JP2002372808A - Image forming method and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method and image forming device with which sufficient image densities can be obtained in low-potential development and full-color images having excellent color reproducibility, high fineness and high image quality can be formed by using a-Si photoreceptors. SOLUTION: The image forming method and image forming device in which the a-Si photoreceptors of 20 to 80 mm in diameter are electrostatically charged to 300 to 450 V in the absolute value of the surface potential in a developing region and a contact type or contactless development system using positive charge type one- component developers of 4.0 to 10.0 μm in toner grain size and using nonmagnetic color toners of 1.0 to 1.8 respective in coloring power and 0 to 0.5 in the difference between the maximum value and minimum value of coloring power as well as a contactless development system of making the minimum spacings between the photoreceptors and developing sleeves to 100 to 500 μm by using magnetic black toners of 0.5 to 1.5 in coloring power are adopted and first to fourth image forming units to perform development by rotating the developing sleeves at a circumferential speed of 1.05 to 2.0 times the circumferential speed of the photoreceptors in the contact development system and at a circumferential speed of 1.1 to 4.0 times the contactless development system are used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method and an image forming apparatus used for a laser beam color printer, a color copying machine, and the like. The present invention relates to an excellent image forming method and apparatus.

[0002]

2. Description of the Related Art Photoreceptors are broadly classified into two types: organic and inorganic. [Organic photoconductor (OPC)] In recent years, various organic photoconductive materials have been developed as photoconductive materials for electrophotographic photoconductors. In particular, a function-separated type photoconductor in which a charge generation layer and a charge transport layer are laminated is already in practical use. And installed in copiers and laser beam printers.

However, one of the major drawbacks of these photosensitive members is that their durability is generally low. The durability is roughly classified into durability of electrophotographic properties such as sensitivity, residual potential, charging ability, image blur, and mechanical durability such as abrasion and scratches on the surface of the photoreceptor due to rubbing. Has become a major factor in determining the lifespan.

[0004] Among them, durability of electrophotographic physical properties, particularly, image blur, relates to ozone generated from a corona charger,
The active substances such as NO _x that the charge transport material contained in the photosensitive member surface layer is deteriorated is known as the cause. Regarding mechanical durability, paper,
It is known that a cleaning member such as a blade / roller, toner, and the like physically contact and rub against each other as a cause of a decrease in mechanical durability.

[0005] In order to improve the durability of the electrophotographic properties surface, ozone, it is important to use a charge transport material hard to be deteriorated by the active substances such as NO _x, to select a high oxidation potential charge transport material Things are known. Also, in order to increase mechanical durability, the surface must be lubricated to reduce friction to withstand rubbing by paper and cleaning members. It is important to improve the releasability, and it is known to mix a lubricant such as a fluororesin powder, a fluorinated graphite, and a polyolefin resin powder in the surface layer.

However, the wear is significantly reduced and the ozone, the hygroscopic material generated by the active substances such as NO _x is deposited on the surface of the photoreceptor, resulting surface resistivity decreases as the surface charge is moved laterally, the image There is a problem that blurring (image deletion) occurs.

[Inorganic photoconductor: Amorphous silicon photoconductor (a-Si)] In electrophotography, a photoconductive material for forming a photosensitive layer in the photoconductor has high sensitivity,
High N ratio [photocurrent (Ip) / dark current (Id)], having an absorption spectrum suitable for the spectral characteristics of the radiated electromagnetic wave, fast photoresponse, having a desired dark resistance value, Are required to be harmless to the human body. In particular, in the case of a photoreceptor incorporated in an image forming apparatus used in an office as an office machine, the above-described non-pollutability during use is important.
Hydrogenated amorphous silicon (hereinafter abbreviated as "a-Si: H") is a photoconductive material exhibiting such excellent properties. For example, Japanese Patent Publication No. 60-35059 discloses a photoconductive material. The application is described.

In the case of a photoreceptor using a-Si: H, a support is generally heated to 50 to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, A-S by a film forming method such as a CVD method, a photo CVD method, and a plasma CVD method (hereinafter, referred to as “PCVD method”).
A photoconductive layer made of i is formed. Among them, the PCVD method, that is, a method in which a raw material gas is decomposed by direct current, high frequency, or microwave glow discharge to form an a-Si deposited film on a support has been put to practical use.

Japanese Patent Application Laid-Open No. 54-83746 discloses a photosensitive material comprising a support and an a-Si (hereinafter referred to as "a-Si: X") photoconductive layer containing a halogen atom as a constituent element. The body has been proposed. The publication states that by including a halogen atom in a-Si of 1 to 40 atomic%, heat resistance is high and favorable electrical and optical characteristics can be obtained as a photoconductive layer of a photoconductor.

Japanese Patent Application Laid-Open No. 57-11556 discloses that a photoconductive member having a photoconductive layer composed of an a-Si deposited film has an electrical property such as a dark resistance value, a photosensitivity, and a photoresponsiveness. In order to improve the use environment characteristics such as optical and photoconductive properties and moisture resistance, as well as the stability over time, silicon atoms and carbon are deposited on a photoconductive layer composed of an amorphous material based on silicon atoms. A technique of providing a surface layer made of a non-photoconductive amorphous material containing atoms is described.

Further, Japanese Patent Application Laid-Open No. 60-67951 describes a technique for a photoconductor in which a light-transmitting insulating overcoat layer containing amorphous silicon, carbon, oxygen and fluorine is laminated. 62-1681
No. 61 describes a technique of using, as a surface layer, an amorphous material containing silicon atoms, carbon atoms, and 41 to 70 atomic% of hydrogen atoms as constituent elements.

Furthermore, in JP-A-57-158650, hydrogen containing 10 to 40 atomic%, 0.2 absorption coefficient ratio of the absorption peak of 2100 cm ^-1 and 2000 cm ^-1 in the infrared absorption spectrum It is described that a photosensitive member having high sensitivity and high resistance can be obtained by using a-Si: H of 1.7 for the photoconductive layer.

On the other hand, Japanese Patent Application Laid-Open No. 60-95551 discloses that in order to improve the image quality of an amorphous silicon photoreceptor, the temperature near the photoreceptor surface is maintained at 30 to 40.degree. By performing such an image forming process, there is disclosed a technique for preventing a reduction in surface resistance due to the adsorption of moisture on the surface of a photoreceptor and an image flow (high-humidity flow) caused thereby.

[0014] These techniques have improved the electrical, optical, photoconductive properties and environmental properties of the photoreceptor, and accordingly the image quality.

[0015]

In recent years, the expansion of office networks and the diversification of information have spread, and printers,
Copiers are also becoming more colorized. In particular, with the increase in the amount of information, there is a demand for further speeding up of color printers and color copiers.

Conventionally, an OPC (organic photoreceptor) has been widely used as a photoreceptor as a latent image holding member of a color copying machine or the like. However, since the OPC has low hardness and is scraped, the frequency of replacing the photoconductor tends to increase as the speed of the machine increases. For this reason, as for the study of a high-speed copying machine using OPC, studies have been made to increase the hardness, prevent shaving, and cope with the high speed.

On the other hand, in an image forming apparatus using an a-Si photoreceptor, since the hardness is high, the frequency of exchanging the photoreceptor due to abrasion of the drum can be reduced. Further, there is an advantage that the dot reproducibility is good and a high quality image can be obtained.

However, there are some problems in converting a-Si to a digital color copier.

The a-Si photoreceptor has a problem that image deletion occurs under a high temperature and high humidity condition and a surface potential fluctuates due to a temperature fluctuation. In order to solve this, a drum heater is inserted inside the photoconductor to control the temperature to be constant.

On the other hand, since the toner for a color copying machine has a configuration in which toners of a plurality of colors are multiplex-fixed, the softening point of the toner is set low. This is because, when a toner having a high softening point is used, the color mixing in the fixing device deteriorates, and a problem is likely to occur in the color reproducibility. When such a toner having a low softening point is used in a high-speed full-color copying machine, the mechanical portion is large in the cleaner portion, the contact portion between the transfer unit roller and the photoconductor, and the calorific value of the photoconductor increases. The toner easily melts on the photoconductor. In particular, when the temperature of the photoreceptor is controlled by the drum heater, it is more remarkable.
The problem of fusion of the toner to the photoconductor and the problem of filming in which the toner resin is uniformly deposited on the surface of the photoconductor are likely to occur. Therefore, even when the a-Si photosensitive member is used, maintenance of the photosensitive member is required, and it has been difficult to sufficiently bring out the advantage of long life of the a-Si.

Further, from the viewpoint of long life, in the case of two-component development using a carrier, in a durability test of tens of thousands of sheets, toner may be spent on the surface of the carrier and the chargeability may be reduced, thereby necessitating replacement of the agent. there were.

Therefore, when an a-Si photoreceptor is mounted on a color machine, the occurrence of fusion to the photoreceptor and filming is reduced, there is no spent on the carrier, and color reproducibility at the time of fixing is compatible. Therefore, there is a need to develop an image forming method and an image forming apparatus including the development of a toner to be used.

When a photoconductor is mounted on a tandem type full-color copying machine, the size of the photoconductor is limited by the space of the apparatus. As a result, the size of each device that performs the functions of charging, exposure, development, transfer, cleaning, and charge removal is limited. In particular, when the width of the charger is limited, a sufficient surface potential (charge potential) on the photoconductor cannot be obtained, and as a result, it becomes difficult to obtain a high-density image. Therefore, it is necessary to establish an image forming method and an image forming apparatus that provide a sufficient image density even in low-potential development and provide high-quality images with excellent color reproducibility.

Another advantage of using the a-Si photoreceptor in a full-color machine is that the quality of an image is improved. The a-Si photosensitive member has good reproducibility of the dot level generated by image exposure, and can obtain a high quality image. However, when an attempt is made to reduce the diameter of the color toner, the charge amount of the toner tends to increase, and the amount of toner generally developed tends to decrease.
It works against low potential development on the photoreceptor. Therefore, development of an image forming method and an image forming apparatus capable of forming a high-definition and high-quality image exhibiting high developability is required.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and in a full-color image formation using an a-Si photoreceptor, the occurrence of toner fusion and filming on the photoreceptor is reduced, and High developability without defects, and compatible with color reproducibility at the time of fixing, sufficient image density can be obtained even at low potential development, and high-definition and high-quality images with excellent color reproducibility are formed. An object of the present invention is to provide an image forming method and an image forming apparatus that can perform the method.

[0026]

SUMMARY OF THE INVENTION The present invention relates to the a-S
In order to solve the problem of mounting the i photoreceptor on a color image forming apparatus, the present inventors have developed a one-component developing method under predetermined conditions in full-color image formation using an a-Si photoreceptor. It has been found that by adopting the method, a full-color image forming method and an image forming apparatus with high definition and high speed can be realized.

That is, according to the present invention, the first toner image formed by the first image forming unit is transferred to a transfer material, and the second toner image formed by the second image forming unit is transferred to the first toner. The image is transferred to a transfer material having an image, and the third toner image formed by the third image forming unit is transferred to the transfer material having the first and second toner images, and is formed by the fourth image forming unit. Transferring the transferred fourth toner image to a transfer material having the first, second and third toner images, and heating and pressing the transfer material having the first, second, third and fourth toner images. To form a full-color image or a multi-color image on a transfer material by performing heat and pressure fixing, wherein (A) the first image formation in the first image forming unit includes (i) First sense having amorphous silicon layer First charging step of charging the body,
A first exposure step of forming a first electrostatic image on the charged first photoconductor by exposure, and a first exposure step formed on the first photoconductor by the developer conveyed by the first developing sleeve. Including at least a first development step of developing an electrostatic image,
(Ii) the first photoreceptor has a diameter of 20 to 80 mm,
In the first charging step, the developing area, which is the part facing the first developing sleeve, is charged to an absolute value of 300 to 450 V. (iii) In the first developing step, a one-component developer containing the first toner is used. (Iv) the first photoconductor and the first developing sleeve are installed in contact or non-contact with each other; and (v) the first developing sleeve is installed in contact with the first photoconductor. It rotates at a peripheral speed of 1.05 to 2.0 times the peripheral speed of the first photoconductor, and when installed in a non-contact manner, is 1.1 to 4.0 times the peripheral speed of the first photoconductor. A first electrostatic image is developed with a one-component developer while rotating at a peripheral speed to form a first toner image on a first photoconductor, and (B) a second image forming unit in a second image forming unit. The image formation is performed by: (i) charging a second photosensitive member having an amorphous silicon layer;
Charging step, a second exposure step of forming a second electrostatic image on the charged second photoconductor by exposure, and forming the second photoconductor on the second photoconductor with the developer conveyed by the second developing sleeve. And (ii) the second photoconductor has a diameter of 20 to 80.
mm, and the absolute value of the developing area, which is the part facing the second developing sleeve in the second charging step, is 300 to 45 mm.
0V, (iii) a one-component developer containing a second toner is used in the second developing step, and (iv) the second photoconductor and the second developing sleeve are in contact with or not in contact with each other. (V) the second developing sleeve rotates at a peripheral speed of 1.05 to 2.0 times the peripheral speed of the second photoconductor when it is installed in contact; In the case where the photosensitive member is installed in contact, the second electrostatic image is developed with a one-component developer while rotating at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the second photosensitive member, and the second electrostatic image is developed. Forming a toner image on the second photoconductor, and (C) forming a third image in the third image forming unit,
(I) a third charging step of charging a third photoconductor having an amorphous silicon layer, a third exposure step of forming a third electrostatic image on the charged third photoconductor by exposure, and Of the developer transported by the developing sleeve
(Ii) the third photoconductor has a diameter of 20 to 80 mm, and the third photoconductor has a third electrostatic image formed on the photoconductor. The developing region, which is the portion facing the developing sleeve, is charged to an absolute value of 300 to 450 V. (iii) In the third developing step, a one-component developer containing a third toner is used,
(Iv) the third photosensitive member and the third developing sleeve are installed in contact or non-contact with each other; and (v) the third developing sleeve is installed in contact with the third photosensitive sleeve. It rotates at a peripheral speed of 1.05 to 2.0 times the peripheral speed of the body, and when installed in a non-contact manner, 1.1 to 4.0 of the peripheral speed of the third photosensitive member.
The third electrostatic image is developed with a one-component developer while rotating at twice the peripheral speed to form a third toner image on the third photoconductor, and (D) the third toner image is formed in the fourth image forming unit. The image formation of No. 4 includes (i) the fourth step having an amorphous silicon layer.
A fourth charging step of charging the photoconductor, a fourth exposure step of forming a fourth electrostatic image on the charged fourth photoconductor by exposure, and a developer conveyed by a fourth developing sleeve. The method further includes at least a fourth developing step of developing a fourth electrostatic charge image formed on the fourth photoconductor, wherein (ii) the fourth photoconductor has a diameter of 20 to 80 mm, and The developing region, which is a portion facing the fourth developing sleeve, is charged to an absolute value of 300 to 450 V, and (iii) the fourth developing sleeve is charged.
In the developing step, a one-component magnetic developer containing a fourth toner is used, and (iv) the fourth photosensitive member and the fourth developing sleeve are set so that the minimum gap is 100 to 500 μm. (V) The fourth developing sleeve develops the fourth electrostatic image with a one-component developer while rotating at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the fourth photoconductor. (E) the first toner, the second toner, the third toner, and the fourth toner have different color tones and are non-magnetic. Each selected from the group consisting of yellow toner, non-magnetic magenta toner, non-magnetic cyan toner and magnetic black toner,
(A) non-magnetic yellow toner, non-magnetic magenta toner,
The non-magnetic cyan toner and the magnetic black toner have positive chargeability, the weight average particle diameter of each toner is 4.0 to 10.0 μm, and (b) the amount of unfixed toner on the transfer material is 0.5 mg. / Cm ² , the coloring power of each of the toners of yellow, magenta, and cyan is 1.0 to 1.8, and the coloring power of the toner is 1.0 to 1.8. The coloring power of the toner is 0.5 to 1.5, and the difference between the coloring power of the yellow toner, the magenta toner, and the cyan toner showing the maximum coloring power and the coloring power of the toner showing the minimum coloring power is different. The image forming method is characterized by being 0 to 0.5.

Further, the present invention has first to fourth image forming units, wherein the first toner image formed by the first image forming unit is transferred to a transfer material and formed by the second image forming unit. The transferred second toner image is transferred to a transfer material having the first toner image, and the third toner image formed by the third image forming unit is transferred to a transfer material having the first and second toner images. And transferring the fourth toner image formed by the fourth image forming unit to a transfer material having first, second, and third toner images, and transferring the first, second, third, and fourth toner images.
An image forming apparatus that conveys a transfer material having a toner image to a heat and pressure fixing unit and forms a full-color image or a multi-color image on the transfer material by performing heat and pressure fixing,
(A) The first image forming unit comprises: (i) a first charging means for charging a first photoconductor having an amorphous silicon layer, and a first electrostatic image on the charged first photoconductor by exposure. A first exposing means for forming, and a first developing means for developing a first electrostatic charge image formed on a first photoconductor with a developer conveyed by the first developing sleeve. (Ii) the first photoreceptor has a diameter of 20 to 80 mm, and the first charging means causes the developing area, which is the part facing the first developing sleeve, to have an absolute value of 300 to 450 V (Iii) the first
Has a one-component developer containing a first toner, and (iv) the first photosensitive member and the first developing sleeve are installed in contact with or not in contact with each other; v) The first developing sleeve rotates at a peripheral speed of 1.05 to 2.0 times the peripheral speed of the first photoconductor when it is installed in contact with the first developing sleeve, and rotates when the non-contact is installed. The first electrostatic image is developed with a one-component developer while rotating at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the first photoconductor, and the first toner image is converted to the first photoconductor. And (B) a second image forming unit,
(I) second charging means for charging a second photoconductor having an amorphous silicon layer, second exposure means for forming a second electrostatic image on the charged second photoconductor by exposure, and second And (ii) a second developing means for developing a second electrostatic image formed on the second photosensitive member with the developer conveyed by the second developing sleeve. The photoconductor of No. 2 has a diameter of 20 to 80 mm, and the developing area, which is the portion facing the second developing sleeve, is charged to an absolute value of 300 to 450 V by the second charging means. The means has a one-component developer containing a second toner, and (iv) a second photoconductor and a second photoconductor.
(V) When the second developing sleeve is installed in contact with the developing sleeve, the peripheral speed of the second photosensitive member is 1.05 to 2. When rotated at a peripheral speed of 0 times, and when installed in a non-contact manner, the second photosensitive member is rotated at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the second photoreceptor, and is rotated by a one-component type developer. The electrostatic image is developed to form a second toner image on the second photoconductor, and (C) the third image forming unit is configured to charge the third photoconductor having the amorphous silicon layer. A third charging means for forming a third electrostatic image on the charged third photoconductor by exposure;
And a third developing means which has a third developing sleeve and which develops a third electrostatic image formed on the third photosensitive member with the developer conveyed by the third developing sleeve. (Ii) the third photoreceptor has a diameter of 20 to 80 mm, and the third charging means charges the developing area facing the third developing sleeve to an absolute value of 300 to 450 V, (Iii) the third developing means has a one-component developer containing a third toner, and (iv) the third developing means.
And the third developing sleeve is installed in contact or non-contact with the third developing sleeve. (V) When the third developing sleeve is installed in contact with the third developing sleeve, the peripheral speed of the third photosensitive member is reduced. 1.05
When it is installed in a non-contact state, it rotates at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the third photosensitive member, and is rotated by a one-component developer. Developing a third electrostatic image to form a third toner image on a third photoreceptor;
(D) a fourth image forming unit comprising: (i) fourth charging means for charging a fourth photoconductor having an amorphous silicon layer, and exposing a fourth electrostatic image to the charged fourth photoconductor by exposure. A fourth exposure means for forming, and a fourth developing sleeve for developing a fourth electrostatic charge image formed on the fourth photoconductor with the developer conveyed by the fourth developing sleeve. (Ii) the fourth photoreceptor has a diameter of 20 to 80 mm, and the fourth charging means causes the developing area, which is the part facing the fourth developing sleeve, to have an absolute value of 300 to 450 V (Iii) the fourth
Has a one-component magnetic developer containing a fourth toner. (Iv) The fourth photosensitive member and the fourth developing sleeve are provided so that the minimum gap is 100 to 500 μm. (V) The fourth developing sleeve develops the fourth electrostatic charge image with the one-component developer while rotating at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the fourth photoconductor. (E) the first toner, the second toner, the third toner, and the fourth toner have different color tones from each other, and Non-magnetic yellow toner, non-magnetic magenta toner, non-magnetic cyan toner and magnetic black toner are each selected from the group consisting of:
(A) non-magnetic yellow toner, non-magnetic magenta toner,
The non-magnetic cyan toner and the magnetic black toner have positive chargeability, the weight average particle diameter of each toner is 4.0 to 10.0 μm, and (b) the amount of unfixed toner on the transfer material is 0.5 mg. / Cm ² , the coloring power of each of the toners of yellow, magenta, and cyan is 1.0 to 1.8, and the coloring power of the toner is 1.0 to 1.8. The coloring power of the toner is 0.5 to 1.5, and the difference between the coloring power of the yellow toner, the magenta toner, and the cyan toner showing the maximum coloring power and the coloring power of the toner showing the minimum coloring power is different. An image forming apparatus characterized by having a value of 0 to 0.5 is provided.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. According to the present invention, in a tandem-type image forming method and an image forming apparatus capable of forming a full-color image, an a-Si photosensitive member having a diameter of 20 to 80 mm is used as a photosensitive member, and the photosensitive member is charged to 300 to 450 V. In the development using a color toner, either a contact or non-contact development method using a one-component non-magnetic developer is used, and in the development using a black toner, a non-contact development method using a one-component magnetic developer is used. In the contact developing method, the developing sleeve is rotated at a peripheral speed of 1.05 to 2.0 times the peripheral speed of the photosensitive member. In the non-contact developing method, the developing sleeve is rotated at a peripheral speed of 1.1 times the peripheral speed of the photosensitive member. In the development using a black toner while rotating at a peripheral speed of up to 4.0 times, a developing sleeve is installed so that the minimum gap between the photosensitive member and the photosensitive member is 100 to 500 μm to form an image.

Further, in the present invention, when a toner having a weight average particle size of 4.0 to 10.0 μm is used and the amount of unfixed toner on the transfer material is 0.5 mg / cm ² , the image after one-time fixing is usually performed. In the coloring power defined by the density, the coloring power of the yellow, magenta and cyan color toners is 1.0 to 1.8, the coloring power of the black toner is 0.5 to 1.5, and , Magenta and cyan color toners have a difference of 0 between the maximum value and the minimum value of the coloring power.
To 0.5 is used.

In the present invention, by satisfying the above conditions, it is possible to obtain a high-quality image with high image density and excellent color reproduction.

In the present invention, a rotatable cylindrical photoconductor having an amorphous silicon layer having a diameter of 20 to 80 mm is used. Photoreceptor diameter 20mm
If it is smaller, the charging width is limited. Since the surface potential (charging potential) of the photoconductor is affected by the charging capability and high-pressure leak, a sufficient charging potential cannot be given with the above-mentioned diameter. Images may not be obtained. Also, since the nip with the developing sleeve described later becomes smaller,
There is a tendency that the development area decreases and the density decreases.

Conversely, when the diameter of the photosensitive member is 80 mm larger, a sufficient charging potential and a sufficient density can be obtained, but the toner image or toner formed on the transfer material formed by the previous image forming unit during transfer is sufficient. Is easily retransferred to the photoreceptor. As a result, toner consumption increases, warpage during transfer, and the like are likely to occur. In particular, when an image is formed using four image forming units, the image of the first image forming unit is re-transferred by the second, third, and fourth image forming units. Become. Further, when a large-diameter photosensitive member is used, there is a disadvantage that the apparatus becomes large.

In the present invention, the photosensitive member is charged to an absolute value of 300 to 450 V in the developing area. If the surface potential in the developing area is smaller than 300 V, it is difficult to obtain a sufficient image density. If the surface potential is larger than 450 V, the photosensitive member such as uneven density due to uneven potential of the photosensitive member and a drum ghost in a one-component developing method. Easy to pick up defects,
This is not preferable because image defects tend to occur easily. In the present invention, the development region is a facing portion of the photoconductor facing a developing sleeve for supplying a developer during development.

In the present invention, in the one-component developing system,
The photoconductor and the developing sleeve are installed so as to be in contact or non-contact with each other. In the contact method, the developing sleeve is rotated at a peripheral speed of 1.05 to 2.0 times the peripheral speed of the photoconductor. Developing with a one-component developer while rotating the sleeve at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the photoreceptor does not cause toner fusion to the photoreceptor surface, and It is possible to stably obtain an image which has sufficient density, is effective with respect to toner deterioration, and has good dot reproducibility.

In the case of the contact system, if the developing is performed with a one-component developer while rotating the developing sleeve at a peripheral speed smaller than 1.05 times the peripheral speed of the photosensitive member, the toner required for the development cannot be supplied. It tends to be impossible to obtain a high image density. Set the developing sleeve to the peripheral speed of 2.0
In the case of rotating at a peripheral speed larger than twice, deterioration of the toner at the contact portion with the photoconductor, fusion of the toner to the photoconductor, rubbing stripes, etc. occur, and the density reduction after continuous use tends to be remarkable. .

In the non-contact system, when developing is performed with a one-component developer while rotating the developing sleeve at a peripheral speed smaller than 1.1 times the peripheral speed of the photosensitive member, toner required for development cannot be supplied. There is a tendency that a sufficient image density cannot be obtained. The developing sleeve is set at the peripheral speed of the photosensitive member of 4.0.
In the case of rotating at a peripheral speed larger than twice, the share in the developing device increases, the toner deteriorates sharply, and the density reduction after continuous use tends to be remarkable.

Further, in a non-contact system using a one-component magnetic developer, a minimum gap (S
D gap) is set to 100 to 500 μm, and the developing sleeve is set to a peripheral speed of 1.1 to 4.
By developing with a one-component developer while rotating at a peripheral speed of 0 times, toner does not fuse to the surface of the photoreceptor, sufficient image density can be obtained, and toner deterioration is also effective. In addition, an image having good dot reproducibility can be stably obtained.

The minimum gap between the photosensitive member and the developing sleeve is 10
If it is smaller than 0 μm, the shear in the gap becomes large, and as a result, fusion tends to occur on the photoconductor. On the other hand, if it is larger than 500 μm, the toner flying distance becomes longer and the toner hardly reaches the drum, so that a sufficient image density tends not to be obtained.

When a one-component magnetic developer is used as the black toner, there is no need to change the developer, and the developer can be used for a long time. This is particularly effective in the case of an image forming system in which more black images are used than color images.

The present invention provides a tandem-type full-color copying machine using amorphous silicon. By using a tandem-type system, a high-speed full-color system that can be reduced in size without increasing the moving speed (process speed) of the photoconductor can be achieved. Further, since there is no potential difference at each developing device position due to dark decay as compared with the one-drum fixed developing system, the density control can be easily performed. Further, it is possible to eliminate problems such as a reduction in density and unevenness due to retransfer when a large-diameter a-Si is used, and characteristic unevenness which is a problem in manufacturing a large-diameter drum.

In the present invention, the weight average particle diameter (D4) is 4.0 to 10.0 μm, more preferably 5.0 to 9.0 μm.
A toner having a size of 0 μm is used. When the weight average particle diameter of the toner is less than 4.0 μm, it is difficult to stabilize the charge, and fog and toner scattering easily occur in durability. When the weight average particle diameter of the toner exceeds 10.0 μm, the reproducibility of the halftone portion is greatly reduced,
The obtained image tends to be a rough image.

In the present invention, the coloring power of the non-magnetic toner in each of the yellow, magenta, and cyan colors is 1.0.
To 1.8, more preferably 1.1 to 1.7. When the coloring power of the non-magnetic toner is 1.0 or less, if the image is formed under the condition that the charging potential of the a-Si photoreceptor is sufficiently obtained, the image density tends to decrease.

On the other hand, regarding the upper limit of the coloring power of the non-magnetic toner, it is necessary to consider various conditions. The coloring power of the non-magnetic toner can be adjusted by the amount of the coloring agent added in the toner and the dispersion of the coloring agent. Because of excessive pigment, toner charging inhibition occurs, the viscoelasticity changes and the fixing property differs, and the pigment is easily detached from the toner during the durability, fog and filming, furthermore, Spent tends to occur on the blade and sleeve, and the transparency is also deteriorated. Therefore, the coloring power of the toner must be controlled in consideration of not only the addition amount but also the selection, dispersion, and state of the pigment.

However, when the coloring power is increased by controlling the charge inhibition and viscoelasticity of the toner, if the coloring power of the non-magnetic toner is larger than 1.8, the reproducibility of halftone is reduced. As a result, the density gradation characteristic rapidly rises, and control for environmental fluctuation tends to be strict, which is not preferable. From such a viewpoint, the coloring power of the non-magnetic toner used in the present invention needs to be 1.0 to 1.8.

The coloring power of the black toner contained in the one-component magnetic developer used in the present invention is also from 0.5 to 1.5, more preferably from 0.6 to 1. It needs to be 4.

Further, the coloring power of the three non-magnetic toners of yellow, magenta, and cyan was examined. As a result, the non-magnetic yellow toner, the non-magnetic magenta toner, and the non-magnetic cyan toner were colored. The difference between the maximum and minimum values of force must be between 0 and 0.5. When the difference in the coloring power is larger than 0.5,
The gloss difference in the same image density portion of each color becomes large, and it tends to be impossible to obtain a high quality image. Further, the environmental characteristics of each toner are easily picked up, and the color balance at the time of full color formation is easily lost due to temperature and humidity.
Therefore, the difference between the maximum value and the minimum value in the coloring power of the three colors yellow, magenta, and cyan is preferably set in the range of 0 to 0.5.

The coloring power in the present invention is the image density when a toner is applied on a transfer material so as to be 0.5 mg / cm ² and the toner is fixed by one fixing. In this case, the fixing may be performed by a commonly used fixing device, although it depends on the physical properties of the toner used. As a fixing condition in the case of using a roller-type heating and pressing fixing device, for example, a fixing temperature is 175 ° C., and a roller load is 40 kgf (392 N).

Next, the image forming method and the image forming apparatus of the present invention will be specifically described below. First, an embodiment of the image forming apparatus of the present invention will be described with reference to the drawings, and the image forming method of the present invention will be described together.

FIG. 1 is a schematic configuration diagram of an electrophotographic full-color machine which is an image forming apparatus embodying the present invention.

The image forming apparatus according to the present embodiment uses the A to D stations, which are the first to fourth image forming units, and transfer paper 24 as a transfer material to which the toner image formed at each station is transferred. A transfer paper transport sheet 27 transported to a transfer position in each station, and a fixing device 25 as a heat and pressure fixing unit for fixing the unfixed toner image transferred in each station to the transfer paper 24 by heat and pressure fixing. Have.

In FIG. 1, each ABCD station forms a yellow, magenta, cyan, and black image of a full-color image, but the order of the stations does not matter. In the following description, for example, the primary charger 21 refers to the primary chargers 21A, 21B, 21C, and 21D in each ABCD station.

In the above-described image forming apparatus, a one-component non-magnetic developer is used for a color toner as a developer.
A one-component magnetic developer is used for the black toner, which satisfies the condition of the developer described above. The above-described image forming apparatus and its image forming process will be described on the assumption that the A station forms a yellow image, the B station forms a magenta image, the C station forms a cyan image, and the D station forms a black image. The developer and toner used in the present invention will be described later in detail.

Each of the above stations includes a rotatable cylindrical photosensitive member 4 having an amorphous silicon layer, a primary charger 21 as a charging means for charging the photosensitive member 4,
A light-emitting element 22 as an exposure unit that forms an electrostatic charge image on the charged photoconductor 4 by exposure, a developing device 9 as a development unit that develops the electrostatic image formed on the photoconductor 4 into a toner image, A transfer charger 23 serving as a transfer unit for transferring the toner image formed by the development from the photoconductor 4 to the transfer paper 24; and a toner remaining on the photoconductor 4 after the transfer.
And a cleaning device 26 as cleaning means for removing from the cleaning device.

The photosensitive member 4 is a rotatable cylindrical a-Si photosensitive member having a diameter of 20 to 80 mm. The photoreceptor used in the present invention will be described later in detail.

The primary charger 21 is a corona charger, and the surface of the photoreceptor 4 has an absolute value of 300 to 4 in the developing area.
It is a charger for charging to 50V. The present invention is not limited to the corona charger, and various charging means capable of charging as described above can be used.

The light emitting element 22 is a means for exposing a signal corresponding to the information of the image to be formed to form an electrostatic image of the image to be formed on the photosensitive member 4. There is no particular limitation as long as the means is used. For example, a laser or the like for exposing a desired information signal can be used.

As the developing device 9, various suitable developing devices can be used according to the type of developer used for development. In the present invention, a one-component non-magnetic developer and a one-component magnetic developer are used as the developer. The developing device is not particularly limited as long as it can be used. The developing devices 9A to 9C using color toner for development and the developing device 9D using black toner for development will be described.

As shown in FIG. 8, the developing devices 9A to 9C include developing containers 8A to 8C for accommodating the developer, developing sleeves 3A to 3C as the first to third developing sleeves, and charging and supplying of the developer. Blade 2 as toner amount regulating member
A to 2C. Power supplies 15A to 15C are connected to the developing sleeves 2A to 2C, respectively, and the power supplies 15A to 15C are configured to apply a desired developing bias to the developing sleeves 3A to 3C.

The developing containers 8A to 8C are open at positions facing the developing area of the photosensitive member 4, and the developing sleeves 3A to 3C are rotatably arranged so as to be partially exposed at the openings. The developing sleeves 3A to 3C are made of a non-magnetic material such as aluminum or stainless steel, and rotate in a direction indicated by an arrow in a developing operation. The blades 2A to 2C are plate-like members having elasticity such as plate-like rubber members, and come into contact with the surfaces of the developing sleeves 3A to 3C while urging them.
The pressure controls the amount of developer on the sleeve.

As shown in FIG. 9, a developing device 9D includes a developing container 8D for storing a developer, a developing sleeve 3D rotatably provided at an opening of the developing container 8D as a fourth developing sleeve, and a developing sleeve 8D. It has a blade 2D for regulating the amount of the developer on the 3D, a magnet roll 5 as a magnetic field generating means fixed in the developing sleeve 3D, and a stirring member 7 for stirring the developer contained in the developing container 8D. I have. A power supply 15D is connected to the developing sleeve 3D, and the power supply 15D is configured to apply a desired developing bias to the developing sleeve 3D.

The developing container 8D is also open at a position facing the developing area of the photosensitive member 4. The developing sleeve 3D is also made of the non-magnetic material as described above, and rotates in the direction of the arrow in the drawing during the developing operation. The developing sleeve 3D is arranged in non-contact with the photoconductor 4D such that the minimum gap (αD in the figure) between the photoconductor 4D and the photoconductor 4D is 100 to 500 μm. The blade 2D is a metal plate-shaped member disposed in non-contact with the surface of the developing sleeve 3D, and controls the amount of developer on the developing sleeve 3D by forming a dense magnetic field between the blade 2D and the developing sleeve 3D. . The stirring member 7 is a stirring blade that rotates in the forward direction with respect to the rotation direction of the developing sleeve 3D.
The developer is frictionally charged with each other, and the developer is transported toward the developing sleeve 3D while making the charge uniform.

The transfer charging device 23 is a device for applying a voltage from the back of the transfer paper to electrostatically transfer the toner image on the photosensitive member 4 onto the transfer paper. In the present embodiment, the electrostatic transfer is adopted. However, in the present invention, any means for transferring the toner image from the photoconductor to the transfer material is not particularly limited, and various transfer means can be used.

The cleaning device 26 has a waste toner container that opens to face the photoreceptor 4 and a cleaning blade that is fixed to the opening of the container and contacts the surface of the photoreceptor 4. The transfer residual toner scraped off is stored in a waste toner container. The cleaning device is not particularly limited as long as it can remove the transfer residual toner, and various configurations can be adopted. However, the cleaning device may be provided as needed.

The transfer device 25 is a heat and pressure fixing means for fixing the toner on the transfer paper by fusing the toner. In this embodiment, the apparatus has a heating roller and a pressure roller, and the transfer paper 24 having the unfixed toner image is introduced into the nip portion formed by both rollers to fix the transfer paper 24. Various means, such as a film-type fixing device having a heat-resistant film interposed between the heater and the transfer paper, can be used to fix the unfixed toner on the transfer paper.

As shown in FIGS. 1 and 8, the image forming apparatus according to the present embodiment includes a toner density detecting means 17 for quantifying the transfer residual toner on the photosensitive member 4,
Each station is provided with a static eliminator, which is a type of exposure device, for partially removing the electrostatic image of the photoconductor 4 before development in accordance with the margin of the transfer paper.

Image formation by the above-described image forming apparatus is performed as follows. First, the photoconductor 4 is uniformly charged by the primary charger 21, an information signal is exposed by the light emitting element 22 to form an electrostatic image, and the image is visualized by the developing device 9. In this embodiment, an electrostatic image is formed by image exposure.

In the formation of an electrostatic charge image in the present invention,
Back scan exposure for exposing the photoreceptor surface excluding the electrostatic charge image where toner is to be adhered to form an electrostatic charge image having a polarity opposite to the charging characteristic of the toner, and exposing the electrostatic charge image portion for toner Any of image exposures that form an electrostatic charge image having the same polarity as the charging characteristics of the above-mentioned can be used. Which exposure method is used can be determined by the charging characteristics of the photoconductor and the charging characteristics of the toner.

In the developing device 9, the one-component developer is carried and transported by the developing sleeve 3, the amount of the developer (layer thickness) on the developing sleeve 3 is regulated by the blade 2, and the developer whose layer thickness is regulated is exposed to light. The latent image is supplied to the photoconductor 4 in a development area facing the body 4 to develop the latent image. At this time, the blade 2 regulates the charge application and the toner amount, and appropriately maintains the amount of the developer conveyed to the developing area. In order to improve the developing efficiency, a developing bias voltage in which, for example, a DC voltage is superimposed on an AC voltage is applied from the power supply 15 to the developing sleeve 3. In the developing area, which is a portion facing the photoconductor 4, the toner on the developing sleeve 3 moves to the electrostatic image side of the photoconductor 4 by applying a bias voltage to the developing sleeve 3, and the electrostatic image becomes a toner image. Is visualized as

The transfer paper transporting sheet 27 transports the transfer paper 24 to each station (for example, in the order of A → B → C → D) in synchronization with the formation of the toner image. The toner image is transferred to the transfer paper 24 by the transfer charging device 23, and the transfer paper 2
In each station 4, a yellow toner image, a magenta toner image, a cyan toner image, and a black toner image are sequentially superimposed and transferred at each station.

The transfer paper 24 on which the toner images of the four colors are stacked is mixed and fixed by heat and pressure by a fixing device 25, and is discharged out of the device as a full-color image. Further, the transfer residual toner on the photoconductor 4 is removed by the cleaning device 26. By the above process, a high-quality image having a sufficient image density and excellent color reproducibility and image reproducibility can be stably formed for a long period of time.

Next, the photoreceptor, developer and the like used in the present invention will be described. First, the photoreceptor used in the present invention will be described. FIGS. 2 to 5 are schematic structural diagrams for explaining the layer structure of the photoreceptor used in the present invention.

The photosensitive member 1100 shown in FIG. 2 has a photosensitive layer 1102 provided on a support 1101 for the photosensitive member. The photosensitive layer 1102 is composed of a photoconductive layer 1103 made of a-Si: H, X and having photoconductivity.

The photosensitive member 1100 shown in FIG. 3 has a photosensitive layer 1102 provided on a support 1101 for the photosensitive member. The photosensitive layer 1102 includes a photoconductive layer 1103 made of a-Si: H, X and having photoconductivity, and an amorphous silicon-based surface layer 1104.

The photosensitive member 1100 shown in FIG. 4 has a photosensitive layer 1102 provided on a support 1101 for the photosensitive member. The photosensitive layer 1102 includes a photoconductive layer 1103 made of a-Si: H, X and having photoconductivity, an amorphous silicon-based surface layer 1104, and an amorphous silicon-based charge injection blocking layer 1105.

The photosensitive member 1100 shown in FIG. 5 has a photosensitive layer 1102 provided on a support 1101 for the photosensitive member. The photosensitive layer 1102 includes a charge generation layer 1106 and a charge transport layer 1107 made of a-Si: H, X constituting the photoconductive layer 1103, and an amorphous silicon-based surface layer 1104.

In the present invention, photosensitive members having various layer structures as described above from a single layer type to a laminated type can be used.

<Support> The support used in the present invention may be either conductive or electrically insulating. Examples of the support include well-known metals such as Al and Fe, and alloys thereof, for example, stainless steel. Further, a support in which at least the surface on the side on which the photosensitive layer is formed of an electrically insulating support such as a film or sheet of a synthetic resin, glass, ceramic or the like can be used.

The support 1101 used in the present invention
May be a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface.

In particular, when image recording is performed using coherent light such as laser light, the surface of the support 1101 is effectively removed in order to more effectively eliminate image defects caused by so-called interference fringe patterns appearing in a visible image. May be provided with irregularities.
The irregularities provided on the surface of the support 1101 are described in
JP-168156, JP-A-60-178457,
It is prepared by a known method described in JP-A-60-225854 and the like.

As another method for more effectively eliminating image defects due to interference fringe patterns when coherent light such as laser light is used, a concave and convex shape formed by a plurality of spherical trace depressions on the surface of the support 1101 is used. It may be provided. That is, the surface of the support 1101 has irregularities smaller than the resolution required for the photoconductor 1100, and the irregularities are caused by a plurality of spherical trace depressions. Unevenness due to a plurality of spherical trace depressions provided on the surface of the support 1101 is described in
It is prepared by a known method described in JP-A-31561.

As still another method for more effectively eliminating image defects due to interference fringe patterns when coherent light such as laser light is used, light may be applied to the inside or below the photosensitive layer 1102. An interference prevention layer or region such as an absorption layer may be provided.

<Photoconductive Layer> In the present invention, at least a part of the photosensitive layer 1102 is formed on the support 1101 and, if necessary, on the undercoat layer (not shown) in order to effectively achieve the object. The photoconductive layer 1103 is formed by a method of forming a vacuum deposited film by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics.

More specifically, for example, a glow discharge method (an AC discharge CVD method such as a low-frequency CVD method, a high-frequency CVD method or a microwave CVD method, or a DC discharge CVD method), a sputtering method, a vacuum deposition method, an ion plating method, or the like. It can be formed by a number of thin film deposition methods such as a printing method, a photo CVD method, and a thermal CVD method. These thin film deposition methods
It is appropriately selected and adopted depending on factors such as the manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the photoconductor to be manufactured. Conditions for manufacturing a photoconductor having desired characteristics are adopted. The glow discharge method is preferable because the control of the temperature is relatively easy.

In order to form the photoconductive layer 1103 by the glow discharge method, basically, a source gas for supplying Si that can supply silicon atoms (Si) and a source gas for supplying H that can supply hydrogen atoms (H) are used. And a source gas such as a source gas for X supply capable of supplying a halogen atom (X) in a desired gas state as necessary into a reaction vessel capable of reducing the pressure therein. A glow discharge is generated in the container, and a predetermined support 11 previously set at a predetermined position is provided.
A layer made of a-Si: H, X may be formed on the layer 01.

Further, in the present invention, it is necessary that at least one of a hydrogen atom and a halogen atom is contained in the photoconductive layer 1103, which compensates for dangling bonds of silicon atoms and improves the layer quality. In particular, it is indispensable for improving photoconductivity and charge retention characteristics.
Therefore, the content of the hydrogen atom or the halogen atom, or the sum of the hydrogen atom and the halogen atom is 10 to 30 atom%, more preferably 15 to 25 atom%, based on the sum of the silicon atom, the hydrogen atom and the halogen atom. It is desirable to be done.

Examples of the substance which can be a gas for supplying Si used in the present invention include those in which gaseous or gaseous silicon hydrides (silanes) are effectively used. SiH ₄ and Si ₂ H ₆ are preferable in terms of easiness and high Si supply efficiency.

Then, hydrogen atoms are structurally introduced into the formed photoconductive layer 1103 so that the introduction ratio of hydrogen atoms can be more easily controlled, and a film characteristic which achieves the object of the present invention can be obtained. Therefore, it is preferable to form a layer by mixing a desired amount of H ₂ , He or a silicon compound gas containing a hydrogen atom with these gases. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

The source gas for supplying a halogen atom used in the present invention is, for example, a gas or a gas such as a halogen gas, a halide, an interhalogen compound containing a halogen, or a silane derivative substituted with a halogen. The obtained halogen compounds are preferred.
Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom which contains a silicon atom and a halogen atom as constituent elements can also be mentioned as an effective compound.

To control the amounts of hydrogen atoms and halogen atoms contained in the photoconductive layer 1103, for example,
Temperature of 101, the amount of raw materials used to contain hydrogen atoms and halogen atoms introduced into the reaction vessel,
What is necessary is just to control discharge electric power etc.

In the present invention, it is preferable that the photoconductive layer 1103 contains atoms for controlling conductivity as necessary. The atoms that control the conductivity are the photoconductive layer 1103.
It may be contained in a uniformly distributed state in the inside, or there may be a part contained in a non-uniform distribution state in the layer thickness direction.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors.
As is well known, an atom belonging to Group 13 of the periodic table that provides p-type conduction characteristics (Group 13 atom) or an atom belonging to Group 15 of the periodic table that provides n-type conduction characteristics (Group 15 atom) can be used. .

Further, these raw materials for introducing atoms for controlling conductivity may be diluted with H ₂ or He as necessary.

Further, in the present invention, the photoconductive layer 110
It is also effective that 3 contains other atoms such as a carbon atom, an oxygen atom, and a nitrogen atom. Carbon atoms, oxygen atoms, and nitrogen atoms may be evenly and uniformly contained in the photoconductive layer, or have a non-uniform distribution such that the content changes in the thickness direction of the photoconductive layer. There may be parts.

In the present invention, the layer thickness of the photoconductive layer 1103 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
It is desirable that the thickness be 0 to 50 μm, more preferably 23 to 45 μm, and most preferably 25 to 40 μm.

In order to achieve the object of the present invention and to form a photoconductive layer 1103 having desired film characteristics, a mixing ratio of a gas for supplying Si and a diluting gas, a gas pressure in a reaction vessel, a discharge power, The temperature of the support can be appropriately set.

The above-mentioned conditions are not usually determined independently and independently. Rather, the optimum values are determined based on mutual and organic relationships in order to form a photoreceptor having desired characteristics. Is desirable.

<Surface Layer> In the present invention, the photoconductive layer 1103 formed on the support 1101 as described above is used.
It is preferable to further form a surface layer 1104 on the above. The surface layer 1104 has a free surface, and is provided to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.

The surface layer 1104 is made of an amorphous silicon (a-Si) -based material, for example, amorphous silicon containing a hydrogen atom (H) or a halogen atom (X) and further containing a carbon atom (hereinafter referred to as “a-Si”). SiC: H, X "), amorphous silicon containing a hydrogen atom (H) or a halogen atom (X), and further containing an oxygen atom (hereinafter referred to as" a-SiO: H, X "); Amorphous silicon containing a hydrogen atom (H) or a halogen atom (X) and further containing a nitrogen atom (hereinafter referred to as “a-SiN:
H, X), amorphous silicon containing a hydrogen atom (H) or a halogen atom (X) and further containing at least one of a carbon atom, an oxygen atom and a nitrogen atom (hereinafter referred to as “a-SiCON: H , X ") are suitably used.

In the present invention, in order to effectively achieve the object, the surface layer 1104 is produced by a vacuum deposition film forming method, with the numerical conditions of film forming parameters appropriately set so as to obtain desired characteristics. . Specifically, for example, a glow discharge method (an AC discharge CVD method such as a low frequency CVD method, a high frequency CVD method or a microwave CVD method, or a DC discharge CVD method), a sputtering method, a vacuum deposition method,
It can be formed by various thin film deposition methods such as an ion plating method, a photo CVD method, and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the photoconductor to be manufactured. Preferably, a deposition method equivalent to that of the photoconductive layer is used.

For example, a-Si is formed by a glow discharge method.
In order to form the surface layer 1104 composed of C: H, X, a source gas for supplying Si that can supply silicon atoms (Si) and a C for supplying C that can supply carbon atoms (C) are basically used. A raw material gas and a raw material gas for supplying H that can supply hydrogen atoms (H) and a raw material gas for X supply that can supply halogen atoms (X) are placed in a reaction vessel that can reduce the pressure inside the reactor to a desired gas state. To generate a glow discharge in the reaction vessel, and the photoconductive layer 110 previously set at a predetermined position.
A layer made of a-SiC: H, X may be formed on the support 1101 on which the substrate 3 is formed.

When the surface layer is composed mainly of a-SiC, the amount of carbon is preferably in the range of 30% to 90% with respect to the sum of silicon atoms and carbon atoms.

In the present invention, it is necessary that the surface layer 1104 contains hydrogen atoms and halogen atoms, which compensates for dangling bonds of silicon atoms and improves the quality of the layer, especially the photoconductive layer. It is indispensable to improve the properties and the charge retention properties. The hydrogen content is usually 30 to 70 atomic%, preferably 3 to 70 atomic%, based on the total amount of the constituent atoms.
It is desirable that the content be 5 to 65 atomic%, optimally 40 to 60 atomic%. The content of fluorine atoms is usually 0.01 to 15 atomic%, preferably 0.1 to 10 atomic%, and most preferably 0.6 to 4 atomic%.

Defects in the surface layer (mainly dangling bonds of silicon atoms and carbon atoms) may be caused by, for example, deterioration of charging characteristics due to injection of charges from the free surface to the photoconductive layer, use environment, for example, under high humidity. The charge characteristics are changed due to the change of the surface structure, and the charge is injected into the surface layer by the photoconductive layer at the time of corona charging or light irradiation, and the charge is trapped by the defects in the surface layer. It is known that the afterimage phenomenon has an adverse effect on the characteristics of the photoconductor.

By controlling the hydrogen content in the surface layer to 30 atomic% or more, defects in the surface layer are greatly reduced, and the electrical characteristics and the high-speed continuous usability can be improved. On the other hand, when the hydrogen content in the surface layer exceeds 70 atomic%, the hardness of the surface layer tends to decrease and the durability tends to decrease.

The fluorine content in the surface layer is set to 0.01
By controlling the content to the range of at least atomic%, it is possible to more effectively achieve the generation of the bond between silicon atoms and carbon atoms in the surface layer. Further, as a function of the fluorine atoms in the surface layer, it is possible to effectively prevent the bond between the silicon atom and the carbon atom from being broken due to damage such as corona.

On the other hand, when the fluorine content in the surface layer exceeds 15 atomic%, the effect of generating the bond between the silicon atom and the carbon atom in the surface layer and the effect of preventing the breaking of the bond between the silicon atom and the carbon atom are almost lost. Will not be recognized. further,
Excessive fluorine atoms hinder the mobility of carriers in the surface layer, so that residual potential and image memory are noticeably observed.

The fluorine content and hydrogen content in the surface layer are as follows:
It can be controlled by the flow rate of F ₂ gas or H ₂ gas, the temperature of the support, the discharge power, the gas pressure, and the like.

The layer thickness of the surface layer 1104 in the present invention is usually 0.01 to 3 μm, preferably 0.05 to 2 μm.
m, and most preferably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to abrasion during use of the photoreceptor, and the
If it exceeds m, the electrophotographic characteristics are lowered, such as an increase in the residual potential.

The surface layer 1104 in the present invention is carefully formed so that the required characteristics are given as desired. In other words, a substance containing Si, C, N, O, H, X, and the like as components is structurally from crystalline to amorphous depending on its formation conditions, and is electrically conductive to semiconductive depending on electrical properties. In the present invention, a compound having desired properties according to the purpose is formed because the properties up to the insulating property and the properties from the photoconductive property to the non-photoconductive property are shown. As such, the choice of forming conditions is strictly made as desired.

For example, in order to provide the surface layer 1104 mainly for the purpose of improving the pressure resistance, the surface layer 1104 is made of a non-single-crystal material having a remarkable electric insulating behavior in a use environment.

When the main purpose is to improve the continuous repetitive use characteristics and the use environment characteristics, the above-described degree of electrical insulation is relaxed to some extent, and non-uniformity having a certain sensitivity to irradiated light is obtained. Formed as a crystalline material.

Further, in order to prevent the image flow due to the low resistance of the surface layer 1104 or to prevent the influence of the residual potential, etc., and to improve the charging efficiency, the resistance value of the layer is appropriately adjusted at the time of forming the layer. It is preferable to control.

Further, in the present invention, it is also possible to provide a blocking layer (lower surface layer) in which the content of carbon atoms, oxygen atoms and nitrogen atoms is smaller than that of the surface layer between the photoconductive layer and the surface layer. It is effective to further improve the characteristics of.

Further, between the surface layer 1104 and the photoconductive layer 1103, the content of atoms such as carbon atoms, oxygen atoms, and nitrogen atoms contained in the surface layer is reduced toward the photoconductive layer 1103. A changing region may be provided. Thereby, the adhesion between the surface layer and the photoconductive layer can be improved, and the influence of interference due to light reflection at the interface can be further reduced.

<Charge Injection Blocking Layer> In the photoreceptor used in the present invention, a charge injection blocking layer having a function of blocking charge injection from the support side is provided between the support and the photoconductive layer. Is more effective. That is, the charge injection blocking layer has a function of preventing charges from being injected from the support side to the photoconductive layer side when the photosensitive layer receives a charging treatment of a fixed polarity on its free surface. Such a function is not exhibited when it is subjected to a charging treatment, that is, it has a so-called polarity dependency. In order to provide such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer.

The atoms for controlling the conductivity contained in the layer may be uniformly distributed in the layer uniformly, or may be uniformly distributed in the thickness direction of the layer. Some portions may be contained in a state of being uniformly distributed. When the distribution concentration is non-uniform, it is preferable that the compound be contained so as to be distributed more on the support side.

However, in any case, it is necessary to uniformly contain the particles in the in-plane direction parallel to the surface of the support from the viewpoint of making the characteristics uniform in the in-plane direction. .

As the atoms for controlling the conductivity contained in the charge injection blocking layer, there can be mentioned so-called impurities in the field of semiconductors. 15 of the periodic table that gives
Group atoms can be used.

In the present invention, the content of atoms for controlling the conductivity contained in the charge injection blocking layer is appropriately determined as desired so that the object of the present invention can be effectively achieved.

Further, carbon atoms,
By containing at least one of a nitrogen atom and an oxygen atom, the adhesion between the charge injection blocking layer and another layer provided in direct contact with the charge injection blocking layer can be further improved.

The carbon atoms, nitrogen atoms, or oxygen atoms contained in the layer may be uniformly distributed throughout the layer, or may be evenly distributed in the thickness direction of the layer. There may be a part contained in a state of being unevenly distributed. However, in any case, it is necessary to uniformly contain the particles in the in-plane direction parallel to the surface of the support from the viewpoint of making the properties uniform in the in-plane direction.

The contents of carbon atoms, nitrogen atoms and oxygen atoms contained in the entire region of the charge injection blocking layer in the present invention are appropriately determined so that the object of the present invention is effectively achieved.

Further, hydrogen atoms and halogen atoms contained in the charge injection blocking layer in the present invention compensate for dangling bonds existing in the layer, and are effective in improving the film quality.

In the present invention, the thickness of the charge injection blocking layer is preferably from 0.1 to 5 μm, more preferably from 0.3 to 4 μm, from the viewpoint of obtaining desired electrophotographic characteristics and economic effects. Most preferably, it is 0.5 to 3 μm.

In the present invention, in order to form the charge injection blocking layer, a vacuum deposition method similar to the above-described method of forming the photoconductive layer is employed.

In addition, in the photoreceptor of the present invention,
It is preferable that a layer region containing at least aluminum atoms, silicon atoms, hydrogen atoms, and halogen atoms in a non-uniform distribution state in a layer thickness direction is provided on the support 1101 side of the photosensitive layer 1102.

In the photoreceptor of the present invention, the support 1101 and the photoconductive layer 1103 or the charge injection preventing layer 1
For the purpose of further improving the adhesiveness between the substrate 105 and Si, for example, Si ₃ N ₄ , SiO ₂ , SiO, or a silicon atom is used as a base material, and at least one of a hydrogen atom and a halogen atom, a carbon atom, an oxygen atom, An adhesion layer formed of an amorphous material containing at least one of atoms and nitrogen atoms may be provided. Further, as described above, a light absorbing layer for preventing the generation of an interference pattern due to light reflected from the support may be provided.

<Manufacturing Apparatus> The photoreceptor as described above is manufactured using a known CVD apparatus. An example of a CVD apparatus capable of manufacturing the photoreceptor used in the present invention is described below.

FIG. 6 shows a high-frequency plasma C using the RF band.
1 shows an example of a VD method (referred to as “RF-PCVD”) apparatus. This apparatus is roughly classified into a deposition apparatus (2100),
Source gas supply device (2200), reaction vessel (211)
1) It comprises an exhaust device (not shown) for reducing the pressure inside. The reaction vessel (2) in the deposition apparatus (2100)
111), a cylindrical support (2112), a heater for heating the support (2113), and a raw material gas introduction pipe (2114)
Is installed, and a high-frequency matching box (211)
5) is connected.

The source gas supply device (2200) is made of SiH
₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH _{3 and} other source gas cylinders (2221-2226) and valves (2231-223)
6, 2241 to 2246, 2251 to 2256) and a mass flow controller (2211 to 2216), and a cylinder for each source gas is supplied via a valve (2260) to a source gas introduction pipe (211) in a reaction vessel (2111).
4) is connected.

FIG. 7 shows an example of an apparatus of a high-frequency plasma CVD method (referred to as “VHF-PCVD”) using a VHF band. This apparatus is a deposition apparatus (2100) shown in FIG.
Is connected to a source gas supply device (2200) instead of the deposition device (3100) shown in FIG.
This is an example in which a manufacturing apparatus is formed by a CVD method.

This apparatus is roughly classified into a reaction vessel (3111) having a vacuum-tight structure and capable of reducing pressure, a supply apparatus (not shown) for raw material gas, and an exhaust apparatus (not shown) for reducing the pressure inside the reaction vessel. (Shown). A cylindrical support (3112), a heater for heating the support (3113), a raw material gas introduction pipe (not shown), and an electrode (3115) are installed in the reaction vessel (3111).
Is further connected to a high frequency matching box (3116). The inside of the reaction vessel (3111) is connected to a diffusion pump (not shown) through an exhaust pipe (3121). The space (3130) surrounded by the support (3112) forms a discharge space. This apparatus is provided with a motor (3120) and is configured to be able to rotate a support (3112) accommodated in a reaction vessel (3111).

The photoreceptor used in the present invention is manufactured by appropriately setting various conditions such as the supply amount of the raw material gas, the temperature and pressure in the reaction vessel, and the electric power required for the discharge by using the above-described CVD apparatus. can do.

Next, the developer and toner used in the present invention will be described. First, the coloring agent used in the present invention will be described. In the present invention, the kind of the colorant is not particularly limited, but it is preferable to use a pigment in the color toner, and to improve the color reproducibility of the resin in dispersibility, the coloring power, and the light resistance. Further, it is appropriately determined in consideration of the fact that it does not become a charging inhibitory factor.

Preferred yellow pigments include C.I. I. Pigment Yellow (CI Pigment Yellow)
ow) 74, 93, 97, 109, 128, 151, 1
54, 155, 166, 168, 180, 185 and the like.

As preferred magenta pigments, quinacridone pigments, C.I. Pigment Red (C.I.
I. Pigment Red) 48: 2, 57: 1, 5
8: 2 and C.I. Pigment Red (C.I.
Pigment Red) 5, 31, 146, 147,
150, 184, 187, 238, 245, and
I Pigment Red (CI Pigment Re)
d) 185, 265 and the like.

Preferred cyan pigments include copper phthalocyanine pigments and aluminum phthalocyanine pigments. As the copper phthalocyanine pigment, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula (I) may be used.

Embedded image

Black magnetic particles can be used as the black pigment, and magnetite is particularly preferable.

By using these pigments, the dispersibility of the pigment in the binder resin is increased, and as a result, the coloring power is increased, low-potential development becomes possible, and a good full-color image can be formed. One or more pigments can be used.

The content of the yellow pigment is OH
The amount of the yellow toner sensitive to the transmittance of the P film is 12 parts by mass or less, more preferably 0.5 to 8 parts by mass, per 100 parts by mass of the binder resin. When the content is 12 parts by mass or more, the reproducibility of human skin color tends to be inferior as a mixed color of yellow, green and red, and as an image.

The other magenta toner, cyan toner and black toner are not particularly limited, but the content of the magenta pigment, cyan pigment or black pigment is 15 parts by mass with respect to 100 parts by mass of the binder resin. Or less, and more preferably 0.1 to 9 parts by mass.

The toner used in the present invention is mixed with a thermoplastic resin, a pigment or dye as a colorant, a charge control material, other control agents, and the like, if necessary, using a mixer such as a ball mill. The resin can be obtained by melting and kneading with a hot kneader such as a roll, kneader, extruder and the like to melt the resins, and after cooling and solidifying, pulverizing and strict classification. The pigment may be dispersed or dissolved in the above-mentioned melt-kneaded material.

However, the amount (M / S) of the unfixed toner such as the toner used in the present invention is determined by M / S = 0.5 mg / cm ^2.
In order to obtain a toner having a coloring power such that the image density (D0.5) after one-time fixing is usually 1.0 or more and 1.8 or less, it is preferable to use the following pigment dispersion method. .

That is, in the present invention, in order to achieve the specific dispersion state of the pigment particles in the color toner particles as described above, the first binder resin and the pigment particles insoluble in the dispersion medium, 5 to 50, are used. The paste pigment containing 1% by mass is charged into a kneader or a mixer, and heated while mixing under non-pressure to melt the first binder resin, and the paste pigment, that is, the pigment in the liquid phase is heated. After being transferred to the first binder resin, that is, the molten resin phase, the first binder resin and the pigment particles are melt-kneaded, a liquid component is removed and evaporated, and the first binder resin and the pigment particles are dried. A first kneaded material having pigment particles is obtained, and then a mixture obtained by adding a second binder resin to the first kneaded material, and further, if necessary, an additive such as a charge control agent, is heated and melt-kneaded. A second kneaded material is obtained, and the obtained second
It is preferable that the kneaded material is cooled and then pulverized and classified to form a toner. Here, the first binder resin and the second binder resin may be the same or different binder resins.

In the present invention, the above-mentioned paste pigment refers to a state in which the pigment particles are present only once in the pigment particle production step without undergoing a drying step. In other words, when the pigment particles are almost primary particles, 5
５０50% by mass. The remaining 50-95% by weight of the paste pigment is occupied by the majority of volatile liquids, together with some dispersants and auxiliaries. The volatile liquid is not particularly limited as long as it is a liquid that evaporates by general heating, but water, which is particularly preferably used in the present invention and is preferably used ecologically, is water.

In the present invention, the insoluble pigment particles are
Pigment particles that are insoluble in the dispersion medium that is a volatile liquid in the paste pigment and can be dispersed in the paste pigment. For example, when water is selected as the volatile liquid, all water-insoluble pigment particles are insoluble pigment particles.

The paste pigment used in the present invention contains water-insoluble pigment particles in an amount of 5 to 50% by mass, more preferably 5 to 50% by mass.
It is good to contain 45 mass%. When the content of the insoluble pigment exceeds 50% by mass, the dispersing efficiency in the binder resin is low, and the kneading temperature tends to be high, or the kneading time tends to be set long. Further, a strong screw or paddle structure is essential for the kneading device, and the polymer chain is likely to be cut.

Conversely, when the paste pigment contains less than 5% by mass of insoluble pigment in solid content, in order to obtain the desired pigment content, a large amount of the paste pigment must be introduced into the mixing device. However, the size of the mixing device is undesirably increased. Further, when the amount is less than 5% by mass, the step of removing water in the step after the first kneading must be strengthened and water must be completely blown off, resulting in a large load on the binder resin. Will be.

When kneading or mixing the paste pigment and the binder resin, the ratio of the pigment to the binder resin in terms of solid content is from 10:90 to 50:50, preferably from 15:85 to 4: 1.
5:55 is good.

When the ratio of the pigment to the resin is less than 10% by mass, a large amount of the resin must be charged into the kneader with respect to the paste pigment, and the segregation of the pigment in the kneaded material is liable to occur. Therefore, the kneading time has to be set long. In this case, an extra load is applied to the resin, and the desired resin characteristics may not be obtained.

When the ratio of the pigment to the resin is more than 50% by weight, it is difficult to smoothly transfer the pigment particles from the liquid phase to the resin. The product is hard to show a uniform molten state, and as a result, good dispersibility may not be obtained.

In the above-described toner production, it is preferable to perform melt-kneading under no pressure. The reason is that under pressure, the liquid (for example, water) in the paste pigment attacks the binder resin and may cause a partial hydrolysis reaction or deterioration of the resin. It may be reduced in some cases. Therefore, in the above-described toner production, it is preferable to perform the melt-kneading of the first binder resin and the paste pigment under no pressure.

Examples of the kneading apparatus used in the production of the toner include a heating kneader, a single-screw extruder, a twin-screw extruder, and a kneader, and particularly preferably a heating kneader.

As the binder resin used in the present invention, various resins conventionally known as binder resins for electrophotography are used. For example, styrene-based copolymers such as polystyrene, styrene-butadiene copolymer, styrene-acrylic copolymer, polyethylene-ethylene-vinyl acetate copolymer, phenolic resin, epoxy resin, acrylic phthalate resin, polyamide resin, polyester resin In the present invention, when a polyester resin is used as the binder resin, good pigment dispersibility and charging stability can be achieved.

Hereinafter, the polyester resin will be described in more detail. As the above polyester resin, a copolymer of a divalent acid and a dihydric alcohol is preferable.Examples of the divalent acid component constituting the preferably used polyester resin include terephthalic acid, isophthalic acid, phthalic acid, and diphenyl acid. -PP'-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylmethane-PP'-dicarboxylic acid,
Aromatic dicarboxylic acids such as benzophenone-4,4'-dicarboxylic acid, 1,2-diphenoxyethane-P, P'-dicarboxylic acid can be used, and as other acids,
For example, maleic acid, fumaric acid, glutaric acid, cyclohexanedicarboxylic acid, succinic acid, malonic acid, adipic acid,
Mesaconic acid, itaconic acid, citraconic acid, sebacic acid,
Derivatives such as anhydrides and lower alkyl esters of these acids can be used.

As the dihydric alcohol, the following formula (II)

Embedded image (In the formula, R ₁ is an alkylene group having 2 to 5 carbon atoms,
X and Y are positive numbers and 2 ≦ X + Y ≦ 6. ), For example, polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl)
Propane, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (13) -2 , 2
-Bis (4-hydroxyphenyl) propane and the like.

Other dihydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
Diols such as 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,4-bis (hydroxymethyl)
Examples include cyclohexane, bisphenol A, hydrogenated bisphenol A, and the like.

In the polyester resin used in the present invention, for example, n-dodecenyl group, isododecenyl group,
maleic acid, fumaric acid, glutaric acid, succinic acid having n-dodecyl group, isododecyl group, isooctyl group,
Acids having an alkyl or alkenyl substituent such as malonic acid and adipic acid, ethylene glycol, 1,3-
Propylene diol, tetramethylene glycol, 1,
Alcohols such as 4-butylene diol and 1,5-pentyldiol may be contained.

The method for producing the polyester resin used for the toner in the present invention is, for example, as follows.

First, a linear condensate is formed, and in the process, the molecular weight is adjusted so as to be 1.5 to 3 times the target acid value and hydroxyl value, and the molecular weight is made higher than before so that the molecular weight becomes uniform. In order for the condensation reaction to proceed slowly and slowly, for example, (i) react at lower temperature and longer time than before, (ii)
The reaction is controlled by reducing the amount of the esterifying agent, (iii) using a less reactive esterifying agent, or (iv) using a combination of these methods. Thereafter, under these conditions, a crosslinking acid component and, if necessary, an esterifying agent are further added, and the mixture is reacted to form a three-dimensional condensate.
The temperature is further increased, the reaction is allowed to proceed slowly for a long time so that the molecular weight distribution becomes uniform, the crosslinking reaction proceeds, and when the hydroxyl value or the acid value or the MI (Meit Index) value decreases to the target value, the reaction is terminated. Get.

In the present invention, the polyester resin has an acid value of 35 mg KOH / g or less, preferably 30 mg KOH / g.
When it is not more than H / g, it is preferable because excellent charging stability can be obtained in each environment.

When the acid value of the toner is larger than 35 mgKOH / g, it is difficult to properly charge the toner positively, and image defects such as low image density and fog are likely to occur.

In the present invention, the glass transition temperature (Tg) of the toner is 50 to 70 in consideration of the storability and fixability of the color toner and the color mixing with other color toners.
° C, preferably 52 to 68 ° C.

When the glass transition temperature of the toner is lower than 50 ° C., although the fixing property is excellent, the offset resistance is lowered, and the fixing roller is contaminated and the fixing roller is wrapped, which is not preferable. Further, the gloss of the image surface after fixing becomes too high, and the image quality deteriorates, which is not preferable.

If the glass transition temperature of the resin is higher than 70 ° C., the fixability deteriorates and the fixing temperature of the copying machine must be increased, and the resulting image generally has low gloss and full color. For toners, the color mixing tends to decrease.

The binder resin used in the present invention preferably has a number average molecular weight (Mn) of from 1,500 to 20,000.
0, more preferably 2,000 to 15,000, and the weight average molecular weight (Mw) is preferably 6,000 to 100,000, more preferably 8,000 to 8
Mw / Mn is preferably 2 to 10
Good to be. A binder resin that satisfies the above conditions has good heat fixability, improves the dispersibility of the colorant, reduces the variation in the charge amount of the color toner, and improves the reliability of image quality.

When the number average molecular weight (Mn) of the binder resin is 1,5
When the weight average molecular weight (Mw) is less than 6,000
When the value is less than 0, the smoothness of the fixed image surface is high and the appearance is vivid, but offset tends to occur in the durability, and further, the storage stability is reduced, and the There is also a new problem such as the occurrence of toner fusion. Furthermore, it is difficult to apply a shear during the melt-kneading of the toner raw material during the production of the color toner particles, the dispersibility of the chromatic colorant is easily reduced, and therefore the toner coloring power is reduced and the toner charge amount is easily changed. .

When the number average molecular weight (Mn) of the binder resin is 20,
000 or a weight average molecular weight (Mw) of 10
If it exceeds 000, all of them have excellent offset resistance, but the fixing temperature must be increased, and even if the degree of dispersion of the pigment can be controlled, the surface smoothness in the image area can be improved. In some cases, the color reproducibility is likely to be reduced.

When the Mw / Mn of the binder resin is less than 2, the molecular weight itself becomes small. Therefore, similarly to the case where the molecular weight is small, offset development due to durability, deterioration of storage stability, deterioration in the developing device, etc. , The toner is easily fused, and the charge amount of the toner tends to vary.

When Mw / Mn of the binder resin exceeds 10, although the offset resistance is excellent, the fixing temperature must be increased, and even if the degree of dispersion of the pigment can be controlled. In some cases, surface lubricity in an image portion is reduced, and color reproducibility is likely to be reduced.

Further, the toner used in the present invention preferably has a softening point temperature (Tm) calculated from a flow tester curve of 85 ° C. ≦ Tm ≦ 120 ° C.

When the softening point temperature of the toner is higher than 120 ° C., although the anti-offset property is excellent, the fixing temperature must be increased, and even if the degree of dispersion of the pigment can be controlled, the image can be controlled. There is a tendency that the surface smoothness in the portion is greatly reduced, and high color reproducibility cannot be expected.

When the softening point temperature of the toner is lower than 85 ° C., although the smoothness of the fixed image is high and the appearance is vivid, the offset tends to occur in the durability. Further, the storage stability is poor, and there is a concern about a new problem such as fusion of a toner in a developing device. Accordingly, the softening point temperature Tm of the color toner is preferably 85 ° C. ≦ Tm ≦ 120 ° C., and more preferably 90 ° C. ≦ Tm ≦ 115 ° C.

In the toner used in the present invention, a positive charge control agent may be added, if necessary, and any one of a quaternary ammonium salt, an imidazole compound, a styrene acrylic copolymer resin containing an ammonio group, and a houshounium compound. It is desirable to contain Above all, a white control material is suitably used for a color toner. The quaternary ammonium salt contained in the magnetic toner used in the present invention is represented by the following general formula (III).

[0176]

Embedded image

In the formula, R _{1 to} R ₄ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an unsubstituted or substituted aromatic group, etc., and A ⁻ represents a counter anion. One or more of R _{1 to} R ₄ is an alkyl or alkenyl group having 6 or more, more preferably 10 or more, and further 12 or more carbon atoms, and an unsubstituted or substituted aromatic group. Particularly preferred.

[0178] The A ^-: Examples of the anion of the ^{counter, Cl -, Br -, I} - and halogen ions; Cl
_{^{O 3 -, ClO 4 -,}} IO 3 -, IO 4 - halogen acid ions, ions represented by the following formula (IV), such as, CH ₃ SO ₄ ^- sulfonic acid ion, sulfuric acid ion, such as, BF ₄ ^- , P
Molybdate, tungstate, molybdenum atom or heteropolyacid ion containing tungsten atom such as F ₆ ⁻ , Mo ₇ O ₂₄ ⁶⁻ , H ₂ W ₁₂ O ₄₂ ¹⁰⁻ , PW ₁₂ O ₄₀ ^3- it can.

[0179]

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Examples of the positive charge control agent as described above include the following. Hoechst VP20
36 (melting point: 200 ° C.), VP2038 (melting point: 215)
TP302 manufactured by Hodogaya Chemical Co., Ltd. (melting point: 215
° C), TP415 (melting point: 204 ° C), TP4040
(Melting point: 209 ° C), A-902 manufactured by Nippon Carlit Co.
(Melting point: 210 ° C).

On the other hand, examples of the functional group for imparting positive charge to the toner in the charge control resin include various groups, and a trisubstituted ammonium group is particularly preferable, and a trialkyl ammonium group represented by the general formula (V) is particularly preferable. The O group is more preferred because it has an excellent function of imparting positive chargeability.

[0182]

Embedded image [Wherein R ^a , R ^b and R ^c are the same or different and each is a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, a hexyl group, etc. X represents an alkyl group;
^- the molybdate ion, phosphate molybdate, chromium molybdate, phosphotungstic acid ion, silicotungstic acid ion, antimony ion,
Bismuthate, chlorine, bromine, iodine, nitrate, sulfate, perchlorate, periodate, benzoate, naphtholsulfonate, benzenesulfonate, toluenesulfonate, xylenesulfone An acid ion, a tetraphenyl boron ion, a tetrafluoro boron ion, a tetrafluoro phosphorus ion, and a hexafluoro phosphorus ion are shown. ]

As the main chain of the charge control resin, various polymer main chains can be employed, but the compatibility with the polyester resin as the fixing resin is particularly important in view of the transparency and the positive charging property of the toner. It is important to use a polymer main chain having good compatibility with the polyester resin. Examples of such a polymer main chain include styrene-acrylic resins such as a styrene-acrylate copolymer and a styrene-methacrylate copolymer.
When the styrene-acrylic resin has a main chain, the functional group is preferably replaced with an acrylic ester moiety.

Next, as the positively charged charge control agent used in the present invention, an imidazole derivative represented by the following formula (VI) is preferably used.

[0185]

Embedded image (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a substituent selected from the group consisting of hydrogen, an alkyl group, an aralkyl group and an aryl group, which are the same or different and are substituted. include those who are, X is a phenylene group, a propenylene group, a vinylene group, an alkylene group and -CR ₅
R ₆ represents a linking group selected from the group consisting of R ₆ —, and R ₅ and R ₆ represent a substituent selected from the group consisting of hydrogen, an alkyl group, an aralkyl group and an aryl group. )

Wherein R ₁ , R ₂ , R ₃ and R ₄ are hydrogen,
It represents a substituent selected from the group consisting of an alkyl group, an aralkyl group and an aryl group, which may be the same or different, and may be substituted by a substituent. The R ₁ , R ₂ , R ₃ and R ₄
When the substituent is further substituted, examples of the substituent include an amino group, a hydroxyl group, an alkyl group, an alkoxy group, and a halogen.

As R ₁ , R ₂ , R ₃ and R ₄ , specifically, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl group, undecyl group, dodecyl group,
Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, henycosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, i-propyl group, i-butyl group, t -Butyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group,
Examples include diphenylmethyl, trityl, cumyl, phenyl, tolyl, xylyl, mesityl, naphthyl and anthryl groups.

Further, in R ₁ , R ₂ , R ₃ and R ₄ ,
The alkyl group preferably has 1 to 25 carbon atoms, the aralkyl group preferably has 7 to 20 carbon atoms, and the aryl group preferably has 6 to 20 carbon atoms.

In the formula, X represents a linking group selected from the group consisting of phenylene, propenylene, vinylene, alkylene and —CR ₅ R ₆ —, and R ₅ and R ₆ represent hydrogen, an alkyl group, an aralkyl group and an aryl group. Represents a substituent selected from the group consisting of:

In R ₅ and R ₆ , the alkyl group preferably has 1 to 20 carbon atoms, the aralkyl group preferably has 7 to 15 carbon atoms, and the aryl group has 6 to 15 carbon atoms. Good to be.

The imidazole derivative represented by the above formula (1) used in the present invention can be obtained by reacting the following formula (VII) or (VIII)
The imidazole derivative represented by is particularly preferable.

[0192]

Embedded image

In the formula, R ₁ and R ₂ are substituents selected from the group consisting of an alkyl group having 5 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. And these include those which are the same or different from each other, and are substituted. Examples of the substituent for this substitution include an amino group, a hydroxyl group,
Examples include an alkyl group, an alkoxy group and a halogen.

R ₃ , R ₄ , R ₅ and R ₆ each represent a substituent selected from the group consisting of hydrogen, an alkyl group, an aralkyl group and an aryl group, which are the same or different, and Including those that are. Examples of the substituent for this substitution include an amino group,
Examples include a hydroxyl group, an alkyl group, an alkoxy group and a halogen.

In R ₃ , R ₄ , R ₅ and R ₆ , the alkyl group preferably has 1 to 6 carbon atoms, the aralkyl group preferably has 7 to 15 carbon atoms, and the aryl group has Preferably has 6 to 15 carbon atoms.

[0196]

Embedded image

In the formula, R ₁ and R ₂ are substituents selected from the group consisting of an alkyl group having 5 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Which are the same or different, and include those substituted. Examples of the substituent in the case of substitution include an amino group, a hydroxyl group, an alkyl group, an alkoxy group, and a halogen.

R ₃ and R ₄ each represent a substituent selected from the group consisting of hydrogen, an alkyl group, an aralkyl group and an aryl group, and these are the same or different, and include those substituted. Examples of the substituent in the case of substitution include an amino group, a hydroxyl group, an alkyl group, an alkoxy group, and a halogen.

In R ₃ and R ₄ , the alkyl group preferably has 1 to 6 carbon atoms, the aralkyl group preferably has 7 to 15 carbon atoms, and the aryl group has 6 to 15 carbon atoms. Good to be.

The imidazole derivative represented by the above formula (VII) has excellent dispersibility in a binder resin, and further has the above formula (VII)
Since the imidazole derivative represented by I) has good dispersibility and excellent adhesion to the binder resin, the occurrence of sleeve contamination due to detachment of the imidazole derivative from the toner is suppressed.

[0201] In the above formula (VII) and (VIII), R ₁
When the carbon number of the alkyl group of R ₂ and R ₂ is less than 5, the positive charging ability is low, and an increase in the amount of addition tends to be required in order to exert an effect as a positive charge control agent. On the other hand, when the carbon number of the alkyl group, aralkyl group and aryl group of R ₁ and R ₂ exceeds 20, the melting point of the imidazole derivative itself decreases, so that the melt viscosity of the imidazole derivative in the melt-kneading step at the time of toner production is reduced. Drop,
Since uniform dispersion in the binder resin becomes difficult, deterioration of image characteristics due to poor dispersion is likely to occur, and the binder resin may be limited.

In the present invention, the imidazole derivative is used in an amount of 0.01 to 20.0 parts by weight, preferably 0.1 to 10.0 parts by weight, more preferably 0.5 to 5.0 parts by weight, per 100 parts by weight of the binder resin. It is preferable to add 0 parts by weight. If the addition amount is less than 0.01 parts by weight, the toner cannot have a sufficient charge amount, and the effect of adding the imidazole derivative does not appear. On the other hand, when the addition amount is more than 20.0 parts by weight, excessive addition results in poor dispersion in the toner, resulting in agglomerates or uneven presence of the imidazole derivative per individual toner particle. This is not preferred.

The imidazole derivative used in the present invention can be used in combination with a conventionally known charge control agent.

The imidazole derivative used in the present invention is synthesized as follows. An aldehyde and potassium hydroxide as a solvent are added to an imidazole derivative represented by the following general formula (D) using ethanol as a solvent and refluxed for several hours. The precipitate is filtered, washed with water, and recrystallized again with methanol.

[0205]

Embedded image (Wherein R represents a substituent selected from the group consisting of hydrogen, an alkyl group, an aryl group, and an aralkyl group, which may be the same or different).

This synthesis method does not limit the imidazole derivative used in the present invention at all.

Examples of the compound of the imidazole derivative used in the present invention are shown below, but these are typical examples in consideration of easy handling, and similarly do not limit the toner used in the present invention.

[0208]

Embedded image

[0209]

Embedded image

The compounds shown below are the same as those having different substituents on the left and right imidazoles, and may be a mixture thereof.

[0211]

Embedded image

Further, as the positively charged charge control agent, a phosphonium compound represented by the following formula (IX) is preferably used.

[0213]

Embedded image

The content of these charge control agents is 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, per 100 parts by mass of the binder resin. The charge control agent addition amount is 0.
When the amount is 5 to 10 parts by mass, the colorant is finely and uniformly dispersed in the resin, and the triboelectric charging property of the toner is adjusted to a suitable range, which is preferable. When the addition amount of the charge control agent is less than 0.5 parts by mass, the positive charge control effect of the positive toner is small. If the amount of the charge control agent is more than 10 parts by mass, the toner is likely to be charged up under low temperature and low humidity.

In the toner used in the present invention, if necessary, a fatty acid metal salt (eg, zinc stearate, aluminum stearate, etc.) as a lubricant, or a fluorine-containing polymer fine powder (eg, polytetrafluoroethylene, polytetrafluoroethylene, etc.) may be used. A fine powder of vinylidene fluoride or the like and tetrafluoroethylene-vinylidene fluoride copolymer) or a conductivity-imparting agent such as tin oxide or zinc oxide may be added.

Further, in the present invention, the toner may contain a release agent. Examples of the release agent used include aliphatic hydrocarbon waxes, oxides of aliphatic hydrocarbon waxes,
Ester wax, fatty acid ester-based wax, saturated linear fatty acid, unsaturated fatty acid, saturated alcohol, polyhydric alcohol, fatty acid amide, saturated fatty acid bisamide, unsaturated fatty acid amide, aromatic Based bisamides.

With respect to the content of the release agent in the toner,
0.1 to 20 parts by mass of binder resin
The parts by mass, more preferably from 0.5 to 10 parts by mass are good. When the content of the release agent is more than 20 parts by mass, the blocking resistance and the high-temperature offset resistance are liable to decrease, and 0.1% or less.
When the amount is less than the mass part, the releasing effect is small.

These release agents are usually prepared by dissolving a binder resin in a solvent, raising the temperature of the resin solution, and adding and mixing the release agent with stirring, or at least containing the binder resin and a colorant. It is desirable that the toner is contained in the binder resin by a method of mixing a release agent at the time of kneading the toner constituent materials.

In the production of the toner, as described above, a toner kneading material such as a hot roll, a kneader, or an extruder is used to knead the components of the toner well, and then mechanically pulverized to classify the pulverized powder to obtain the toner. Alternatively, a method in which another toner constituent material such as a colorant is dispersed in a binder resin solution, followed by spray drying may be applied.

The developer used in the present invention is a non-magnetic or magnetic one-component developer and contains the toner described above. It is desirable to add a fluidity improver to the developer used in the present invention, in addition to the toner, for the purpose of improving the fluidity of the toner. Any fluidity improver can be used as long as the fluidity can be increased before and after the addition. For example, fine powders of metal oxides such as silicic acid fine powder, alumina fine powder, titanium oxide fine powder, zirconium oxide fine powder, magnesium oxide fine powder, zinc oxide; boron nitride fine powder, aluminum nitride fine powder, carbon nitride fine powder Nitrides such as a body; and further include calcium titanate, strontium titanate, barium titanate, and magnesium titanate. The external additive is usually used in an amount of 0.1 to 5 based on 100 parts by weight of the toner particles.
Used by weight.

In the present invention, it is particularly preferable to use an inorganic fine powder which has been subjected to a hydrophobic treatment and has an average primary particle diameter of 0.001 to 0.2 μm. An important factor in the above additives is that not only does the fluidity of the toner increase, but also the chargeability of the toner is not impaired. In other words, by being subjected to the hydrophobic treatment, it is possible to improve the environmental characteristics by excluding the influence of water, which is a factor affecting the charge amount, and reducing the difference in the charging ability under high humidity and low humidity. In addition, by performing the hydrophobic treatment in the manufacturing process, it is possible to prevent aggregation of the primary particles, and it is possible to uniformly charge the toner.

Therefore, the additives (external additives) used in the present invention are preferably subjected to a surface hydrophobizing treatment, and the use of such an external additive is effective in imparting the fluidity of the toner. And stabilization of charging can be simultaneously satisfied.

In the present invention, in particular, titanium oxide fine powder or alumina fine powder having an average primary particle size of 0.001 to 0.2 μm has a good fluidity. This is preferable because the charging of the conductive toner becomes more uniform, and as a result, toner scattering and fogging hardly occur. Further, the toner is less likely to be embedded in the surface of the toner particles, the toner is hardly deteriorated, and the durability of a large number of sheets is improved. This tendency is more remarkable in a toner having a sharp melt property.

The above tendency is that silica fine particles themselves have strong negative chargeability, whereas titanium oxide fine powder or alumina powder has almost neutral chargeability, and depending on the degree of hydrophobic treatment, This is because the charge level can be controlled to a desired level.

The hydrophobizing agent used in the present invention may be used for the purpose of surface modification, for example, control of charging characteristics,
Furthermore, depending on the stability and reactivity of charging under high humidity,
What is necessary is just to select suitably.

Of these, silane coupling agents having a substituent containing a nitrogen atom in the side chain, titanium coupling agents, and those surface-treated with silicone oil are preferred from the viewpoint of positive charge imparting properties.

As the coupling agent having a substituent containing a nitrogen atom in the side chain, any of conventionally known coupling agents can be used. Among them, a silane coupling agent and a titanium coupling agent are preferable. preferable.

[0228] As the silane coupling agent and titanium coupling agent, generally each _{R m Si-Z n, R} m Ti-
A structure represented with at Z _n (wherein, R represents an alkoxy group or a halogen atom, Z is a group having an amino group .m and n and m + n = 4 a integer of 1 to 3) .

As the substituent containing a nitrogen atom, an amino group is preferable. As the amino group, a primary amine, a secondary amine,
Any of a tertiary amine and a quaternary amine may be used. For example, the following are mentioned.

[0230]

Embedded image _{-NH 2 -NH-CH 3, -NH} -C 2 H 5, -NH-C 3 H 7 -N (CH 3) 2 -N (C 2 H 5) 2, -NH-C 2 _{H 4 -NH 2 -N (C 3} H 6) 2, -NH-C 2 H 4 -N (CH 3) 2 -N (C 4 H 9) 2 -N (CH 3) 3 + Cl -, - ^{_{N (CH 3) 3 + ·}} HCO 3 - -N (C 2 H 5) 3 + Cl -, -N (C 2 H 5) 3 + · HCO 3 - -N (C 3 H 7) 3 + Cl - _{-N (C 4 H 9) 3} + Cl -

[0231]

Embedded image

Along with these coupling agents having a substituent containing a nitrogen atom in the side chain, a coupling agent having no nitrogen atom in the side chain, silicone oil, and hexamethyldisilazane react, adsorb and absorb on the surface. Those that are attached are also preferably used.

The specific surface area of these particles is from 0.1 to
500 m ² / g is preferred, more preferably 0.5 to 4
50 m ² / g, even from those preferably 1~400m ² / g.

The treatment amount of the particles is preferably 0.1 to 70 parts by weight based on 100 parts by weight of the particles.

The average particle size of the fine titanium oxide powder or fine alumina powder used in the present invention is preferably from 0.001 to 0.2 μm, more preferably from 0.005 to 0.1 μm from the viewpoint of imparting fluidity. good.

When the average particle size is larger than 0.2 μm, the fluidity is reduced, and when the average particle size is smaller than 0.001 μm, the toner is easily embedded in the toner surface, and the durability of the toner is easily reduced. This tendency is more remarkable than when applied to a color toner having a sharp melt property. 0.001μ
When it is smaller than m, the activity of the inorganic fine powder itself becomes too high, and the particles are likely to aggregate with each other, so that it becomes difficult to obtain the desired high fluidity. The particle diameter of the treated titanium oxide fine powder or the treated alumina fine powder can be measured by a transmission electron microscope.

In the present invention, the above-described one-component non-magnetic developer is used for the yellow, magenta, and cyan toners, while the one-component magnetic developer is used for the black toner. Although the toner used in the present invention has been described above, the same applies to the black toner. However, since the black toner is a magnetic toner, it may have characteristics that other toners do not have, or may have preferable characteristics different from other toners. Therefore, the black toner used in the present invention will be particularly described below.

The particle diameter of the magnetic one-component black toner used in the present invention ranges from 4 to 10 as in the case of the color toner described above.
μm, preferably 5 to 9 μm. If the particle size is smaller than 4 μm, the image may be deteriorated in image quality because it is partially overcharged by three and a uniform coat is impaired. Further, due to the presence of the excessively charged particles in the lower layer of the sleeve, the triboelectric charging of other particles is hindered, so that it is impossible to faithfully respond to the developing electric field, and as a result, white background fog tends to occur. This phenomenon is remarkable in a low-humidity environment where the charge of the toner is high.

On the other hand, when the particle size is larger than 10 μm, the dot reproducibility is lowered, which is not preferable. In a particularly preferred embodiment, it is preferable that the diameter is larger than the particle diameter of the yellow, magenta, and cyan color toners within a range of 2 μm or less. Since it is frequently used for black-and-white images, it is preferable that the particles have a large particle diameter with high durability stability in development, transfer and fixing. However, if it is too large, it is not desirable because the dot reproducibility of a single black color is inferior and the image quality balance with a color image is greatly different. Therefore, it is preferable that the diameter of the color toner is larger than the particle diameter of the color toner within 2 μm.

Further, as the positively chargeable charge control agent for the magnetic one-component black toner used in the present invention, not only those usable for two-component color toner but also those of the material itself are not limited. All chargeable charge control agents can be used.

As the magnetic material contained in the magnetic one-component black toner used in the present invention, known materials can be used. Particularly preferred magnetic material is triiron tetroxide (Fe
₃ O ₄ ) or γ-iron sesquioxide (γ-Fe ₂ O ₃ ).

The magnetic properties of the magnetic particles of the magnetic one-component black toner used in the present invention are such that the saturation magnetization at 796 kA / m is 50 to 100 Am ² / kg, more preferably 65 to 100 Am ² / kg.
~90Am a ² / kg, residual magnetization 2~30Am ² /
kg, more preferably 4 to 20 Am2 / kg.

If the saturation magnetization is smaller than 50 Am ² / kg, it becomes impossible to receive the magnetic regulation force from the sleeve.
There is a tendency for fog to the non-image portion to increase. Also,
On the other hand, if the saturation magnetization is larger than 100 Am ² / kg, the magnetic regulation force from the sleeve becomes too large, which makes it difficult for the toner to fly to the photoconductor, resulting in a low image density. Furthermore, the remanent magnetization is ² Am ² /
If kg less than, can be a problem because the fog is increased to the non-image portion, the residual magnetization conversely 30 Am ²
If it is larger than / kg, the aggregation of the toner in the developing device is large, the mixing property after the replenishment of the toner becomes insufficient, and the image density decreases, which is not preferable.

The content of the magnetic material in the magnetic one-component black toner is 50 to 1 with respect to 100 parts by weight of the binder resin.
30 parts by weight, more preferably 60 to 110 parts by weight. If the amount is less than 50 parts by weight, the magnetic regulation force from the sleeve is weakened, and the fog tends to be deteriorated. In addition, uniform coatability on the sleeve may be a problem. Conversely, if it exceeds 130 parts by weight, the magnetic binding force is too strong,
It is not preferable because a sufficient image density cannot be obtained.

In order to sufficiently exhibit the characteristics of the magnetic one-component black toner, it is preferable to use the above-mentioned inorganic fine powder. In particular, it is preferable to use two types of inorganic fine powders in order to improve the chargeability, the lubrication of the drum, and the polishing property.

As the metal oxide (A) in the inorganic fine powder, a fluidizing agent such as silica, titanium oxide and alumina is preferable. Among them, silica is best for improving the chargeability. The content in the toner is 0.3 to 1.8 parts by weight, preferably 0.5 to 1.3 parts by weight. 0.3
When the amount is less than the weight part, the fluidity of the toner becomes insufficient, and good charging characteristics cannot be obtained, so that problems such as a decrease in image density and generation of fog tend to occur. Conversely, when the amount is more than 1.8 parts by weight, abnormal charging due to the charging property of the inorganic fine powder is caused, the uniform coating property on the sleeve is impaired, and the image quality and fog tend to deteriorate. Therefore, it is not preferable.

As the inorganic fine powder (B), silicon, titanium, strontium, manganese, zinc, cobalt, nickel, cerium, aluminum, barium are used from the viewpoint of lubrication of the drum, abrasion and prevention of excessive charging of the developing sleeve. , Calcium, zirconium and the like are preferred. Above all,
Strontium titanate is preferred.

The inorganic fine powder (B) has a weight average particle diameter of 0.1.
4-5 μm, preferably 0.7-3 μm is good. 0.
If it is smaller than 4 μm, the inorganic fine powder (B) accumulates on the lower layer of the sleeve and prevents the toner from being excessively charged. is there. Conversely, if it is larger than 5 μm, the effect of preventing the toner from being excessively charged in a low-humidity environment cannot be suitably exhibited, and the uniform coatability of the sleeve tends to be impaired and fogging tends to occur.

The addition amount of the inorganic fine powder (B) is 0.1
The amount is preferably 1 to 5 parts by weight, more preferably 0.5 to 4 parts by weight. If the amount is less than 0.1 part by weight, the image density becomes low,
The uniform coatability of the sleeve in a low-humidity environment is lost, and image deletion in a high-humidity environment is also likely to occur. vice versa,
If the amount is more than 5 parts by weight, the chargeability of the toner is hindered and fog in a low humidity environment tends to increase, which is not preferable.

Next, the method for measuring each physical property will be described below. <Measurement of Toner Particle Size Distribution> As a preferred measuring device for measuring the weight average particle size of the toner of the present invention, Coulter Counter TA-II or Coulter Multisizer I is used.
I (manufactured by Coulter Inc.). When measuring the weight average particle diameter using this measuring device, about 1% prepared using primary grade sodium chloride as the electrolytic solution.
An aqueous NaCl solution is used. As such an electrolytic solution, for example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used.

The measuring method is as follows.
0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) as a dispersant in ~ 150 ml.
In addition, 2 to 20 mg of the measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and 10
Using a 0 μm aperture, the volume and number of toner particles are measured for each channel, and the volume distribution and number distribution of the toner are calculated. Then, the weight-average particle diameter (D4) of the toner on a weight basis determined from the volume distribution of the toner particles.
(The central value of each channel is set as a representative value for each channel).

The above channels are 2.00 to 2.00.
2.52 μm; 2.52 to 3.17 μm; 3.17 to
4.00 μm; 4.00 to 5.04 μm; 5.04 to
6.35 μm; 6.35 to 8.00 μm; 8.01 to 1
0.08 μm; 10.08 to 12.70 μm; 12.7
0-16.00 μm; 16.0-20.20 μm; 2
0.20-25.40 μm; 25.40-32.00 μ
m; 13 channels of 32.00 to 40.30 μm are used.

<Method of Measuring Coloring Power> First, the amount of toner on an unfixed transfer material is adjusted to 0.5 mg / cm ² .
Adjust the contrast potential of the main body and other development conditions. Thereafter, under the same conditions, the image is usually fixed through a fixing device to form an image for measuring coloring power, and the image density of the obtained image is measured. For the measurement of the image density, it is preferable to use a 504 type reflection densitometer manufactured by X-Rite Co. In this specification, the numerical value measured by using the reflection densitometer is used.

<Measurement Method of Glass Transition Temperature of Toner> As preferred measurement devices for measuring the glass transition temperature (Tg) of the toner used in the present invention, differential thermal analysis measurement device (DSC measurement device), DSC-7 (Manufactured by PerkinElmer).

In the case of using the above measuring device, 5-20 mg, preferably 10 mg, of a measuring sample is precisely weighed,
This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and the measurement is performed at a temperature rising rate of 10 ° C./min under normal temperature and normal humidity in a measurement temperature range of 30 ° C. to 200 ° C. In this heating process, an endothermic peak of a main peak in a temperature range of 40 to 100 ° C. is obtained.

At this time, the intersection between the line of the midpoint of the baseline before and after the endothermic peak appears and the differential heat curve is defined as the above glass transition temperature (Tg).

<Measurement Method of Molecular Weight of Binder Resin> In the toner used in the present invention, a suitable measuring device for measuring the molecular weight of the binder resin includes gel permeation chromatography (GPC). A method for measuring the molecular weight of the binder resin with this measuring device will be described below.

First, the column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was passed through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution was injected and measured. I do.
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.

As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is used.
It is appropriate to use about a few standard polystyrene samples. An R1 (refractive index) detector is used as the detector. As the column, a combination of a plurality of commercially available polystyrene gel columns is preferably used.

Examples of the column include, for example, Shodex GPC KF-801, 802 manufactured by Showa Denko KK,
803, 804, 805, 806, 807, 800P combination or Tosoh TSKgelG1000H
(HXL), G2000H (HXL), G3000H
(HXL), G4000H (HXL), G5000H
(HXL), G6000H (HXL), G7000H
(HXL) and a combination of TSKguardcolumn.

The sample is prepared as follows. After placing the sample in THF and leaving it to stand for several hours,
Mix well with F (until the sample is no longer united) and add 1 more
Leave for at least 2 hours. At this time, the time of being left in THF is set to be 24 hours or more. Thereafter, a sample processing filter (pore size: 0.45 to 0.5 μm, for example, Mishori Disc H-25-5 (manufactured by Tosoh Corporation),
After passing through an Exikuro Disk 25CR (available from Germanic Science Japan) or the like,
GPC sample. The sample concentration is 0.5 to
Adjust to 5 mg / ml.

<Method of Measuring Acid Value> The acid value of the toner used in the present invention can be measured according to a conventional method.
An example of the method for measuring the acid value of a toner will be described below.

Samples 2 to 10 g in 200 to 300 ml
Weighed in an Erlenmeyer flask, and methanol: toluene = 3
About 50 ml of a 0:70 mixed solvent is added to dissolve the resin. If the solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% bromthymol blue and phenol red, a standardized N /
Titrate with a 10 caustic potash-alcohol solution, and calculate the acid value from the consumption of the potash alcohol solution by the following calculation.

## EQU1 ## Acid value = KOH (ml number) × N × 56.1 / sample weight (where N is a factor of N / 10 KOH)

[0264]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to the drawings, but the present invention is not limited to the embodiments.

<Example of manufacturing photoreceptor> The aforementioned RF-PCV
Using a D-manufacturing apparatus, a positively charged photoreceptor was produced under the conditions shown in Table 1 and a negatively charged photoreceptor was produced under the conditions shown in Table 2 on a mirror-finished aluminum cylinder having a diameter of 60 mm. Hereinafter, the photoreceptor manufactured by the method of Table 1 is referred to as Photoreceptor 1, and the photoreceptor manufactured by the method of Table 2 is referred to as Photoreceptor 2.

[0266]

[Table 1]

[0267]

[Table 2]

<Binder Resin Production Example 1> Polyoxyfluoro (2,2) -2,2 bis (4-human peroxyphenyl) fluoro 15 mol% Polyoxyethylene (2,2) -2,2 bis (4-human peroxy) Phenyl) fluoromethane 34 mol% Terephthalic acid 15 mol% Fumaric acid 36 mol% Trimellitic acid 2 mol% These were charged into a four-necked flask, equipped with a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer, and a stirrer. The mixture was subjected to condensation polymerization while introducing nitrogen into the reactor. Further, xylene 5 was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux tube, and an isocyanate compound dropping device.
00 parts by weight and 100 parts by weight of the polyester resin were charged. The polyester resin was dissolved in xylene by heating with stirring. A xylene solution containing 5 parts by weight of diphenylmethane-4,4 'diisocyanate was added dropwise in a fixed amount over 2 hours under reflux of xylene. After completion of the dropwise addition, stirring was continued for another hour to complete the reaction. Xylene was distilled off to obtain a urethane-modified polyester resin (1).

<Binder Resin Production Examples 2 to 6 and 8> Condensation polymerization similar to that of the polyester resin (1) was carried out by appropriately changing the constituent components and the compounding amount, and as shown in Table 3, the polyester resins (2) to (6) ) And (8).

<Binder Resin Production Example 7> Styrene 75 parts by mass n-butyl acrylate 25 parts by mass mono-n-butyl malate 10 parts by mass Divinylbenzene 0.3 parts by mass Benzoyl peroxide 1.2 parts by mass

To the above mixture was added 170 parts by mass of water in which 0.12 parts by mass of a saponified polyvinyl alcohol was dissolved, and the mixture was vigorously stirred to obtain a suspension polymerization solution. The suspension dispersion was added to a reactor charged with 300 parts by mass of water and purged with nitrogen, and subjected to suspension reaction polymerization. After completion of the reaction, the product was washed with water and dehydrated.
After drying for 24 hours, a vinyl resin (7) was obtained. As shown in Table 3, this resin (7) had an acid value of 13.2 and a Tg of 63.
C, Mn: 6000, Mw: 18,800.

<Preparation Example 9 of Binder Resin> Polymerization similar to that of the vinyl resin (7) was carried out by appropriately changing the constituting components and the compounding amount to obtain a vinyl resin (9) as shown in Table 3.

[0273]

[Table 3]

<Example of producing yellow toner> A yellow toner was produced as follows. Polyester resin (1) 70 parts by mass C.I. I. Pigment Yellow 180 is manufactured by a known method. A certain amount of water is removed from the pigment slurry before the filtration step, and a paste pigment having a fixed amount of 30% by mass obtained without any drying step (the remaining 70% by mass) 100% by mass) The above-mentioned raw materials are first charged into a kneader-type mixer with the above-mentioned formulation, and the temperature is raised under non-pressure while mixing. Maximum temperature (necessarily determined by the boiling point of the solvent in the paste)
In this case, the pigment in the aqueous phase is dispersed or transferred to the molten resin phase when the temperature reaches about 100 to 100 ° C., and after confirming this, the mixture is heated and kneaded for another 30 minutes to sufficiently remove the pigment in the paste. Migrate. After that, the mixer was stopped once, the hot water was discharged, the temperature was further raised to 130 ° C., and the mixture was heated and kneaded for about 30 minutes to disperse the pigment and distill off the water. And the kneaded material was taken out. The water content of the final kneaded product was about 0.8% by mass.

The above kneaded material (pigment particle content: 30% by mass) 20.0 parts by mass Polyester resin (1) 86.0 parts by mass Quaternary ammonium salt 4.0 parts by mass The above formulation was sufficiently mixed with a Henschel mixer. The mixture is melt-kneaded at a temperature of 120 ° C. with a twin-screw extruder, cooled, coarsely pulverized to about 1 to 2 mm using a hammer mill, and then pulverized to 40 μm or less with a fine pulverizer using an air jet method. Finely ground to a diameter. Furthermore, the obtained finely pulverized product is classified and selected so that the weight average particle size in the particle size distribution is 8.0 μm to obtain yellow toner particles (classified product). For the purpose of improving fluidity and imparting charging characteristics, 1.0 part by mass of titanium oxide fine powder hydrophobically treated with a Si-based compound was externally added to 100 parts by mass of yellow toner particles to obtain a yellow toner (Y1).

Next, the types of the pigments and the amounts of the pigments were changed, and the same procedure was followed to change the yellow toners Y2 to Y12.
And Y17 and Y18.

Next, yellow toners Y13 to Y16 having different toner particle sizes were obtained in substantially the same manner as the yellow toner Y1 and by changing the pulverization and classification conditions and the amount of the external additive.

<Production Example of Yellow Toners Y19 and Y20> Polyester Resin (1) 70 parts by mass I. Pigment Yellow 93 30 parts by mass The above-mentioned materials are charged into a kneader-type mixer, and while mixing, the temperature is raised under non-pressurization, and the mixture is sufficiently premixed. Thereafter, the mixture was kneaded twice with three rolls to obtain a first kneaded product.

The above first kneaded material 26.7 parts by mass Polyester resin (1) 81.3 parts by mass Quaternary ammonium salt 4 parts by mass The above materials were sufficiently premixed by a Henschel mixer, and melt-kneaded by a twin screw extruder. Then, a yellow toner Y19 was obtained in the same manner as the yellow toner Y1. In a similar manner, a yellow toner Y20 having a pigment content of 4 parts by mass was obtained.

<Production Example of Yellow Toner Y21> 100 parts by mass of polyester resin (1) I. Pigment Yellow 93 4 parts by mass Quaternary ammonium salt 4 parts by mass The above materials were sufficiently premixed with a Henschel mixer, melt-kneaded with a twin screw extruder, and thereafter yellow toner Y21 was obtained in the same manner as yellow toner Y1. .

<Example of Preparation of Yellow Toner Y22> The first kneaded product (30% by mass of pigment particles) prepared with Yellow Toner Y18 was further kneaded five times with a three-roll mill to disperse the pigment more sufficiently. Then, in the same manner, a yellow toner Y22 was obtained. Table 4 shows the production method of each yellow toner.

[0282]

[Table 4]

<Production Example of Magenta Toner> A first kneaded product was obtained in substantially the same manner as the yellow toner Y1, that is, using the paste pigments of the magenta pigments shown in Table 5, and the desired pigment content was obtained. And the mixture is diluted and kneaded as described above, and then the weight average diameter is 7 to 7.5 in substantially the same manner.
μm magenta toners M1 to M16 were obtained.

[0284]

[Table 5]

<Preparation Example of Cyan Toner> A first kneaded material was obtained in substantially the same manner as the yellow toner Y1, that is, using the paste pigments of the cyan materials shown in Table 6, and then the desired pigment content was obtained. And then kneading, and then the weight average diameter is from 6.0 to 8.
0 μm cyan toners C1 and C2 were obtained. Further, the external additive of C1 was changed from titanium oxide shown in Table 7 to alumina, and C4 was added.
To C6 were similarly obtained.

<Production Example of Cyan Toner C3> Almost in the same manner as for the yellow toner Y21, that is, 100 parts by mass of the polyester resin (1). I. Pigment Blue 15: 3 2 parts by mass Quaternary ammonium salt 4 parts by mass was sufficiently premixed with a Henschel mixer, melt-kneaded with a twin-screw extruder, and the cyan toner C3 shown in Table 6 was prepared in substantially the same manner as described above. Obtained.

<Examples of Preparation of Cyan Toners C7 to C9> Instead of the charge control agent used in cyan toner C1, imidazole compound (C7), styrene acrylic copolymer resin containing ammonium group (C8), quaternary ammonium salt and imidazole Except that the mixture of compounds (C9) was used, the rest was the same as in the case of cyan toners C7 to C7 shown in Table 6.
9 was obtained.

<Production Examples of Cyan Toners C10 to C15>
Cyan toners C10 to C15 shown in Table 6 were obtained in the same manner except that resins (2) to (7) were used instead of resin (1) used for cyan toner C1.

[0289]

[Table 6]

Tables 7 and 8 show the external additives used in the toner production examples.

[0291]

[Table 7]

[0292]

[Table 8]

<Production Example of Black Toner> 100 parts by mass of polyester resin (8) 85 parts by mass of magnetic particles (a) 4 parts by mass of quaternary ammonium salt 5 parts by mass of low-molecular-weight polypropylene 5 parts by mass of Henschel mixer (Mitsui Mining Co., Ltd.) After that, the mixture was sufficiently kneaded at 130 ° C. by a twin-screw extruder. After allowing the kneaded material to cool, it was coarsely pulverized by a cutter mill, pulverized using a fine pulverizer using a jet stream, and further classified using an air classifier to obtain a magnetic black toner. 0.9 parts by mass of metal oxide (A) -4 and 100 parts by mass of composite metal oxide (B) -1 based on 100 parts by mass of the magnetic toner
Was externally added with a Henschel mixer to obtain a magnetic black toner Bk1 having a weight average particle diameter of 8.1 μm.

<Production Example of Black Toners Bk2 to Bk10>
Black toners Bk2 to Bk10 shown in Table 9 were prepared in substantially the same manner as black toner Bk1 except that black magnetic particles (b) to (nu) were used instead of magnetic particles (a) used for black toner Bk1. I got

<Examples of Production of Black Toners Bk11 and Bk12> Magnetic Particles Used in Black Toner Bk1 (A)
Were changed to 60 parts and 110 parts, respectively, to obtain black toners Bk11 and Bk12 shown in Table 9 in the same manner.

<Examples of Production of Black Toners Bk13 and Bk14> Except that the addition amounts of the metal oxide (A) -4 used in the black toner Bk1 were changed to 0.2 parts and 2.0 parts, respectively. In the same manner, black toners Bk13 and Bk14 shown in Table 9 were obtained.

<Examples of Production of Black Toners Bk15 and Bk16> Except that the addition amount of the metal oxide (B) -1 used in the black toner Bk1 was changed to 0.05 parts and 5.2 parts, respectively. Were similarly used to obtain black toners Bk15 and Bk16 shown in Tables 9 and 10.

<Examples of Preparation of Black Toners Bk17 to Bk20> The toner particle diameters are 3.8 μm and 5.5 respectively by changing the pulverization and classification conditions when preparing black toner Bk1.
μm, 9.4 μm, and 10.8 μm except that the black toners Bk17 to Bk shown in Table 10 were changed in the same manner.
20 was obtained.

<Production Example of Black Toners Bk21 and Bk22> Except that the type of metal oxide (A) -4 used in black toner Bk1 was changed to (A) -1, (A) -2, In the same manner, black toners Bk21 and Bk22 shown in Table 10 were obtained.

<Production Example of Black Toners Bk23 to Bk27> Metal oxide (B) used in black toner Bk1
-1 are (B) -2, (B) -3, (B) -4,
Except for changing to (B) -5 and (B) -6, the rest was the same as in the case of black toner Bk2 shown in Table 10.
3-Bk27 were obtained.

<Example of Preparation of Black Toner Bk28> Except for changing the addition amount of the quaternary ammonium salt, which is the charge control agent used in the black toner Bk1, to 5.5 parts by mass, the remaining tables were made in the same manner. 10 black toner Bk28 was obtained.

<Examples of Production of Black Toners Bk29 and Bk30> The black toner shown in Table 10 was similarly prepared except that the type of the binder resin used in the black toner Bk1 was changed to resin (3) and resin (9), respectively. Toners Bk29 and Bk30 were obtained.

[0303]

[Table 9]

[0304]

[Table 10]

<Experimental Example 1> RF-PC under the conditions shown in Table 1 above
Using a photoreceptor manufacturing apparatus by a VD method, a positively charged photoreceptor was produced on an aluminum cylinder having a mirror surface with a diameter of 15 mm to 100 mm. The produced photoreceptor was evaluated with an experimental machine capable of producing four full-color images provided with charging, exposure, development, transfer, cleaning, and charge elimination.

One-component yellow toner is used in the first image forming unit, one-component magenta toner is used in the second image forming unit, one-component cyan toner is used in the third image forming unit, and the fourth image forming unit is used. Each unit was provided with a magnetic one-component black toner. The peripheral speed (process speed) of the photoconductor was set to 200 mm / s, and the surface potential of the photoconductor was set to 350 V at the developing device position. The distance between the photoconductor and the developing sleeve is 300 μm in the first, second and third image forming units.
m, 280 μm for the fourth image forming unit, and the developing sleeve was rotated at twice the peripheral speed of the photoconductor. Image exposure was employed for image formation. As for the toner, Y1 is used for the yellow toner, and M is used for the magenta toner.
1, C1 for cyan toner, Bk1 for black toner
Were used.

In the evaluation of the image, the image density when only the black toner was developed, the image density when only the yellow toner was developed, and the image density of the yellow portion when the four colors were developed were examined. Table 11 shows the results.

[0308]

[Table 11]

When a photosensitive member having a diameter of 15 mm was used, a surface potential of 350 V could not be obtained, and a high-density image could not be obtained. Therefore, the peripheral speed of the photoconductor is set to 100
Although the image was reduced to mm / s and imaged at the same potential, a sufficient image could not be obtained in this case.

When a photoreceptor having a diameter of 100 mm is used,
Although the density in a single color was sufficiently obtained, when the image was formed in four colors, a decrease in the image density was observed in the image formed by the first image forming unit. It is considered that this is because the toner on the transfer material was re-transferred onto the photosensitive member due to the increase in the diameter of the photosensitive member.

<Experimental Example 2> Using the experimental apparatus used in Experimental Example 1, an image was formed using an a-Si photosensitive member having a diameter of 60 mm. The charging potential is changed from 250 V to 500 V, and the image density in each black image, the variation in the density when the reflection density is 0.6, and the density after one round of the exposed part and the non-exposed part called the ghost when the reflection density is 0.6 The difference was examined. Table 12 shows the results.

[0312]

[Table 12]

When the surface potential was smaller than 300 V in absolute value, the image density was low. On the other hand, when the voltage is higher than 450 V, the dispersion of the density of the image having the reflection density of 0.3 becomes worse,
Also, the drum ghost has grown.

<Experimental Example 3> The dependence of the distance between sleeve drums (SD gap) was evaluated using the experimental apparatus used in Experimental Example 1 and an a-Si photosensitive member having a diameter of 60 mm. The SD gap was changed from 80 μm to 550 μm, and the initial black image density and the drum fusion and image density when 10,000 sheets of 7% black original were imaged were examined. Table 13 shows the results.

[0315]

[Table 13]

<Experimental Example 4> The dependence of the peripheral speed ratio of the sleeve on the a-Si photosensitive member having a diameter of 60 mm was evaluated using the experimental apparatus used in Experimental Example 1. The peripheral speed of the sleeve was changed from 1.05 times to 5 times the peripheral speed of the photosensitive member, and the initial black image density and the image density when 50,000 sheets of a 7% black original were imaged were examined. Table 14 shows the results.

[0317]

[Table 14]

Next, non-contact one-component development was examined.
The toner used was Y1 toner, and the distance between the photosensitive member and the developing sleeve was set to 300 μm.

[0319]

[Table 15]

Next, contact one-component development was examined. The toner used was Y1 toner, and the contact portion between the photosensitive member and the developing sleeve was set to 3 mm.

[0321]

[Table 16]

If the sleeve peripheral speed ratio is smaller than 1.1,
A decrease in image density was observed from the beginning. When the sleeve peripheral speed ratio was greater than 4.0, the density was reduced after 50,000 sheets were run. Further, fog occurred and a good image was not obtained.

<Experimental Example 5> Using the experimental apparatus used in Experimental Example 1, an a-Si photosensitive member having a diameter of 60 mm was used to evaluate the image quality dependence on the particle size of the toner. Yellow toners Y1, Y13-16, Bk1, Bk21-2
4 was used. The results are shown in Tables 17 and 18.

[0324]

[Table 17]

[0325]

[Table 18]

<Experimental Example 6> Using the experimental apparatus used in Experimental Example 1, an a-Si photosensitive member having a diameter of 60 mm was used to evaluate the dependence of the toner on the coloring power. The coloring power of the toner is obtained by calculating the amount of unfixed toner (M / S) on the transfer material by M / S =
Evaluation was made based on the image density (D0.5) after fixing once, usually at 0.5 mg / cm ² . For the yellow toner, toners having different coloring powers were prepared, and 16
A gradation image was output, and the density and gradation were evaluated. The results are shown in Table 19.

[0327]

[Table 19]

As can be seen from the results shown in the table, D0.
When D5 is small, a sufficient image density cannot be obtained, and when D0.5 is large, a problem occurs in the reproducibility of the density of the intermediate color due to environmental changes, and a good image cannot be obtained.

<Experimental Example 7> Using the experimental apparatus used in Experimental Example 1, an a-Si photosensitive member having a diameter of 60 mm was used to evaluate the image dependency on the binder resin of the toner. Toner C10 to C1 having different resins from cyan toner C1
5 were prepared, and the initial and 5
Density transition at endurance of 10,000 sheets (initial density → density at 50,000 sheets),
The image quality under high temperature and high humidity environment and the transparency of OHP were evaluated. The results are shown in Table 20.

[0330]

[Table 20]

<Example 1> Under the conditions shown in Table 1 above, RF-P
Using a photoreceptor manufacturing apparatus by the CVD method, a diameter of 60 mm
A positively charged photoreceptor was prepared on an aluminum cylinder which had been subjected to mirror finishing.

[0332] The produced photoreceptor was transferred to a Canon copier CL.
C1000 was modified as shown in FIG. 1 and images were evaluated using this experimental apparatus. The fourth developing unit was an NP6085 developing device. One component cyan toner is used for the first image forming unit, one component magenta toner is used for the second image forming unit, one component yellow toner is used for the third image forming unit, and one component yellow toner is used for the fourth image forming unit. A magnetic one-component black toner was disposed.

The photosensitive member has a peripheral speed (process speed) of 133.
It was rotated at mm / s. The surface potential of the photoreceptor was set at 400 V at the developing device. The distance between the photosensitive member and the developing sleeve is 300 μm for the first, second and third image forming units and 300 μm for the fourth image forming unit. The developing sleeve is rotated at a speed of 1.75 times the peripheral speed of the photosensitive member. Was. Image exposure was used for image formation, and the image forming conditions were set so that 30 sheets could be formed per minute.

The toner used was Y1 for the yellow toner, M1 for the magenta toner, C1 for the cyan toner, and BK1 for the black toner.

The amount of unfixed toner on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the image density after one-time fixing is D0.5Y: 1.43, D0.5M:
1.23, D0.5C: 1.30, D0.5Bk: 1.
01. D0.5Y, D0.5M, D0.5
The maximum (D0.5max) and minimum (D0.5mi) of C
The difference in n) was 0.20.

The gloss difference of each color, the saturation of a color image, and the color reproducibility when the environment fluctuated were measured. Table 2 shows the measurement results.
It is shown in FIG. The measurement method and evaluation criteria for the above measurement are shown below.

<Gloss Measurement Method> For measurement of gloss (gloss), a VG-10 gloss meter manufactured by Nippon Denshoku Co., Ltd. was used.
At the time of measurement, first set the voltage to 6V with a constant voltage device, then adjust the light projection angle and light reception angle to 60 °, adjust the zero point and use a standard plate, set the standard, and set the sample image on the sample table. Then, three sheets of white paper were further superimposed on each other for measurement, and the numerical value shown on the display was read in%.

For the sample image, an image was prepared for each of the yellow, magenta, and cyan colors with a reading value of 1.50 using a 504 type reflection densitometer manufactured by X-Rite, and the gloss was read for each color. The difference between the value and the minimum value was determined. When the difference in the gloss was less than 3, the result was evaluated as A: when the difference was 3 or more and less than 6, the result was evaluated as Δ when the difference was 6 or more and less than 10.

<Method of Measuring Color Saturation of Color Image> The saturation of an image is calculated by the following equation.

(Equation 2) The larger the value of C ^* , the clearer the image. When forming an image of a full-color image, the larger the C ^* and the spread of each color, the more vivid an image can be reproduced even for single colors and intermediate colors.

The color tone of the toner was quantitatively measured based on the definition of the color system standardized by the International Commission on Illumination (CIE) in 1976. That is, a ^* and b ^* (a ^* and b ^* are chromaticities representing hue and saturation) and L ^* (brightness) were measured. A spectrocolorimeter type 938 manufactured by X-rite was used as the measuring instrument, the light source for measurement was C light source, and the viewing angle was 2 °.

As the sample image, an image having a reading value of 1.50 using a 404 type reflection densitometer manufactured by X-Rite for each color of yellow, magenta, and cyan was prepared, and a ^* and b ^{* for} each color were prepared ^.
After reading, the color space that can be formed was determined, and the color saturation was evaluated.

Next, regarding the color reproducibility when a full-color image using three colors was formed, flesh color and green images were prepared and evaluated. Good images with good color reproducibility were obtained for yellow, magenta, cyan, flesh color and green. ◎ Only one color was slightly applied to saturation. Other colors were good for color reproducibility. The sample having poor color reproducibility but having no problem in practical use was evaluated as Δ, and the sample having poor color reproducibility was evaluated as ×.

<Method of Measuring Color Reproducibility During Environmental Fluctuations> In a low-temperature and low-humidity environment (23 ° C./5%), L ^* (lightness) 55 to 65, a ^* ,
Gray images were formed in which b ^* was a ^* : -2 to 2, and b ^* : -2 to 2, respectively. Without changing the setting conditions of the image forming apparatus, the environment was set to a high temperature and high humidity environment (30 ° C./80%), and a gray image was imaged.

With respect to the gray tint fluctuation, a circle having a good tint variation was evaluated as good, a triangular tint having a slight tint variation but having no problem was evaluated as being poor, and a gray tint change having a clear tint variation was evaluated as x.
Was evaluated.

Example 2 An image was formed using the image forming apparatus used in Example 1 except that Y5 was used for the yellow toner, M5 for the magenta toner, and C2 for the cyan toner.

The amount of unfixed toner on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the image density after normal single fixing is D0.5Y: 1.12, D0.5M:
1.15, D0.5C: 1.25, D0.5Bk: 1.
01. D0.5Y, D0.5M, D0.5
The maximum (D0.5max) and minimum (D0.5mi) of C
The difference in n) was 0.13. Table 2 shows the gloss difference for each color, the saturation of the color image, and the color reproducibility when the environment changes.
It is shown in FIG.

<Example 3> The image forming apparatus used in Example 1 was used except that Y5 was used for the yellow toner, M10 was used for the magenta toner, and C2 was used for the cyan toner.
An image was formed.

The amount of unfixed toner on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the maximum (D0.5max) and minimum (D0.5min) values of the image densities after fixing once, D0.5Y, D0.5M, and D0.5C. )
Table 21 shows the difference between the colors, the gloss difference in each color in this case, the saturation of the color image, and the color reproducibility when the environment changes.

Comparative Example 1 An image was formed using the image forming apparatus used in Example 1 except that Y5 was used for the yellow toner, M13 was used for the magenta toner, and C2 was used for the cyan toner.

The amount of unfixed toner on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the maximum (D0.5max) and minimum (D0.5min) values of the image densities after fixing once, D0.5Y, D0.5M, and D0.5C. )
Table 21 shows the difference between the colors, the gloss difference in each color in this case, the saturation of the color image, and the color reproducibility when the environment changes.

In this case, when the image was evaluated, the gloss difference between the colors was large, and a clear image could not be obtained. Strict control over concentration fluctuations due to environmental differences,
Density unevenness became severe due to environmental differences.

Example 4 An image was formed using the image forming apparatus used in Example 1 except that Y5 was used for the yellow toner, M5 for the magenta toner, and C4 for the cyan toner.

The amount of unfixed toner on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the maximum (D0.5max) and minimum (D0.5min) values of the image densities after fixing once, D0.5Y, D0.5M, and D0.5C. )
Table 21 shows the difference between the colors, the gloss difference in each color in this case, the saturation of the color image, and the color reproducibility when the environment changes.

Comparative Example 2 An image was formed using the image forming apparatus used in Example 1 except that Y5 was used for the yellow toner, M5 for the magenta toner, and C5 for the cyan toner.

The amount of unfixed toner on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the maximum (D0.5max) and minimum (D0.5min) values of the image densities after fixing once, D0.5Y, D0.5M, and D0.5C. )
Table 21 shows the difference between the colors, the gloss difference in each color in this case, the saturation of the color image, and the color reproducibility when the environment changes.

In this case, when the image was evaluated, the gloss difference between each color was large, and a clear image could not be obtained. Further, the control of the density fluctuation due to the environmental difference was severe, and the density unevenness became severe due to the environmental difference.

<Embodiment 5> Y18 was used for the yellow toner.
The image forming apparatus used in Example 1 was used except that M13 was used for the magenta toner and C5 was used for the cyan toner.
An image was formed.

The amount of unfixed toner on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the image density after normal single fixing is D0.5Y: 1.58, D0.5M:
1.66, D0.5C: 1.69, D0.5Bk: 1.
30. D0.5Y, D0.5M, D0.5
The maximum (D0.5max) and minimum (D0.5mi) of C
The difference in n) was 0.11.

Table 21 shows the gloss difference of each color, the saturation of the color image, and the color reproducibility when the environment changes.

<Embodiment 6> Y18 is used for the yellow toner.
An image was formed using the image forming apparatus used in Example 1 except that M1 was used for the magenta toner and C5 was used for the cyan toner.

The amount of unfixed toner on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the maximum (D0.5max) and minimum (D0.5min) values of the image densities after fixing once, D0.5Y, D0.5M, and D0.5C. )
Table 21 shows the difference between the colors, the gloss difference in each color in this case, the saturation of the color image, and the color reproducibility when the environment changes.

<Comparative Example 3> Y18 was used for the yellow toner.
An image was formed using the image forming apparatus used in Example 1 except that M5 was used for the magenta toner and C5 was used for the cyan toner.

The amount of unfixed toner on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the maximum (D0.5max) and minimum (D0.5min) values of the image densities after fixing once, D0.5Y, D0.5M, and D0.5C. )
Table 21 shows the difference between the colors, the gloss difference in each color in this case, the saturation of the color image, and the color reproducibility when the environment changes.

In this case, when the image was evaluated, the gloss difference between the colors was large, and a clear image could not be obtained. Further, the control of the density fluctuation due to the environmental difference was severe, and the density unevenness became severe due to the environmental difference.

Example 7 An image was formed using the image forming apparatus used in Example 1 except that Y8 was used for the yellow toner, M13 was used for the magenta toner, and C5 was used for the cyan toner.

The amount of unfixed toner on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the maximum (D0.5max) and minimum (D0.5min) values of the image densities after fixing once, D0.5Y, D0.5M, and D0.5C. )
Table 21 shows the difference between the colors, the gloss difference in each color in this case, the saturation of the color image, and the color reproducibility when the environment changes.

Comparative Example 4 The image forming apparatus used in Example 1 was used except that Y5 was used for the yellow toner, M13 was used for the magenta toner, and C5 was used for the cyan toner.
An image was formed.

The amount of unfixed toner on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the maximum (D0.5max) and minimum (D0.5min) values of the image densities after fixing once, D0.5Y, D0.5M, and D0.5C. )
Table 21 shows the difference between the colors, the gloss difference in each color in this case, the saturation of the color image, and the color reproducibility when the environment changes.

In this case, when the image was evaluated, the gloss difference between each color was large, and a clear image could not be obtained. Further, the control of the density fluctuation due to the environmental difference was severe, and the density unevenness became severe due to the environmental difference.

<Embodiment 8> Under the conditions shown in Table 1 above, RF-P
40mm diameter using a photoreceptor manufacturing device by CVD method
A positively charged photoreceptor was prepared on an aluminum cylinder which had been subjected to mirror finishing.

[0370] The produced photoreceptor was used with a Canon copier CL.
C1000 was modified, and images were evaluated using this experimental apparatus. Cyan toner is arranged in the first image forming unit, magenta toner is arranged in the second image forming unit, yellow toner is arranged in the third image forming unit, and black toner is arranged in the fourth image forming unit. .

The peripheral speed (process speed) of the photosensitive member is 10
0 mm / s, the surface potential of the photoconductor is 320 V at the developing device
Set to. In the first, second and third image forming units, the photoconductor and the developing sleeve were developed in a contact system, and in the fourth image forming unit, the distance between the photoconductor and the developing sleeve was 300 μm. In the non-contact one-component development, the developing sleeve was rotated at a speed of 1.2 times the peripheral speed of the photoconductor, and in the one-component magnetic developing method, the developing sleeve was rotated at a speed twice the peripheral speed of the photoconductor. Image exposure was used for image formation, and image forming conditions were set so that 21 sheets could be formed per minute.

The toner used was Y2 for the yellow toner, M2 for the magenta toner, C2 for the cyan toner, and Bk2 for the black toner.

Unfixed toner amount on each color transfer material (M / S)
When M / S = 0.5 mg / cm ² , the image density after one-time fixing is D0.5Y: 1.42, D0.5M:
1.40, D0.5C: 1.25, D0.5Bk: 1.
01. Gloss difference for each color, saturation of color image,
Table 21 shows the color reproducibility when the environment changes.

<Embodiment 9> Under the conditions shown in Table 1 above, RF-P
Using a photoreceptor manufacturing apparatus by the CVD method, a diameter of 60 mm
A positively charged photoreceptor was prepared on an aluminum cylinder which had been subjected to mirror finishing.

[0376] The produced photoreceptor was used with a Canon copier CL.
C1000 was modified, and images were evaluated using this experimental apparatus. Cyan toner is arranged in the first image forming unit, magenta toner is arranged in the second image forming unit, yellow toner is arranged in the third image forming unit, and black toner is arranged in the fourth image forming unit. .

The peripheral speed (process speed) of the photosensitive member is 30.
0 mm / s, the surface potential of the photoconductor is 380 V at the developing device
Set to. The distance between the photoconductor and the developing sleeve is the first, second,
The image forming unit of No. 3 was 400 μm, and the image forming unit of No. 3 was 450 μm. The developing sleeve was rotated at a speed three times the peripheral speed of the photoconductor. Image exposure was employed for image formation, and image forming conditions for forming 70 images per minute were set.

The toner used was Y3 for the yellow toner, M3 for the magenta toner, C1 for the cyan toner, and Bk7 for the black toner.

For each color, the amount of unfixed toner on the transfer material (M /
When S) is M / S = 0.5 mg / cm ² , the image density after one-time fixing is usually D0.5Y: 1.40, D0.5
M: 1.30, D0.5C: 1.30, D0.5Bk:
1.01. Table 21 shows the gloss difference for each color, the saturation of the color image, and the color reproducibility when the environment changes.

<Examples 10 to 20> The yellow toner was changed to Y
Image formation was performed under the same conditions as in Example 1 except that Y2 was changed from Y2. Tables 21 and 22 show the gloss difference of each color, the saturation of the color image, and the color reproducibility when the environment changes.

<Examples 21 to 35> The magenta toner was changed to M
An image was formed under the same conditions as in Example 1 except that M16 was changed from M2. Tables 22 and 23 show the gloss difference for each color, the saturation of the color image, and the color reproducibility when the environment fluctuates.

<Examples 36 to 39> The cyan toner was changed to C
2. Image formation was performed under the same conditions as in Example 1 except that C7 was changed to C9. Table 23 shows the gloss difference for each color, the saturation of the color image, and the color reproducibility when the environment changes.

<Examples 40 to 61>
Image formation was performed under the same conditions as in Example 1 except that k2 to Bk16 and Bk21 to BkBk27 were used. Tables 23 to 25 show the gloss difference for each color, the saturation of the color image, and the color reproducibility when the environment fluctuates.

<Example 62> Under the conditions of Table 2 above, RF-
Using a photoreceptor manufacturing device by the PCVD method, a diameter of 60 m
A negatively charged photoreceptor was prepared on an aluminum cylinder having a mirror surface of m.

[0387] The produced photoreceptor was transferred to a Canon copier CL.
C1000 was modified, and images were evaluated using this experimental apparatus. Cyan toner is arranged in the first image forming unit, magenta toner is arranged in the second image forming unit, yellow toner is arranged in the third image forming unit, and black toner is arranged in the fourth image forming unit. .

The photosensitive member has a peripheral speed (process speed) of 200.
It was rotated at mm / s. The surface potential of the photoreceptor was set at -380 V at the developing device. The distance between the photosensitive member and the developing sleeve is 300 μm in the first, second and third image forming units,
And the developing sleeve was rotated at a speed 1.9 times the peripheral speed of the photoconductor. Back scan exposure is used for image formation, and 50
Image forming conditions for forming a single sheet were set.

The toner used was Y1 for the yellow toner, M1 for the magenta toner, C1 for the cyan toner, and BK1 for the black toner.

The amount of unfixed toner on the transfer material for each color (M /
When S) is M / S = 0.5 mg / cm ² , the image density after normal fixing once is D0.5Y: 1.43, D0.5
M: 1.23, D0.5C: 1.30, D0.5Bk:
1.01. Table 25 shows the gloss difference for each color, the saturation of the color image, and the color reproducibility when the environment changes.

[0389]

[Table 21]

[0390]

[Table 22]

[0391]

[Table 23]

[0392]

[Table 24]

[0393]

[Table 25]

[0394]

According to the present invention, the first to fourth image forming units are used, and the first to third image forming units use a one-component non-magnetic developer containing a color toner for contact or non-contact development. The fourth image forming unit employs a non-contact developing method using a one-component magnetic developer containing black toner. The first to fourth image forming units have an amorphous silicon layer having a diameter of 20 mm. ~ 80mm
Of the photoreceptor, and the photoreceptor is placed in the developing area for 30 minutes.
0 to 450 V, and in the contact developing system, the developing sleeve is moved at a peripheral speed of 1.05 to 2.0.
In the non-contact developing method, the developing sleeve is rotated at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the photoconductor, and the toner has a weight average particle diameter of 4.0. To 10.
0 μm, a positively-chargeable toner, a color toner having a coloring power of 1.0 to 1.8, a black toner having a coloring power of 0.5 to 1.5, and a coloring power between color toners. Since a toner having a difference between the maximum value and the minimum value of 0 to 0.5 is used, in full-color image formation using an a-Si photoconductor, the occurrence of fusion of the toner to the photoconductor and filming can be reduced. , High developability with no spent on carrier, compatible with color reproducibility during fixing, sufficient image density is obtained even at low potential development, high definition and high image quality with excellent color reproducibility An image forming method and an image forming apparatus capable of forming the image of the present invention can be provided.

In the present invention, non-magnetic yellow toners include CI Pigment Yellow 74, 93, 9
7, 109, 128, 151, 154, 155, 16
6, 168, 180 and 185; a non-magnetic magenta toner, a quinacridone pigment; and C.I. Pigment Red 5, 31, 48: 2, 57: 1, 58: 2,14
6, 147, 150, 184, 185, 187, 23
8, 245 and 265, the non-magnetic cyan toner contains a Cu-phthalocyanine pigment or an Al-phthalocyanine pigment, and the magnetic black toner contains at least magnetite. It is more effective in forming an image with excellent image quality.

In the present invention, when the coloring power of each of the yellow, magenta, and cyan toners is 1.1 to 1.7, respectively, the above-described excellent image quality can be further improved. It is effective.

In the present invention, a photoreceptor having a positively or negatively charged amorphous silicon layer can be preferably used, and a negatively charged photoreceptor is used for back scan exposure or a positively charged photoreceptor is used for image exposure. Performing the latent image formation is more effective in forming an image of excellent quality as described above.

In the present invention, when the first to fourth toners contain at least one or more positive charge control agents selected from quaternary ammonium salts, imidazole compounds, and styrene-acrylic copolymer resins containing an ammonio group, It is more effective in forming an image with excellent image quality.

In the present invention, when the first to fourth toners contain a binder resin containing, as a main component, one selected from the group consisting of polyester, styrene acryl and modified products thereof, excellent image quality as described above is obtained. Is more effective in forming an image of polyester, and the polyester has an acid value of 35 mg KO.
When the glass transition temperature of the toner of H / g or less or the first to fourth toners is 50 to 70 ° C., it is more effective in forming an image having excellent image quality as described above.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view showing one embodiment of an image forming apparatus of the present invention.

FIG. 2 is a schematic configuration diagram illustrating an example of a layer configuration in a photoreceptor used in the present invention.

FIG. 3 is a schematic configuration diagram showing another example of a layer configuration in a photoreceptor used in the present invention.

FIG. 4 is a schematic configuration diagram showing another example of a layer configuration in a photoreceptor used in the present invention.

FIG. 5 is a schematic configuration diagram showing another example of a layer configuration in a photoreceptor used in the present invention.

FIG. 6 is a view showing an example of an RF-PCVD apparatus used for manufacturing a photoreceptor used in the present invention.

FIG. 7 is a diagram showing an example of a VHF-PCVD apparatus used for manufacturing a photoreceptor used in the present invention.

8 is a schematic configuration diagram of stations A to C of the image forming apparatus shown in FIG.

FIG. 9 is a schematic configuration diagram of a developing device 9D shown in FIG.

[Explanation of symbols]

2 Blade 3 Developing Sleeve 4, 1100 Photoconductor 8 Developing Container 9 Developing Device 15 Power Supply 17 Toner Density Detecting Means 21 Primary Charger 22 Light Emitting Element 23 Transfer Charging Device 24 Transfer Paper 25 Fixing Device 26 Cleaning Device 27 Transfer Paper Conveying Sheet 1101, 2112, 3112 Support 1102 Photosensitive layer 1103 Photoconductive layer 1104 Surface layer 1105 Charge injection blocking layer 1106 Charge generation layer 1107 Charge transport layer 2100, 3100 Deposition device 2111, 3111 Reaction vessel 2113, 3113 Heater for supporting body support 2114 Source gas introduction Tube 2115, 3116 High frequency matching box 2200 Source gas supply device 2211-2216 Mass flow controller 2221-2226 Source gas cylinder 2231-2236, 221-2246, 225 1 to
2256, 2260 valve 3115 electrode 3120 motor 3121 exhaust pipe 3130 space A symbol indicating A station B symbol indicating B station CC symbol indicating C station DD symbol indicating D station

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/00 550 G03G 9/08 361 2H076 15/01 113 101 2H077 15/04 351 15/043 331 15 / 08 506 325 507 15/08 507H 21/00 350 507L 15/04 120 (72) Inventor Yuji Mikuri 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Takaaki Kaba, Tokyo 3-30-2 Shimomaruko-ku Canon Inc. (72) Inventor Iku Iku 3-30-2 Shimomaruko Tokyo-Ota-ku Inside Canon Inc. (72) Inventor Takaaki Uetaki 3 Shimomaruko 3 Ota-ku, Tokyo C term 30-2 Canon Inc. F term (reference) 2H005 AA02 AA21 CA21 CA28 CB03 DA03 DA04 EA03 EA05 EA10 FA06 FA 07 2H030 AB02 AD01 BB02 BB21 BB28 BB63 2H035 CA07 CB01 CG00 2H068 DA00 FB13 FC02 FC03 FC05 2H071 CA01 CA02 DA08 DA15 DA26 EA18 2H076 AB05 AB21 DA39 EA01 2H077 AB03 AC03 AD02 AD06 AD13 EA13 EA13 GA13 EA13 GA15

Claims (26)

[Claims] 1. A first toner image formed by a first image forming unit is transferred to a transfer material, and a second toner image formed by a second image forming unit has a first toner image. The third toner image formed by the third image forming unit is transferred to the transfer material having the first and second toner images, and the fourth toner image formed by the fourth image forming unit is transferred to the transfer material having the first and second toner images. Is transferred to a transfer material having first, second, and third toner images, and the transfer material having first, second, third, and fourth toner images is conveyed to a heat and pressure fixing unit. An image forming method for forming a full-color image or a multi-color image on a transfer material by performing heating and pressure fixing, wherein (A) the first image forming in the first image forming unit comprises: (i) an amorphous silicon layer To charge the first photoconductor having A first charging step, a first exposure step of forming a first electrostatic image on the charged first photoconductor by exposure, and formation on the first photoconductor with the developer conveyed by the first developing sleeve (Ii) the first photoconductor has a diameter of 20 to 80 mm, and the first photoconductor has a diameter of 20 to 80 mm in the first charging step. The developing area, which is the opposing portion, is charged to an absolute value of 300 to 450 V, (iii) in the first developing step, a one-component developer containing the first toner is used, and (iv) the first photoconductor and (V) when the first developing sleeve is installed in contact with the first developing sleeve, the peripheral speed of the first photosensitive member is 1.05 to less than 1.05. It rotates at a peripheral speed of 2.0 times, and when it is installed in a non-contact manner, it rotates at a peripheral speed of the first photosensitive member. Developing the first electrostatic image with a one-component developer while rotating at a peripheral speed of 0.1 to 4.0 times to form a first toner image on the first photosensitive member; (I) a second charging step of charging a second photoconductor having an amorphous silicon layer, and exposing a second electrostatic image to the charged second photoconductor. And a second developing step of developing the second electrostatic image formed on the second photoconductor with the developer conveyed by the second developing sleeve. ii) The second photoreceptor has a diameter of 20 to 80 mm, and in a second charging step, a developing region, which is a portion facing the second developing sleeve, is charged to an absolute value of 300 to 450 V, and (ii)
i) In the second development step, a one-component developer containing a second toner is used, and (iv) the second photoconductor and the second development sleeve are placed in contact or non-contact. , (V)
The second developing sleeve rotates at a peripheral speed of 1.05 to 2.0 times the peripheral speed of the second photoreceptor when installed in contact, and the second developing sleeve rotates when installed in a non-contact manner. While rotating at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the photoconductor, the second electrostatic image is developed with a one-component developer to form a second toner image on the second photoconductor. (C) the third image formation in the third image forming unit includes (i) a third charging step of charging a third photosensitive member having an amorphous silicon layer, and a third charging step in which the charged third photosensitive member is charged. A third exposure step of forming the third electrostatic image by exposure, and a third step of developing the third electrostatic image formed on the third photoconductor with the developer conveyed by the third developing sleeve. (Ii) the third photoconductor has a diameter of 20 to 80 mm, and includes a third charging step. In the third developing step, a developing region, which is a portion facing the third developing sleeve, is charged to an absolute value of 300 to 450 V, and (iii) a one-component developer containing a third toner is used in the third developing step. (Iv) Third photoconductor and third photoconductor
(V) When the third developing sleeve is installed in contact with the developing sleeve, the peripheral speed of the third photosensitive member is 1.05 to 2. When the photoconductor rotates at a peripheral speed of 0 times and is installed in a non-contact manner, it rotates at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the third photosensitive member, and the third photosensitive member is rotated by a one-component developer to form a third photosensitive member. The electrostatic image is developed to form a third toner image on the third photoreceptor, and (D) fourth image formation in the fourth image forming unit includes (i) a fourth image formation having an amorphous silicon layer. 4th charge of photoconductor
Charging step, a fourth exposure step for forming a fourth electrostatic charge image on the charged fourth photoconductor by exposure, and a fourth photoconductor formed on the fourth photoconductor with the developer conveyed by the fourth developing sleeve. And (ii) the fourth photoconductor has a diameter of 20 to 80.
mm in the fourth charging step, and the developing area, which is a part facing the fourth developing sleeve, is 300 to 45 in absolute value.
0V, (iii) a one-component magnetic developer containing a fourth toner is used in the fourth developing step, and (iv) the minimum gap between the fourth photosensitive member and the fourth developing sleeve is 100 to 100. 5
(V) the fourth developing sleeve is rotated at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the fourth photosensitive member, and is rotated by the one-component developer. Developing a fourth toner image on the fourth photoconductor by developing the electrostatic image of No. 4; and (E) the first toner, the second toner, the third toner, and the fourth toner (A) a non-magnetic yellow toner selected from a group consisting of a non-magnetic yellow toner, a non-magnetic magenta toner, a non-magnetic cyan toner, and a magnetic black toner;
The non-magnetic magenta toner, the non-magnetic cyan toner and the magnetic black toner have a positive charging property, each toner has a weight average particle diameter of 4.0 to 10.0 μm, and (b) an unfixed toner on the transfer material. With respect to the toner coloring power defined by the image density after a single fixing when the amount is 0.5 mg / cm ² , the coloring power of the yellow, magenta, and cyan toners is 1.0 to 1. 8, the coloring power of the black toner is 0.5 to 1.5, and the yellow toner, the magenta toner, and the cyan toner exhibit the maximum coloring power and the minimum coloring power. An image forming method, wherein the difference in coloring power is 0 to 0.5. 2. The non-magnetic yellow toner includes C.I. Pigment Yellow 74, 93, 97, 109,
128, 151, 154, 155, 166, 168, 1
The image forming method according to claim 1, further comprising a yellow pigment selected from the group consisting of 80 and 185. 3. The non-magnetic magenta toner includes a quinacridone pigment and C.I. Pigment Red 5, 31, 48: 2, 57: 1, 58: 2, 146, 1
47, 150, 184, 185, 187, 238, 24
2. The image forming method according to claim 1, further comprising a magenta pigment selected from the group consisting of 5,265. 4. The image forming method according to claim 1, wherein said non-magnetic cyan toner contains a Cu-phthalocyanine pigment or an Al-phthalocyanine pigment. 5. The image forming method according to claim 1, wherein the magnetic black toner has at least magnetite. 6. The image forming method according to claim 1, wherein the coloring power of each of the yellow, magenta, and cyan toners is 1.1 to 1.7, respectively. 7. The image forming method according to claim 1, wherein the first to fourth photoconductors are photoconductors having a positively or negatively charged amorphous silicon layer. 8. The photoconductor according to claim 1, wherein the first to fourth photoconductors have a negatively charged amorphous silicon layer, and form a latent image by back scan exposure. Image forming method. 9. The image according to claim 1, wherein the first to fourth photoconductors have a positively charged amorphous silicon layer, and form a latent image by image exposure. Forming method. 10. The toner according to claim 1, wherein the first to fourth toners contain at least one positive charge control agent selected from a quaternary ammonium salt, an imidazole compound and a styrene acrylic copolymer resin containing an ammonium group. Item 1
Or the image forming method according to 9. 11. The toner according to claim 1, wherein the first to fourth toners contain a binder resin mainly composed of one selected from the group consisting of polyester, styrene acryl, and modified products thereof. Image forming method. 12. The polyester has an acid value of 35 mgK.
The image forming method according to claim 11, wherein OH / g or less. 13. The image forming method according to claim 1, wherein the first to fourth toners have a glass transition temperature of 50 to 70 ° C. 14. It has first to fourth image forming units,
The first toner image formed by the first image forming unit is transferred to a transfer material, and the second toner image formed by the second image forming unit is transferred to a transfer material having the first toner image. Transferring the third toner image formed by the third image forming unit to a transfer material having the first and second toner images, and transferring the fourth toner image formed by the fourth image forming unit to the fourth toner image. The transfer material having the first, second, and third toner images is transferred to a transfer material having the first, second, and third toner images, and the transfer material having the first, second, third, and fourth toner images is transported to a heat-press fixing device, and is heat-press-fixed. To form a full-color image or a multi-color image on a transfer material, wherein (A) the first image forming unit is (i) charging the first photosensitive member having an amorphous silicon layer. 1 charging means, charged first photoconductor A first exposure unit for forming a first electrostatic image by exposure, and a first developing sleeve having a first developing sleeve, the first developing sleeve being formed on the first photosensitive member by the developer conveyed by the first developing sleeve. (Ii) the first photoconductor has a diameter of 20 to 80 mm, and the first photoconductor has a first developing means for developing the electrostatic image.
The developing area, which is the part facing the developing sleeve, is 3 in absolute value.
(Iii) the first developing means has a one-component developer containing the first toner, and (iii)
v) the first photoconductor and the first developing sleeve are provided in contact or non-contact with each other; and (v) the first developing sleeve is provided when the first photoconductor is installed in contact with the first photoconductor. Rotates at a peripheral speed of 1.05 to 2.0 times the peripheral speed of the first photosensitive member, and rotates at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the first photoreceptor when installed in a non-contact manner. The first electrostatic image is developed with a one-component developer to form a first toner image on the first photoconductor, and (B) the second image forming unit comprises (i) an amorphous silicon layer. A second photosensitive member having a second charge
Charging means, a second exposing means for forming a second electrostatic image on a charged second photoreceptor by exposure, and a developer transported by the second developing sleeve. And at least a second developing means for developing the second electrostatic image formed on the second photoconductor.
The photoreceptor has a diameter of 20 to 80 mm, and the developing area, which is the portion facing the second developing sleeve, is charged to an absolute value of 300 to 450 V by the second charging means, and (iii)
The second developing means has a one-component developer containing a second toner, and (iv) the second photosensitive member and the second developing sleeve are placed in contact or non-contact with each other. , (V) second
The developing sleeve rotates at a peripheral speed of 1.05 to 2.0 times the peripheral speed of the second photoconductor when it is installed in contact with the developing sleeve,
In the case where the photoconductor is installed in a non-contact manner, the peripheral speed of the second photoconductor is set to 1.
The second electrostatic image is developed with the one-component developer while rotating at a peripheral speed of 1 to 4.0 times to form the second toner image into the second toner image.
And (C) a third image forming unit,
(I) third charging means for charging a third photoconductor having an amorphous silicon layer, third exposure means for forming a third electrostatic image on the charged third photoconductor by exposure, and third And (iii) developing means for developing a third electrostatic image formed on the third photosensitive member with the developer conveyed by the third developing sleeve. The photosensitive member No. 3 has a diameter of 20 to 80 mm, and the developing area, which is the portion facing the third developing sleeve, is charged to an absolute value of 300 to 450 V by the third charging means, and (iii) the third developing means The means has a one-component developer containing a third toner, and (iv) a third photoconductor and a third photoconductor.
(V) When the third developing sleeve is installed in contact with the developing sleeve, the peripheral speed of the third photosensitive member is 1.05 to 2. When the photoconductor rotates at a peripheral speed of 0 times and is installed in a non-contact manner, it rotates at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the third photosensitive member, and the third photosensitive member is rotated by a one-component developer to form a third photosensitive member. The electrostatic image is developed to form a third toner image on the third photoconductor, and (D) the fourth image forming unit charges the fourth photoconductor having the (i) amorphous silicon layer. A fourth charging means for forming a fourth electrostatic image on the charged fourth photoconductor by exposure;
And a fourth developing means which has a fourth developing sleeve and develops a fourth electrostatic image formed on the fourth photosensitive member with the developer conveyed by the fourth developing sleeve. (Ii) the fourth photoreceptor has a diameter of 20 to 80 mm, and a developing area, which is a portion facing the fourth developing sleeve, is charged to an absolute value of 300 to 450 V by a fourth charging means; (Iii) the fourth developing means has a one-component magnetic developer containing a fourth toner, and (iv) the minimum gap between the fourth photosensitive member and the fourth developing sleeve is 100.
(V) the fourth developing sleeve is rotated at a peripheral speed of 1.1 to 4.0 times the peripheral speed of the fourth photosensitive member while being rotated by the one-component developer. The fourth electrostatic image is developed to form a fourth toner image on the fourth photoconductor, and (E) the first toner, the second toner, and the third toner image.
And the fourth toner have different color tones and are each selected from the group consisting of a non-magnetic yellow toner, a non-magnetic magenta toner, a non-magnetic cyan toner, and a magnetic black toner. The yellow toner, the non-magnetic magenta toner, the non-magnetic cyan toner, and the magnetic black toner have positive chargeability, and the weight average particle diameter of each toner is 4.0 to 10.0 μm. 0.5mg / c unfixed toner amount
In terms of the coloring power of the toner defined by the image density after one fixing when m ² , the coloring power of the yellow, magenta, and cyan toners is 1.0 to 1.8, respectively, and the black toner Is 0.5 to 1.5, and the difference between the coloring power of the toner of each color of yellow, magenta, and cyan which shows the maximum coloring power and the coloring power of the toner which shows the minimum coloring power is 0. An image forming apparatus, wherein the number is from 0.5 to 0.5. 15. The non-magnetic yellow toner,
Eye Pigment Yellow 74, 93, 97, 109,
128, 151, 154, 155, 166, 168, 1
The image forming apparatus according to claim 14, further comprising a yellow pigment selected from the group consisting of 80 and 185. 16. The non-magnetic magenta toner comprises a quinacridone pigment and C.I. Pigment Red 5, 31, 48: 2, 57: 1, 58: 2, 146, 1
47, 150, 184, 185, 187, 238, 24
The image forming apparatus according to claim 14, further comprising a magenta pigment selected from the group consisting of 5, 265. 17. The image forming apparatus according to claim 14, wherein the non-magnetic cyan toner contains a Cu-phthalocyanine pigment or an Al-phthalocyanine pigment. 18. The image forming apparatus according to claim 14, wherein the magnetic black toner contains at least magnetite. 19. The image forming apparatus according to claim 14, wherein the coloring power of each of the yellow, magenta, and cyan toners is 1.1 to 1.7, respectively. 20. The image forming apparatus according to claim 14, wherein said first to fourth photoconductors are photoconductors having a positively or negatively charged amorphous silicon layer. 21. The photoconductor according to claim 1, wherein the first to fourth photoconductors have a negatively charged amorphous silicon layer, and form a latent image by back scan exposure.
21. The image forming apparatus according to 4 or 20. 22. The image according to claim 14, wherein the first to fourth photoconductors have a positively charged amorphous silicon layer and form a latent image by image exposure. Forming equipment. 23. The toner according to claim 1, wherein the first to fourth toners contain at least one positive charge control agent selected from a quaternary ammonium salt, an imidazole compound and a styrene acrylic copolymer resin containing an ammonium group. Item 1
23. The image forming apparatus according to 4 or 22. 24. The toner according to claim 14, wherein the first to fourth toners contain a binder resin mainly composed of one selected from the group consisting of polyester, styrene acryl, and modified products thereof. Image forming device. 25. The polyester having an acid value of 35 mgK.
25. The image forming apparatus according to claim 24, wherein the pressure is OH / g or less. 26. The toner according to claim 14, wherein the first to fourth toners have a glass transition temperature of 50 to 70 ° C.
Or the image forming apparatus according to 24.