers units above Xa mol%, carbon number 5-30
When the content of the polycarboxylic acid monomer unit having a saturated or unsaturated aliphatic hydrocarbon group and / or the polyhydric alcohol monomer unit is defined as Ya mol%, the following condition: 0.5 <Xa < Non-linear polyester resin A satisfying 155 <Ya <302 2 ≦ Ya / Xa ≦ 10, and containing a trivalent or higher polyvalent carboxylic acid monomer unit and a trivalent or higher polyhydric alcohol monomer unit At least a non-linear polyester resin B, a mixed weight ratio of the non-linear polyester resin A and the linear polyester resin B is 25/75 to 75/25, and a differential scanning calorimeter (DSC) measurement A step of developing an electrostatic latent image using a color toner having a maximum endothermic peak of 60 to 135 ° C. to form a toner image. 22. The fixing step, wherein the coating amount of fixing oil supplied from the fixing member to the fixing surface of the toner image of the recording material per unit area of the recording material is 0 to 1 × 10 ⁻⁷ g / cm ^2.
22. The method according to claim 21, further comprising fixing the toner image on the recording material. 23. The image forming apparatus according to claim 2, wherein the fixing step is a step of fixing the toner image on the recording material without supplying fixing oil from the fixing member to the recording material.
23. The color image forming method according to 1 or 22. 24. The developing step, wherein the content of the organometallic compound in the toner is from 0.2 to 10% by weight, and the polyvalent carboxylic acid monomer unit having 3 or more valences in the binder resin. Is the total content of Xc mol% and the content of the organometallic compound in the toner is Z% by weight, and an electrostatic latent image is developed using a color toner satisfying the following condition: 2 ≦ Xc × Z ≦ 50 24. The color image forming method according to claim 21, further comprising the step of forming a toner image. 25. The developing step, wherein the organometallic compound has zirconium as a metal element and is selected from the group consisting of aromatic diols, aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids, and aromatic polycarboxylic acids. 25. A process for developing a latent electrostatic image using a color toner, which is an organic zirconium compound having an aromatic compound coordinated and / or bound, to form a toner image. The color image forming method according to any one of the above. 26. The developing step, wherein the organometallic compound has aluminum as a metal element and is selected from the group consisting of aromatic diols, aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids, and aromatic polycarboxylic acids. 25. A step of forming a toner image by developing an electrostatic latent image using a color toner which is an organoaluminum compound to which an aromatic compound is coordinated and / or bound. The color image forming method according to any one of the above. 27. The developing step, wherein the wax has a maximum endothermic peak of 60 to 1 as measured by a differential scanning calorimeter (DSC).
27. The color image forming method according to claim 21, further comprising a step of developing the electrostatic latent image using a color toner at 20 [deg.] C. to form a toner image. 28. The developing step using a color toner in which the ratio Mw / Mn of the number average molecular weight (Mn) to the weight average molecular weight (Mw) in the GPC molecular weight distribution of the wax is 1.0 to 2.0. The color image forming method according to any one of claims 21 to 27, comprising a step of forming a toner image by developing the electrostatic latent image. 29. The developing step, wherein the wax has a number average molecular weight (Mn) in a GPC molecular weight distribution of 200 to 20.
00 and a weight average molecular weight (Mw) of 200 to 250.
3. The step of developing an electrostatic latent image using a color toner of 0 to form a toner image.
29. The color image forming method according to any one of 1 to 28. 30. In the developing step, a toner image is formed by developing an electrostatic latent image using a color toner having a wax content ratio of 0.3 to 4.5% by weight based on the toner. 30. The step of carrying out
The color image forming method according to any one of the above. 31. The developing step according to claim 21, wherein the developing step is a step of developing an electrostatic latent image using a color toner having a hydrocarbon-based wax to form a toner image. The color image forming method according to any one of the above. 32. The developing method according to claim 21, wherein the developing step is a step of forming a toner image by developing an electrostatic latent image by using a color toner having a polyethylene wax as the wax. A color image forming method according to any one of the above. 33. A color toner according to claim 33, wherein the non-linear polyester resin A constituting the binder resin contains at least 3 mol% of a trivalent or higher polyvalent carboxylic acid monomer unit. 33. The color image forming method according to claim 21, further comprising a step of developing the electrostatic latent image by using a toner to form a toner image. 34. The developing step, wherein the non-linear polyester resin A, which is a component constituting the binder resin, contains a polycarboxylic acid monomer unit having a trivalent or higher valence of at least 10 mol%. The color image forming method according to any one of claims 21 to 33, comprising a step of forming a toner image by developing an electrostatic latent image using a toner. 35. The developing step, wherein the non-linear polyester resin A, which is a component of the binder resin, comprises a skeleton of the polyester resin in which a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms is branched. 35. The color image forming method according to claim 21, further comprising a step of developing an electrostatic latent image using the color toner introduced in a form of a toner to form a toner image. 36. In the developing step, the non-linear polyester resin A as a component constituting the binder resin has 5 to 30 carbon atoms.
Using a color toner obtained by synthesizing at least one monomer unit of an aliphatic dicarboxylic acid and / or an aliphatic diol substituted with a saturated or unsaturated aliphatic hydrocarbon group. 3. The method according to claim 2, further comprising the step of developing the image to form a toner image.
35. The color image forming method according to any one of 1 to 35. 37. The developing step, wherein the number-average molecular weight (Mn) in the GPC molecular weight distribution of the THF-soluble component of the non-linear polyester resin B as a component constituting the binder resin is 2;
000-8000 and a weight average molecular weight (Mw) of 8
An electrostatic latent image is developed using a color toner having a number average molecular weight (Mn) and a weight average molecular weight (Mw) ratio Mw / Mn of 2 to 3.5 to form a toner image. 37. The color image forming method according to claim 21, wherein the method is a process. 38. The developing step, wherein a toner image is formed by developing an electrostatic latent image using a color toner having an acid value of a resin component of the toner of 2 to 20 mgKOH / g. The color image forming method according to any one of claims 21 to 37. 39. The developing step in which a toner image is formed by developing an electrostatic latent image using a color toner in which a resin component of the toner contains 0 to less than 5.0% by weight of a THF-insoluble component. The color image forming method according to any one of claims 21 to 38, wherein: 40. In the developing step, in the GPC molecular weight distribution of the THF-soluble portion of the resin component of the toner, a component content (M1) of less than 10,000 is 45 to 65%, and a component content of 10,000 to 50,000 is used. (M2) 25 to 50%, 50,000 to 500,000 component content (M3) 2 to 20%, component content exceeding 500,000 (M
4) 0.1 to 10% and M1>M2>M3>
The color image forming method according to any one of claims 21 to 39, wherein the step of developing the electrostatic latent image using a color toner satisfying the relationship of M4 to form a toner image. 41. a first charging step of charging the latent image holding member; a first latent image forming step of forming an electrostatic latent image on the charged latent image holding member; A first developing step of forming a first toner image by developing with toner; a first transferring step of transferring the developed first toner image onto an intermediate transfer body; a second charging step of charging a latent image holding member Charging step; second latent image forming step of forming an electrostatic latent image on the charged latent image carrier; developing the electrostatic latent image with a second toner to form a second toner image Developing step 2; developed second
A second transfer step of transferring the toner image of FIG. 1 to the intermediate transfer member onto which the first toner image has been transferred; a third charging step of charging the latent image holder; and an electrostatic latent image on the charged latent image holder. A third latent image forming step of forming an image; a third developing step of developing the electrostatic latent image with a third toner to form a third toner image; A third transfer step of transferring the toner image on the intermediate transfer body onto which the first toner image and the second toner image have been transferred; a fourth step of charging the latent image holding member
A fourth latent image forming step of forming an electrostatic latent image on the charged latent image holding member; a fourth latent image forming step of developing the electrostatic latent image with a fourth toner to form a fourth toner image Developing step 4; developing the fourth toner image into a first toner image;
A fourth transfer step of transferring the second toner image and the third toner image onto the intermediate transfer member to which the second toner image and the third toner image have been transferred; a first toner image, a second toner image transferred onto the intermediate transfer member, A batch transfer step of collectively and secondarily transferring a multicolor toner image having a third toner image and a fourth toner image onto a recording material; and the multicolor toner collectively and secondarily transferred onto the recording material. Fixing the multicolor toner image to the recording material by bringing a fixing member into contact with the surface of the image and applying heat and pressure to the multicolor toner image. The first toner is a cyan toner,
A color toner selected from the group consisting of magenta toner, yellow toner, and black toner, and the second toner is a color toner selected from the remaining group excluding the color toner selected as the first toner. The third toner is a color toner selected from the remaining groups excluding the color toner selected as the first toner and the color toner selected as the second toner, and the fourth toner is 22. The remaining color toner excluding the color toner selected as the first toner, the color toner selected as the second toner, and the color toner selected as the third toner.
41. The method for forming a color image according to any one of the above items. 42. a first charging step of charging the latent image holding member; a first latent image forming step of forming an electrostatic latent image on the charged latent image holding member; A first developing step of developing with a toner to form a first toner image; a first transferring step of transferring the developed first toner image onto a recording material without passing through an intermediate transfer member; The second to charge the body
Charging step; second latent image forming step of forming an electrostatic latent image on the charged latent image carrier; developing the electrostatic latent image with a second toner to form a second toner image Developing step 2: transferring the developed second toner image onto a recording material on which the first toner image has been transferred; third charging step of charging the latent image holding member; A third latent image forming step of forming an electrostatic latent image on the formed latent image holding member; a third developing step of developing the electrostatic latent image with a third toner to form a third toner image; A third transfer step of transferring the developed third toner image onto a recording material onto which the first toner image and the second toner image have been transferred; a fourth charging step of charging the latent image holding member; A fourth latent image forming step of forming an electrostatic latent image on the charged latent image holding member;
Developing a fourth toner image by developing with the first toner image; transferring the developed fourth toner image to the first toner image, the second toner image, and the third toner image; A fourth transfer step of transferring onto a recording material that is present; a multicolor toner image having a first toner image, a second toner image, a third toner image, and a fourth toner image sequentially transferred onto a recording material Fixing the multicolor toner image to the recording material by bringing a fixing member into contact with the surface of the multicolor toner image and applying heat and pressure to the multicolor toner image. Is a color toner selected from the group consisting of a cyan toner, a magenta toner, a yellow toner, and a black toner, and the second toner is the color toner selected as the first toner. A color toner selected from the remaining group, wherein the third toner is a color toner selected from the remaining group excluding the color toner selected as the first toner and the color toner selected as the second toner. The fourth toner is a color toner selected as the first toner, the color toner selected as the second toner, and the remaining color toner excluding the color toner selected as the third toner. 22. The method according to claim 21, wherein
41. The method for forming a color image according to any one of the above items. 43. A toner for developing at least an electrostatic latent image, a toner container for holding the toner, and a toner carrier for carrying the toner held in the toner container and transporting the toner to a development area And a toner layer thickness regulating member for regulating the layer thickness of the toner carried on the toner carrier. The toner has a color having at least a binder resin, a wax, an organometallic compound and a colorant. A toner, wherein the binder resin is a polyvalent carboxylic acid monomer having at least a trivalent or higher polyvalent carboxylic acid monomer unit and a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms. A binder unit and / or a polyhydric alcohol monomer unit, wherein the content of the trivalent or higher polyvalent carboxylic acid monomer unit in the binder resin is Xa mol%, and the number of carbon atoms is 5 to 30.
When the content of the polycarboxylic acid monomer unit having a saturated or unsaturated aliphatic hydrocarbon group and / or the polyhydric alcohol monomer unit is defined as Ya mol%, the following condition: 0.5 <Xa < Non-linear polyester resin A satisfying 155 <Ya <302 2 ≦ Ya / Xa ≦ 10, and containing a trivalent or higher polyvalent carboxylic acid monomer unit and a trivalent or higher polyhydric alcohol monomer unit At least a non-linear polyester resin B, a mixed weight ratio of the non-linear polyester resin A and the linear polyester resin B is 25/75 to 75/25, and a differential scanning calorimeter (DSC) measurement Wherein the maximum endothermic peak is in the range of 60 to 135 [deg.] C. and is detachably attached to the main body of the color image forming apparatus. 44. The toner, wherein the content of the organometallic compound in the toner is from 0.2 to 10% by weight and the trivalent or higher polyvalent carboxylic acid monomer unit in the binder resin is contained. 44. The color according to claim 43, wherein the following condition 2 ≦ Xc × Z ≦ 50 is satisfied when the total content is Xc mol% and the content of the organometallic compound in the toner is Z% by weight. An apparatus unit detachably attached to the image forming apparatus main body. 45. The organic metal compound has zirconium as a metal element, and an aromatic compound selected from the group consisting of aromatic diols, aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids, and aromatic polycarboxylic acids. 45. The apparatus unit detachably mounted on the color image forming apparatus body according to claim 43, wherein the apparatus unit is an organic zirconium compound coordinated and / or bound. 46. The organic metal compound has aluminum as a metal element, and an aromatic compound selected from the group consisting of aromatic diols, aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids, and aromatic polycarboxylic acids. The apparatus unit according to claim 43 or 44, wherein the apparatus unit is an organic aluminum compound that is coordinated and / or bound. 47. A differential scanning calorimeter (DS) of the wax.
The apparatus unit detachably mounted on the color image forming apparatus main body according to any one of claims 43 to 46, wherein the maximum endothermic peak measured by C) is 60 to 120 ° C. 48. The wax according to claim 43, wherein a ratio Mw / Mn of the number average molecular weight (Mn) to the weight average molecular weight (Mw) in the GPC molecular weight distribution of the wax is 1.0 to 2.0. An apparatus unit detachably attached to the color image forming apparatus main body according to any one of the above. 49. The wax according to claim 43, wherein the wax has a number average molecular weight (Mn) of 200 to 2,000 and a weight average molecular weight (Mw) of 200 to 2500 in a GPC molecular weight distribution. An apparatus unit detachably attached to the color image forming apparatus main body according to the above. 50. The color image forming apparatus main body according to claim 43, wherein the content ratio of the wax is 0.3 to 4.5% by weight based on the toner. A device unit that is detachably mounted. 51. The apparatus unit according to claim 43, wherein said wax comprises a hydrocarbon-based wax. 52. The apparatus unit according to claim 43, wherein said wax comprises a polyethylene wax. 53. The non-linear polyester resin A, which is a component constituting the binder resin, contains at least 3 mol% of a trivalent or higher polyvalent carboxylic acid monomer unit. Item 53. An apparatus unit detachably attached to the color image forming apparatus main body according to any one of Items 43 to 52. 54. The non-linear polyester resin A, which is a component constituting the binder resin, is characterized by containing at least 10 mol% or less of a trivalent or higher polyvalent carboxylic acid monomer unit. An apparatus unit detachably attached to the color image forming apparatus main body according to any one of claims 43 to 53. 55. The non-linear polyester resin A, which is a component constituting the binder resin, is obtained by introducing a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms into the skeleton of the polyester resin. An apparatus unit detachably mounted on the color image forming apparatus main body according to any one of claims 43 to 54. 56. The non-linear polyester resin A, which is a component constituting the binder resin, comprises an aliphatic dicarboxylic acid and an aliphatic dicarboxylic acid substituted with a saturated or unsaturated aliphatic hydrocarbon group having 5 to 30 carbon atoms. 56. An apparatus detachably mounted on a color image forming apparatus main body according to claim 43, wherein the apparatus is obtained by synthesizing using at least one monomer unit of diols. unit. 57. The non-linear polyester resin B as a component constituting the binder resin has a number-average molecular weight (Mn) in the GPC molecular weight distribution of THF-soluble components of 2,000 to 800.
0 and a weight average molecular weight (Mw) of 8000 to 300
57. The color image forming apparatus according to claim 43, wherein the ratio Mw / Mn of the number average molecular weight (Mn) to the weight average molecular weight (Mw) is 2 to 3.5. An equipment unit that is detachably attached to the main unit. 58. The resin component of the toner having an acid value of 2 to 20.
58. The apparatus unit according to claim 43, wherein the apparatus unit is mgKOH / g. 59. The color image forming apparatus main body according to claim 43, wherein the resin component of the toner contains a THF-insoluble content of 0 to less than 5.0% by weight. An equipment unit that can be mounted. 60. The GPC molecular weight distribution of the THF-soluble component in the resin component of the toner is 45 to 65% of a component content (M1) of less than 10,000, and a component content (M1) of 10,000 to 50,000.
2) 25 to 50%, 50,000 to 500,000 component content (M3)
2-20%, component content exceeding 500,000 (M4) 0.1
60. The apparatus detachably mounted on the color image forming apparatus main body according to claim 43, wherein the relation of M1>M2>M3> M4 is satisfied. unit. 61. The toner according to claim 43, wherein the toner is a cyan toner containing a cyan colorant for forming a full-color image by combining at least a cyan toner, a magenta toner, and a yellow toner. An apparatus unit detachably mounted on the color image forming apparatus main body according to the above item (1). 62. The toner according to claim 43, wherein the toner is a magenta toner containing a magenta colorant for forming a full-color image by combining at least a cyan toner, a magenta toner and a yellow toner.
61. An apparatus unit detachably mounted on the color image forming apparatus main body according to any one of items 60 to 60. 63. The toner according to claim 43, wherein the toner is a yellow toner containing a yellow colorant for forming a full-color image by combining at least a cyan toner, a magenta toner, and a yellow toner.
61. An apparatus unit detachably mounted on the color image forming apparatus main body according to any one of items 60 to 60. 64. The toner according to claim 43, wherein the toner is a black toner containing a black colorant for forming a full-color image by combining at least a cyan toner, a magenta toner, a yellow toner and a black toner. 60. An apparatus unit detachably attached to the color image forming apparatus main body according to any one of items 60.