JP2002258535A - Image forming method, image forming device and color toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color toners which have excellent durable stability and are capable of forming images satisfying high colorfulness, an image forming method and an image forming device. SOLUTION: This method has an electrostatic latent image forming process step for forming the electrostatic latent images on an image carrying member using an organic photoconductor, a developing process step, a transfer process step and a fixing process step and forms the color images by using a one- component developer consisting of magnetic toners for performing black development and two-component developers consisting of magnetic carriers and nonmagnetic carriers for performing color development. The nonmagnetic color toners have binder resins, coloring agents and wax. The modulus of elasticity in storage (G'80 ) thereof at 80 deg.C ranges from 1×10<6> to 1×10<10> [dN/m<2> ], the modulus of elasticity in storage (G'120-180 ) thereof at 120 to 180 deg.C ranges from 5×10<3> to 1×10<6> [dN/m<2> ] and the peak temperature of the maximum endothermic peak in a range of 30 to 200 deg.C at the endothermic curve in differential thermal analysis (DSC) measurement exists in a range of 50 to 110 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an OPC (organic photoconductor) photoconductor as an image carrier used in a color printer, a color copier, and the like. The present invention relates to an image forming method, an image forming apparatus and a color toner using the two-component type non-magnetic toner.

[0002]

2. Description of the Related Art Apparatuses to which an electrophotographic process is applied are widely used in addition to a conventional so-called copying machine for copying originals, as well as a computer whose demand is remarkably growing in recent years and a printer as an output means of a word processor. . It is important for such a printer that a color image output is provided in addition to a conventional monochrome image output.

In such an environment, a plurality of developing devices each containing a developer of a different color are provided, and a plurality of developing devices are mounted on a photosensitive drum, which is an image carrier, using an electrophotographic method in one or more recording cycles. A multi-color (color) image forming apparatus has been proposed which forms a color toner image, transfers the plurality of color toner images to a recording material, and fixes the toner image to obtain a desired multi-color image.

[0004] At this time, in color development, it is necessary to sufficiently mix colors of the respective toners in the heating and pressing fixing step without increasing the color reproducibility or deteriorating the transparency of an overhead projector (OHP) image. Compared with general black and white copiers and black toner for printers, toner for full-color images is
A binder resin having a low molecular weight and a low softening point having a sharp melt property is preferred. This is because, when a toner having a high softening point is used, the color mixing in the fixing device deteriorates, and a problem occurs in color reproducibility. However, when such a low softening point toner is used in a high-speed full-color copying machine,
At the contact portion between the cleaner unit and the transfer unit roller and the photoconductor, the mechanical share increases, and the calorific value of the photoconductor increases, so that the phenomenon that the toner is softened on the photoconductor occurs. This leads to the problem that toner adheres (fuses) to the photoconductor and the problem of filming that toner resin accumulates on the surface of the photoconductor. Therefore, the photoconductor cannot have a sufficient life.

Therefore, when the OPC photoreceptor is mounted on a color machine requiring a high-definition image, fusion to the photoreceptor is prevented, filming is reduced, and color reproducibility is hindered during fixing. There has been a demand for the development of toners that satisfy all of the requirements.

Hitherto, various proposals have been made for a toner having a specific storage modulus in order to solve the offset problem in the fixing step without impairing the transparency of an OHP image. For example, JP-A-11-84716,
There is JP-A-11-7151.

However, these methods are not satisfactory from the viewpoint of color reproducibility in the fixing step, that is, transparency in OHP, fixed temperature fixing property at the time of fixing by heating and pressure, and high temperature offset resistance. Fusing and sufficient color mixture, ideal fixing properties, storability,
In order to obtain OHP transparency, there was room for improvement.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color toner, an image forming method and an image forming apparatus which solve the above-mentioned problems. That is, an object of the present invention is to provide a color toner capable of forming an image having excellent durability stability and satisfying high definition when an OPC (organic photoconductor) photoreceptor is mounted on a full-color machine. An object of the present invention is to provide an image forming method and an image forming apparatus. Specifically, the toner does not fuse to the surface of the photoreceptor, filming can be reduced, transparency in OHP can be increased, the problem of high-temperature offset resistance can be solved without interfering with low-temperature fixing during fixing, and the degree of color mixing can be improved. An object of the present invention is to provide an excellent color toner, an image forming method and an image forming apparatus having the color toner.

[0009]

Means for Solving the Problems Accordingly, the present inventors have made a sharp
After careful consideration, the following color toners can be used.
And that the above-mentioned problem can be solved.
And completed the present invention. (1) An electrostatic latent image for an image carrier using an organic photoconductor
Forming an electrostatic latent image on the image carrier
The toner corresponding to the latent image is transferred by transferring the toner to the electrostatic latent image.
Developing process for forming and visualizing a toner image, and
Transfer step of electrostatically transferring the formed toner image to a transfer material
And the electrostatically transferred toner image is fixed by a fixing member.
And a black developing process in the developing process.
-Component developer composed of magnetic toner and color developer
A magnetic carrier and a non-magnetic toner
A color image is formed by using a component developer.
An image forming method capable of performing
The non-magnetic color toner has at least a binder resin and a colored resin.
Agent and wax, and in viscoelastic properties, at a temperature of 80
Storage elastic modulus at ℃ (G '₈₀) Is 1 × 10⁶~ 1 × 10
^Ten[DN / m^Two], And the temperature is 120 to 180 ° C.
Storage modulus (G '_120-180) Is 5 × 10^Three~ 1 ×
10⁶[DN / m^Two] Range, and differential thermal analysis
In the endothermic curve in the (DSC) measurement, the temperature was 30 to
The peak temperature of the maximum endothermic peak in the range of 200 ° C.
Color toner in the range of 50 to 110 ° C
A featured image forming method. (2) The color toner has a viscoelasticity property of a temperature.
Storage modulus at 80 ° C. (G ′₈₀) Is 1 × 10⁶~ 1 ×
10⁸[DN / m^TwoAnd a temperature of 120 to 180
Storage elastic modulus at ℃ (G '_120-180) Is 1 × 10^Four~ 5
× 10^Five[DN / m ^TwoSatisfies the range of
The image forming method according to (1). (3) Differential thermal analysis (DSC) measurement of the color toner
In the endothermic curve at a temperature in the range of 30 to 200 ° C.
The peak temperature of the maximum endothermic peak at 55 to 100 ° C
(1) or (2).
Image forming method. (4) The color toner is measured by differential thermal analysis (DSC).
In the endothermic curve in the range of temperature 30 to 200 ° C
Peak temperature of the maximum endothermic peak in
(1) or (2).
Image forming method. (5) The binder resin is a polyester unit and vinyl
Hybrid resin having a copolymer unit or
Any mixture of polyester resin and vinyl copolymer
Any of (1) to (4),
2. The image forming method according to 1., (6) The binder resin is a gel permeation chromatograph.
Molecular weight distribution by GPC
Main peak exists in the area of 6000-8000, weight average
The ratio of molecular weight (Mw) to number average molecular weight (Mn) (Mw /
Mn) is 300 or more (1)-
The image forming method according to any one of (5). (7) The binder resin is a gel permeation chromatograph.
Molecular weight distribution by GPC
Main peak exists in the area of 6000-8000, weight average
The ratio of molecular weight (Mw) to number average molecular weight (Mn) (Mw /
(Mn) is 500 or more (1)-
The image forming method according to any one of (5). (8) The color toner contains an organometallic compound.
The image according to any one of (1) to (7),
Forming method. (9) The organic metal compound is an aromatic carboxylic acid derivative
The image according to (8), which is a metal compound.
Forming method. (10) The metal compound of the aromatic carboxylic acid derivative is
Be an aluminum compound of an aromatic carboxylic acid derivative
The image forming method according to (9), wherein (11) The organic metal compound is contained in the color toner.
0.1 to 10% by mass based on the mass of Lartner
Image form according to any one of (8) to (10)
Method. (12) A small amount of magnetic toner for performing the black development
At least contains a magnetic iron oxide, the magnetic iron oxide is a Si compound
Alternatively, it contains 0.3 to 1.4% of an Al compound.
Image forming method according to any one of (1) to (11)
Law. (13) There is little magnetic toner in the black toner for developing.
At least a magnetic iron oxide, wherein the magnetic iron oxide is
Silicon whose iron element dissolution rate of iron fossil is present up to 20% by weight
Element content BSi and total silicon present in the magnetic iron oxide
Element content ratio to ASi (BSi / ASi) x 100 is 35
(1)-(12)
An image forming method according to any of the above. (14) Form an electrostatic latent image on an image carrier using an organic photoconductor
Forming means for forming an electrostatic latent image on the image carrier;
The toner corresponding to the latent image is transferred by transferring the toner to the electric latent image.
Developing means for forming and visualizing an image, and forming on an image carrier
Transfer means for electrostatically transferring the transferred toner image to a transfer material.
A magnetic toner for performing black development by the developing means.
And a magnetic component for color development.
And a two-component developer composed of non-magnetic toner
Developing to form a color image by using
Image forming apparatus, wherein the non-magnetic color
The toner contains at least a binder resin, a colorant and a wax.
Has a viscoelastic property, a storage bullet at a temperature of 80 ° C.
Sex rate (G '₈₀) Is 1 × 10⁶~ 1 × 10^Ten[DN / m^Two]
Storage elasticity at a temperature of 120 to 180 ° C
Rate (G '_120-180) Is 5 × 10^Three~ 1 × 10⁶[DN /
m^Two] Range, and was measured by differential thermal analysis (DSC).
In the endothermic curve at a constant
The maximum endothermic peak temperature in the range is 50 to 110.
Image characterized by being a color toner in the range of
Image forming device. (15) The color toner has a viscoelastic property that is
Storage modulus at 80 ° C (G '₈₀) Is 1 × 10⁶~ 1
× 10⁸[DN / m^TwoAnd a temperature of 120 to 18
Storage modulus at 0 ° C. (G ′_120-180) Is 1 × 10^Four~
5 × 10^Five[DN / m^TwoSatisfies the range of
The image forming apparatus according to (14). (16) The color toner is measured by differential thermal analysis (DSC).
In the endothermic curve at a constant
The peak temperature of the maximum endothermic peak in the
(14) or (15), which is in the range of ° C.
An image forming apparatus according to claim 1. (17) The color toner is measured by differential thermal analysis (DSC).
In the endothermic curve at a constant
The maximum endothermic peak temperature in the range is 60 to 90 ° C.
(14) or (15), characterized in that
The image forming apparatus as described in the above. (18) The binder resin is a polyester unit and a vinyl
Hybrid resin having a copolymer unit
Is a mixture of polyester resin and vinyl copolymer
(14) to (17), wherein
An image forming apparatus according to any of the preceding claims. (19) The binder resin is a gel permeation chroma.
In the molecular weight distribution by chromatography (GPC),
The main peak exists in the region of
Ratio (Mw) between the average molecular weight (Mw) and the number average molecular weight (Mn)
/ Mn) is 300 or more (14)-
The image forming apparatus according to any one of (18). (20) The binder resin is a gel permeation chroma
In the molecular weight distribution by chromatography (GPC),
The main peak exists in the region of
Ratio (Mw) between the average molecular weight (Mw) and the number average molecular weight (Mn)
/ Mn) is 500 or more (14)-
The image forming apparatus according to any one of (18). (21) The color toner has an organometallic compound
According to any one of (14) to (20),
Image forming apparatus. (22) The organic metal compound is an aromatic carboxylic acid derivative
(21) wherein the metal compound is
Image forming device. (23) The metal compound of the aromatic carboxylic acid derivative is
Be an aluminum compound of an aromatic carboxylic acid derivative
(22) The image forming apparatus according to (22). (24) The organic metal compound is contained in the color toner.
0.1 to 10% by mass based on the mass of Lartner
The image according to any one of (21) to (23)
Forming equipment. (25) There is little magnetic toner for performing the black development.
It contains at least a magnetic iron oxide, and the magnetic iron oxide contains Si or
Contains 0.3 to 1.4% of Al element
(14) The image forming apparatus according to any one of (24) to (24). (26) The magnetic toner for performing the black development has little
At least a magnetic iron oxide, wherein the magnetic iron oxide is
Silicon whose iron element dissolution rate of iron fossil is present up to 20% by weight
Element content BSi and total silicon present in the magnetic iron oxide
Element content ratio to ASi (BSi / ASi) x 100 is 35
(14)-(25)
An image forming apparatus according to any one of the above. (27) Forming an electrostatic latent image on an image carrier using an organic photoconductor
Forming an electrostatic latent image formed on the image bearing member.
The toner corresponding to the latent image is transferred by transferring the toner to the electric latent image.
Developing process for forming and visualizing an image, and forming on image carrier
A transfer step of electrostatically transferring the transferred toner image to a transfer material,
Fixing the electrostatically transferred toner image by a fixing member
Fixing step, and performing black development in the developing step.
One-component developer consisting of magnetic toner and color development
Two components consisting of magnetic carrier and non-magnetic toner for performing
To form a color image by using
Non-magnetic used in image forming method, capable of performing image
The non-magnetic color toner
Has at least a binder resin, a colorant and a wax,
In the viscoelastic properties, the storage elastic modulus at 80 ° C
(G '₈₀) Is 1 × 10⁶~ 1 × 10^Ten[DN / m^Two]
Box, storage modulus at 120-180 ° C
(G '_120-180) Is 5 × 10^Three~ 1 × 10⁶[DN / m^Two]
Satisfies the range of
The endothermic curve in the temperature range of 30 to 200 ° C.
Peak temperature of the maximum endothermic peak in the range of 50 to 110 ° C.
A color toner characterized by being enclosed. (28) The color toner has a viscoelastic property that is
Storage modulus at 80 ° C (G '₈₀) Is 1 × 10⁶~ 1
× 10⁸[DN / m^TwoAnd a temperature of 120 to 18
Storage modulus at 0 ° C. (G ′_120-180) Is 1 × 10^Four~
5 × 10^Five[DN / m^TwoSatisfies the range of
(27) The color toner according to (27). (29) The color toner is measured by differential thermal analysis (DSC).
In the endothermic curve at a constant
The peak temperature of the maximum endothermic peak in the
(27) or (28), which is in the range of ° C.
2. The color toner according to 1. (30) The color toner is measured by differential thermal analysis (DSC).
In the endothermic curve at a constant
The maximum endothermic peak temperature in the range is 60 to 90 ° C.
(27) or (28), characterized in that
The color toner described in the above. (31) The binder resin is a polyester unit and a vinyl
Hybrid resin having a copolymer unit
Is a mixture of polyester resin and vinyl copolymer
Any of (27) to (30), wherein
The color toner described in any of the above. (32) The binder resin is a gel permeation chroma.
In the molecular weight distribution by chromatography (GPC),
The main peak exists in the region of
Ratio (Mw) between the average molecular weight (Mw) and the number average molecular weight (Mn)
/ Mn) is 300 or more (27)-
(31) The color toner according to any one of (31). (33) The binder resin is a gel permeation chroma.
In the molecular weight distribution by chromatography (GPC),
The main peak exists in the region of
Ratio (Mw) between the average molecular weight (Mw) and the number average molecular weight (Mn)
/ Mn) is 500 or more (27)-
The color toner according to any one of (31) to (31). (34) The color toner has an organometallic compound
According to any one of (27) to (33),
Color toner. (35) The organic metal compound is an aromatic carboxylic acid derivative
The metal compound of (34), wherein
Color toner. (36) The metal compound of the aromatic carboxylic acid derivative is
Be an aluminum compound of an aromatic carboxylic acid derivative
(35) The color toner as described in (35) above. (37) The organic metal compound is contained in the color toner.
0.1 to 10% by mass based on the mass of Lartner
Color according to any one of (34) to (36)
-Toner.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An image forming method according to the present invention comprises an OPC
An electrostatic latent image forming step of forming an electrostatic latent image on the image carrier using the (organic photoconductor); and transferring the toner to the electrostatic latent image formed on the image carrier by transferring the toner to the latent image. A developing step of forming and visualizing a corresponding toner image, a transfer step of electrostatically transferring the toner image formed on the image carrier to a transfer material, and fixing the electrostatically transferred toner image by a fixing member Fixing step. FIG. 1 shows an embodiment of an image forming apparatus that performs this image forming method. The image forming apparatus includes a plurality of developing devices each containing a developer of a different color, and forms a toner image of a plurality of colors on one photosensitive drum in one or a plurality of recording cycles. This is a digital full-color multi-color (color) image forming apparatus that transfers a toner image to a transfer material and fixes it to obtain a desired multi-color image.

The apparatus comprises a photosensitive drum 20 as an image carrier.
Two. The image bearing member is a drum-type electrophotographic photosensitive member that is driven to rotate at a predetermined peripheral speed (process speed) in the clockwise direction of arrow A. Reference numeral 201 denotes a charging unit for uniformly charging the photoconductor 202. The photoconductor 202
Is uniformly charged by the charging unit 201 and then supplied to the electrostatic latent image forming unit. A latent image is formed by the image signal providing unit 203, and a visible image (toner image) corresponding to the latent image is formed by the next developing unit 204. The developing means 204
Is a first developing device 204 that develops a first color developer
(A) Second developing device 204 that develops a second color developer
(B), third developing device 204 (c), fourth developing device 204
(D) (each containing a different color toner).

The toner image is electrostatically transferred to a transfer material by a transfer unit. In other words, the drive system 221 also serves as a transfer unit.
Thus, the intermediate transfer material 222 is driven, and the toner image is transferred to the intermediate transfer material 222. Thereafter, the image is further transferred from the intermediate transfer material 222 to a final transfer material P made of paper or the like. After transferring the toner image onto the final transfer material P, the intermediate transfer material 222 is cleaned by an intermediate transfer material cleaning unit 223 including a cleaning blade 224 and the like, and is provided for the next transfer process. The transfer step may have a configuration in which the final transfer material P is directly transferred to the final transfer material P. In this case, the final transfer material P is circulated in the apparatus a plurality of times. The configuration is slightly different.

On the other hand, the surface of the photosensitive member 202 is cleaned by a cleaning means (cleaner) 207 after being separated from the transfer material (222 or P) on which the toner image has been transferred. Thereafter, the electrostatic latent image remaining on the surface of the photoreceptor is subjected to charge removal by the charge removing means 208, and then is subjected to the charging step again.

On the other hand, the transfer material P made of paper or the like
05 after passing through the paper feed path 219 of the register roller 22.
The timing is controlled by 0 or the like and supplied to the photoconductor side. Further, the visible image on the surface of the intermediate transfer material 222 (or the photoconductor 202) is transferred to the transfer material P by the transfer means 206 (a),
The transfer material P is separated from the photoreceptor side by the separating means 206 (b). After the transfer material P is separated, the toner image is fixed by a fixing unit 211 including a roller-212 and the like via a transport system 210, and is discharged out of the apparatus.

The image signal applying means reflects the irradiation light from the light source 215 onto the document 213 placed on the document table 214,
Signals from an external computer or the like are directly stored instead of being stored in the scanner 216 or from a document. In response to the stored signal, a latent image light source 217 made of a laser or the like is scanned and intensity-modulated, and is supplied to an image signal providing unit 203 via a polarizing unit such as a mirror 218. When forming a multicolor (two or more colors) image of the present invention, the above steps are repeated as many times as necessary according to the color of the toner to form an image.

Next, the developing step of the present invention will be described. In the developing step, a one-component developer composed of a magnetic toner for performing black development and a two-component developer composed of a magnetic carrier and a non-magnetic toner for performing color development are used. As described above, by changing the developing method between black and color and using the different methods, black developing is frequently used, but maintenance such as carrier replacement can be suppressed.

In many cases, a black toner such as a character document is frequently used even in a color copying machine, so that a tendency is observed that a large amount of the black toner is consumed. Therefore, it is desired to supply a large amount of black toner,
The use of the magnetic toner increases the specific gravity of the toner, which is advantageous for increasing the fluidity of the toner, and the degree of freedom in designing the developing position and the shape of the toner hopper is widened.

On the other hand, in the development for color (other than black), the selection range of the toner which can be used for achieving the purpose of sharpening the color can be expanded.

Here, the developing means using the developer of the present invention will be described with reference to FIG. FIG. 2 shows the inside of the developing means,
And a schematic diagram of the vicinity of a region facing a photoconductor. Figure
2A shows a case where a one-component developer is used in black development, and FIG. 2B shows a case where a two-component developer is used in color development. Developing means 5
0 denotes at least the developer 51, the sleeve 52, and the blade 5
3. It has a developer reservoir 54 and a peeling member 55. FIG. 2A illustrates the case of a magnetic one-component developer, in which a magnetic body 56 is provided in the sleeve 52.
Further, the developing means 50 may have a stirring screw or the like (not shown). The sleeve 52 has a predetermined DC voltage or an AC voltage applied to the DC voltage, and is rotationally driven at a predetermined speed. The developer 51 adheres onto the sleeve 52 from the developer reservoir 54 and is conveyed. Further developer 51
Passes between the sleeve 52 and the blade 53, is controlled to a predetermined coat thickness, and after a predetermined charge is applied,
The sheet is transported to a region facing the photoconductor. In the above-mentioned region, the developer 51 has a potential difference between the photosensitive member and the sleeve 52,
The surface of the photoconductor is developed by the applied voltage.
The developer 51 remaining on the surface of the sleeve 52 is
By (2), the toner is collected in the developing means 50 and is peeled and removed from the sleeve by the peeling member 55.

In the one-component development system, the developer 51 is composed of the toner 511. In the two-component development system, the developer 51 is
It comprises a toner 511 and a carrier 512. One more component,
Both components have external additives (not shown). In the magnetic one-component developer, as shown in FIG. 2A, the blade 53 is made of a magnetic member and is installed at a predetermined distance from the sleeve 52. On the other hand, in non-magnetic two-component development,
As shown in (b), the toner blade 53 is made of an elastic member and is in contact with the sleeve 52 with a predetermined contact pressure. Here, the carrier 512 and the toner 511 are coated on the developing sleeve 52 with a predetermined thickness, and come into contact with the photoconductor 1002 in a state where a so-called “spike” is formed. At the contact portion, the toner adheres to the photoreceptor 1002 with an electrostatic force according to the latent image to form a toner image.

<Regarding the Color Toner of the Present Invention> The color toner of the present invention has at least a binder resin, a colorant and a wax, and has a storage elastic modulus (G _'80 ) at a temperature of 80 ° C. of 1 × 10 3 in viscoelastic properties. ⁶ to 1 × 10 ¹⁰ [dN / m
² ], and the storage elastic modulus (G ′ _120-180 ) at a temperature of _{120 to 180} ° C. is 5 × 10 ³ to 1 × 10 ⁶ [dN /
m ² ], and in the endothermic curve in the differential thermal analysis (DSC) measurement, the peak temperature of the maximum endothermic peak in the temperature range of 30 to 200 ° C. is 50 to 110.
It is a color toner in the range of ° C.

In the present invention, the measurement of the viscoelasticity and the measurement of the differential thermal analysis were performed as follows. In addition, it measured similarly also in the Example mentioned later.

Measurement of Viscoelasticity of Toner The toner is pressed into a disk-shaped sample having a diameter of 25 mm and a thickness of about 2 to 3 mm. Next, set on a parallel plate,
Gradually raise the temperature within the temperature range of 200 ° C and measure the temperature dispersion. The heating rate is 2 ° C / min and the angular frequency (ω) is 6.28r
It is fixed to ad / sec and the distortion rate is automatic. Take the temperature on the horizontal axis and the storage modulus (G`) on the vertical axis, and read the value at each temperature. In the measurement, RDA-II (manufactured by Rheometrics) is used.

Differential Thermal Analysis Measurement ASTM D3418-8 using a differential scanning calorimeter (DSC measuring apparatus) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2. A measurement sample is precisely weighed in an amount of 2 to 10 mg, preferably 5 mg. This was put in an aluminum pan, and an empty aluminum pan was used as a reference. The temperature was raised at a rate of 10 ° C./min between 30 and 200 ° C.
At normal temperature and normal humidity. During the heating and cooling processes, the endothermic and exothermic peaks of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. are obtained.

In the above viscoelastic properties, the storage elastic modulus (G'80) of the nonmagnetic color toner at a temperature of 80 ° C.
Is preferably in the range of 1 × 10 ⁶ to 1 × 10 ¹⁰ [dN / m ² ]. More preferably, 1 × 10 ⁶ to 1 ×
It is in the range of 10 ⁸ [dN / m ² ]. Thereby, the storage stability, heat resistance and blocking resistance of the toner in a high temperature environment can be improved. The value of the above viscoelastic modulus is
It can be adjusted by appropriately considering various factors such as the type and molecular weight of the binder resin itself, the amount of the crosslinking component, and the structure of the molecular chain.

The storage elastic modulus (G _'80 ) is 1 × 10 ⁶ [d
N / m ² ], the storage stability, heat resistance, and blocking resistance in a high-temperature environment are poor, and the toner particles coalesce to form a large toner agglomerate. There is a problem that filming occurs. On the other hand, the storage elastic modulus (G ′ ₈₀ ) is 1 × 10 ¹⁰ [d
N / m ² ], there is a problem that although the storage stability, heat resistance and blocking resistance are sufficient, sufficient fixability at a low temperature cannot be obtained.

Next, the temperature of the non-magnetic color toner 120
The storage elastic modulus (G ' _120-180 ) at -180 ° C is 5 ×
It is preferably in the range of 10 ³ to 1 × 10 ⁶ [dN / m ² ]. More preferably, 1 × 10 ^{4 to} 5 × 10 ⁵ [d
N / m ² ]. As a result, sufficient low-temperature fixability and high-temperature offset resistance can both be achieved.

The storage elastic modulus ( _G'120-180 ) is 5 × 10
If it is smaller than ³ [dN / m ² ], it is not preferable because sufficient high-temperature offset resistance of the toner cannot be obtained, and the storage elastic modulus (G ′ _120-180 ) is 1 × 10 3.
If it is larger than ⁶ [dN / m ² ], it is not preferable because sufficient low-temperature fixability of the toner cannot be obtained.

Next, in the endothermic curve of the nonmagnetic color toner in the differential thermal analysis (DSC) measurement,
The peak temperature of the maximum endothermic peak in the range of 200 ° C. is
Preferably it is in the range of 50 to 110 ° C. Further, the temperature is more preferably in the range of 55 to 100 ° C, and still more preferably 6 to 100 ° C.
The range is 0 to 90 ° C. The value of the above-mentioned endothermic peak can be adjusted by appropriately considering the type of wax and the like. Thereby, low-temperature fixability and blocking resistance,
Good results are shown from the viewpoint of preventing filming on the OPC photoreceptor surface.

If the maximum peak of the endothermic curve exceeds 110 ° C., the low-temperature fixability of the toner deteriorates,
Saturation failure occurs due to insufficient melting of the toner in the fixed image. On the other hand, when the maximum peak of the endothermic curve is lower than 50 ° C., the blocking resistance of the toner is deteriorated, and the fusion and filming to the surface of the OPC photosensitive member occur.

Next, the binder resin contained in the color toner of the present invention will be described.

The binder resin contained in the color toner of the present invention includes (a) a hybrid resin having a polyester unit and a vinyl copolymer unit, or (b)
Mixture of hybrid resin and polyester resin,
Either (c) a mixture of a hybrid resin and a vinyl copolymer, (d) a polyester resin, or (e) a mixture of a polyester resin and a vinyl copolymer can be used. A hybrid resin having a polyester unit and a vinyl copolymer unit or a mixture of a polyester resin and a vinyl copolymer is used because sufficient hot offset resistance, heat resistance, and blocking resistance can be obtained. Is preferred.

The binder resin has a peak molecular weight (MP) of 6,000 to 8,000 in a molecular weight distribution measured by gel permeation chromatography (GPC), and has a weight average molecular weight (Mw) and a number average molecular weight (Mn). (Mw / Mn) is preferably 300 or more, more preferably 500 or more.

When the peak molecular weight (MP) of the binder resin is less than 6000, the fixability at a low temperature is good, but the hot offset temperature decreases, and as a result, the non-offset temperature region becomes narrower. The problem of fusing to the photoconductor and filming occurs. On the other hand, when the peak molecular weight (MP) exceeds 8000, the hot offset temperature becomes high, and as a result, the non-offset temperature region becomes wide, but the gloss of the image becomes low and the OHP transparency is also adversely affected. . Also,
When the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin is less than 300,
There is a problem that a high-temperature offset easily occurs.

In the present invention, the measurement of the molecular weight distribution by GPC measurement was performed as follows. In addition, it measured similarly also in the Example mentioned later.

Measurement of Molecular Weight Distribution by GPC Measurement The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was passed through the column at this temperature as a solvent at a flow rate of 1 ml / min. About 50 to 200 μl of a THF sample solution of the resin adjusted to 0.6% by mass is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number (retention time). As a standard polystyrene sample for preparing a calibration curve, for example, Tosoh Corporation or Pressure Ch
electronic Co. Having a molecular weight of 6 × 10 ² , 2.1
× 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 1
^{0 4, 1.1 × 10 5,} 3.9 × 10 5, 8.6 × 10 5,
It is suitable to use 2 × 10 ⁶ and 4.48 × 10 ⁶ , and to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector. In order to accurately measure the molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, Sho column manufactured by Showa Denko KK
dex GPC KF-801,802,803,80
4,805,806,807,
rs Co., Ltd. μ-styragel 500, 10 ³ , 1
0 ⁴ and 10 ⁵ can be mentioned.

Next, the material of the binder resin will be described.
When a polyester resin is used as the binder resin, an alcohol and a carboxylic acid, a carboxylic anhydride, or a carboxylic acid ester can be used as a raw material monomer.

Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2 -Bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0)-
2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl)
Alkylene oxide adducts of bisphenol A such as propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4- Examples thereof include cyclohexane dimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, and hydrogenated bisphenol A.

Examples of the trihydric or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3
5-trihydroxymethylbenzene and the like.

Examples of the carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; Succinic acid or an anhydride thereof substituted with an alkyl group of the number 6 to 12; and unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid, or anhydrides thereof.

Among the above, particularly, a carboxylic acid composed of a divalent or higher carboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof using a bisphenol derivative represented by the following general formula (1) as a diol component: A polyester resin obtained by condensation-polymerizing a component (eg, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component is particularly preferable. The polyester resin having this composition has good charging characteristics as a color toner.

[0042]

Embedded image

Next, in the binder resin, the “hybrid resin component” means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded.
Specifically, a polyester unit and a vinyl-based polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl-based polymer. Is a backbone polymer and a graft copolymer (or block copolymer) using a polyester unit as a branch polymer.
Is formed.

The vinyl monomers for producing the vinyl resin include the following. Styrene; o-methylstyrene, m-methylstyrene, p-
Methyl styrene, α-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn- Octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitro Styrene and its derivatives such as styrene and p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride, vinyldene chloride;
Vinyl halides such as vinyl bromide and vinyl fluoride;
Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-methacrylate
Α-methylene aliphatic monocarboxylic acids such as butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate Esters: methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate,
Dodecyl acrylate, 2-ethylhexyl acrylate,
Stearyl acrylate, 2-chloroethyl acrylate,
Acrylates such as phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole;
N-vinyl compounds such as vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydrides such as those; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl half mesaconic acid; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic anhydride;
anhydrides of β-unsaturated acids and lower fatty acids; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Monomers having a hydroxy group such as (hydroxy-1-methylhexyl) styrene are exemplified.

The vinyl polymer unit of the binder resin referred to in the present invention may have a crosslinked structure which is crosslinked with a crosslinking agent having two or more vinyl groups. The following are mentioned as a crosslinking agent used in this case.

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

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

In the present invention, the vinyl copolymer component and / or the polyester resin component preferably contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer include, for example, phthalic acid, maleic acid,
Unsaturated dicarboxylic acids such as citraconic acid and itaconic acid or anhydrides thereof are exemplified. Among the monomers constituting the vinyl copolymer component, those which can react with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

As a method for obtaining a reaction product of a vinyl resin and a polyester resin, one of the above-mentioned methods is used in the presence of a polymer containing a monomer component capable of reacting with each of the above-mentioned vinyl resins and polyester resins. Alternatively, a method obtained by polymerizing both resins is preferable.

Examples of the polymerization initiator used for producing the vinyl copolymer of the present invention include, for example, 2,2′-
Azobisisobutyronitrile, 2,2′-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate,
1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4- Dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide,
Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide, 2,2-
Bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α,
α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m- Trioil peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate,
Di-2-ethoxyethyl peroxycarbonate, di-
Methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneo Decanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butyl peroxyallyl carbonate,
t-amyl peroxy 2-ethylhexanoate, di-
t-butyl peroxyhexahydroterephthalate,
Di-t-butyl peroxyazelate.

Next, a method for producing a hybrid resin used as the binder resin of the present invention will be described. The following (1)-
The hybrid resin of the present invention can be produced by the production method shown in (6) or the like.

(1) A method in which a vinyl resin, a polyester resin and a hybrid resin component are blended after each production, and the blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. You. Incidentally, the hybrid resin component, after separately producing a vinyl polymer and a polyester resin, dissolved and swelled in a small amount of an organic solvent, an esterification catalyst and an alcohol were added,
An ester compound synthesized by performing a transesterification reaction by heating can be used.

(2) After the production of the vinyl polymer unit,
This is a method for producing a polyester unit and a hybrid resin component in the presence of this. The hybrid resin component is produced by reacting a vinyl-based polymer unit (a vinyl-based monomer can be added if necessary) with a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used.

(3) This is a method of producing a vinyl polymer unit and a hybrid resin component in the presence of a polyester unit after the production. The hybrid resin component is produced by reacting a polyester unit (a polyester monomer can be added if necessary) with a vinyl monomer and / or a vinyl polymer unit.

(4) After the production of the vinyl polymer unit and the polyester unit, a hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. You. Also in this case, an organic solvent can be appropriately used.

(5) After the production of the hybrid resin component, a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) are added to carry out an addition polymerization and / or a polycondensation reaction to obtain a vinyl polymer unit and a polyester. The unit is manufactured. In this case, as the hybrid resin component, one produced by the production method of the above (2) to (4) can be used, and if necessary, one produced by a known production method can be used. Further, an organic solvent can be appropriately used.

(6) A vinyl-based polymer unit, a polyester unit and a hybrid resin component are produced by mixing a vinyl-based monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization. Is done. Further, an organic solvent can be appropriately used.

In the above production methods (1) to (5),
As the vinyl-based polymer unit and / or polyester unit, polymer units having a plurality of different molecular weights and crosslinking degrees can be used.

Next, one or more waxes of the color toner of the present invention will be described.

Examples of the wax used in the present invention include the following. Low molecular weight polyethylene,
Low molecular weight polypropylene, microcrystalline wax, aliphatic hydrocarbon wax such as paraffin wax, or aliphatic hydrocarbon wax oxide such as oxidized polyethylene wax, or a block copolymer thereof; carnauba wax, sasol wax, Examples include waxes mainly containing a fatty acid ester such as montanic acid ester wax, and those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax.

Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brandic acid, eleostearic acid and barinaric acid;
Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melisyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide;
Unsaturated fatty acid amides such as hexamethylene bisoleic acid amide, N, N 'dioleyl adipamide, N, N' dioleyl sebacic acid amide; m-xylene bis stearic acid amide, N, N 'distearyl isophthalic acid Aromatic bisamides such as amides; calcium stearate, calcium laurate, zinc stearate,
Aliphatic metal salts such as magnesium stearate (commonly referred to as metallic soaps); waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; behenic acid monoglyceride And a partially esterified product of a fatty acid and a polyhydric alcohol; and a methyl ester compound having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.

As the wax particularly preferably used in the present invention, an aliphatic hydrocarbon wax is exemplified. For example, a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or a Ziegler catalyst under low pressure; an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer; Preferred is a synthetic hydrocarbon wax obtained from a hydrocarbon distillation residue obtained by the method or by hydrogenating them.

Further, those obtained by separating a hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation or a fractional crystallization method are more preferably used.

The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often a multi-component system of two or more types) [for example, the Zintol method, the hydrochol method (fluidization) Hydrocarbon compounds synthesized by the use of a catalyst bed); hydrocarbons having a carbon number of up to about several hundred obtained by the Aggé method (using an identified catalyst bed) in which a large amount of waxy hydrocarbons can be obtained; Hydrocarbons polymerized by the Ziegler catalyst are preferred because they are straight chains with little branching, small branching and long saturation. Particularly, a wax synthesized by a method not based on the polymerization of alkylene is preferable in view of its molecular weight distribution.

In the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight of 400 to 2400, more preferably in the region of 4300 to 2000. With such a molecular weight distribution, the toner can be given favorable thermal characteristics.

In order to function more effectively at the time of fixing the toner, the melting point of the wax is preferably from 60 to 100 ° C., and more preferably from 65 to 90 ° C. The wax is 0.1 per 100 parts by mass of the binder resin.
-20 parts by mass, preferably 0.5-10 parts by mass.

The wax is usually contained in the binder resin by dissolving the resin in a solvent, increasing the temperature of the resin solution, and adding and mixing while stirring, or by mixing at the time of kneading.

Next, the colorant of the color toner of the present invention will be described. As the colorant used in the present invention, a pigment and / or a dye can be used.

For example, dyes include C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I.
Modant Red 30, C.I. I. Direct Blue 1,
C. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I.
I. Basic Green 4, C.I. I. Basic Green 6 and the like.

Examples of pigments include mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G, permanent red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3
B, manganese purple, fast violet B, methyl violet lake, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue,
First Sky Blue, Indanthrene Blue BC,
Chrome Green, Pigment Green B, Malachite Green Lake, Final Yellow Green G, and the like.

Examples of the magenta coloring pigment include C.I.
I. Pigment Red 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
17, 18, 19, 21, 22, 23, 30, 31, 3
2,37,38,39,40,41,48,49,5
0, 51, 52, 53, 54, 55, 57, 58, 6
0, 63, 64, 68, 81, 83, 87, 88, 8
9, 90, 112, 114, 122, 123, 163,
202, 206, 207, 209, 238, C.I. I. Pigment Violet 19, C.I. I. Bat Red 1,
2, 10, 13, 15, 23, 29, 35 and the like.

The above-mentioned pigments may be used alone, but it is more preferable to use the dyes and the pigments together to improve the sharpness from the viewpoint of the image quality of a full-color image. Various dyes and pigments that can be used are further exemplified.

The dyes for magenta include C.I. I. Solvent Red 1,3,8,23,24,25,27,3
0, 49, 81, 82, 83, 84, 100, 109,
121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I.
I. Oil-soluble dyes such as Disperse Violet 1;
I. Basic Red 1,2,9,12,13,14,
15, 17, 18, 22, 23, 24, 27, 29, 3
2, 34, 35, 36, 37, 38, 39, 40, C.I.
I. Basic violet 1,3,7,10,14,
And basic dyes such as 15, 21, 25, 26, 27, and 28.

Examples of the coloring pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 16, 17; I. Acid Blue 6; C.I. I. Acid Blue 45 or a copper phthalocyanine pigment having a phthalocyanine skeleton substituted with 1 to 5 phthalimidomethyl groups.

The yellow color pigments include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5,73,83,93,97,180, C.I. I. Bat Yellow 1, 3, 20 and the like.

The colorant is used in an amount of 1 to 15 parts by weight, preferably 3 to 12 parts by weight, more preferably 4 to 10 parts by weight, based on 100 parts by weight of the binder resin. When the content of the coloring agent is more than 15 parts by mass,
Transparency decreases, and in addition, the reproducibility of intermediate colors represented by human skin color also tends to decrease, and furthermore, the stability of toner chargeability decreases, and it becomes difficult to obtain a desired charge amount. . On the other hand, when the content of the coloring agent is less than 1 part by mass, it is difficult to obtain a desired coloring power, and it is difficult to obtain a high-quality image having a high image density.

Incidentally, the color toner of the present invention may further contain an organometallic compound. The inclusion of the organometallic compound is a more preferable embodiment in that the charge level can be adjusted, the rise of charge can be improved, and the heat melting property of the toner can be improved.

The organic metal compound used is preferably an aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, and a metal compound of the aromatic carboxylic acid derivative. Is preferably a divalent or higher valent metal atom.

As a divalent metal, Mg²⁺, Ca²⁺, S
r²⁺, Pb²⁺, Fe²⁺, Co²⁺, Ni²⁺, Zn²⁺, Cu
²⁺, Are mentioned. As the divalent metal, Zn²⁺, Ca
²⁺, Mg ²⁺, Sr²⁺Is preferred. Trivalent or higher metal
Is Al³⁺, Cr³⁺, Fe³⁺, Ni ³⁺, Is raised. This
Of these trivalent or higher metals, preferred is Al³⁺, Cr
³⁺And particularly preferred is Al³⁺It is.

In the present invention, as the organometallic compound, an aluminum compound of di-tert-butylsalicylic acid is particularly preferred.

An aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, and a metal compound of the aromatic carboxylic acid derivative include, for example, oxycarboxylic acid and alkoxycarboxylic acid in an aqueous sodium hydroxide solution. An aqueous solution in which a metal atom having a valence of 2 or more is melted is dropped into an aqueous sodium hydroxide solution, and the mixture is heated and stirred. Then, the pH of the aqueous solution is adjusted, cooled to room temperature, and then filtered to wash with an aromatic solution. Metal compounds of oxycarboxylic acids and aromatic alkoxycarboxylic acids can be synthesized. However, the present invention is not limited to the above synthesis method.

The organometallic compound is preferably contained in an amount of 0.1 to 10% by mass based on the mass of the color toner.
With this content, the initial variation of the charge amount of the toner is small, and the absolute charge amount required at the time of development is easily obtained. As a result, deterioration in image quality such as "fog" and reduction in image density can be suppressed.

<About the magnetic toner for black of the present invention> The magnetic toner for black used in the present invention will be described.

The magnetic toner contains a magnetic substance. In that case,
The magnetic material also has a function as a colorant. Examples of the magnetic material include iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; Fe, Co, N
i, or these metals and Al, C
o, Cu, Pb, Mg, Ni, Sn, Zn, Sb, B
alloys with metals such as e, Bi, Cd, Ca, Mn, Se, Ti, W and V, and mixtures thereof.

For example, as a magnetic material, triiron tetroxide
(Fe_ThreeO_Four), Iron sesquioxide (γ-Fe _TwoO_Three), Iron oxide
Lead (ZnFe_TwoO_Four), Yttrium iron oxide (Y_ThreeFe_FiveO
₁₂), Cadmium iron oxide (CdFe_TwoO_Four), Iron oxide gado
Linium (Gd_ThreeFe_Five-O₁₂), Iron oxide copper (CuFe_Two
O_Four), Lead iron oxide (PbFe₁₂-O₁₉), Iron oxide nickel
(NiFe_TwoO_Four), Iron neodymium oxide (NdFe
_TwoO_Three), Barium iron oxide (BaFe)₁₂O₁₉), Iron oxide
Gnesium (MgFe_TwoO_Four), Iron manganese oxide (MnF)
e _TwoO_Four), Iron oxide lanthanum (LaFeO)_Three), Iron powder (F
e), cobalt powder (Co), nickel powder (Ni), etc.
I can do it. Preferred magnetic materials are ferric oxide, magnetic ferrite
Or fine powder of γ-iron sesquioxide. Magnetic material content
Is 15 to 85% by mass based on the weight of the toner.
preferable.

In the magnetic toner for black, it is more difficult to stabilize the charging because the resistance value tends to be lower than that of the other color toners. In the present invention, intensive studies have been made to improve this point.

As a result, it is preferable that the magnetic toner for black contains magnetic iron oxide. In particular, the developability is improved by the influence of a small amount of Si or Al element on the surface of the magnetic material, and the magnetic toner for other color toners is improved. It has been found that the mixing properties are improved.

Specifically, the magnetic iron oxide is prepared by adding an aluminum element or a silicon element in an amount of 0.3 to
It has been found that the content of 1.4% by weight is effective. This makes it possible to reduce the difference in charge stability with respect to other color toners and, in turn, the developability, and to obtain an image that is faithful to a document and has no variation.

The magnetic iron oxide has a content BSi of silicon element present when the dissolution rate of iron element of the magnetic iron oxide is up to 20% by weight and a content ASi of total silicon element present in the magnetic iron oxide. (BSi / ASi) x 100 is 35 to 85%
Is more preferable, and 40 to 80% is further preferable.

If (BSi / ASi) × 100 is less than 35%, the dispersion of the magnetic material in the toner is deteriorated, and the toner may be unstable in developability, particularly in image uniformity. In addition, the resolution of the character image tends to be inferior. When (BSi / ASi) × 100 is more than 85%, a large amount of silicon element is present in the surface layer of the magnetic iron oxide, and the distribution of the charge amount of the toner tends to be widened. Is easy to occur.

In the present invention, the magnetic iron oxide preferably has a number average particle size based on the measurement method described below.
0.05 to 1.00 μm, more preferably 0.10 to
A thickness of 0.40 μm is good in terms of the dispersibility of the magnetic toner in the binder resin and the uniformity of charging.

The number average particle size of the magnetic iron oxide is 1.00 μm
If it is larger than the above, the number of magnetic iron oxide particles contained in the toner is reduced, so that the dispersion of the magnetic iron oxide in the binder resin is likely to be biased and the uniformity of charging is impaired. When the number average particle diameter of the magnetic iron oxide is smaller than 0.05 μm, the adhesive force between the magnetic iron oxide particles is increased, and the dispersibility in the binder resin is deteriorated.

By using a magnetic material satisfying the above conditions, the mixing property of the black toner with other color toners is improved, and more uniform color reproduction can be performed. Further, there is no adverse effect on the fixing property.

In the present invention, the measurement method for the magnetic material used for the black toner was performed as follows. In addition, it measured similarly also in the Example mentioned later.

In the present invention, in the present invention, the content (based on iron) of metal elements other than iron in the magnetic iron oxide, the dissolution rate of iron element, and The content can be determined by the following method.

For example, about 3 liters of deionized water is placed in a 5 liter beaker and heated to 45 to 50 ° C. in a water bath. About 25 g of magnetic iron oxide slurried with about 400 ml of deionized water is added to the 5 liter beaker with the deionized water while washing with about 300 ml of deionized water.

Next, while maintaining the temperature at about 50 ° C. and the stirring speed at about 200 rpm, a special grade hydrochloric acid or a mixed acid of hydrochloric acid and hydrofluoric acid is added to start dissolution. At this time, the hydrochloric acid aqueous solution is about 3N. Approximately 20m several times from the start of dissolution until it is completely dissolved and transparent
Sample 1 and filter through a 0.1 μm membrane filter to collect the filtrate. Filter the filtrate to plasma emission spectroscopy (IC
By P), the iron element and the metal element other than the iron element are quantified. The iron element dissolution rate for each sample is calculated by the following equation.

[0100]

(Equation 1)

The content of metal elements other than iron for each sample is calculated by the following equation.

[0102]

(Equation 2)

The total content A of the metal elements other than the iron element in the magnetic iron oxide is defined as the metal element concentration (mg / l) per unit weight of the magnetic iron oxide after being completely dissolved. Also,
The content B of the metal element other than the iron element in the magnetic iron oxide is determined by the concentration of the metal element other than the iron element per unit weight of the detected magnetic iron oxide (mg) when the solubility of the magnetic iron oxide is 20%.
/ L).

Measurement of Number Average Particle Diameter of Magnetic Iron Oxide From a transmission electron micrograph (magnification: 30,000 times), 100 particles were randomly selected on the photograph, the particle diameter was measured, and the average value was used as the number average particle diameter. Diameter.

<Regarding Black Magnetic Toner and Color Non-Magnetic Toner> A fluidity improver may be added to the black magnetic toner and the color non-magnetic toner. here,
Fluidity improver is an external addition to toner particles,
It has a function of increasing fluidity, and is added from the viewpoint of improving image quality.

For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder;
Silica fine powder such as silica fine powder by a wet method, silica fine powder by a dry method, and silica fine powder obtained by subjecting the silica fine powder to a surface treatment with a treating agent such as a silane coupling agent, a titanium coupling agent, and silicon oil. Fine powder of titanium oxide; fine powder of alumina, fine powder of treated titanium oxide, and fine powder of treated alumina oxide are used.

The flow improver having a specific surface area of 30 m ² / g or more, preferably 50 m ² / g or more by nitrogen adsorption measured by a BET method gives a good result. It is preferable to use 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass of the fluidity improver based on 100 parts by mass of the toner particles.

The measurement by the above-mentioned BET method was performed as follows. The BET specific surface area is determined by a BET multipoint method using a fully automatic gas adsorption amount measuring apparatus: Autosorb 1, manufactured by Yuasa Ionics Co., Ltd., and using nitrogen gas as the adsorption gas. As a pretreatment of the sample, degassing is performed at a temperature of 50 ° C. for 10 hours.

The toner particles (including both magnetic and non-magnetic particles) of the present invention can be obtained by the method described below. That is, necessary components are selected from binder resins, coloring agents, waxes, organometallic compounds, magnetic substances and other optional additives, and the components are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. The mixture is melted, kneaded and kneaded using a hot kneader such as a kneader or an extruder. Can be obtained. When a toner having a fluidity improver on the surface of toner particles is obtained, the fluidity improver and the toner particles may be further mixed with a mixer such as a Henschel mixer.

<Magnetic Carrier for Performing Color Development of the Present Invention> Carriers used in the two-component developer of the present invention include, for example, iron, nickel, copper, zinc, cobalt, manganese, surface oxidized or unoxidized. Metals such as chromium and rare earth and their alloys or oxides and ferrites can be used.

Particularly, magnetic ferrite particles of three elements of Mn-Mg-Fe formed mainly of manganese, magnesium and iron components are preferable as carrier particles, and magnetic ferrite particles of three elements of Mn-Mg-Fe are further preferred. It is particularly preferred that the element contains 0.001 to 1% by mass (more preferably 0.005 to 0.5% by mass) of a silicon element when a silicone resin is used as a coating resin for the magnetic ferrite particles.

The magnetic carrier particles are preferably coated with a resin, and the resin is preferably a silicone resin. In particular, a nitrogen-containing silicone resin or a modified silicone resin formed by the reaction of a nitrogen-containing silane coupling agent with a silicone resin is capable of imparting a negative triboelectric charge to the color toner of the present invention, environmental stability, and carrier. This is preferable in terms of suppressing contamination of the surface. The magnetic carrier preferably has an average particle size of 15 to 70 μm (more preferably 25 to 60 μm) in relation to the weight average particle size of the color toner.

[0113]

EXAMPLES The present invention will be described more specifically with reference to the following examples.

The production examples of the toner of the present invention will be described, but the invention is not limited to these toner production examples.

(Hybrid resin production example 1) As a vinyl copolymer, 1.8 mol of styrene, 0.21 mol of 2-ethylhexyl acrylate, 0.15 m of fumaric acid
ol, 0.03 mol of a dimer of α-methylstyrene, and 0.05 mol of dicumyl peroxide are placed in a dropping funnel. In addition, polyoxypropylene (2.2) -2,2
-Bis (4-hydroxyphenyl) propane 6.9 mo
l, polyoxyethylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane (3.0 mol), succinic acid (3.0 mol), trimellitic anhydride (2.0 mol), fumaric acid (4.9 mol) and dibutyltin oxide (0.2 g) were placed in a 4 liter glass four-necked flask and placed in a thermometer. , A stirring rod, a condenser, and a nitrogen inlet tube were attached and placed in a heating mantle. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and while stirring at a temperature of 145 ° C., a vinyl resin monomer was
The crosslinking agent and the polymerization initiator were added dropwise over 4 hours. Next, the temperature was raised to 200 ° C., and the mixture was reacted for 4 hours to obtain a hybrid resin (1). In this production example, the viscoelastic properties of the present invention were obtained by optimizing the production conditions for a hybrid resin of a polyester resin and a styrene-acrylic resin. Table 1 shows the results of the molecular weight measurement by GPC.

[0116]

[Table 1]

(Hybrid resin production example 2) Styrene 3.9 mol, α-methylstyrene dimer 0.07 m
ol, except that 0.1 mol of dicumyl peroxide was used, the reaction was carried out in the same manner as in Production Example 1 of Hybrid Resin to obtain Hybrid Resin (2). Table 1 shows the results of the molecular weight measurement by GPC.

(Production Example 3 of Hybrid Resin) 3.9 mol of maleic acid and 3.6 mol of itaconic acid were used instead of 4.9 mol of fumaric acid, and 0.1 mol of isobutyl peroxide was used instead of 0.05 mol of dicumyl peroxide. The reaction was carried out in the same manner as in Production example 1 of Hybrid resin except that was used, to obtain Hybrid resin (3). Table 1 shows the results of the molecular weight measurement by GPC.

(Production Example 4 of Hybrid Resin) Instead of 3.0 mol of terephthalic acid and 2.0 mol of trimellitic anhydride, 5.2 mol of trimellitic anhydride was used, and the reaction was carried out in the same manner as in Production Example 1 of the hybrid resin. 4) was obtained. Table 1 shows the results of molecular weight measurement by GPC.
Shown in

(Production Example 1 of Polyester Resin) 3.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis ( 4-hydroxyphenyl)
1.6 mol of propane, 1.7 mol of terephthalic acid, 1.1 mol of trimellitic anhydride, 2.4 mol of fumaric acid
0.1 g of dibutyltin oxide and 4 liters of glass
The flask was placed in a one-necked flask, fitted with a thermometer, a stirring rod, a condenser and a nitrogen inlet tube, and placed in a heating mantle.
The mixture was reacted at 215 ° C. for 5 hours under a nitrogen atmosphere to obtain a polyester resin (1). The results of molecular weight measurement by GPC are shown in Table 1.

(Production Example 2 of Polyester Resin) 1.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis ( 4-hydroxyphenyl)
3.3 mol of propane, 1.6 mol of terephthalic acid, 0.3 mol of trimellitic anhydride, 3.2 mol of fumaric acid
Was reacted in the same manner as described above to obtain a polyester resin (2). Table 1 shows the results of the molecular weight measurement by GPC.

(Production Example 1 of Vinyl Resin) Toluene Solvent
1000 ml and 2.3 mol of styrene as a vinyl copolymer
l, n-butyl acrylate 0.25 mol, monobutyl malate 0.07 mol, di-t-butyl peroxide 0.1
1 mol was placed in a 3 liter 4-neck flask equipped with a thermometer, a stainless steel stirring rod, a falling condenser, and a nitrogen inlet tube, and heated in a mantle heater under a nitrogen atmosphere.
The reaction was carried out while refluxing toluene while stirring at a temperature of ° C to obtain a vinyl resin (1). Table 1 shows the results of the molecular weight measurement by GPC.

Next, Table 2 shows the wax used in the present invention.

[0124]

[Table 2]

<Production Example 1 of Color Toner> A cyan toner 1 was prepared as an example of a non-magnetic color toner by the following method. Hybrid resin (1) 100 parts by mass Wax (A) 5 parts by mass C.I. I. Pigment Blue 15:35 5 parts by mass Di-tert-butylsalicylate aluminum complex 6 parts by mass was sufficiently premixed with a Henschel mixer,
The mixture was melt-kneaded by a twin-screw extruder, cooled, and coarsely ground to a particle size of about 1 to 2 mm using a hammer mill. Next, it was pulverized by a pulverizer using an air jet method. Further, the obtained finely pulverized product was classified by a multi-segment classifier to obtain cyan toner particles having a weight average particle size of 7.6 μm.

[0126] with respect to the cyan-based toner particles 100 parts by _{mass, i-C 4 H 9 Si} (OCH 3) 3: Measurement results for treated hydrophobic aluminum oxide (BET method at 25 parts by mass 1
70 m ^{2 /} g), and 1.1 parts by mass were combined to obtain Cyan Toner 1. Table 1 shows the measurement results of the storage elastic modulus and the endothermic peak of the color toner.

<Production Example 2 of Color Toner> A cyan toner 2 was obtained in the same manner as in Production Example 1 of color toner except that the hybrid resin (2) was used instead of the hybrid resin (1). Table 1 shows the measurement results of the color toner.

<Production Example 3 of Color Toner> A mixture of 50 parts by mass of the polyester resin (1) and 50 parts by mass of the hybrid resin (1) was used in place of the hybrid resin (1). Cyan Toner 3 was obtained in the same manner as in Color Toner Production Example 1, except that 8 parts by mass of the aluminum butylsalicylate complex was used. Table 1 shows the measurement results of the color toner.

<Color toner production example 4> Color toner production example 1 except that hybrid resin (3) was used in place of hybrid resin (1) and that 9.5 parts by mass of aluminum di-tert-butylsalicylate was used.
In the same manner as in the above, cyan toner 4 was obtained. Table 1 shows the measurement results of the color toner.

<Production Example 5 of Color Toner> Wax (A)
A cyan toner 5 was obtained in the same manner as in the color toner production example 1 except that the wax (B) was used in place of the above. Table 1 shows the measurement results of the color toner.

<Color toner production example 6> Di-tert-
A cyan toner was obtained in the same manner as in Production Example 1 of the color toner except that 2 parts by mass of the aluminum butylsalicylate complex was used. Table 1 shows the measurement results of the color toner.

<Color toner production example 7> Di-tert-
Cyan Toner 7 was obtained in the same manner as in Color Toner Production Example 1, except that 3 parts by mass of the aluminum butylsalicylate complex was used, and that wax (D) was used instead of wax (A). Table 1 shows the measurement results of the color toner.

<Color toner production example 8> Di-tert-
Except that the aluminum butylsalicylate complex was not used, a cyan toner 8 was prepared in the same manner as in the color toner production example 1.
I got Table 1 shows the measurement results of the color toner.

<Production Example 9 of Color Toner> I. Pigment Blue 15: 3 and C.I. I. Magenta Toner 1 was obtained in the same manner as in Color Toner Production Example 1, except that 6 parts by mass of CI Pigment Red 202 was used. Table 1 shows the measurement results of the color toner.

<Color toner production example 10> I. Pigment Blue 15: 3 and C.I. I. Pigment Yellow 17 was used in the same manner as in Color Toner Production Example 1, except that 4 parts by mass of CI Pigment Yellow 17 was used and that the polyester resin (1) was used instead of the hybrid resin (1). Table 1 shows the measurement results of the color toner.

<Production Example 11 of Color Toner> Di-tert-
A cyan toner 9 was obtained in the same manner as in Color Toner Production Example 1, except that 6 parts by mass of the zinc butylsalicylate complex was used. Table 1 shows the measurement results of the color toner.

<Comparative Toner Production Example 1> Color toner production was performed except that hybrid resin (4) was used in place of hybrid resin (1), and that 7.5 parts by mass of aluminum di-tert-butylsalicylate was used. A cyan toner 10 was obtained in the same manner as in Example 1. Table 1 shows the measurement results of the color toner.

<Comparative Toner Production Example 2> Color toner production example 1 except that the polyester resin (2) was used instead of the hybrid resin (1), and that 4 parts by mass of the aluminum di-tert-butylsalicylate complex was used. In the same manner as in the above, cyan toner 11 was obtained. Table 1 shows the measurement results of the color toner.

<Comparative Toner Production Example 3> The vinyl resin (1) was used in place of the hybrid resin (1), and aluminum di-tert-butylsalicylate was used.
A cyan toner 12 was obtained in the same manner as in Color Toner Production Example 1 except that 5 parts by mass was used. Table 1 shows the measurement results of the color toner.

<Comparative Toner Production Example 4> Color toner production example 1 except that the polyester resin (1) was used in place of the hybrid resin (1), and that 12 parts by mass of an aluminum di-tert-butylsalicylate complex was used.
In the same manner as in the above, cyan toner 13 was obtained. Table 1 shows the measurement results of the color toner.

Comparative Toner Production Example 5> A cyan toner 14 was obtained in the same manner as in the color toner production example 1 except that the wax (E) was used instead of the wax (A). Table 1 shows the measurement results of the color toner.

<Comparative Toner Production Example 6> In the color toner production example 1, the purified normal paraffin wax (A)
A cyan toner 15 was obtained in the same manner except that paraffin wax (C) having a low melting point was used in place of the above.
Table 1 shows the measurement results of the color toner.

<Black Toner Production Example 1> A black toner 1 was prepared as an example of a magnetic black toner by the following method. Hybrid resin (1) 100 parts by mass Wax (A) 7 parts by mass Magnetic iron oxide 190 parts by mass Di-tert-butylsalicylate aluminum complex 9 parts by mass was sufficiently premixed with a Henschel mixer.
The mixture was melt-kneaded by a twin-screw extruder, cooled, and coarsely ground to a particle size of about 1 to 2 mm using a hammer mill. Next, it was pulverized by a pulverizer using an air jet method. Further, the obtained finely pulverized product was classified by a multi-segment classifier to obtain a black toner 1 having a weight average particle size of 8.2 μm. The properties of the magnetic iron oxide used are as shown in Table 3.

[0144]

[Table 3]

<Production Example 2 of Black Toner>
A black toner 2 having a weight average particle size of 8.3 μm was obtained in the same manner as in Black toner production example 1 except that 5 parts by mass was used. Table 3 shows the measurement results of the black toner 2.

<Production Example 3 of Black Toner>
Black toner 3 having a weight average particle size of 8.4 μm was obtained in the same manner as in Black toner production example 1 except that 5 parts by mass was used. Table 3 shows the measurement results of the black toner 3.

[0147]

Example 1 Cyan toner 1 obtained in color toner production example 1 was mixed with magnetic ferrite carrier particles (average particle size: 50 μm) surface-coated with a silicone resin so that the toner concentration became 6% by mass. , Two-component cyan developer 1
And

As an evaluation machine, a color developing device was used as a non-magnetic
A color copier CP-660 (manufactured by Canon) which was modified from a one-component toner to a non-magnetic two-component developer was used.

The cyan developer 1 was loaded into the color station of this evaluation machine, and was operated in a high temperature and high humidity environment (30
° C., 80%), normal temperature and low humidity environment (23 ℃, 5%) with an original document image area ratio of 20%, the toner amount per unit area was set to 0.7 mg / cm ^2, 1 million copies A printing durability test was carried out by outputting an unfixed image.

For the evaluation of the fixable area of the output unfixed image, the fixing unit (fixing oilless) of the color copying machine CP-660 (manufactured by Canon) was modified so that the fixing temperature could be set manually. evaluated.

The OHP transparency was measured using a Shimadzu self-recording spectrophotometer UV2200 (manufactured by Shimadzu Corporation) with the transmittance of the OHP film alone as 100%. The magenta toner: 650 nm, and the cyan toner: 500 nm. ,
For yellow toner: Measure the transmittance at the maximum absorption wavelength at 600 nm. As an evaluation method, A: 85% or more, B: 75 to 85%, C: 65 to 75%, D: 65%
Display less than.

The transferability was measured by using a modified color copying machine CP-660 (manufactured by Canon) under normal temperature and low humidity environment (23 ° C.,
5%), a solid image before and after the endurance is developed and transferred, and the amount of toner on the photoreceptor before transfer (per unit area) and the amount of toner on the transfer material (per unit area) Per) was measured and determined by the following equation.

[0153]

(Equation 3)

The blocking resistance of the color toner was evaluated by leaving it in an oven at 50 ° C. for 2 weeks. As the evaluation, the level of cohesiveness was visually determined.

The evaluation criteria for the color toner cohesion are shown below. A: No aggregates are seen at all, and the fluidity is very good. B: Aggregates are not seen at all. C: Some aggregates are seen but loosened immediately. D: Aggregates are loosened with a developer stirring device (normal). E: Aggregates are not sufficiently loosened by the developer stirring device (slightly bad). Cyan developer 1 has excellent transferability and glossiness.
OHT transparency was good, and excellent fixing property and blocking resistance were exhibited. The environmental stability was also good. Table 4 shows the results. In Table 4, the image density (Macbeth) under each environment shows the value at the initial stage / after the endurance.

[0156]

[Table 4]

[0157]

Example 2 Using cyan toner 2, a cyan developer 2 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the cyan developer 2 was excellent in transferability, good in glossiness and OHT transparency, and exhibited excellent fixability, blocking resistance, and environmental stability. Table 4 shows the results.

[0158]

Example 3 A cyan developer 3 was prepared in the same manner as in Example 1 using the cyan toner 3, and each item was evaluated. As a result, the obtained image has excellent transferability, glossiness,
Both OHT permeability was good and excellent fixing property, blocking resistance and environmental stability were exhibited. Table 4 shows the results.

[0159]

Example 4 A cyan developer 4 was prepared in the same manner as in Example 1 using the cyan toner 4, and each item was evaluated. As a result, the resulting image has a slightly lower transferability in a low humidity environment,
Although slightly lacking in glossiness and slightly lower in OHT permeability, it exhibited excellent fixability and blocking resistance. Table 4 shows the results.

[0160]

Example 5 Using a cyan toner 5, a cyan developer 5 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the obtained image has excellent transferability, glossiness,
Both OHT permeability was good and excellent fixing property, blocking resistance and environmental stability were exhibited. Table 4 shows the results.

[0161]

Example 6 A cyan developer 6 was prepared in the same manner as in Example 1 using the cyan toner 6, and each item was evaluated. As a result, the obtained image has excellent transferability, glossiness,
Both OHT permeability was good and excellent fixability and environmental stability were exhibited. The blocking resistance was slightly deteriorated but not at a level that would cause a problem in practical use. Table 4 shows the results.

[0162]

Example 7 Using a cyan toner 7, a cyan developer 7 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the resulting image was slightly affected by the high crystallinity of the wax, and thus the OHP permeability was slightly poor, and the high melting point made it difficult for the wax to appear on the toner surface at the time of fixing, thus slightly deteriorating the low-temperature fixability. However, relatively good results were obtained. The transferability of the obtained image was good, and the blocking resistance and environmental stability were also good. Table 4 shows the results.

[0163]

Example 8 Using a cyan toner 8, a cyan developer 8 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, there was no particular problem except that the charge amount of the toner was slightly reduced and the high temperature side of the fixing temperature range was slightly narrowed because the di-tert-butylsalicylate aluminum complex was not contained. . Table 4 shows the results.

[0164]

Example 9 Magenta developer 1 was prepared in the same manner as in Example 1 using magenta toner 1, and each item was evaluated. As a result, it was possible to obtain a high-definition full-color image with good gloss and OHT transparency. Table 4 shows the results.

[0165]

Example 10 Using the yellow toner 1, a yellow developer 1 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, it was possible to obtain a high-definition full-color image with good gloss and OHT transparency. Because the polyester resin was used alone, compared to cyan toner 1, slightly
Although the temperature range in which fixing was possible changed, the fixing temperature range was at a level at which there was no practical problem. Table 4 shows the results.

[0166]

Example 11 Using a cyan toner 9, a cyan developer 9 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the obtained image showed relatively good results although the image density and the transfer rate were slightly lowered after the durability and the blocking resistance was slightly deteriorated. Table 4 shows the results.

[0167]

Example 12 A black toner, a cyan toner 1, a yellow toner 1, and a magenta toner 1 were used in combination. The color toner was prepared in the same manner as in Example 1, and the black toner was prepared as a one-component developer. , Each item was evaluated. as a result,
The obtained image had excellent color reproducibility, a clear character image, high resolution, and good results. Table 4 shows the results. The color image quality reproducibility was determined using a photograph original and a black character original. ：: Almost all colors and characters were faithfully reproduced. ：: The blackish portion of the photographic image portion was slightly unclear. The blackish part of the image part was slightly unclear, and the resolution of the character image was slightly inferior.
Indicates that The image density, transfer rate, and blocking resistance show the results of the black toner alone.

[0168]

Embodiment 13 A combination of a black toner 2, a cyan toner 1, a yellow toner 1, and a magenta toner 1 was used.
Each developer was prepared in the same manner as in Example 2, and each item was evaluated.
As a result, the obtained image was slightly inferior in color reproducibility of the dark color portion, but the character image was clear and high resolution was obtained, and good results were shown. Table 4 shows the results. still,
The image density, transfer rate, and blocking resistance show the results of the black toner alone.

[0169]

Embodiment 14 Embodiment 1 uses a combination of black toner 3, cyan toner 1, yellow toner 1, and magenta toner 1.
Each developer was prepared in the same manner as in Example 2, and each item was evaluated.
As a result, the obtained image showed good results although the color reproducibility of the dark color portion and the resolution of the character image were slightly inferior. Table 4 shows the results. The image density, transfer rate, and blocking resistance show the results of the black toner alone.

[0170]

Comparative Example 1 Using a cyan toner 10, a cyan developer 10 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the cyan toner 10 becomes very hard toner, the larger storage elastic modulus (G _'80) is, poor permeability of gloss and OHT, also it makes the wax is hard to come to toner particle surfaces at the time of fixing, low-temperature fixing Made sex worse. Further, in a high-temperature and high-humidity environment, a small amount of fusion to a drum occurs, and in a low-humidity environment, the charge amount is significantly increased, so that a sufficient image density cannot be obtained. Table 4 shows the results.

[0171]

Comparative Example 2 Using the cyan toner 11, a cyan developer 11 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the cyan toner 11 became a very soft toner, the blocking resistance was deteriorated, and the high-temperature offset resistance was deteriorated. In a high-temperature, high-humidity environment, remarkable drum fusion and filming occurred. Further, since the content of the organometallic compound is large, the charge amount is significantly increased in a low humidity environment, and a sufficient image density cannot be obtained. Table 4 shows the results.

[0172]

Comparative Example 3 Using the cyan toner 12, a cyan developer 12 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the cyan toner 12 has poor glossiness and OHT permeability,
The fixing temperature range also became narrow. In a high-temperature, high-humidity environment, some fusion to the drum occurred. Table 4 shows the results.

[0173]

Comparative Example 4 Using the cyan toner 13, a cyan developer 13 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the cyan toner 13 had poor glossiness and OHT permeability. In a high-temperature, high-humidity environment, some fusion to the drum occurred. Table 4 shows the results.

[0174]

Comparative Example 5 Using the cyan toner 14, a cyan developer 14 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, because of the high melting point, the wax hardly appeared on the toner surface at the time of fixing, the low-temperature fixability was deteriorated, and the OHT permeability was deteriorated. Table 4 shows the charging results of the toner.

[0175]

Comparative Example 6 A cyan developer 15 was prepared in the same manner as in Example 1 using the cyan toner 15, and each item was evaluated. As a result, fogging and scattering became worse around 1000 sheets of durability, and the durability was interrupted. Further, the fluidity of the toner was poor, and the transferability was poor from the beginning. Cyan toner 15.
Because it contains a low melting point wax, the fixability is insufficient, and the wax emerges on the toner surface, especially in a high temperature environment, and deteriorates the chargeability, heat resistance, and blocking resistance. Conceivable. In a high-temperature, high-humidity environment, remarkable drum fusion and filming occurred. Table 4 shows the results.

[0176]

According to the present invention, an OPC (organic photoconductor) is provided.
When a photoreceptor is mounted on a full-color machine, it is possible to provide a color toner which is excellent in durability stability and can form an image satisfying high definition, an image forming method and an image forming apparatus having the color toner. Specifically, the toner does not fuse to the photoreceptor surface, filming can be reduced,
Provided is a color toner which enhances transparency in OHP, eliminates the problem of high-temperature offset without hindering low-temperature fixing at the time of fixing, and has excellent color mixing degree, and an image forming method and an image forming apparatus having the color toner. Can be.

[Brief description of the drawings]

FIG. 1 is a diagram showing an embodiment of an image forming apparatus according to the present invention.

FIG. 2 is a schematic diagram of a developing unit. FIG. 3A illustrates an example of a developing unit using a one-component developer. FIG. 3B is a diagram illustrating an example of a developing unit using a two-component developer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 9/08 365 G03G 9/08 331 346 (72) Inventor Iku Iku Ikuta 3-30 Shimomaruko, Ota-ku, Tokyo Inside No.2 Canon Inc. (72) Takaaki Kayaki, Inventor 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Yoyoshi Sugawara 3-30-2 Shimomaruko, Ota-ku, Tokyo Kyano (72) Inventor Yojiro Hotta 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Takaaki Uetaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F term (reference) 2H005 AA01 AA02 AA06 AA21 CA02 CA08 CA14 CA25 CB03 DA01 EA03 EA06 FA02

Claims (37)

[Claims] 1. An image carrier using an organic photoconductor,
An electrostatic latent image forming step of forming an electrostatic latent image, and a developing step of transferring toner to the electrostatic latent image formed on the image carrier to form a toner image corresponding to the latent image and visualizing the toner image And a fixing step of electrostatically transferring the toner image formed on the image carrier to a transfer material; and a fixing step of fixing the electrostatically transferred toner image by a fixing member. The development for forming a color image can be performed by using a one-component developer composed of a magnetic toner for development and a two-component developer composed of a magnetic carrier and a non-magnetic toner for color development. An image forming method, wherein the non-magnetic color toner has at least a binder resin, a colorant, and a wax, and has a storage elastic modulus (G ′ ₈₀ ) at a temperature of 80 ° C. of 1 × 10 in viscoelastic properties. ⁶ to 1 × 10 ¹⁰ [ dN / m ² ] and the storage elastic modulus (G ′ _120-180 ) at a temperature of _{120 to 180} ° C. is 5 × 10 ³ to 1 × 10 ⁶ [dN / m ² ].
In the endothermic curve in the differential thermal analysis (DSC) measurement,
An image forming method, wherein the color toner has a peak temperature of a maximum endothermic peak in a temperature range of 30 to 200 ° C. in a range of 50 to 110 ° C. 2. The color toner has a storage elastic modulus (G ′ ₈₀ ) at a temperature of 80 ° C. of 1 × 1 in viscoelastic properties.
0 ⁶ ~1 × 10 ⁸ in the range of [dN / m ^2], the temperature 12
Storage elastic modulus (G ' _120-180 ) at 0 to 180 ° C. is 1 ×
The image forming method according to claim 1, wherein a range of 10 ^{4 to} 5 × 10 ⁵ [dN / m ² ] is satisfied. 3. The color toner is characterized by differential thermal analysis (DS).
C) In the endothermic curve in the measurement, the temperature was 30 to 200.
The peak temperature of the maximum endothermic peak in the range of
3. The method according to claim 1, wherein the temperature is in a range of 100 ° C.
2. The image forming method according to 1., 4. The color toner according to claim 1, wherein said color toner is differential thermal analysis (DS).
C) In the endothermic curve in the measurement, the temperature was 30 to 200.
The maximum endothermic peak temperature in the range of
The image forming method according to claim 1, wherein the temperature is in a range of 90 ° C. 4. 5. The binder resin according to claim 1, wherein the binder resin is a hybrid resin having a polyester unit and a vinyl copolymer unit or a mixture of a polyester resin and a vinyl copolymer. Item 5. The image forming method according to any one of Items 1 to 4. 6. The binder resin has a main peak in a molecular weight region of 6,000 to 8,000 in a molecular weight distribution by gel permeation chromatography (GPC),
The image forming method according to any one of claims 1 to 5, wherein a ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 300 or more. 7. The binder resin has a main peak in a molecular weight range of 6,000 to 8,000 in a molecular weight distribution by gel permeation chromatography (GPC),
The image forming method according to any one of claims 1 to 5, wherein a ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 500 or more. 8. The image forming method according to claim 1, wherein the color toner contains an organometallic compound. 9. The image forming method according to claim 8, wherein the organometallic compound is a metal compound of an aromatic carboxylic acid derivative. 10. The image forming method according to claim 9, wherein the metal compound of the aromatic carboxylic acid derivative is an aluminum compound of an aromatic carboxylic acid derivative. 11. The image forming method according to claim 8, wherein the organic metal compound is contained in the color toner in an amount of 0.1 to 10% by mass based on the mass of the color toner. . 12. The magnetic toner for performing black color development contains at least a magnetic iron oxide, wherein the magnetic iron oxide comprises:
The image forming method according to any one of claims 1 to 11, wherein the compound contains 0.3 to 1.4% of a Si compound or an Al compound. 13. The magnetic toner for performing black color development contains at least a magnetic iron oxide, wherein the magnetic iron oxide is
Ratio (BSi / ASi) × 10 of the content BSi of silicon element present in the magnetic iron oxide when the iron element dissolution rate is up to 20% by weight and the content ASi of total silicon element present in the magnetic iron oxide.
0 is 35 to 85%.
3. The image forming method according to any one of 2. 14. An electrostatic latent image forming means for forming an electrostatic latent image on an image carrier using an organic photoconductor; and transferring toner to the electrostatic latent image formed on the image carrier by transferring the toner to the electrostatic latent image. Developing means for forming and visualizing a toner image corresponding to the latent image; and transfer means for electrostatically transferring the toner image formed on the image carrier to a transfer material. The development to form a color image can be performed by using a one-component developer composed of a magnetic toner and a magnetic carrier for performing color development, and a two-component developer composed of a non-magnetic toner. An image forming apparatus, wherein the nonmagnetic color toner has at least a binder resin, a colorant, and a wax, and has a storage elastic modulus (G ′ ₈₀ ) at a temperature of 80 ° C. of 1 × 10 ^{6 in} viscoelastic characteristics. ~ 1 × 10 ¹⁰ [dN / m ² ] And the storage elastic modulus (G ′ _120-180 ) at a temperature of _{120 to 180} ° C. is 5 × 10 ³ to 1 × 10 ⁶ [dN / m ² ].
In the endothermic curve in the differential thermal analysis (DSC) measurement,
An image forming apparatus comprising: a color toner having a maximum endothermic peak temperature in a temperature range of 30 to 200 ° C. in a range of 50 to 110 ° C. 15. The color toner has a storage elastic modulus (G ′ ₈₀ ) at a temperature of 80 ° C. of 1 × in viscoelastic properties.
It is in the range of 10 ⁶ to 1 × 10 ⁸ [dN / m ² ].
Storage elastic modulus (G ' _120-180 ) at 20-180 ° C is 1
The image forming apparatus according to claim 14, wherein a range of × 10 ^{4 to} 5 × 10 ⁵ [dN / m ² ] is satisfied. 16. The color toner is characterized by a differential thermal analysis (D
SC) In the endothermic curve in the measurement, the temperature was 30 to 20.
The peak temperature of the maximum endothermic peak in the range of 0 ° C. is 55
The image forming apparatus according to claim 14, wherein the temperature is in a range of about −100 ° C. 16. 17. The method according to claim 17, wherein the color toner is a differential thermal analyzer (D
SC) In the endothermic curve in the measurement, the temperature was 30 to 20.
The peak temperature of the maximum endothermic peak in the range of 0 ° C. is 60
The image forming apparatus according to claim 14, wherein the temperature is in a range of from −90 ° C. 18. The method according to claim 18, wherein the binder resin is one of a hybrid resin having a polyester unit and a vinyl copolymer unit or a mixture of a polyester resin and a vinyl copolymer. Item 14-1
8. The image forming apparatus according to claim 7. 19. The binder resin has a main peak in a molecular weight range of 6,000 to 8,000 in a molecular weight distribution by gel permeation chromatography (GPC), and has a weight average molecular weight (Mw) and a number average molecular weight (Mn). The image forming apparatus according to claim 14, wherein a ratio (Mw / Mn) of the image forming apparatus is 300 or more. 20. The binder resin has a main peak in a molecular weight distribution of 6,000 to 8,000 in a molecular weight distribution determined by gel permeation chromatography (GPC), and has a weight average molecular weight (Mw) and a number average molecular weight (Mn). The image forming apparatus according to any one of claims 14 to 18, wherein a ratio (Mw / Mn) is 500 or more. 21. The image forming apparatus according to claim 14, wherein the color toner has an organometallic compound. 22. The method according to claim 2, wherein the organometallic compound is a metal compound of an aromatic carboxylic acid derivative.
2. The image forming apparatus according to 1. 23. The image forming apparatus according to claim 22, wherein the metal compound of the aromatic carboxylic acid derivative is an aluminum compound of an aromatic carboxylic acid derivative. 24. The image forming apparatus according to claim 21, wherein the organometallic compound is contained in the color toner in an amount of 0.1 to 10% by mass based on the mass of the color toner. . 25. The magnetic toner for performing black color development contains at least a magnetic iron oxide, wherein the magnetic iron oxide comprises:
The image forming apparatus according to any one of claims 14 to 24, comprising 0.3 to 1.4% of Si or Al element. 26. The magnetic toner for performing black color development contains at least a magnetic iron oxide, wherein the magnetic iron oxide comprises:
Ratio (BSi / ASi) × 10 of the content BSi of silicon element present in the magnetic iron oxide when the iron element dissolution rate is up to 20% by weight and the content ASi of total silicon element present in the magnetic iron oxide.
0 is 35 to 85%.
The image forming apparatus according to any one of claims 25. 27. An electrostatic latent image forming step of forming an electrostatic latent image on an image carrier using an organic photoconductor, and transferring a toner to the electrostatic latent image formed on the image carrier. A developing step of forming and visualizing a toner image corresponding to the latent image; a transfer step of electrostatically transferring the toner image formed on the image carrier to a transfer material; and a fixing member for transferring the electrostatically transferred toner image. A one-component developer composed of a magnetic toner for performing black development and a two-component developer composed of a magnetic carrier and a non-magnetic toner for performing color development in the development process. And a non-magnetic color toner that can be developed to form a color image by using a non-magnetic color toner used in an image forming method. The non-magnetic color toner contains at least a binder resin, a colorant, and a wax. And viscoelastic characteristics In terms of properties, the storage elastic modulus (G ′ ₈₀ ) at a temperature of 80 ° C. is in the range of 1 × 10 ⁶ to 1 × 10 ¹⁰ [dN / m ² ], and the storage elastic modulus (G ′ _{120−) at} a temperature of 120 to 180 ° C. ₁₈₀ ) is 5 × 10 ³ to 1 × 10 ⁶ [dN / m ² ].
In the endothermic curve in the differential thermal analysis (DSC) measurement,
A color toner, wherein a peak temperature of a maximum endothermic peak in a temperature range of 30 to 200 ° C is in a range of 50 to 110 ° C. 28. The color toner has a storage elastic modulus (G ′ ₈₀ ) at a temperature of 80 ° C. of 1 × in viscoelastic properties.
It is in the range of 10 ⁶ to 1 × 10 ⁸ [dN / m ² ].
Storage elastic modulus (G ' _120-180 ) at 20-180 ° C is 1
The color toner according to claim 27, wherein the color toner satisfies the range of × 10 ^{4 to} 5 × 10 ⁵ [dN / m ² ]. 29. The method according to claim 29, wherein the color toner is obtained by differential thermal analysis (D
SC) In the endothermic curve in the measurement, the temperature was 30 to 20.
The peak temperature of the maximum endothermic peak in the range of 0 ° C. is 55
The color toner according to claim 27 or 28, wherein the temperature is in the range of -100C. 30. The color toner as described in Differential Thermal Analysis (D
SC) In the endothermic curve in the measurement, the temperature was 30 to 20.
The peak temperature of the maximum endothermic peak in the range of 0 ° C. is 60
The color toner according to claim 27 or 28, wherein the temperature is in the range of -90 ° C. 31. The method according to claim 31, wherein the binder resin is one of a hybrid resin having a polyester unit and a vinyl copolymer unit, or a mixture of a polyester resin and a vinyl copolymer. Items 27-3
0. The color toner according to any one of 0. 32. The binder resin has a main peak in a molecular weight range of 6,000 to 8,000 in a molecular weight distribution by gel permeation chromatography (GPC), and has a weight average molecular weight (Mw) and a number average molecular weight (Mn). 32. The color toner according to claim 27, wherein the ratio (Mw / Mn) is 300 or more. 33. The binder resin has a main peak in a molecular weight range of 6000 to 8000 in a molecular weight distribution by gel permeation chromatography (GPC), and has a weight average molecular weight (Mw) and a number average molecular weight (Mn). 32. The color toner according to claim 27, wherein the ratio (Mw / Mn) is 500 or more. 34. The color toner according to claim 27, wherein the color toner contains an organometallic compound. 35. The organic metal compound is a metal compound of an aromatic carboxylic acid derivative.
5. The color toner according to item 4. 36. The color toner according to claim 35, wherein the metal compound of the aromatic carboxylic acid derivative is an aluminum compound of an aromatic carboxylic acid derivative. 37. The color toner according to claim 34, wherein the organometallic compound is contained in the color toner in an amount of 0.1 to 10% by mass based on the mass of the color toner.