JPH09106202A - Electrophotographic formation of color image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to easily and stably obtain color images having high fineness and high image quality free from color smears, to execute transfer at a low transfer temp. and high speed and to obtain good color copies without selecting the materials to be transferred. SOLUTION: Peelable transfer layers 12 having a laminated structure consisting of a first transfer layer 12T1 formed by an electrodeposition coating method using thermoplastic resin particles contg. a specific resin (AH) and a specific resin (AL1 ) within the same particle and a second transfer layer 12T2 contg. the specific resin (AL2 ) on this layer are formed on the surface of an electrophotographic photoreceptor 11. Toner images of >=1 colors are formed on the transfer layers 12 by an electrophotographic process. These toner images are thermally transferred onto the materials 16 to be transferred at each of the transfer layers 12.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic color image forming method applicable to the fields of electrophotographic color copying machines, color printers, color proofers, color checkers and the like. In particular, the present invention relates to an electrophotographic color image forming method for stably and repeatedly forming high-quality copied images.

[0002]

2. Description of the Related Art Toners of a plurality of colors are successively superposed and developed on a surface of an electrophotographic photosensitive member by a direct electrophotographic process to form a multicolor image, which is then transferred onto a transfer material such as a printing main paper at a time. Accordingly, a method for producing a color print, a color copy or a color proof (proof for printing) is known. Such a developing method includes a so-called dry developing method and a wet developing method. A color image obtained by using the wet development method is preferable, as compared with the case of the dry development method, because there is no color shift of each color and a high resolution color image can be obtained.
It is extremely difficult to completely transfer the wet toner image directly from the surface of the photoconductor to the actual paper.

In order to solve this problem, Japanese Patent Laid-Open No. 2-272
Japanese Patent No. 469 discloses a technique in which a non-aqueous solvent is supplied between a material to be transferred and a photoconductor at the time of transfer and then electrostatically transferred. Further, JP-A Nos. 2-115865 and 2-11
No. 5866, after a transparent film was previously laminated on the surface of the photoconductor, a wet toner image was formed on the film by an electrophotographic process, and then the film was peeled from the photoconductor.
A method of transferring an image by attaching it to plain paper is disclosed. However, in this case, the film to be laminated preferably has a thickness of 9 μm, but the production and handling of a film having such a thickness are extremely troublesome, and it is necessary to separately take measures for that purpose.

Further, in Japanese Patent Publication No. 43185/1990, a photosensitive material having a photoconductive layer on a light transmissive substrate and a transparent dielectric support thereon is imagewise exposed through the light transmissive substrate to obtain a dielectric support. There is disclosed a method in which color separation images are formed so as to overlap each other and then transferred together with a support onto a transfer target material.
This method is extremely disadvantageous in terms of cost because the light-transmitting substrate must be used even though the photosensitive material is disposable.

On the other hand, Japanese Patent Application Laid-Open Nos.
No. 281464 and No. 3-11347, in an electrophotographic transfer method using a dry developing method, a peelable transfer layer is provided on the surface of a photoreceptor in advance, a toner image is formed thereon, and then the toner image is transferred. A technique is disclosed in which the layers are transferred to the paper. However, in these techniques, when the photoreceptor is used repeatedly, there are problems that a special operation is required at the time of transfer and that formation of a transfer layer involves difficulty. Further, in a method using a photoreceptor on which a transfer layer (or a release layer) has been formed in advance, the photoreceptor must be disposable, and the disadvantage in terms of cost cannot be avoided.

On the other hand, Japanese Patent Application Laid-Open No. 2-265280 describes a method of transferring a toner image on a photosensitive layer to a highly smooth primary intermediate transfer medium and then retransferring it onto a final transfer material. JP-A-3-243973 and 4-908
No. 7 and the like describe a method of obtaining a good final color image even with a wet toner by using a special transfer medium. In these methods, it is said that the toner image can be clearly transferred without being affected by the surface unevenness of the final transfer material.
Further, since the image is transferred onto the final transfer target material, a missing toner image or uneven image density is observed in the obtained color image.
In particular, it is often recognized that fine image parts such as fine lines and fine characters are missing. Further, a toner image remains on the surface of the photoconductor after the transfer process. This means that when the photoconductor is used repeatedly, it becomes necessary to clean the photoconductor surface.
For this reason, the setting of the apparatus and the damage to the surface of the photoconductor due to cleaning and the like pose problems.

Further, JP-A-5-181324 and JP-A-5-181324
No. 181325 and No. 5-197169, a releasable transfer layer made of a thermoplastic resin is provided on a photoreceptor having a releasable surface, and a toner image is formed thereon by an electrophotographic process. A method for transferring an image onto a transfer material is described. According to these methods, the toner image can be completely transferred to the transfer target material by using the wet toner without deterioration, and the photoconductor can be repeatedly used, so that the cost can be reduced. However, even in these technologies, the transfer layer must be designed so as not to adversely affect the electrophotographic process, or the toner image is formed on the transfer layer, so that the transfer layer is sufficiently adhered to the transfer material during transfer. However, the toner image portion is liable to be peeled off, and the surface state of the material to be transferred is easily affected, and there is a problem that the complete transfer of the toner image is not always performed.

[0008]

As described above, in the conventional color image forming method using the intermediate medium, a sufficiently satisfactory color image cannot be obtained, and the properties of the intermediate medium change and become stable when repeatedly used. There are various problems such that it is difficult to maintain the performance for a long period of time, a disposable member is generated to maintain the performance, and it is necessary to use a special transfer medium. On the other hand, in the color image forming method in which the transfer layer is provided on the photoreceptor, regardless of the type of toner or the type of material to be transferred,
There are still problems to be solved, such as difficulty in obtaining stable and high-definition images.

The present invention solves the above-mentioned problems of the conventional electrophotographic color image forming method.
An object of the present invention is to select a material to be transferred without causing color shift,
An object of the present invention is to provide an electrophotographic color image forming method using a transfer layer that can easily and stably obtain a high-definition and high-quality color image. A further object of the present invention is that the transfer layer is thin and the transfer conditions are relaxed, and the transfer layer and the toner image are still good even if the transfer temperature becomes low or the transfer speed becomes high. Another object of the present invention is to provide an electrophotographic color image forming method in which the image is transferred to a transfer material.

[0010]

The above object of the present invention is to provide an electric power source.
A peelable transfer layer is formed on the surface of the sub-photoreceptor,
One or more toner images on the transfer layer by photographic process
Form and transfer the toner image together with the transfer layer to the transfer material
In the electrophotographic color image forming method, the transfer layer is
Lath transition point 20 ° C to 140 ° C or softening point 30 ° C to 180
Resin (AH) and glass transition point of -40 ° C to 40 ° C
Is a resin with a softening point of 0 ° C to 60 ° C (AL₁) And the resin
The glass transition point or softening point of (AH) is resin (AL₁) Noso
At least two kinds of resin that are higher than that by 2 ℃ or more
Electrodeposition coating using thermoplastic resin particles (AR) contained in
The first transfer layer (T₁) And this layer
Glass transition point -40 ° C to 35 ° C or softening provided above
Point 0 ℃ -45 ℃ resin (AL _Two2) mainly containing
Transfer layer (T_Two) Is a laminated structure
What can be achieved by the electrophotographic color image forming method
Was found.

The electrophotographic color image forming method of the present invention, as shown in FIG.
And the photosensitive layer 2 on the surface of the electrophotographic photosensitive member 11.
A thermoplastic resin particle (AR) is formed as a transfer layer (T ₁ ) by an electrodeposition coating method, and a second transfer layer (T ₂ ) mainly containing a thermoplastic resin (AL ₂ ) is further provided thereon. After the peelable transfer layer 12 having a laminated structure is formed, a toner image 3 of one or more colors is formed by a normal electrophotographic process, and the toner image 3 is transferred onto the transfer material 16 by thermal transfer, and the toner image 3 is transferred together with the transfer layer 12. This is a color copy. In the present invention, the transfer layer has a laminated structure and the first transfer layer (T ₁ ) on the photoreceptor side.
The thermoplastic resin particles (AR) forming the second transfer layer (T ₂ ) contain at least two kinds of resins (AH) and resins (AL ₁ ) having different glass transition points or softening points in the same particles. The major feature is that () is made of resin (AL ₂ ).

According to the present invention, the transfer layer has the laminated structure as described above, so that the surface of the photoreceptor and the first transfer layer (T
_It is presumed that a synergistic effect of reducing the adhesive force at the interface with ₁ ) and increasing the adhesive force between the surface of the material to be transferred and the second transfer layer (T ₂ ) can be obtained, and thus the transferability of the transfer layer can be improved. Dramatically improved and the latitude of transfer conditions expanded. That is, the transfer temperature and transfer pressure can be reduced and the transfer speed can be improved. As a result, the heating and pressurization of the photoconductor can be reduced to suppress the deterioration of the electrophotographic characteristics, and the repeated durability of the photoconductor can be suppressed. And the time required for the transfer process can be shortened and the color image forming speed can be improved. In addition, the transfer is easily performed regardless of the type of the transferred material. Further, since the toner image is transferred together with the transfer layer at once, it is possible to easily and stably obtain a high-definition and high-quality color image without color shift. Furthermore, since the surface of the photoconductor is protected by the transfer layer and does not come into direct contact with the material to be transferred, damage to the surface of the electrophotographic photoconductor is reduced, and the photoconductor can be repeatedly used or used for a long time. Further, by forming the transfer layer on the photoconductor in the electrophotographic apparatus each time, the photoconductor after the transfer layer is peeled off can be used repeatedly, so that the electrophotographic process can be performed without disposing the photoconductor. Can be performed continuously.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Transfer layer used in the present invention
Will be described in detail. As described above, the transfer layer of the present invention
Has a laminated structure, and the first transfer layer (T₁) And the second transfer layer (T
_Two), The first transfer layer (T₁)
And the second transfer layer (T _Two) Are collectively referred to as a transfer layer (T).
There is also. The transfer layer (T) is previously provided on the electrophotographic photosensitive member.
It may be prepared, or formed each time in the electrophotographic device.
May be done. The transfer layer (T) of the present invention has a light-transmitting property.
And wavelength light in the spectral sensitivity region of the electrophotographic photosensitive member.
Be transparent to at least a part of
However, it is not particularly limited and may be colored.
No. Usually, a colorless and transparent transfer layer is used. Transfer layer of the present invention
(T) is preferably at a temperature of 180 ° C. or lower and / or 3
0 kgf / cm^TwoThe following pressure, more preferably 160 ° C or higher
Lower temperature and / or 20kgf / cm^TwoTransfer of the following pressure
It is preferable that peeling is possible under the conditions. Below the above value
The transfer layer to separate and transfer the transfer layer from the photoreceptor surface.
Enlarge the equipment to maintain the heat capacity and pressure of the copying equipment
There is almost no need to do it, and it is sufficiently transferred at an appropriate transfer speed.
Can be performed, and there is no problem in practical use. The lower limit is particularly limited
Not specified, but usually above room temperature or 100 gf / cm
^TwoThe above pressure is preferable. The transfer layer (T) has an electric charge on it.
Because the toner image is formed by the sub-photo process,
Electrophotographic characteristics of photoconductor (chargeability, charge retention in the dark, photosensitivity
Etc.) is desirable. In addition, the transfer layer (T
₁) Is the top layer when it is transferred to the transfer material, so
It is desirable to maintain the desired strength. First transfer layer of the present invention
(T₁Resin particles (AR) used for forming
As described above, the glass transition point or softening point differs by 2 ° C or more.
Two types of resin (AH) and resin (AL₁) At least
It is contained in the same particle. In the present invention, the glass transition point and
Resin (AH) and resin having a softening point within the scope of the present invention
(AL₁) Can be arbitrarily selected and provided.

The resin (AH) preferably has a glass transition point of 30 ° C to 120 ° C or a softening point of 38 ° C to 160 ° C,
The glass transition point is more preferably 35 ° C to 90 ° C or the softening point is 40 ° C to 120 ° C, and the resin (AL ₁ ) is preferably the glass transition point -30 ° C to 40 ° C or the softening point 0 ° C to 40 ° C.
And more preferably a glass transition point of -20 ° C to 33 ° C.
Alternatively, the softening point is 5 ° C to 35 ° C. Further, the difference between the glass transition point or the softening point of the resin (AH) and the resin (AL ₁ ) is preferably 5 ° C. or higher, more preferably 10 ° C. or higher. Here, the resin (A
H) or the resin (AL ₁ ) contains two or more kinds, the difference in the glass transition point or the softening point is the one having the lowest glass transition point or the softening point in the resin (AH), and the resin (AL ₁ )
Among them, the difference from the one having the highest glass transition point or softening point. Resin (AH) and the resin (AL _1), the resin (AH) / the resin (AL ₁₎ is preferably 10 / 90-95
When the resin particles (AR) are contained in a ratio of / 5 (weight ratio) in the resin particles (AR), good transferability can be obtained. Also, the obtained color copy has excellent filing characteristics. That is, even when a color copy is filed with a plastic sheet or the like, there is no inconvenience that the transfer layer adheres to the plastic sheet and peels off. A more preferable ratio is resin (AH) / resin (AL
₁ ) is 30/70 to 90/10 (weight ratio).

Further, at least two kinds of resin (AH) and resin (AL ₁ ) contained in the resin particles (AR) of the present invention.
Is in any state of being mixed in the particles or in a state of forming a layered structure in which the resin (AH) main part and the resin (AL ₁ ) main part are separated (that is, core-shell structure particles). Well, and in the case of core-shell structure,
Even if the core part is resin (AH), resin (AL ₁ )
However, it is not particularly limited. Resin (A
Resin particles (A) having a core-shell structure in which H) is a shell
When R) is used, the surface side of the transfer layer transferred to the material to be transferred is mainly composed of a resin (AH) having a high glass transition point or softening point, so that the storage stability of the copy such as the filing characteristics described above. Is further improved, and resin (AH)
By selecting the type of, it becomes possible to impart the writing property and the imprinting property similar to plain paper.

The transfer layer of the present invention is further characterized in that the second transfer layer (T ₂ ) provided on the first transfer layer (T ₁ ) mainly contains a resin (AL ₂ ). Resin (AL ₂ )
Is preferably a glass transition point of -20 ° C to 30 ° C or a softening point of 20 ° C to 45 ° C, and more preferably a glass transition point of -10 ° C to 30 ° C or a softening point of 25 ° C to 45 ° C. The first transfer layer (T ₁₎ in the resin (AL ₁₎ and the second transfer layer (T ₂₎ of the resin (AL _2), may be the same or different. Resin used in the second transfer layer (T ₂₎ (AL ₂₎ the first transfer layer (T ₁₎
Having a glass transition point or a softening point lower than that of the resin (AH) in the resin particles (AR) to be used for, preferably 2 ° C. or higher,
It is more preferable that the temperature is 5 ° C. or higher. Furthermore, the resin (AH) in the resin particles (AR) has a glass transition point of 25 ° C.
Or higher, or the softening point is 35 ° C. or higher, and the resin (AL ₂ ) contained in the second transfer layer (T ₂ ) is lower than the resin (AH) in the glass transition point or the softening point in the range of 10 ° C. to 40 ° C. Are preferred. The weight average molecular weights of the resins (AH), (AL ₁ ) and (AL ₂ ) (hereinafter sometimes collectively referred to as the resin (A)) used in the transfer layer of the present invention are preferably 1 × 10 ³ respectively. ˜5 × 10 ⁵ , more preferably 3 × 10 ³ to 8 × 10 ⁴ . Here, the molecular weight is measured by the GPC method and converted into polystyrene,
Hereinafter, it may be abbreviated as Mw.

Specific examples of the resin (A) that can be used in the transfer layer (T) include thermoplastic resins, resins known as adhesives or pressure-sensitive adhesives, such as olefin polymers and copolymers. , Vinyl chloride copolymer, vinylidene chloride copolymer, vinyl alkanoate polymer and copolymer, olefin-styrene copolymer, olefin-unsaturated carboxylic acid ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer Polymers, alkyl vinyl ether copolymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, itaconic acid diesters Polymers and copolymers, maleic anhydride copolymers, acrylamide copolymers, methacrylic acid Amide copolymer, hydroxyl-modified silicone resins, polycarbonate resins, ketone resins, polyester resins, silicone resins, amide resins, hydroxy- and carboxy-modified polyester resins, butyral resins,
Polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, cyclized rubber-acrylic acid ester copolymer, copolymer containing a vinyl ring (as the vinyl ring, for example,
Furan ring, tetrahydrofuran ring, thiophene ring, dioxane ring, dioxofuran ring, lactone ring, benzofuran ring, benzothiophene ring, 1,3-dioxetane ring, etc.), cellulose resin, fatty acid-modified cellulose resin, epoxy resin and the like. .

[0018] For example, "Plastic Material Course Series" Vol. 1 to 18 (1981) published by Nikkan Kogyo Shimbun, "Polyvinyl chloride" edited by Kinki Chemical Association Vinyl Section, published by Nikkan Kogyo Shimbun (1988), Hide Omori Three "Functional Acrylic Resins" Techno System Co., Ltd. (1985), Eiichiro Takiyama "Polyester Resin Handbook" Nikkan Kogyo Shimbun (1988), Kazuo Yuki "Saturated Polyester Resin Handbook" Nikkan Kogyo Shimbun ( 1989), "Polymer Data Handbook (Applied)" edited by The Polymer Society of Japan, Chapter 1 Baifukan (1986), Yuji Harazaki "Latest Handbook of Binder Technology" Chapter 2 General Technology Center Co., Ltd. (1985)
), Tadashi Okuda, "Polymer Processing, Separate Volume 8 20th Volume Special Issue" Adhesive "" Polymer Publishing Association (1976), Keiji Fukuzawa "Adhesive Technology" Polymer Publishing Association (1987), Mamoru Nishiguchi "Adhesion" Handbook, 14th edition, Polymer Society (1985),
Various resins described in “Adhesion Handbook, Second Edition” edited by The Japan Adhesive Association, published by Nikkan Kogyo Shimbun (1980) and the like can be mentioned. The resin (A) is a polymer containing a substituent containing a fluorine atom and / or a silicon atom, which has a function of improving the releasability of the resin (A) when used in the first transfer layer (T ₁ ). You may contain a component (c). As a result, the releasability from the electrophotographic photosensitive member is further improved, and as a result, the transferability is improved. The content of the polymer component (c) is preferably 3 to 40 parts by weight, more preferably 5 to 25 parts by weight based on 100 parts by weight of all the polymer components of the resin (A). The fluorine atom- and / or silicon atom-containing substituent may be incorporated in the polymer main chain of the polymer, or may be present as a substituent on the side chain of the polymer. The polymer component (c) may be contained in either the resin (AH) or the resin (AL ₁ ). Preferably, the polymer component (c) is contained as a block in the resin (A). Specific examples of the polymer component (c) include those similar to the polymer component (F) containing a substituent containing a fluorine atom and / or a silicon atom, which may be contained in the resin (P) described below. You can Also, the aspect of the polymerization pattern of the block copolymer when the polymer component (c) is contained in a block, and the method for synthesizing the copolymer are the same as those in the case of the block copolymer containing the polymer component (F) described below. It is the same.

The transfer layer (T) may optionally contain other additives in order to improve various physical properties such as adhesiveness, film-forming property and film strength. For example, rosin, petroleum resin, silicone oil, etc. for adjusting the adhesiveness. Polybutene, DOP, DBP, low molecular weight styrene resin, low molecular weight as a plasticizer and softener for improving the wettability to the photoreceptor and lowering the melt viscosity. Polyethylene wax, microcrystalline wax, paraffin wax and the like, and high molecular weight hindered polyhydric phenol, triazine derivative and the like as an antioxidant can be added. For details, see “Actual Hot Melt Adhesion” (Hiroshi Fukada, Kobunshi Kogakukai, published in 1983), pages 29 to 107.

If the film thickness of the transfer layer is too thin, transfer failure tends to occur, and if it is too thick, the color image after transfer may be distorted due to the expansion and contraction of the resin. Therefore,
The total thickness of the transfer layer is appropriately 0.1 to 20 μm, preferably 0.5 to 10 μm, more preferably 1 to 10 μm.
5 μm. The film thickness ratio of the first transfer layer and the second transfer layer is 99.
5 to 1 to 95, preferably 95 to 30/5 to 70.

In the present invention, the thermoplastic resin as described above is a resin particle (AR) containing at least one of the resin (AH) having a specific glass transition point and the resin (AL ₁ ) in the same particle. In this state, it is applied to the surface of the photoreceptor by the electrodeposition coating method, and a uniform thin film is formed by, for example, heating to form the first transfer layer (T ₁ ). Here, the electrodeposition coating method means a method in which resin particles (AR) are electrostatically attached or electrodeposited on the surface of the photoreceptor. Therefore, the thermoplastic resin particles (A
R) is required to have either positive charge or negative charge, and its electroscopic property is arbitrarily determined by the charge property of the electrophotographic photosensitive member to be combined.

The resin particles (AR) are in the range satisfying the above-mentioned physical properties, and the average particle diameter thereof is usually 0.01.
μm to 10 μm, preferably 0.05 μm
To 5 μm, more preferably 0.1 μm to 1 μm. These particles are either particle powder (dry type), resin particles dispersed in a non-aqueous system (wet type), or resin particles dispersed in an electrically insulating organic substance that is solid at room temperature and becomes a liquid by heating (pseudo-wet type). Good. Preferably, it is a non-aqueous dispersion resin particle in which the thickness of the transfer layer for peeling can be easily adjusted to a thin film with a uniform thickness. The resin particles of the present invention can be produced by a conventionally known mechanical pulverization method or polymerization granulation method. These production methods can be applied to particles of either dry electrodeposition or wet electrodeposition.

In the case of producing resin particles used in the dry electrodeposition method, the mechanical pulverization method is a method of directly pulverizing with a conventionally known pulverizer to obtain fine particles (for example, a ball mill, a paint shaker, a jet mill). Method to be used, etc.), and if necessary, the materials to be resin particles are mixed, and the mixture is subjected to melting and kneading and then pulverized. Etc. can be appropriately combined and performed. A spray dry method is also known. Specifically, "Granulation Handbook", Part II (edited by Ohmsha, 1991), edited by Japan Powder Industrial Technology Association, Kanagawa Business Development Center, "Actual state of the latest granulation technology" (Published by Kanagawa Business Development Center) Department, 1984
Ed., Arakawa Masafumi et al., “Latest powder design technology” (Techno System Co., Ltd., 1988), etc., and can be easily manufactured by appropriately using the methods described in detail in the textbooks.

As the polymerization granulation method, conventionally known methods such as an emulsion polymerization reaction carried out in an aqueous system, a seed polymerization reaction, a suspension polymerization reaction, and a dispersion polymerization reaction carried out in a non-aqueous solvent system are known. Specifically, Soichi Muroi "Chemistry of Polymer Latex" Polymer Publishing Association (1970), Taira Okuda, Hiroshi Inagaki "Synthetic Resin Emulsion" Polymer Publishing Association (1978), Soichi Muroi "Polymer Latex""Introduction" Kobunsha (1983), I.
Piirma, PC Wang "Emulsion Polymerization", I.
Piirma & JL Gardon, ACS symp. Sev. 24, p.34
(1974), Fumio Kitahara et al., "Chemistry of Dispersion Emulsion System" Engineering Book (1979), Soichi Muroi, "Cutting-edge Technology of Ultrafine Polymer" CMC (1991), etc. After being made into particles, it can be produced by collecting and pulverizing by various methods as described in the above-mentioned mechanical method textbooks.

As a method of dry electrodeposition of the obtained fine particle powder, a conventionally known coating method of electrostatic powder or a developing method of a dry electrostatic photograph developer can be used. Specifically, as described in "Electrostatic Powder Coating" by JF Hughes (Translated by Hideo Nagasaka and Machiko Midorikawa), corona charging, friction charging, induction charging, ionic wind charging, reverse ionization, etc. are used. As described in the textbooks such as "Method of Electrodepositing Charged Fine Particles", Koichi Nakamura, "Development and Practical Use of Recent Electrophotographic Development System and Toner Material", Chapter 1 (Japan Science Information Co., Ltd., 1985). , Cascade method, magnetic brush method, fur brush method, electrostatic method, induction method,
This can be appropriately performed using a development method such as a touchdown method or a powder cloud method.

The non-aqueous latex used in the wet electrodeposition method can also be produced by either the mechanical method or the polymerization granulation method as described above. For example, a method in which a dispersing polymer is used in combination and further dispersed by a wet disperser (for example, a ball mill, a paint shaker, a Keddy mill, a Dyno mill, etc.), and a material serving as a resin particle component and a dispersion assisting polymer (or a coating polymer) are previously kneaded. And then pulverized, and then dispersed in the presence of a dispersing polymer. Specifically, a method for producing a paint or a developer for electrostatic photography can be used.
), DH Solomon "The Chemistry of Organic Fil
m Formers '' John Wiles & Sons (1967), `` Paint and Su
rface Coating Theory and Practice ", Yuji Harazaki" Coating Engineering "Asakura Shoten (1971), Yuji Harasaki" Basic Science of Coating "Asakura Shoten (1977), etc.

Further, a seed polymerization method is used as a polymerization granulation method.
It can be easily produced by using
"The latest technology of ultrafine polymer" Chapter 2, "Recent Electrode
Development and practical application of child photo development system and toner materials "
Chapter, K.E.J.Barvett `` Dispersion Polymerization in
 Organic media ”John Wiley (1975) and other publications
First, the resin is prepared by the conventionally known non-aqueous dispersion polymerization method.
(AH) or resin (AL ₁) Fine particles, and then
And the resin (A
L₁) Or the monomers corresponding to the resin (AH)
A method of producing by polymerization is preferred.

In the polymerization granulation method, in order to introduce the polymer component (c) into the resin particles for improving the releasability, a single amount which is soluble in the organic solvent forming the resin particles and which is insolubilized by polymerization is used. A polymer corresponding to the polymer component (c) is allowed to coexist with the polymer to carry out the polymerization reaction, whereby the resin is copolymerized in the resin (A), and the resin particles of the random copolymer are easily obtained.

Furthermore, in order to introduce the polymer component (c) in blocks, a method of using at least a block copolymer containing the polymer component (c) in blocks in the dispersion stabilizing resin to be used, or the polymer component ( A monomer having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ (preferably 3 × 10 ^{3 to} 1.5 × 10 ⁴ ) composed of c) as a main repeating unit is allowed to coexist. It can be easily carried out by a method of copolymerization. Further, as another method, a polymer initiator containing the polymer component (c) as a main repeating unit (azobis polymer initiator or peroxide polymer initiator) may be used to similarly obtain the block copolymer. Resin particles of can be obtained.

The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or in combination of two or more kinds. Specific examples of such organic solvents include methanol, ethanol, propanol, butanol, fluorinated alcohols, alcohols such as benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ketones such as diethyl ketone, diethyl ether,
Ethers such as tetrahydrofuran and dioxane; carboxylic esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; and fats having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane and cyclooctane. Group hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane, and trichloroethane. However, the present invention is not limited to the compound examples described above. By synthesizing the dispersed resin particles by a dispersion polymerization method in these non-aqueous solvent systems, the average particle size of the resin particles can be easily reduced to 1 μm or less, and the particle size distribution is very narrow and monodispersed. Can be.

Since these non-aqueous dispersion resin particles are subjected to a wet electrostatic development method or a method in which they are electrophoresed in a pressure field of an electric field, they are electro-deposited. It is preferable to adjust to a non-aqueous solvent system having a dielectric constant of 3.5 or less and ⁸ Ω · cm or more. Specifically, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, and halogen-substituted products thereof can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane,
Cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L (Isoper; trade name of Exxon), Shelsol 70, Shersol 71 (Shersol; trade name of Shell Oil Co.), Amsco OMS, Amsco 46
0 solvent (Amsco; trade name of American Mineral Spirits, Inc.) and the like can be used alone or in combination. Therefore, the above-mentioned insulating organic solvent is preferably used from the beginning as the solvent to be used during the polymerization granulation, but it may be prepared by granulating with a solvent other than these solvents and then substituting the dispersion medium.

In order to electrophoretically disperse dispersed particles in a dispersion medium, the particles must be positively or negatively charged electrophoretic particles. Providing the particles with an electric detecting property can be achieved by appropriately utilizing the technique of a developer for wet electrostatography. Specifically, "Recent Development and Practical Use of Electrophotographic Development System and Toner Material" pp. 139-148, and "Basics and Applications of Electrophotography" edited by The Institute of Electrophotography, pp. 497-505 (Corona, 1988). Annual), Yuji Harasaki "Electronic Photography" 16 (No.
2), page 44 (1977), etc., and using other electro-detection materials and other additives. For example, British Patent 893
429, 934,038, U.S. Pat. No. 1,122,
397, 3,900,412, 4,606,9
89, JP-A-60-179751, and JP-A-60-185.
No. 963, JP-A-2-13965 and the like. The composition of the non-aqueous latex used for electrodeposition is usually at least 1 liter of the electrically insulating dispersion medium,
Particles mainly containing a thermoplastic resin are 0.1 to 20
g, 0.01 to 50 g of the dispersion stabilizing resin, and 0.0001 to 10 g of the charge control agent added if necessary.

Further, other additives may be added in order to maintain dispersion stability of particles, charge stability, and the like.
Examples thereof include rosin, petroleum resin, higher alcohols, polyethers, silicone oils, paraffin waxes, and triazine derivatives. However, it is not limited to these. The upper limit of the total amount of these additives is regulated by the electrical resistance of the latex for electrodeposition. That is, if the electric resistance is lower than 10 ⁸ Ω · cm, it becomes difficult to obtain a sufficient amount of the thermoplastic resin particles, so the amount of each additive is controlled within this limit.

In this way, thermoplastic resin particles (AR) which are made into fine particles and imparted with an electric charge and dispersed in an electrically insulating liquid
Shows a behavior similar to that of the electrophotographic liquid developer. Therefore, for example, it is possible to perform electrophoresis on the surface of the photoconductor by using the developing device, for example, the slit developing electrode device shown in the above-mentioned "Basics and Applications of Electrophotographic Technology" pages 275 to 285. That is, particles (AR) mainly containing a thermoplastic resin are
The film is supplied between the counter electrodes provided so as to face the electrophotographic photosensitive member, and is electrophoresed according to a potential gradient applied from an external power source to be attached or electrodeposited on the electrophotographic photosensitive member to form a film.

In general, when the particles are positively charged, a voltage is applied from an external power source between the conductive support of the photoconductor and the developing electrode of the developing device so that the photoconductor has a negative potential. Then, the particles are electrostatically electrodeposited on the surface of the photoreceptor. Electrodeposition can also be performed by wet toner development using a normal electrophotographic process. That is, as shown in the premise `` Basics and application of electrophotographic technology '' on pages 46 to 79, without performing exposure after uniformly charging the photoreceptor, or performing so-called burn-off to expose only unnecessary regions, and then Perform normal wet toner development.

On the other hand, when the resin particles dispersed in a medium which is liquefied by heating are used, the medium is solid at room temperature and the heating temperature is 30 to 80 ° C. (preferably 4 ° C.).
(0-70 ° C.) is an electrically insulating organic compound which becomes liquid at a freezing point of 30-80 ° C.
Paraffins, waxes, low molecular weight polypropylene having a freezing point of 20 to 80 ° C, tallow having a freezing point of 20 to 50 ° C, and hardened oil having a freezing point of 30 to 80 ° C. These can be used alone or in combination. Other necessary characteristics are the same as those of the electrodeposited resin particle dispersion used in the wet development method.

Further, in the resin particles of the present invention used in this pseudo-wet method, the resin component having a high glass transition point or a high softening point which does not soften at the liquefying temperature of the medium used constitutes the outer shell of the particles. , So-called core-shell type particles (resin having a low glass transition point in the core portion and resin having a high glass transition point in the shell portion) are used, so that the dispersed resin particles are not fused by heating and are stable. It is possible to maintain a dispersed state.

The amount of the thermoplastic resin particles deposited on the photoconductor can be arbitrarily adjusted by the applied voltage of the external bias, the charging potential of the photoconductor, the processing time and the like. After electrodeposition, the developer is wiped off by a squeeze using a known rubber roller, gap roller, reverse roller or the like. Methods such as corona quiz and air squeeze are also known. In addition, cold or warm air,
Alternatively, the first transfer layer (T ₁ ) is formed by drying with an infrared lamp or the like, preferably forming a film of the thermoplastic resin particles.

First transfer layer formed on the surface of the photoconductor
(T₁) A second transfer layer (T _Two) Is the normal way
It is formed accordingly. The mode of forming in the electrophotographic apparatus is low
It is preferable in terms of cost reduction. Second transfer layer (T_Two)
First transfer layer (T₁) As a method of forming on the surface, heat melting
Coating method, electrodeposition coating method and transfer method make uniform and thin layer easy
It is preferably used because it can be formed. By these methods
In the electrophotographic apparatus, the first transfer layer (T₁)surface
The second transfer layer (T_Two) Can be easily formed.

Hereinafter, each method will be described in detail. In the hot melt coating method, the transfer layer composition is hot melt coated by a known method. For this purpose, a mechanism of a solventless coating machine, for example, a hot melt coating apparatus for hot melt adhesives (hot melt coater) described in “Actual of hot melt adhesion” on pages 197 to 215 is used as a second transfer layer (T ₂ ) Can be used as a coating specification. Examples include direct roll coaters, offset gravure roll coaters, rod coaters, extrusion coaters, slot orifice coaters, curtain coaters and the like.

The melting temperature of the resin constituting the transfer layer at the time of coating is optimized depending on the component composition of the resin constituting the transfer layer used, but it is usually in the range of 40 to 180 ° C. It is desirable that the temperature be raised to an appropriate temperature in a short time at a position where it is applied to the first transfer layer after being preliminarily melted by using a closed preheating device having an automatic temperature control means. By doing so, it is possible to prevent alteration or coating unevenness due to thermal oxidation of the resin forming the transfer layer. The coating speed depends on the fluidity of the resin constituting the transfer layer during heat melting, the coater method, the coating amount, etc., but is appropriately 1 to 200 mm / sec, preferably 50 to 150 mm / sec. .

Next, the formation of the transfer layer by the transfer method will be described. In this method, a transfer layer (T) held on a releasable support typified by release paper (hereinafter simply referred to as release paper) is used.
₂ ) is transferred onto the surface of the first transfer layer (T ₁ ). The release paper on which the transfer layer is formed can be easily supplied to the transfer device in the form of a roll or a sheet. As the release paper used in the present invention, any conventionally known release paper can be used.
(Issue: Management Development Center Publishing Department, May 20, 1978)
Sun), “All Paper Guide Paper Product Encyclopedia, First Volume / Culture Industry Edition” (Published; Paper Industry Times Co., Ltd., 1983 12)
Those described in (1st of a month) and the like.

Specifically, the release paper is an unbleached Clupak paper in which a release agent mainly composed of silicone is laminated with a polyethylene resin, a high-grade paper precoated with a solvent resistant resin, a kraft paper, and an undercoated PET. It is applied on a base or a substrate such as glassine paper. A silicone of a solvent type is generally used, and a gravure roll, a reverse roll, and a concentration of 3 to 7% are used on the substrate.
After coating and drying with a wire bar etc., it is heat-treated at 150 ° C or higher to be cured. The coating amount is about 1 g / m ² .

As the release paper, tapes, labels, forming industry and cast coat industry, which are generally commercially available from paper makers, can be used. For example, Separate Paper (Oji Paper Co., Ltd.), King Leeds (Shikoku Paper Co., Ltd.), Sun Release (Sanyo Kokusaku Pulp Co., Ltd.)
Manufactured by Nippon Paper Industries Co., Ltd., and the like.

To form the transfer layer (T ₂ ) on the release paper,
This can be easily carried out by applying a transfer layer composition containing a resin constituting the transfer layer as a main component by bar coating, spin coating, spray coating or the like according to a conventional method. The transfer layer (T ₂ ) on the release paper is replaced with the first transfer layer (T ₁ ) on the electrophotographic photosensitive member.
For thermal transfer onto the surface, a conventional thermal transfer method can be used. That is, it is sufficient thermal transfer layer (T ₂₎ transfer layer release paper holding the (T ₂₎ and pressed on the first transfer layer on the electrophotographic photosensitive member (T _1). Transfer the release layer (T ₂ ) from the release paper to the first transfer layer (T ₁ ).
The conditions for transferring to the surface are preferably as follows. The roller nip pressure is 0.1 to 10 kgf / cm ² , more preferably 0.2 to 8 kgf / cm ² , and the transfer temperature is 25.
C. to 100.degree. C., more preferably 40.degree. C. to 80.degree.
The transport speed is 0.5 to 200 mm / sec, more preferably 10 to 150 mm / sec.

The electrodeposition coating method is substantially the same as that described for the formation of the first transfer layer (T ₁ ). First transfer layer (T
Instead of the resin particles (AR) forming ₁ ), a thermoplastic resin (AL ₂ ) may be used as the resin particles (AL ₂ R). The transfer layer forming apparatus can be made compact by forming the second transfer layer (T ₂ ) by the electrodeposition coating method as in the case of forming the first transfer layer (T ₁ ).

Next, the electrophotographic photosensitive member used in the present invention will be described. As the electrophotographic photosensitive member, any conventionally known one can be used. What is important is that the surface of the photoconductor has releasability when the transfer layer is formed so that the transfer layer provided on the surface of the photoconductor can be easily peeled later together with the toner image.

That is, in the present invention, at least when the first transfer layer (T ₁ ) is formed by the film formation of the resin particles (AR) by the electrodeposition coating method, it is adjacent to the transfer layer (T ₁ ). The adhesive strength of the surface of the electrophotographic photoreceptor according to JIS Z0237-1980 "Test method for adhesive tape / sheet" is 100 gram force.
It is desirable to be less than (g · f). Thereby, the releasability between the photoconductor and the transfer layer can be better exhibited, and the transfer layer can be easily peeled off from the photoconductor at the time of transfer to the transfer material.

The measurement of the adhesive strength by the above-mentioned JIS Z 0237-1980 "Test method for adhesive tape / adhesive sheet" is 18
Follow the 0-degree peeling method with the following modifications. An electrophotographic photosensitive member on which a transfer layer is to be formed is used as a “test plate”. An adhesive tape having a width of 6 mm and manufactured according to JIS C 2338-1984 is used as a "test piece". Peel off at a speed of 120 mm / min using a constant speed tension type tensile tester. That is, a roller is reciprocated from the top of the test piece at a speed of about 300 mm / min, with the adhesive surface of the test piece facing down, and pressure-bonded to the test plate. During 20 to 40 minutes after crimping, using a constant speed tension type tensile tester, after peeling off about 25 mm, 120
Peel off at a speed of mm / min. The force is read every 20 mm peeling, for a total of 4 readings. The test is performed on three test pieces, and an average value of twelve pieces measured from the three test pieces is obtained, and this is converted into a proportional value per 10 mm width. The adhesive force on the surface of the electrophotographic photosensitive member is more preferably 50 g · f or less,
It is particularly preferably 30 g · f or less.

As a method for obtaining a photoreceptor having releasability on the surface adjacent to the transfer layer, a method of using a photoreceptor having the releasability on the surface itself (first method), a method of exhibiting releasability Method (second method) of applying the compound (S) to the surface of the photoconductor before forming the transfer layer, and in a dispersion liquid in which the resin particles (AR) of the present invention are dispersed in an insulating organic solvent. A method (third method) in which a compound (S ′) exhibiting peelability is coexistent and electrodeposition is performed. Also, any of these methods can be used in combination.

Examples of the photosensitive material having a releasable surface which can be used in the first method include a photoconductor obtained by modifying the surface of amorphous silicon to have a releasable property. As a method for modifying the peelability, fluorine atoms and /
Alternatively, there is a method of treating the surface of amorphous silicon with a coupling agent containing a silicon atom (for example, a silane coupling agent, a titanium coupling agent, etc.).
-89844, JP-A-4-231318, JP-A-6
0-170860, 59-102244, 60
No. 17750 and the like. Further, as another method, a compound (S) described later, particularly a fluorine atom and / or
Alternatively, a compound containing a component containing a silicon atom as a substituent in a block (for example, polyether, carboxylic acid,
Examples include a method of adsorbing and fixing modified polydialkylsilicones such as amino groups and carbinol groups. Further, as another example of the photoreceptor having a releasable surface, a polymer component in which the electrophotographic photoreceptor contains at least one of a silicon atom and a fluorine atom in the vicinity of the surface (containing a silicon atom and / or a fluorine atom) is provided. The thing containing the polymer to contain is mentioned. Since the surface of such a photoreceptor has a good releasability, the transfer layer (T) is easily and completely transferred onto the transfer material at once. Here, the vicinity of the surface of the electrophotographic photosensitive member means the uppermost layer of the photosensitive member, and includes the overcoat layer and the uppermost photoconductive layer provided on the photoconductive layer. That is, an overcoat layer is provided as the uppermost layer of a photoconductor having a photoconductive layer, and the polymer is added to the overcoat layer to impart releasability, or a photoconductive layer (photoconductive single layer and photoconductive layer The above-mentioned polymer may be contained in the uppermost layer of any of the body laminates), and the surface thereof may be modified to a state in which releasability is exhibited.

In order to impart releasability to the overcoat layer or the uppermost photoconductive layer, a polymer containing silicon atoms and / or fluorine atoms may be used as a binder resin for the layer. Alternatively, it is also preferable to use a small amount of a block copolymer (surface unevenly distributed copolymer) containing a polymer segment composed of a polymer component containing a silicon atom and / or a fluorine atom as described below, together with another binder resin. Also,
The resin containing silicon atoms and / or fluorine atoms can also be used in the form of particles. The surface unevenly distributed copolymer is usually 0.1 to 30 in 100 parts by weight of the total composition of the uppermost layer.
It can be used in a proportion of parts by weight.

As such an overcoat layer, specifically, in a PPC photosensitive member using a dry toner,
A protective layer used for providing a surface layer on the photoconductor to protect the photoconductor is known as one means for maintaining durability of the photoconductor surface against repeated use of the photoconductor. For example, as a technique relating to a protective layer using a silicone block copolymer, JP-A-61-95358 is known.
No. 55, No. 55-83049, No. 62-89771, No. 61-189559, No. 62-75461, No. 61.
-139555, 62-139557, 62-
Examples thereof include those described in No. 208055. Further, examples of the protective layer using a fluorine-based block copolymer include those described in JP-A Nos. 61-116362, 61-117563, 61-20768, and 62-14657. Further, as a protective layer using a resin containing a fluorine atom-containing polymer component in the form of particles, those described in JP-A-63-249152 and JP-A-63-221355 can be mentioned.

Further, the method of modifying the surface of the uppermost photoconductive layer to a state in which releasability is exhibited is a method of using a so-called dispersion type photoconductor in which at least a photoconductor and a binder resin are used. Effectively applied. That is, in the layer constituting the uppermost layer of the photoconductive layer, a resin of a block copolymer containing, as a block, a polymer segment containing a polymer component containing a silicon atom and / or a fluorine atom, and silicon atom and / or By coexisting at least one of the resin particles containing the fluorine-containing polymer component, these materials are concentrated and migrated to the surface and unevenly distributed, so that the surface can be modified into a peelable surface. Examples of the copolymer and resin particles include those described in JP-A-5-197169.

To further strengthen the surface ubiquity,
As a binder resin for the overcoat layer or the photoconductive layer, a polymer segment containing a silicon atom and / or a fluorine atom,
It is possible to use a block copolymer obtained by binding at least one kind of polymer segment containing a heat and / or photocurable group-containing component in a block. Examples of the polymer segment containing such a heat- and / or photo-curable group-containing component include those described in JP-A-5197169. Alternatively, a light and / or thermosetting resin may be used together with a resin containing a fluorine atom and / or a silicon atom.

A polymer containing a polymer component containing a silicon atom and / or a fluorine atom (hereinafter sometimes referred to as polymer component (F)) of the present invention which is effective for modifying the surface of a photoreceptor is , Resin (hereinafter sometimes referred to as resin (P)) or resin particles (hereinafter sometimes referred to as resin particles (PL)).

When the polymer is a random copolymer, the content of the polymer component containing silicon atoms and / or fluorine atoms is preferably 60% by weight or more, more preferably 80% by weight based on the total polymer components. It is more than weight%. More preferably, a polymer segment (α) containing 50% by weight or more of a polymer component containing a silicon atom and / or a fluorine atom and a polymer segment (α) containing 0 to 20% by weight of a polymer component containing a silicon and / or a fluorine atom. It is a block copolymer in which united segments (β) are linked by blocks. More preferably, it is a block copolymer containing at least one polymer component containing a light and / or thermosetting functional group in the segment (β) in the block copolymer. In these block copolymers, it is preferable that the segment (β) does not contain any polymer component containing a fluorine atom and / or a silicon atom.

When the block copolymer containing the polymer segments (α) and (β) (surface uneven distribution type copolymer) is used, the surface peeling property itself is improved as compared with the random copolymer, Furthermore, peelability is maintained. That is, when a coating film is formed in the presence of a small amount of a fluorine- and / or silicon-atom-containing block copolymer, these are easily transferred and concentrated to the surface of the film before the drying step after coating. Then, the surface of the film is modified so that the film can exhibit peelability. As described above, in the resin (P), when the fluorine atom- and / or silicon atom-containing polymer segment (α) is blocked, the other fluorine atom- and / or silicon atom-containing polymer component is used. Since the polymer segment (β) containing a small amount of the polymer has a good compatibility with the binder resin for film formation, the polymer segment (β) sufficiently interacts with the binder resin to form a toner image or a transfer layer. The transfer of these resins to the transfer layer is suppressed or eliminated, and the interface between the transfer layer and the electrophotographic photosensitive member can be clearly formed and maintained (that is, the anchor effect). By using a polymer containing a curable group in the segment (β) of the block copolymer and crosslinking between the polymers at the time of film formation, an effect of further maintaining the interface with the photoreceptor clearly is exhibited. . Such a crosslinked state is particularly preferable when the photoreceptor is repeatedly used and used in combination with a liquid developer.

The polymer is the resin particles (PL) as described above.
May be used as. Preferred resin particles (PL)
Are resin particles dispersed in a non-aqueous solvent. Such resin particles include a polymer component containing a fluorine atom and / or a silicon atom-containing polymer component, which is insoluble in a non-aqueous solvent, and a polymer component containing a fluorine atom and / or a silicon atom. Even if it is 20% or less, a polymer segment (β) soluble in a non-aqueous solvent is preferably bonded. In the case of resin particles (PL), the insolubilized polymer segment (α) causes migration and concentration on the surface, and further, a polymer segment soluble in the non-aqueous solvent bound to the particles ( β) interacts with the binder resin to perform an anchor effect, as in the case of the resin. Further, when the curable group is contained in the polymer or the binder resin, transfer to the transfer layer is eliminated.

The above-mentioned polymer component containing a substituent containing a fluorine atom and / or a silicon atom is contained as a substituent of a side chain of a polymer even if the substituent is incorporated in the polymer main chain of the polymer. It may have been done. Examples of the substituent containing a fluorine atom include the following monovalent or divalent organic residues.

[0061]

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[0062]

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Examples of the silicon atom-containing substituent include the following monovalent or divalent organic residues.

[0064]

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However, R ³¹ , R ³² , R ³³ , R ³⁴ and R
^{35's, which} may be the same or different, each represents an optionally substituted hydrocarbon group or an -OR ³⁶ group (B ³⁶ represents an optionally substituted hydrocarbon group). As the hydrocarbon group represented by R ^{31 to} R ³⁶ , specifically, an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group,
Decyl group, dodecyl group, hexadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 2-cyanoethyl group, 3,3,3-trifluoropropylethyl group, 2-methoxy Ethyl group, 3-
Bromopropyl group, 2-methoxycarbonylethyl group,
2,2,2,2 ', 2', 2'-hexafluoroisopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1-propenyl, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), substituted with 7 to 12 carbon atoms Aralkyl group (eg benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethyl group) Benzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic group having 5 to 8 carbon atoms (eg cyclohexyl group,
2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group) , Octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxy Carbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.).

Further, the organic residue containing a fluorine atom and / or a silicon atom may be constituted in combination, in which case it may be directly bonded or further combined via another linking group. May be done. Specific examples of the linking group include a divalent organic residue, and -O-, -S-, -N
^{(D 1) -, - CO} -, - SO -, - SO 2 -, - CO
O-, -OCO-, -CONHCO-, -NHCONH
^{-, - CON (d 1)} -, - SO 2 N (d 1) - may be interposed selected linking groups from such a divalent aliphatic group or a divalent aromatic group, or these It represents an organic residue composed of a combination of divalent residues. Where d
¹ has the same meaning as R ³¹ .

Examples of the divalent aliphatic group include the groups shown below.

[0068]

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Here, e ¹ and e ² may be the same as or different from each other, and each is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (eg, methyl group). , Ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group,
Octyl group, nonyl group, decyl group, etc.). Q is-
O -, - S- or -N (d ²⁾ - represents, d ² represents an alkyl group having 1 to 4 carbon atoms, a -CH ₂ Cl or -CH ₂ Br.

Examples of the divalent aromatic group include a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (as a hetero atom constituting the hetero ring, selected from an oxygen atom, a sulfur atom and a nitrogen atom). Containing at least one hetero atom). These aromatic groups may have a substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group). , A butyl group, a hexyl group, an octyl group, etc.) and an alkoxy group having 1 to 6 carbon atoms (eg, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) can be given as examples of the substituent. Examples of the heterocyclic group include a furan ring, a thiophen ring, a pyridine ring, a piperazine ring, a tetrahydrofuran ring, a pyrrole ring, a tetrahydropyran ring, and a 1,3-oxazoline ring.

Specific examples of the repeating unit having a substituent containing a fluorine atom and / or a silicon atom as described above are shown below. However, the scope of the present invention is not limited to these. Following (F-1) ~ (F-32)
In each example in, R _f is as follows (1) to (1
Represents any one of the groups 1), and b represents a hydrogen atom or a methyl group.

[0072]

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However, in the above (1) to (11),
R _f ′ represents a group represented by the above (1) to (8), n represents an integer of 1 to 18, m represents an integer of 1 to 18, and p
Represents an integer of 1 to 5.

[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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In the resin (P) and the resin particles (PL), in the case of a so-called surface uneven distribution type copolymer, in the segment (α) containing a polymer component containing a silicon atom and / or a fluorine atom, this polymer The component contains at least 50% by weight of the total amount of the entire segment (α),
Preferably 70% by weight or more, more preferably 80% by weight
That is all. In the segment (β), the content of the polymer component containing a fluorine atom and / or a silicon atom is 20% by weight or less, preferably 0% by weight, of the total amount of the segment (β). The weight ratio of the segment (α) to the segment (β) is 1 to 95: 5 to 99 (weight ratio),
It is preferably 5 to 90 to 10 to 95 (weight ratio).
Within this range, both the resin (P) and the resin particles (PL) can exhibit good concentration effect and anchor effect on the uppermost surface of the photoconductive layer.

The weight average molecular weight of the resin (P) is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 1 × 10 ^4.
５5 × 10 ⁵ . The weight average molecular weight of the segment (α) in the resin (P) is preferably 1 × 10 ³ or more. The resin particles (PL) have an average particle size of preferably 0.001 to 1 μm, more preferably 0.05 to 1 μm.
It is 0.5 μm.

Preferred embodiments of the so-called surface unevenly distributed copolymer in the resin (P) will be described below. The resin (P) may be in any form as long as the polymer component containing a fluorine atom and / or a silicon atom is composed of a block. Here, to be composed of a block means that the polymer has a polymer segment (α) containing 50% by weight or more of a fluorine atom and / or a silicon atom, for example, A-B as shown below. Examples thereof include mold blocks, ABA type blocks, BAB type blocks, graft type blocks and step type blocks.

[0082]

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These various block copolymers can be synthesized according to conventionally known polymerization methods. For example,
W. J. Burrant, A.A. S. Hoffman "Block and G
"Raft Polymers" (1986, Reuhold), R.P. J. Cev
esa "Block and Craft Copolymers" 1962, B
utterworths), D. C. Allport, W.A. H. James
"Block Copo1ymers" (1972, App1ied Sci),
A. Noshay, J .; E. FIG. McGrath "Block Copolymers
(1977, Academis Press), G. Huvterg,
D. J. Wilson, G .; Riess, NATO ASIser
. Ser E., 1985 , 149, V.I. Perces, Appl
ide Polymer Sci., 285 , 95 (1985), T.I.
E. FIG. Ho geu-Esch, J .; Smid "Recent Advances in
Anion Polmerization "(1987, Elsevier N
ew York), S.W. Kobayashi, T .; Saegusa "Ring
Opining Po1ymerization "(1984, Applied S
cence Publishers Ltd.), Fumio Ide, "Graft Polymerization and Its Application" (1977, Kobunshi Kogakukai), etc.

That is, organometallic compounds (eg, alkyllithium, lithium diisopropylamide, alkali metal alcoholates, alkylmagnesium halides,
Alkyl aluminum halides, etc.) as an initiator, an ionic polymerization reaction, a group transfer polymerization reaction, a living polymerization reaction using a metalloporphyrin complex, a photo-living polymerization reaction using a dithiocarbamate compound or a xanthate compound as an initiator, an azo A radical polymerization reaction using a polymer having a group or a peroxide group as an initiator, a polymerization reaction using a macromonomer, or a method of grafting using a polymer is known. More specifically,
The method illustrated in No. 197169 etc. is mentioned. The synthesis of the above block copolymer is not limited to these polymerization methods.

Next, a preferred embodiment of the resin particles (PL) will be described. As mentioned above, resin particles (PL)
Is preferably a fluorine atom and / or insoluble in a non-aqueous solvent.
Alternatively, it comprises a polymer segment (α) containing a silicon atom and a polymer segment (β) soluble in the solvent and containing almost no fluorine atom and / or silicon atom. Furthermore, the polymer segment (α) part that constitutes the insoluble portion of the resin particles (PL) may form a crosslinked structure. As a preferable method for producing the resin particles (PL), a non-aqueous dispersion polymerization method which will be described later regarding production of the non-aqueous dispersion resin particles can be mentioned.

The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or in combination of two or more kinds. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol and benzyl alcohol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and diethyl ketone, ethers such as diethyl ether, tetrahydrofuran and dioxane. , Carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate, aliphatic hydrocarbons having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane and cyclooctane, benzene, Aromatic hydrocarbons such as toluene, xylene, chlorobenzene,
Examples include halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane, and trichloroethane. However, the present invention is not limited to the compound examples described above.

By synthesizing the dispersed resin particles in these non-aqueous solvent systems by the dispersion polymerization method, the average particle diameter of the resin particles easily becomes 1 μm or less, and the distribution of the particle diameter is very narrow. It can be a particle. Furthermore, the inside of the polymer particles in which the resin particles (PL) are insolubilized may have a crosslinked structure. Any of the conventionally known methods can be used to shape these crosslinked structures. For example, a method of crosslinking a polymer containing a polymer segment (α) with various crosslinking agents or curing agents, and a polymerization reaction is carried out by containing at least a monomer (a) corresponding to the polymer segment (α). At this time, a method of forming a network structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups is preferably used.

As the cross-linking agent, curing agent, polyfunctional compound and the like, there can be mentioned known compounds which are usually used. Specifically, Shinzo Yamashita and Tosuke Kaneko, “Handbook of Crosslinking Agents” published by Taiseisha (1981), Polymer Society of Japan, “Polymer Data Handbook, Basic Edition”, Baifukan (198)
6), Shin Ogawara, Takeo Saegusa, Toshinobu Higashimura, "Oligomer" Kodansha (Published in 1976), Eizo Omori "Functional Acrylic Resin" Techno System (published in 1985) and the like. For example, organic silane compounds, organic titanate compounds, organic aluminate compounds, polyisocyanate compounds and polyblocked isocyanate compounds, polyol compounds, polyamine compounds, modified aliphatic polyamine compounds, polyepoxy group-containing Examples thereof include compounds and epoxy resins, melamine resins, poly (meth) acrylate compounds, and the like. The total amount of the polymerizable compound is 5 to 80 relative to 100 parts by weight of the non-aqueous solvent.
It is about 10 parts by weight, preferably 10 to 50 parts by weight. The amount of the polymerization initiator is 0.1 to the total amount of the polymerizable compound.
5% by weight. The polymerization temperature is about 30 to 180 ° C, preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours.

Next, the case where the light and / or thermosetting group is contained in the resin (P) as a polymer component, or the case where the curable group-containing resin is used in combination with the resin (P) will be described. . Examples of the polymer component containing at least one photo- and / or thermosetting group that can be contained in the resin (P) include those described in the above-mentioned known documents, and more specifically, Examples of the functional group include the same functional groups as those described above.

The polymer component containing at least one light and / or curable group contained in these polymers is the polymer segment (β) of the block copolymer (P).
1 to 95 parts by weight in 100 parts by weight, preferably 10
７０70 parts by weight. Furthermore, it is preferable that the total amount of the polymer components of the whole copolymer (P) is 5 to 40 parts by weight based on 100 parts by weight. When the photo- and / or curable group-containing polymer component is contained in an amount of 1 part by weight or more, the curing of the photoconductive layer after the film formation is sufficiently advanced, which effectively acts on the releasability of the toner image. Further, when the content is 95 parts by weight or less, good electrophotographic characteristics as a binder resin for the photoconductive layer can be obtained without lowering the original reproducibility of a copied image or causing background fog in the non-image area. It is preferable to use the light and / or thermosetting group-containing block copolymer (P) in an amount of 40 parts by weight or less based on 100 parts by weight of the total binder resin. Within this range, good electrophotographic characteristics can be obtained.

A photo- and / or thermosetting resin (D) may be used in combination with the above-mentioned fluorine atom and / or silicon atom-containing resin. The light and / or thermosetting resin (D) may be any conventionally known curable resin, for example,
An example thereof is a resin containing a curable group as described for the block copolymer (P).

The binder resin for the photoconductive layer will be described in detail later. In the present invention, a reaction accelerator may be added to the binder resin, if necessary, in order to accelerate the crosslinking reaction in the film. When the crosslinking reaction is a reaction mode in which a chemical bond between functional groups is formed, for example, organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), phenols (phenol, chlorophenol,
Nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc.), organometallic compounds (acetylacetonate zirconium salt, acetylacetone zirconium salt, acetylacetocobalt salt,
Dilauric acid dibutoxytin, etc.), dithiocarbamic acid compound (diethyldithiocarbamate, etc.), thiuram disulfide compound (tetramethylthiuram disulfide, etc.), carboxylic acid anhydride (phthalic anhydride, maleic anhydride, succinic anhydride, butylsuccinic anhydride, Three
3 ', 4,4'-tetracarboxylic acid benzophenone dianhydride, trimellitic anhydride, etc.). When the crosslinking reaction is a polymerizable reaction mode, a polymerization initiator (peroxide, azobis compound, etc.) may be used.

The binder resin is preferably cured by light and / or heat after applying the layered product. In order to carry out heat curing, for example, the drying conditions are set to be more severe than the conventional drying conditions for producing a photoreceptor. For example, it is preferable to set the drying conditions to a high temperature and / or a long time, or to further heat-treat after drying the coating solvent. For example, 60 ° C to 150
Treat for 5 to 120 minutes. When the above-mentioned reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As a method of curing the specific functional group in the resin by irradiation with light, a step of irradiating with light of chemically active light may be included. The chemical actinic rays may be any of visible rays, ultraviolet rays, far ultraviolet rays, electron rays, X rays, γ rays, α rays, etc., but preferably ultraviolet rays, more preferably light rays in the wavelength range of 310 nm to 500 nm. . Generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp, or the like is used. Light irradiation is usually 5 cm to 5
Irradiation from a distance of 0 cm for 10 seconds to 10 minutes is sufficient. Next, the peeling compound (S) is applied onto a normal electrophotographic photosensitive member before the formation of the first transfer layer (T ₁ ), which is a second method of obtaining a photosensitive member having a peelable surface, and the photosensitive member is exposed. A method for making the body surface peelable will be described.

As the compound (S), a fluorine atom and /
Or a compound containing at least a silicon atom, as long as it improves the releasability of the electrophotographic photoreceptor surface, the structure is not particularly limited, and may be any of a low-molecular compound, oligomer, or polymer. . In the case of an oligomer or polymer, the substituent containing a fluorine atom and / or a silicon atom may be incorporated into the main chain of the polymer, or may be present as a substituent on the side chain of the polymer. Preferably, in the oligomer or polymer, the repeating unit containing this substituent is included in a block, and these exhibit particularly effectively the adsorbability to the electrophotographic photosensitive member surface and the releasability.

These substituents containing a fluorine atom and / or a silicon atom are specifically the same as those described in connection with the resin (P). Specific examples of the compound (S) containing a fluorine atom and / or a silicon atom used in the present invention include “New Edition Surfactant Handbook” edited by Toshiyuki Yoshida et al., Engineering Book Co., Ltd. (1987), "Silicon Handbook" edited by Takao Karime, "Latest Surfactant Application Technology", CMC (1990), edited by Kunio Ito
Published by Nikkan Kogyo Shimbun (1990), supervised by Takao Karime “Special Function Surfactant” C.I. M. C (1986), AM Schw
artz et al "Surface Active Agents and Detergents v
ol.II ”and the like, and fluorine-based and / or silicon-based organic compounds. Furthermore, Nobuo Ishikawa “Synthesis and Function of Fluorine Compounds” C.I. M. C (1987), edited by Jiro Hirano, “Fluorine-Containing Organic Compounds-Synthesis and Application-”, Technical Information Institute Co., Ltd. (1991), Mitsuo Ishikawa, “Organic Silicon Strategy Materials” Chapter 3, Science Forum Co., Ltd. (1991
Compound (S) using the synthetic method described in the literature
Can be synthesized.

Specific examples of the polymer component containing a substituent containing a fluorine atom and / or a silicon atom as the oligomer or polymer include the polymer component (F) described in the resin (P). You can

When the compound (S) is a so-called block copolymer, the polymer component containing a fluorine atom and / or a silicon atom may be composed of a block. Here, to be composed of blocks means that the polymer has a polymer segment containing 70% by weight or more of a polymer component having a fluorine atom and / or a silicon atom, for example, the above-mentioned resin (P) The AB type block, the ABA type block, the BAB type block, the graft type block, the star type block, and the like similar to those mentioned above can be used. These can be synthesized by the same method as described above.

By applying the compound (S) to the surface of the electrophotographic photosensitive member, the surface is improved so as to have a desired releasability. Applying the compound (S) to the surface of the electrophotographic photoreceptor means that the compound (S) is supplied to the surface of the electrophotographic photoreceptor to form a state in which the compound (S) is adsorbed or attached to the surface of the photoreceptor. say.

In order to apply the compound (S) as described above to the surface of the electrophotographic photosensitive member, any conventionally known method may be used. For example, Yuji Harasaki “Coating Engineering” Co., Ltd.
Asakura Shoten (1971), Yuji Harasaki “Coating method”
Air Doctor Coater, Blade Coater, Knife Coater, etc. described in Maki Shoten (1979), Hiroshi Fukada, "The Reality of Hot Melt Bonding" Polymer Publishing Association (1979), etc.
Examples include squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, spray coater, curtain coater and calendar coater.

Further, cloth, paper impregnated with the compound (S),
A method in which a felt or the like is brought into close contact with the photoconductor, a method in which a curable resin impregnated with the compound (S) is brought into pressure contact with the photoconductor, and the photoconductor is wet with a non-aqueous solvent in which the compound (S) is dissolved, and then the solvent is dried. And a method in which a nonaqueous solvent in which the compound (S) is dispersed is electrophoresed and adhered to the photoconductor in the same manner as the above-mentioned electrodeposition coating method. Furthermore, the non-aqueous solution of the compound (S) can be uniformly applied to the surface of the photoconductor by the ink jet method, and then dried to adhere the compound (S). The ink jet method is, for example, edited by Shin Ohno, “Non-Impact Printing” Co., Ltd.
C. M. This is achieved by the principle and means described in C (published in 1986). Examples include continuous jet type Sweet method, Hertz method, intermittent jet type Winston method, ink-on-demand type pulse jet method, bubble jet method and ink mist type mist method.

In each case, the compound (S) is used directly or diluted with a solvent instead of the ink and filled in the ink tank and / or the ink head cartridge. Normal liquid viscosity is 1-10cP, surface tension is 30-60dyne / cm
Then, if necessary, a surfactant or the like may be added, or the liquid may be heated. Conventional ink jet printers use a three-head orifice system for finer character drawing.
It is about 0 to 100 μm, and the particle diameter of the flying ink is about the same, but in the present invention, it may be larger than this. In this case, the amount of liquid discharged increases, so
The time required for coating can be shortened. Further, the use of a multi-nozzle is extremely effective for shortening the coating time.

On the other hand, silicone rubber can be used as the compound (S). Preferably, it may be wound on a metal core roller to form a silicone rubber roller, which may be directly pressed onto the surface of the photoreceptor. Nip pressure is 0.5-10kgf / cm
^{2. The} contact time may be 1 second to 30 minutes. At this time, the photoconductor and / or the silicone rubber roller may be heated to about 150 ° C. It is considered that a part of the low molecular weight component in the silicone rubber is transferred from the roller surface to the photoreceptor surface by pressing. The silicone rubber may be swollen with silicone oil. The silicone rubber may be in the form of a sponge, or the sponge roller may be further impregnated with a silicone oil, a silicone surfactant solution or the like.

In the present invention, these methods are not particularly limited, and various methods are selected depending on the state of the compound (S) used (liquid, waxy substance, solid), and if necessary, a heating medium is used in combination. Thus, the fluidity of the compound (S) used can be adjusted. The application of the compound (S) may be appropriately performed according to the photoreceptor used and the ability to retain the releasability of the compound (S) and the combination of the means. The compound (S) is preferably applied in such a manner that it can be easily incorporated in the electrophotographic apparatus used in the present invention.

The amount of the compound (S) applied to the surface of the photoconductor is not particularly limited, and may be set within a range where the adverse effect on the electrophotographic characteristics of the photoconductor does not pose a practical problem. Usually, a coating film thickness of 1 μm or less is sufficient, and “Weak boundary Layer” (Bikerman “Th
e Science of Adhesive Joints ”Academic Press (1961
Stated as defined by the annual publication) is sufficient. That is, at the time of forming the first transfer layer (T ₁ ), the compound (S) is adsorbed or adhered on the electrophotographic photosensitive member and imparts releasability to the surface thereof, and preferably the surface adhesive force is 100 gf or less. Good luck
It is not always necessary to repeat this step in the method of the invention. In the present invention, third for imparting releasability to the photoconductor
In the method of ( ₁ ), the compound (S ') exhibiting releasability is added to the dispersion liquid containing the resin particles (AR) of the present invention used when the first transfer layer (T1) is formed by the electrodeposition coating method. It is processed in coexistence. That is, a conventionally known electrophotographic photoreceptor is electrodeposited with an electrodeposition dispersion liquid containing a compound (S ′), whereby the photoreceptor surface exhibits releasability.

Specifically, the compound (S ') exhibiting releasability in an electrically insulating organic solvent having a relative dielectric constant of 3.5 or less.
Containing at least one of the resin particles of the present invention (A
The resin particles (A
By depositing (R) on the surface of the electrophotographic photosensitive member by electrophoresis to form a film, it is possible to impart releasability to the photosensitive member and to form a transfer layer capable of peeling. The compound (S ') contained in the electrocoating dispersion for forming the transfer layer is adsorbed or attached to the photoreceptor before the dispersed resin particles (AR) are electrophoresed and electrodeposited on the photoreceptor surface. Therefore, as a result, a photoreceptor having a peeling property before the formation of the transfer layer is obtained.

Examples of the compound (S ') include the same compounds as the compound (S) used in the second method, and more specifically, the dispersion solvent 1 in which the resin particles (AR) are dispersed. Any substance that can be dissolved in 0.05 g or more in liter may be used. Preferably, 0.1 g or more is dissolved in 1 liter of the dispersion solvent. The addition amount of the compound (S ′) in the electrically insulating organic solvent varies depending on the compound (S ′) and the electrically insulating organic solvent used, but adversely affects the electrophoresis of the resin particles (reduction of liquid resistance, viscosity It is added to the extent that it does not increase). It is preferably about 0.05 g / liter to 20 g / liter. The constitution and material of the electrophotographic photosensitive member provided in the present invention may be any conventionally known ones and are not limited.

For example, "Basics and Applications of Electrophotographic Technology" (published by Corona Publishing Co., Ltd. (1988)) edited by The Institute of Electrophotography, Hiroshi Komon, "Development and Practical Use of Recent Photoconductive Materials and Photoreceptors" (Japan Scientific Information) 1985, Ryuji Shibata, Jiro Ishiwatari, Kogaku, Vol. 17, 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 , (No.8), The Institute of Electrophotography. Ed. "Present Symposium on Organic Photoconductors for Electrophotography" Proceedings (1985), RM Schaffert, "Electrophotography" Fo
cal Press London (1980), SW Ing, MD Tabak,
WE Haas, "Electrophotograrphy Fourth Internatio
nal Conference "SPSE (1983), Isao Shinohara, Hidetoshi Tsuchida, Hideaki Kusagawa," Recording Materials and Photosensitive Resins ", published by Japan Society of Publishing Center (1979), Hiroshi Komon, Kagaku to Kogyo, 39 (3), 1
61 (1986) and the like. That is, a single layer consisting of the photoconductive compound itself, or a photoconductive layer in which the photoconductive compound is dispersed in a binder resin,
The dispersed photoconductive layer may be a single layer type or a laminated type. The photoconductive compound used in the present invention may be either an inorganic compound or an organic compound.

As the inorganic compound used as the photoconductive compound of the present invention, for example, zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, selenium, selenium-tellurium, amorphous silicon, lead sulfide and the like known inorganic photoconductive materials are known. Compounds. These may form a photoconductive layer together with a binder resin, or may be independently formed by vapor deposition or sputtering. When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used as the photoconductive compound, the binder resin is contained in an amount of 10 to 100 parts by weight, preferably 15 parts by weight, based on 100 parts by weight of the inorganic photoconductive compound. Used in a proportion of -40 parts by weight.
On the other hand, when an organic compound is used, any of conventionally known compounds may be used. Specifically, an organic photoconductive compound, a sensitizing dye, a photoconductive layer mainly composed of a binder resin, a charge generating agent, a charge transfer agent, a photoconductive layer mainly composed of a binder resin and a charge generator and a charge transfer agent. A photoconductive layer having a two-layered structure in which each of these is contained in a separate layer. The electrophotographic photoreceptor of the present invention may take any form of the above-mentioned photoconductive layer.

Examples of the organic photoconductive compound in the present invention include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, arylamine derivatives, azurenium salt derivatives, amino-substituted chalcone derivatives, N, N-bicarbazyl derivative, oxazole derivative, styrylanthracene derivative, fluorenone derivative, hydrazone derivative, benzidine derivative, stilbene derivative, polyvinylcarbazole and its derivative, polyvinylpyrene, polyvinylanthracene, poly-2-
Vinyl-4- (4'-dimethylaminophenyl) -5
Vinyl polymers such as phenyloxazole, poly-3-vinyl-N-ethylcarbazole, polyacenaphthylene,
Examples thereof include polyindene, polymers such as copolymers of acenaphthylene and styrene, triphenylmethane polymers, condensation resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin and the like.

In the present invention, the organic photoconductive compound is not limited to these compounds, and all known organic photoconductive compounds can be used. Two or more of these organic photoconductive compounds can be used in combination, if necessary. Examples of the charge generating agent contained in the photoconductive layer include various organic and inorganic charge generating agents that are conventionally known in electrophotographic photoreceptors. For example, selenium, selenium-tellurium, cadmium sulfide, zinc oxide, organic pigments can be used. A charge generating agent having a spectral sensitivity matching the wavelength range of the light source can be arbitrarily selected. Examples of organic pigments include azo pigments such as monoazo, bisazo, trisazo, and tetraazo pigments, phthalocyanine pigments such as metal-free or metal phthalocyanine, perylene pigments, indigo, thioindigo derivatives, quinacridone pigments, polycyclic quinone pigments, and bisbenz. Imidazole-based pigments, squalium salt-based pigments, azurenium salt-based pigments, and the like,
These may be used alone or in combination of two or more.

Examples of the charge transfer agent include the compounds known as the above-mentioned organic photoconductive compounds. For the photoconductive layer, one having good compatibility with the charge generating agent used in combination is selected. The upper limit of the content of the organic photoconductive compound is determined by the compatibility between the organic photoconductive compound and the binding resin. Crystallization of the compound occurs, which is not preferable. Since the electrophotographic photosensitivity decreases as the content of the organic photoconductive compound decreases, it is preferable to include as many organic photoconductive compounds as possible within a range in which crystallization of the organic photoconductive compound does not occur. As the content of the organic photoconductive compound, the binder resin 1
The organic photoconductive compound is usually 5 to 120 parts by weight relative to 00 parts by weight.
Parts by weight, preferably 10 to 100 parts by weight of organic photoconductive compound.

In the photoreceptor of the present invention, a binder resin other than the above resins (hereinafter sometimes referred to as binder resin (B)) can be used. The weight average molecular weight of the binder resin (B) is preferably 5 × 10 ³ to 1 × 10 ⁶ , and more preferably 2 × 10 ^{4 to} 5 × 10 ⁵ . Further, the glass transition point of the binder resin (B) is preferably −40 ° C. to 200.
C, more preferably -10 to 140C. Examples thereof include resins used in conventionally known electrophotographic photoreceptors. For example, review articles cited in relation to the electrophotographic photoreceptor,
Nakamura, Koichi "Practical Technology of Binders for Recording Materials" No. 10
Chapter, C.I. M. C Publishing (published in 1985), Takeshi Endo "Precision of thermosetting polymers" (CMC, 1986), Yuji Harazaki "Latest binder technology handbook" Chapter II-1 (Comprehensive technology) Center, published in 1985), Takayuki Otsu "Synthesis and design of acrylic resins and development of new applications" (Chubu Business Development Center Publishing Department, published in 1985), Eizo Omori "Functional acrylic resin"
(Techno System, 1985), D. Tatt, SC Heide
cker, Tappi, 49 (No.10), 439 (1966), ES Baltazzi,
RG Blanclotte et al, Phot. Sci. Eng. 16 (No.5),
354 (1972), Nguyen Chan Kae, Isamu Shimizu, Eiichi Inoue, Journal of the Institute of Electrophotography, 18 (No. 2), 22 (1980), etc.
Examples include the compounds described in the reviews.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Polymers and copolymers of the derivatives, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers. Polymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, itaconic acid diester polymers and copolymers , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymer, hydroxyl group-modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl group- and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, Cyclized rubber-acrylic acid ester copolymer, copolymer containing a nitrogen atom-free heterocycle (as a heterocycle, for example, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, a benzofuran ring , Benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy resin and the like.

In particular, when a resin having a relatively low molecular weight (about 10 ³ to 10 ⁴ ) containing an acidic group such as a carboxyl group, a sulfo group or a phosphono group is used as a binder resin for the photoconductor, The electrical characteristics can be improved. For example,
JP-A-64-70761, JP-A-2-67563,
JP-A-3-181948, JP-A-3-24959 and the like can be mentioned. Further, by using a specific medium to high molecular weight resin, stable performance can be maintained even when the environment is significantly changed. For example, JP-A-3-2995.
No. 4, No. 3-77954, No. 3-92861, and No. 3-53257, and a resin or an acidic group for bonding the acidic group described in No. 3 to No. 3-53257 to the end of the graft portion of the graft copolymer. Resin contained in the glift portion, JP-A-3-
Examples thereof include graft-type copolymers containing an AB block-type copolymer composed of an acidic group-containing A block and an acidic group-free B block described in Nos. 206464 and 3-223762 in a graft portion. By using these resins, the photoconductor can be uniformly dispersed and a photoconductive layer having good smoothness can be formed, and in the case of using a scanning exposure method using environmental changes or semiconductor laser light. Also, excellent electrostatic characteristics can be maintained.

In the present invention, various dyes can be used together as a spectral sensitizer depending on the kind of light source such as visible light exposure or semiconductor laser light exposure. For example, the above-mentioned review articles and documents on electrophotographic photoreceptors, "Electrophotography" 12 , 9 (1973), "Organic synthetic chemistry" 24 (1
1), 1010 (1966), Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (No. 8), page 12, C.I. J. Young et al. RCA Review, 15 , 469 (1954), Kouhei Kiyota et al. , Transactions of the Institute of Electrical Communication, J63-C (No.2),
97 pages (1980), Yuji Harazaki et al., Journal of Industrial Chemistry, 66 ,
78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan, 35 , 208 (1972), "Research Disclosure".
1982, 216 pages 117-118, FM Hamer
Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryls) described in reviews such as "The Cyanine Dyes and Related Compounds" Dyes, etc.), phthalocyanine dyes (which may contain a metal), and the like. Furthermore, if necessary, various conventionally known additives for electrophotographic photoreceptors can be used in combination. These additives include a chemical sensitizer for improving electrophotographic sensitivity, various plasticizers for improving film properties, and a surfactant.

Examples of the chemical sensitizer include halogen, benzoquinone, chloranil, fluoranyl, promannyl,
Dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, phthalic anhydride, maleic anhydride, N-hydroxymaleimide, N-hydroxyphthalimide, 2,3-dichloro-5,6- Electron-withdrawing compounds such as dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone, tetracyanoethylene, nitrobenzoic acid and dinitrobenzoic acid, Hiroshi Komon et al. "Recent Development and Practical Use of Photoconductive Materials and Photoreceptors" Chapter 4 -Chapter 6: Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds and the like described in Japanese Scientific Information Co., Ltd. (1986). Further, JP-A Nos. 58-65439, 58-102239, 58-129439 and 6
The compound etc. which are described in 2-71965 can also be mentioned. Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl glycolate, and dimethyl glycol phthalate. It can be added to improve the flexibility of the conductive layer. These plasticizers can be contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer. The addition amount of these various additives is not particularly limited, but is usually 0.00 per 100 parts by weight of the photoconductor.
1 to 2.0 parts by weight. The thickness of the photoconductive layer is 1-100.
μ, particularly 10 to 50 μ is preferable. When a photoconductive layer is used as the charge generation layer of the laminated type photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.01-5.
μ, and particularly preferably 0.05 to 2 μ.

The electrophotographic photosensitive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive.
As the conductive support, just like the conventional one, for example, a metal,
Conductive treatment by impregnating a substrate such as paper or plastic sheet with a low-resistance substance, etc., imparting conductivity to the back surface of the substrate (opposite to the surface on which the photosensitive layer is provided), and further prevent curling, etc. One coated with at least one layer for the purpose of, one provided with a water-resistant adhesive layer on the surface of the support,
If necessary, at least one precoat layer may be provided on the surface layer of the support, or a base conductive plastic having aluminum or the like deposited thereon may be laminated on paper. Specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14 (No. 1) 2
Pp. 11 (1975), Hiroyuki Moriga "Introduction to Special Paper Chemistry"
Polymer Society (1975), MF Hoover, J. Macromo
l.Sci. Chem. A-4 (6), 1327-1417 (1
970) and the like are used.

Next, a method for forming a toner image on the electrophotographic photosensitive material having the transfer layer (T) will be described.

A toner image is formed on the electrophotographic photosensitive member having the transfer layer (T) by a usual electrophotographic process. That is, each step of charging-exposure-developing-fixing is performed by a conventionally known method.

The developer used in the developing process may be a conventionally known developer for electrostatic photography, and may be either a dry developer or a liquid developer. For example, "Basics and Applications of Electrophotographic Technology", pages 497 to 505, Koichi Nakamura, "Development and Practical Use of Toner Material," Chapter 3 (published by Nihon Kagaku Information Co., Ltd., 1985), Moto Machida "Recording Materials and Photosensitive resin "107
Pp. 127 (1983), Academic Society Publishing Center, The Electrophotographic Society "Imagen No. 2-5 Development, Fixing, Charging, Transfer of Electrophotography" and so on. As a dry developer, a one-component magnetic toner, a two-component toner, a one-component non-magnetic toner, a capsule toner, or the like is practically used.
Any of these can be used.

On the other hand, the basic constitution of the liquid developer is, as is well known, an electrically insulating organic solvent {for example, isoparaffin aliphatic hydrocarbon: Ansoper H, Isopar G (manufactured by Esso Co.) Shellsol 70, Shellsol 71 (Shell Company). Made),
IP-solvent 1620 (manufactured by Idemitsu Petrochemical Co., Ltd.) is used as a dispersion medium (carrier liquid), and an inorganic or organic pigment or dye, which is a coloring agent, and an alkyd resin, an acrylic resin,
Polyester resin, styrene-butadiene resin, rosin and other resins for imparting dispersion stability, fixability and chargeability are dispersed, and various additives are added as desired to enhance charge characteristics or improve image characteristics. It is made by adding agents.

Known dyes and pigments are arbitrarily selected as the colorant. Examples thereof include benzidine type, azo type, azomethine type, xanthene type, anthraquinone type, phthalocyanine type (including metal containing), titanium white, nigrosine, aniline black, carbon black and the like.

As other additives, for example, those specifically described in Yuji Harazaki "Electrophotography" Vol. 16, No. 2, p. 44 are used. For example, di-2-ethylhexyl sulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, alkylbenzene sulfonic acid metal salt, alkyl phosphoric acid metal salt, lecithin, polyvinylpyrrolidone, a copolymer containing a half maleic acid amide component, Examples include coumarone indene resin, higher alcohols, polyethers, polysiloxanes, waxes and the like.

The amount of each main component of the liquid developer is usually as follows. The toner particles containing a resin and a colorant as main components are preferably 0.5 to 50 parts by weight with respect to 1000 parts by weight of the carrier liquid. If the amount is less than 0.5 parts by weight, the image density becomes insufficient, and if it exceeds 50 parts by weight, fogging to a non-image portion is apt to occur. The carrier liquid-soluble resin for stabilizing the dispersion is also used, if necessary, and can be added in an amount of about 0.5 to 100 parts by weight with respect to 1000 parts by weight of the carrier liquid. The charge control agent is preferably used in an amount of 0.001 to 1.0 part by weight based on 1,000 parts by weight of the carrier liquid. Further, various additives may be added if desired. The upper limit of the total amount of these additives is regulated by the electric resistance of the liquid developer. That is, if the electric resistance of the liquid developer with the toner particles removed is lower than 10 ⁹ Ω · cm, it becomes difficult to obtain a high-quality continuous tone image. It

Specific examples of the method for producing a liquid developer include:
A method of producing colored particles by mechanically dispersing a colorant and a resin by using a disperser such as a sand mill, a ball mill, a jet mill and an attritor is described in, for example, JP-B-35-551.
1, No. 35-13424, No. 50-40017,
JP-A-49-98634, JP-A-58-129438 and JP-A-61-180248. As another method of producing colored particles, for example, a method of producing dispersed resin particles by a non-aqueous dispersion polymerization method which obtains fine resin particles having a fine particle size and good monodispersibility, and coloring the particles can be mentioned.

As one of the coloring methods, there is disclosed in JP-A-57-57.
No. 48738, etc., a method of dyeing a dispersion resin with a preferred dye, a method of chemically bonding a dispersion resin and a dye, as described in JP-A-53-54029, JP-B-44- As described in No. 22955 and the like, there is a method of preparing a dye-containing copolymer by using a dye-containing monomer in advance during the production by the polymerization granulation method.

In particular, a combination of the scanning exposure method using laser light based on digital information and the developing method using a liquid developer is an effective process because a high-definition image can be formed. An example is shown below. First, the photosensitive member is positioned on the flat bed by the register pin method, and then sucked and fixed by air suction from the back surface. Then, the photoreceptor is charged by a charging device described on page 212 and subsequent pages, for example, "Basics and Applications of Electrophotographic Technology" (edited by The Electrophotographic Society of Japan, published by Corona, June 15, 1988). Corotron or scorotron systems are common. At this time, it is also preferable to control the charging condition by giving feedback so that the surface potential is always within a predetermined range based on the information from the charging potential detection means of the photoconductor.

Thereafter, for example, scanning exposure with a laser light source is performed by using the method described on page 254 and subsequent pages of the above cited material. First, an image corresponding to yellow in a color image divided into four colors is converted into a dot pattern and exposed. Then, a toner image is formed using the liquid developer. The photoconductor charged and exposed on a flat bed can be removed from the photoconductor and the wet development method described on page 275 and after of the above cited document can be used. The exposure mode at this time is performed corresponding to the toner image development mode. For example, in the case of reversal development, a negative image, that is, an image portion is irradiated with laser light and the same charge polarity as when the photoconductor is charged. The toner having the toner is used and a developing bias voltage is applied so that the toner is electrodeposited on the exposed portion. The details of the principle are explained on pages 157 and after of the cited material. After development, in order to remove excess developer, squeeze as shown on page 283 of the cited document is performed and then dried. It is also preferable to rinse only the carrier liquid of the developer before squeezing. By repeating the above process for each color of magenta, cyan, and black, an image of four colors can be obtained on the photoconductor.

The toner image formed on the transfer layer (T) of the photosensitive material is then transferred to the transfer material together with the transfer layer (T). A known method and apparatus can be used for this thermal transfer. Specifically, for example, the material to be transferred is pressure-bonded to the light-sensitive material with a heating roller, for example, a metal roller having a built-in heating element coated with rubber, and then passed under a cooling roller. If necessary, the photosensitive material and the material to be transferred may be preheated in a predetermined manner by using a heating means.
The heating means is preferably a non-contact type infrared line heater or flash heater.

The surface temperature of the heating roller at the time of thermal transfer is preferably 40 to 150 ° C, more preferably 45 to 120 ° C. The surface temperature of the roller is preferably kept within a predetermined range by a known surface temperature detecting means and temperature controller. The nip pressure of the roller in the transfer step is preferably 0.2 to 20 kgf / cm ² , more preferably 0.
It is 5 to 10 kgf / cm ² . As the roller pressing means, a spring or an air cylinder using compressed air at both ends of the roller shaft can be used. Transport speed is preferably 1 to 500 mm / sec, more preferably 10 to 300
mm / sec. The transport speed may be different in the electrophotographic process and the thermal transfer process.

The material of the cooling roller is, for example, a heat conductive metal such as aluminum or copper coated with silicone rubber,
It is desirable to use a cooling means to radiate heat to the inside of the roller or the outer peripheral portion that is not in contact with the transferred material. A cooling fan, a cooling circuit, an electronic cooling element, or the like is used as the cooling means, and it is preferable to maintain it in a predetermined temperature range in combination with a temperature controller.

In the color image forming method of the present invention, the conditions for transferring the toner image are optimally set depending on the physical properties of the materials such as the photoconductor (photosensitive layer and support), the transfer layer, the material to be transferred, etc. used. It is natural to make it. Temperature conditions such as preheating, roller heating, and cooling in the heat transfer step are determined in consideration of factors such as the glass transition point of the transfer layer, the softening temperature, the fluidity, the tackiness, the film property, and the film thickness. That is, the transfer layer that has been softened to some extent by the preheating means passes through the bottom of the heating roller to increase the tackiness and adheres to the material to be transferred, and after passing below the cooling roller, the temperature decreases and the fluidity and the tackiness are reduced. It is desirable to set the conditions so that the toner as it is as a film is peeled off from the surface of the photosensitive layer together with the toner.

The material to be transferred used in the present invention is not particularly limited, and may be natural paper such as high-quality paper, coated paper, art paper, synthetic paper, metal support such as aluminum, iron and SUS. Any of a reflective material and a transmissive material such as polyester, polyolefin, polyvinyl chloride, and a plastic film such as polyacetate may be used.

The electrophotographic color image forming method of the present invention will be described in detail below with reference to the accompanying drawings. FIG. 2 is a schematic view of an electrophotographic color image forming apparatus capable of carrying out the formation of a transfer layer, the electrophotographic process and the thermal transfer of the transfer layer, which are suitable for carrying out the method of the present invention, in the same apparatus.

As described above, when the electrophotographic photosensitive member 11 whose surface retains peelability is used, the photosensitive member 1 is used as it is.
A first transfer layer (T ₁ ) 12T ₁ is formed on the first transfer layer ₁ . Also,
When the releasability of the surface of the photoconductor 11 is insufficient, a device for adsorbing or adhering the compound (S) before the formation of the first transfer layer (T ₁ ) 12T ₁ is provided as described above (second Of the transfer layer-forming resin particles (AR) of the present invention (third method), and the compound (S ′) is contained in the electrocoating dispersion of the present invention (third method). It is possible to impart sex. In the case of the second method, by appropriately providing the compound (S) application unit 10 using the method as described above, the compound (S) is formed on the surface of the photoreceptor 11.
Supply. The unit 10 for applying the compound (S) to the surface of the photoreceptor may be fixed or movable.

Dispersion 12a of thermoplastic resin particles (AR)
Is supplied to the first transfer layer electrodeposition unit 13a in the movable liquid developing unit set 14. First, the electrodeposition unit 13a is brought close to the photoreceptor surface 11 and fixed so that the distance between the electrodeposition unit 13a and the developing electrode is 1 mm. The dispersion liquid 12a is supplied between the gaps and rotated while applying a voltage from an external power source (not shown) so that the resin particles (AR) are electrodeposited on the entire surface of the image forming area on the surface 11 of the photoconductor. The squeeze device built in the electrodeposition unit 13a removes the dispersion liquid 12a adhering to the surface 11 of the photoconductor, and then it is passed under the air intake / exhaust unit 15 to be dried, and the thermoplastic resin particles (A
R) is heat-melted to form a film, and a first transfer layer (T ₁ ) 12T ₁ of a thermoplastic resin is obtained.

First transfer layer (T ₁ ) made of a thermoplastic resin
The photoconductor 11 on which 12T ₁ is formed is then subjected to the step of forming the second transfer layer (T ₂ ) 12T ₂ . When the dispersion liquid 12b of thermoplastic resin particles (AL ₂ R) is used in the electrodeposition coating method, the second transfer layer electrodeposition unit 13b is provided in the liquid developing unit set 14 as shown in FIG. , The first transfer layer (T ₁ ) can be formed in the same manner. Thereafter, if necessary, a cooling device (not shown) similar to the intake / exhaust unit 15 is used to cool the photosensitive member from the outside or the inside of the photosensitive drum to a predetermined temperature.

First transfer layer and second layer made of thermoplastic resin
The photoconductor on which the transfer layer is formed then enters an electrophotographic process. After uniformly charging the photoconductor 11 positively by the corona charging device 18, for example, an exposure device (for example, a semiconductor laser)
First, in 19, when image exposure is performed based on yellow image information, the potential of the exposed portion is reduced, and a potential contrast is obtained between the exposed portion and the unexposed portion. Only the yellow liquid developing unit 14Y containing the liquid developer in which the yellow pigment having the positive electrostatic charge is dispersed in the electrically insulating dispersion medium is brought close to the surface of the photoconductor 11 from the liquid developing unit 14 and the gap is set to 1 mm. To fix.

The photoconductor 11 is pre-bused by the pre-bus means provided in the developing unit set, and then a developing bias voltage is applied between the photoconductor 11 and the developing electrode by a bias power source and electric connection not shown in the figure. Meanwhile, the yellow liquid developer is supplied to the surface of the photoconductor 11. The bias voltage at this time is connected so that the developing electrode side is positive and the photoconductor side is negative, and the applied voltage is slightly lower than the surface potential of the unexposed portion. If the applied voltage is too low, a sufficient toner image density cannot be obtained.

After that, the developing solution is washed off by the rinse unit 14R built in the developing unit set, and subsequently, the rinse solution adhering to the surface of the photosensitive member is removed by the squeeze means, and then it is dried by passing under the intake / exhaust unit 15. . A carrier liquid of a liquid developer is usually used as the prefabricated liquid and the rinse liquid. The above steps are repeated for magenta, cyan, and black to form a color toner image. Next, the toner image is thermally transferred onto the transfer material 16 by the transfer unit 17 together with the transfer layer. That is,
If necessary, the transfer layer holding the toner image is subjected to predetermined preheating by the heating means 17a for thermal transfer, and then the transfer back hoop roller 17b via the transfer material 16.
As a backing roller 17c for peeling, a metal roller coated with a rubber having a built-in heating element having a temperature control means is pressed and passed under a cooling roller to be cooled to transfer the toner image on the photoreceptor 11 together with the transfer layer. Thermal transfer is performed on the transfer material 16, and a series of color image forming steps is completed.
Further, by stopping the device with the transfer layer formed, the electrophotographic process can be started immediately when the next device is in operation, and it is possible to protect the surface of the photosensitive layer and prevent characteristic deterioration due to the influence of the external environment. .

Another example of a suitable apparatus for carrying out the method of the present invention is shown in FIG. In this example, the second transfer layer (T
₂ ) is formed by the hot melt coating method. In FIG. 3, the second
The thermoplastic resin 12c for the transfer layer is applied onto the first transfer layer (T ₁ ) 12T ₁ on the photoconductor 11 on the drum peripheral surface by the hot melt coater 13c, and when it passes under the intake / exhaust unit 15, a predetermined amount is obtained. second transfer layer is cooled to a temperature (T ₂₎ is formed. Hot melt coater 13
After c has moved to the standby position, the liquid developing unit set 14 is moved to that position to enter the electrophotographic process.
Subsequent steps are substantially the same as described with respect to FIG.

Yet another suitable device example is shown in FIG.
You. Second transfer layer (T_Two) Is formed according to the transfer method.
You. In FIG. 4, the second transfer layer (T_Two) 12T_TwoIs photosensitive
The first transfer layer (T ₁) 12T₁To the photoconductor on
It is simply formed by the transfer unit 117. That is,
2 transfer layers (T_Two) 12T_TwoThe release paper 20 provided with
The second transfer layer (T_Two) 1
2T_TwoThe first transfer layer (T₁) 12T₁Transfer to the surface of
You. The release paper 20 is cooled by the cooling roller 117c and rotated.
Will be collected. If necessary, the photoconductor 11 itself is heated by the heating means 1
The second transfer layer (T_Two) 12T_TwoHot pressing
May improve the transferability.

The position of incorporating the transfer unit 117 onto the photosensitive member is not particularly limited. The transfer layer (T
₁ ) 12T ₁ and transfer layer (T ₂ ) 12T ₂ on the transfer material 1
6 may be replaced with the transfer unit 17 for transferring a material to be transferred. Alternatively, this unit 117 is used first for forming the second transfer layer (T ₂ ) 12T ₂ and then for transferring the transfer layer (T ₁ ) 12T ₁ and the transfer layer (T ₂ ) 12T _{2 to} the transfer material 16. It can also be used. Other configurations in FIGS. 3 and 4 are essentially the same as those in FIG.

[0145]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention.

Synthesis Example of Resin Particles (AR) 1: (AR-
1) 12 g of a dispersion stabilizing resin (Q-1) having the following structure, 70 g of vinyl acetate, 30 g of vinyl butyrate and 388 g of Isopar H.
The mixed solution of was heated to a temperature of 80 ° C. while stirring under a nitrogen stream. To this, 1.5 g of azobisisobutyronitrile (abbreviation AIBN) as an initiator was added, and the mixture was reacted for 2 hours. I. B. N. The reaction was carried out by adding 0.8 g twice every 2 hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having a degree of polymerization of 93% and an average particle diameter of 0.18 μm and having good monodispersity. The particle size was measured by CAPA-500 (manufactured by Horiba, Ltd.) (the same applies hereinafter). A part of the white dispersion was subjected to a centrifuge (rotation speed 1 × 10 ⁴ rpm, rotation time 60 minutes) to collect the precipitated resin particles, which was dried to obtain a weight average molecular weight (Mw) of the resin particles. When the glass transition point (Tg) was measured, Mw was 8 × 10 ⁴ , and Tg was 18 ° C. The resin particles obtained here are designated as (RL-1).

This resin particle dispersion (that is, seed particles)
And a mixed solution of 10 g of the dispersion stabilizing resin (Q-2) having the following structure was heated to a temperature of 60 ° C. with stirring under a nitrogen stream.
To this, methyl methacrylate (60 g), methyl acrylate (40 g), methyl 3-mercaptopropionate 2.0
g, azobisisovaleronitrile (abbreviation A.I.V.
N. ) A mixture of 0.8 g and 400 g of Isopar G was added dropwise over 2 hours, and the reaction was continued for another 2 hours. Next, 0.8 g of an initiator was added, the temperature was raised to 70 ° C., and the mixture was reacted for 2 hours. Further, 0.6 g of an initiator was added and reacted for 3 hours. After cooling, 20
The white dispersion obtained through a 0-mesh nylon cloth was a latex having a degree of polymerization of 98% and an average particle size of 0.25 μm and having good monodispersibility.

[0148]

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Next, whether or not the obtained resin particles were formed as individual particles was examined by observing the state of the particles using a scanning electron microscope (SEM). A film prepared by dispersing resin particles on a PET film was heated at a temperature of 20 ° C. and 50 ° C. for 5 minutes, and each sample was subjected to JEOL JSL-T330 Scan.
When observed at 20,000 times using a ning Microscope, the sample at a temperature of 20 ° C. was observed to be in a particulate state, but at 50 ° C.
No particles were observed. That is, the particles were melted by heating. Similarly, the above resin particles (RL-1) (Tg 18 ° C.) and the following resin particles (R) each consisting of two kinds of resins (copolymers) constituting the particles of the present invention
L-2) (Tg 45 ° C.) and dispersed resin particles obtained by mixing the two types of resin particles at a 1/1 weight ratio were examined.

The sample composed of the resin particles (RL-1) had a temperature of 20 although the sample not heated was in a particle state.
No particle state was observed at 0 ° C., and particles of the resin particles (RL-2) became invisible at a temperature of 50 ° C. Furthermore,
When a sample consisting of mixed particles was examined for a non-heated sample and a sample at a temperature of 20 ° C., it was confirmed that no particles were visible at a temperature of 20 ° C. as compared with an unheated sample.

As a result of visual observation of the thermal behavior of the particles as described above, the resin particles produced as described above are not a mixture of two kinds of resin particles, but two kinds of particles in one particle. It was confirmed that the resin was contained, and in this case, the high Tg resin was a core-shell particle in which the low Tg resin was distributed in the outer layer and the low Tg resin was distributed in the inner layer.

Production of Resin Particles (RL-2) 18 g of the dispersion stabilizing resin (Q-2) and Isopar H
553 g of the mixed solution was stirred at a temperature of 5 under a nitrogen stream.
Warmed to 5 ° C. 60g of methyl methacrylate,
40 g of methyl acrylate, 1.3 g of methyl 3-mercaptopropionate and A.I. I. V. N. 1.0 g of the mixture was added dropwise at a dropping time of 60 minutes, and the reaction was continued for another 1.5 hours. Further, A. I. V. N. Add 0.8g 2
React for a period of time and then start initiator A. I. B. N. 0.8 g was added and the temperature was set to 80 ° C. for 2 hours. I. B.
N. 0.5g was added and reaction was performed for 2 hours. After cooling,
The white dispersion obtained through a 200-mesh nylon cloth was a latex having a polymerization rate of 99% and an average particle size of 0.15 μm and good monodispersity. The Mw of the resin particles was 1.5 × 10 ⁴ , and the Tg was 45 ° C.

Synthesis Examples 2-8 of Resin Particles (AR): (AR
-2) to (AR-8) In Synthesis Example 1 of resin particles (AR), resin particles (A) were prepared in the same manner except that the monomers shown in Table A below were used.
R-2) to (AR-8) were produced. The degree of polymerization of each latex particle obtained was 95 to 99%, and the average particle diameter was 0.2.
Within the range of 0 to 0.30 μm, the monodispersity was good.

[0154]

[Table 1]

Synthesis Example 9 of resin particles (AR): (AR-
9) A mixed solution of 20 g of the dispersion stabilizing resin Q-1, 60 g of vinyl acetate, 40 g of vinyl valerate and 388 g of Isopar H was heated to 80 ° C. while stirring under a nitrogen stream. As an initiator, A. I. B. N. Add 1.5g 2
Reacts for a time, and I. B. N. The reaction was carried out by adding 0.8 g twice every 2 hours. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth had a polymerization rate of 95.
%, A latex having an average particle size of 0.14 μm and good monodispersity. This resin particle dispersion, 10 g of a dispersion stabilizing resin (Q-3) having the following structure, a dimethylsiloxane macromonomer (FM-0725 manufactured by Chisso Corporation), Mw:
A mixed solution of 1 × 10 ⁴ ) (macromonomer (M-1)) (10 g) and Isopar H (200 g) was heated to a temperature of 50 ° C. with stirring under a nitrogen stream. To this, 70 g of benzyl methacrylate and 30 of 2-ethylhexyl acrylate
g, a mixture of 1.3 g of methyl 3-mercaptopropionate and 1.0 g of 2,2′-azobis (2-cyclopropylpropionitrile) (abbreviation: ACPP) at a dropping time of 30 minutes. The mixture was dropped, and the reaction was continued for another 1.5 hours. Further, A.I. C. P. P. 0.8 g was added and the mixture was reacted for 2 hours. I. V. N. Add 0.8g and temperature 80
C. for 2 hours and then A. I. V. N. 0.5g was added and reaction was performed for 2 hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having a polymerization rate of 99% and an average particle size of 0.19 μm and good monodispersity.

[0156]

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Synthesis Examples 10 to 14 of Resin Particles (AR):
(AR-10) to (AR-14) In Production Example 9 of resin particles (AR), instead of 10 g of the macromonomer (M-1), each macromonomer shown in Table B below (Mw is 8 × 10 ³ to). Each resin particle was synthesized in the same manner except that 1 × 10 ⁴ ) was used. The degree of polymerization of each latex particle obtained was 98 to 99%, the average particle diameter was within the range of 0.15 to 0.25 μm, the particle size distribution was narrow, and the monodispersibility was good.

[0158]

[Table 2]

Synthesis Example 15 of resin particles (AR): (AR-
15) As the resin (A), a vinyl acetate / ethylene (46/54 weight ratio) copolymer (Evaflex 45) at Tg-25 ° C
X: manufactured by Mitsui DuPont Chemical Co., Ltd., Tg 38 ° C.
And polyvinyl acetate at a ratio of 1/1 weight ratio and melt-kneaded at 120 ° C. in a three-roll mill. The kneaded material is roughly pulverized by a tribender of a pulverizer.
g, 4 g of a dispersion stabilizing resin (Sorprene 1205 manufactured by Asahi Kasei Co., Ltd.) and 51 g of Isopar H of about 4 mm in diameter
Was placed in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) using the glass beads as a medium, and preliminarily dispersed for 20 minutes. The predispersion was wet-dispersed at 4500 rpm for 6 hours using a Dynomill KDL type (Shinmaru Enterprises Co., Ltd.) using glass beads having a diameter of 0.75 to 1 mm as a media. A white dispersion obtained by passing these through a 200 mesh nylon cloth was a latex having an average particle size of 0.4 μm.

Synthesis Examples 16-20 of Resin Particles (AR):
(AR-16) to (AR-20) Similar wet dispersion method except that each resin shown in Table C below was used instead of the two kinds of resin (A) used in Synthesis Example 15 of resin particles (AR). To prepare a dispersion. The obtained white dispersion had an average particle size of 0.3 to 0.6 μm.

[0161]

[Table 3]

Synthesis Example of Resin Particles (AL ₂ R) 1: (AL
₂ R-1) 10 g of dispersion stabilizing resin (Q-1), 70 g of vinyl acetate,
30g vinyl propionate and 384g Isopar H
The mixed solution of was heated to 70 ° C. while stirring under a nitrogen stream. As a polymerization initiator, A.I. I. V. N. 0.8 g was added and reacted for 3 hours. Twenty minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88 ° C. Furthermore, 0.5
After adding g and reacting for 2 hours, the temperature was raised to 100 ° C. and stirred for 2 hours to distill off unreacted monomers. After cooling, the white dispersion obtained through a 200-mesh nylon cloth had a polymerization rate of 9
The latex was 0% and had an average particle size of 0.23 μm and good monodispersity. Mw of resin particles is 8 × 10 ⁴ , Tg is 2
8 ° C.

Synthesis Example 2 of Resin Particles (AL ₂ R): (AL
₂ R-2) 20 g of dispersion stabilizing resin (Q-4) and Isopar G 3
82 g of the mixed solution was stirred under a nitrogen stream and the temperature was 60 ° C.
Was heated. 30 g of methyl methacrylate, 70 g of ethyl acrylate, 0.6 g of methyl 3-mercaptopropionate and A.I. I. V. A mixture of 1.0 g of N was added dropwise over 1 hour, and the reaction was continued for another 1 hour. Further, A. I. V. N 0.8 g was added and reacted for 2 hours. I. B. N. 0.8 g was added and the mixture was heated to a temperature of 80 ° C. for 2 hours. I. B. N. 0.5g was added and reaction was performed for 2 hours. Next, the temperature was raised to 100 ° C., and the unreacted monomer was distilled off under a reduced pressure of 10 to 20 mmHg. After cooling 2
The white dispersion obtained by passing through a 00 mesh nylon cloth was a latex having a polymerization rate of 98% and an average particle size of 0.17 μm and good monodispersity. Mw of resin particles is 8 × 10 ⁴ ,
Tg was 16 ° C.

[0164]

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Synthesis Examples 3 to 13 of Resin Particles (AL ₂ R):
(AL ₂ R-3) to (AL ₂ R-13) In Synthesis Example 2 of resin particles (AL ₂ R), each monomer shown in Table D below was used instead of methyl methacrylate and ethyl acrylate. Similarly to each resin particle (A
L ₂ R) was synthesized. Each white dispersion was a latex having a polymerization rate of 90 to 99% and an average particle size of 0.13 to 0.20 μm and good monodispersity.

[0166]

[Table 4]

Synthesis Example of Resin Particles (PL) 1: (PL-
1) 40 g of a monomer (LM-1) having the following structure, 2 g of ethylene glycol dimethacrylate, 4.0 g of a dispersion stabilizing resin (LP-1) having the following structure, and 180 g of methyl ethyl ketone.
The mixed solution of 1 was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. A. I. V. 0.3 g of N was added and reacted for 3 hours. Further, A.I. I. V. N 0.1g was added and it reacted for 4 hours. After cooling, a white dispersion was obtained through a 200 mesh nylon cloth. It was a latex having an average particle size of 0.25 μm.

[0168]

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Synthesis Example 2 of Resin Particles (PL): (PL-
2) Resin macromonomer (LP-2) for dispersion stabilization having the following structure
A mixed solution of 5 g and 140 g of methyl ethyl ketone was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. to this,
40 g of a monomer (LM-2) having the following structure, 1.5 g of ethylene glycol diacrylate, A.I. I. V. N 0.2
g and a mixed solution of 40 g of methyl ethyl ketone were added dropwise over 1 hour. After reacting for 2 hours as it is, A. I. V. N
0.1 g was added and reacted for 3 hours to obtain a white dispersion.
After cooling, the average particle size of the dispersion obtained through a 200-mesh nylon cloth was 0.35 μm.

[0170]

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Synthesis Examples 3 to 6 of Resin Particles (PL): (PL
-3) to (PL-6) In Synthesis Example 1 of resin particles (PL), the monomer (LM-
1), resin particles were produced in the same manner except that each compound shown in Table E below was used instead of ethylene glycol dimethacrylate and methyl ethyl ketone. The average particle size of the obtained resin particles was in the range of 0.15 to 0.30 μm.

[0172]

[Table 5]

Example 1 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 2
g, 14.4 g of the binder resin (B-1) having the structure shown below, 3.6 g of the binder resin (B-2) having the structure shown below, 0.15 g of the compound (A) having the structure shown below, and 80 g of tetrahydrofuran were added to 500 ml of a mixture. Put it in a glass container with glass beads,
After dispersing with a paint shaker (manufactured by Toyo Seiki Seisakusho) for 60 minutes, the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0174]

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The dispersion was applied on a degreased 0.2 mm thick aluminum plate with a wire bar, dried by touch with a finger, and then heated in a circulating oven at 110 ° C. for 20 seconds. The film thickness of the obtained photosensitive layer was 8 μm. A peelable surface layer was formed on the photosensitive layer. That is, 10 g of a silicone resin having the following structure, 1 g of a crosslinking agent having the following structure, 0.2 g of a crosslinking controller having the following structure, and 0.1 g of a platinum catalyst for crosslinking were n-
The coating material contained in 100 g of hexane was coated using a wire round rod to a film thickness of 1.5 μm, dried by touch and then heated at 120 ° C. for 10 minutes. The adhesive strength of the obtained surface was 1 g · f or less.

[0176]

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The electrophotographic photosensitive member having a peelable surface obtained as described above was loaded into an apparatus as shown in FIG. 2 and a transfer layer was formed thereon. That is, the surface temperature of the photoconductor 11 is set to 60 ° C., the photoconductor drum is rotated at a peripheral speed of 100 mm / sec, and the following positively charged resin particle dispersion liquid is formed on the photoconductor surface by using a slit electrodeposition device as the electrodeposition unit 13a. (L-
While supplying 1), the photoreceptor side was grounded and a voltage of +140 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit and fix the resin particles. The thickness of the obtained first transfer layer (T ₁ ) was 1.5 μm.

Resin particle dispersion liquid (L-1) Resin particles (AR-1) 10 g (as solid content) Regulator for positive charge (CD-1) 0.08 g Octadecyl vinyl ether / N-hexadecyl maleic acid half amide ( (1/1 molar ratio) Copolymer Charge control auxiliary agent 0.1 g Dodecyl methacrylate / methacrylic acid (94/6 weight ratio) A copolymer was prepared with Isopar G to a total amount of 1.0 liter.

On the first transfer layer, 10 g of resin particles (AL ₂ R-1) (as solid content) in place of 10 g of resin particles (AR-1) in the above resin particle dispersion (L-1). Using a positively charged resin dispersion liquid (L-2) prepared in the same manner as above, a film thickness of 1.0 μm was obtained in the same manner as above.
m second transfer layer (T ₂ ) was formed. Then an electrophotographic process was performed. That is, the photoconductor 11 on which the transfer layer is formed
Pass under corona charging device 18 in the dark,
After the corona charging to 0V, the original was read by a color scanner in advance, color separation was performed, and some corrections related to system-specific color reproduction were added, and then stored as digital image data in the hard disk in the system. The exposure apparatus 1 is based on the information about yellow among the colors of yellow, yellow, magenta, cyan, and black.
As a sample No. 9, a semiconductor laser drawing apparatus was used to perform exposure with light of 788 nm so that the exposure amount on the photosensitive material was 30 erg / m ² .

Subsequently, the positively charged yellow toner for the signature system (manufactured by Kodak) is 75 times as much as Isopar H.
It is diluted with (Esso Standard Petroleum) and supplied to the yellow liquid developing unit 14Y, a bias voltage of + 350V is applied to the developing unit 14Y side, and reversal development is performed so that the toner is electrodeposited on the exposed portion. The H-only bath was rinsed to remove stains on the non-image area, and then passed through the air intake / exhaust unit 15 and the heating means 17a to be dried. The above toner image forming process is magenta,
Toner images of four colors were obtained by repeating each of cyan and black.

Next, the transfer material 16 is coated between the photosensitive drum provided with the toner image having the surface temperature adjusted to 60 ° C. and the transfer backup roller 17b and the peeling backup roller 17c set to the temperature of 100 ° C. Guide the paper, nip pressure 4kgf / cm ² , drum peripheral speed 150mm /
Heating and pressurization were performed for seconds. The color toner images were all transferred onto coated paper to obtain a multicolor color copy. The copied image thus formed on the coated paper was visually observed using a 200 × optical microscope. No background stains on the non-image area were observed, and the toner image was transferred to the coated paper without being left untransferred on the photoconductor together with the transfer layer. No loss or disorder of halftone dots was observed in the high-definition image area in the halftone portion, and it was a very good copy image.

Comparative Example 1 Toner image formation and coated paper were carried out in the same manner as in Example 1 except that a photoreceptor having a transfer layer having a film thickness of 2.5 μm was formed using the resin particle dispersion liquid (L-1). Transfer to. The color image on the obtained coated paper had many missing image portions and was not completely transferred. Therefore, when the transfer conditions for complete transfer were examined, the same good color copy as in Example 1 was obtained under the following conditions.・ Surface temperature 100 ℃ ・ Transfer backup roller temperature 130 ℃ ・ Drum peripheral speed 30mm / sec ・ Nip pressure 6kgf / cm ²

Comparative Example 2 In Example 1, 5 g each of the resin particles (RL-1) and the resin particles (RL-2) were used instead of the resin (AR-1) in the resin particle dispersion liquid (L-1). The toner image formation and the transfer onto the coated paper were performed in the same manner except that the photosensitive member was used as the first transfer layer having a film thickness of 1.5 μm (as the solid content). The color image on the obtained coated paper had many missing image areas and was not completely transferred. Therefore, when the transfer conditions for complete transfer were examined, the same good color copy as in Example 1 was obtained under the following conditions.・ Surface temperature 80 ℃ ・ Backup roller temperature for transfer 100 ℃ ・ Drum peripheral speed 50mm / sec ・ Nip pressure 4kgf / cm ²

From the above results, according to the method of the present invention,
The toner image is sufficiently peeled from the photoconductor, and the problems such as the loss of the image portion as described above do not occur, and the toner image is in sufficient contact with the transfer layer, so that the stability of the color copy obtained is stable. It turns out that the property is also excellent. In addition, the ability to write on a copy with a pencil, a ballpoint pen, etc., the imprintability, and the filing property to a file made of a plastic film such as a vinyl chloride sheet were almost the same as those of plain paper and did not cause any problems. Furthermore, instead of coated paper as the material to be transferred, fine paper, copy paper for PPC, plain paper, P
When a color image was similarly prepared using the ET film, a color copy exactly the same as that of Example 1 was obtained. In this way, a stable and good color copy can be easily obtained even if transfer materials having different surface smoothness and different compositions are used.

Example 2 An amorphous silicon electrophotographic photosensitive member (manufactured by Kyocera Corp.) was attached to the apparatus as shown in FIG. The adhesive force on the surface of the photoconductor was 230 g · f. The release property was imparted to the photoreceptor by a method of immersing the compound (S) of the present invention in a solution in the apparatus (immersion method). That is, 1.0 g of the following compound (S-1) was dissolved in 1 liter of Isopar G (manufactured by Esso Co., Ltd.), and the photoreceptor was rotated at a rotational speed of 10 mm / sec in a bath containing a solution. It was touched for 7 seconds and dried by air squeeze.
The adhesion of the surface of the photoconductor thus treated is 3 gf
Showed good peelability.

[0186]

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Next, the photoconductor drum was rotated at a peripheral speed of 100 mm / sec, and while supplying the following positively charged resin particle dispersion (L-3) to the photoconductor surface using a slit electrodeposition device, the photoconductor side was set. + 130V on the electrode side of the slit electrodeposition device
Voltage was applied to electrodeposit and fix the resin particles. The film thickness of the obtained first transfer layer (T ₁ ) was 1.0 μm.

Resin Particle Dispersion Liquid (L-3) Resin Particles (AR-3) 10 g (as Solid Content) Positive Charge Regulator (CD-2) 0.09 g 1-Hexadecene / N-decyl Maleic Acid Half Amide (1/1 mole ratio) Copolymer Branched tetradecyl alcohol (FOC-1400 5g, manufactured by Nissan Kagaku Co., Ltd.) was prepared with Isopar G to a total volume of 1.0 liter.

Next, a second transfer layer (T ₂ ) was formed on the first transfer layer (T ₁ ) by a transfer method from release paper. That is, as the release paper 20, a separate paper (Oji Paper Co., Ltd.)
Made from a vinyl acetate / vinyl propionate (75/25 weight ratio) copolymer as a resin (AL ₂ ) on which a film having a thickness of 1.5 μm is formed. Attached to 117, under the conditions of a roller pressure of 3 kgf / cm ² , a roller surface temperature of 80 ° C. and a passing speed of 50 mm / sec,
The second transfer layer (T ₂ ) was transferred and formed on the photoreceptor 11 on which the first transfer layer (T ₁ ) was formed.

Next, the transfer layer and the formed photoconductor 11 are set to +7.
After corona charging to 00V, using the same digital image data as in Example 1, first, based on the information about yellow, a semiconductor laser was used to make the exposure amount of the photosensitive material surface 25 erg / cm ² with light of 780 nm. Exposure. The residual potential of the exposed part was + 120V. Then, yellow toner for Versatec 3000 (Xerox color electrostatic plotter) was diluted with 50 times Isopar H (Esso Standard Petroleum) and used, and +300 V was applied to the developing electrode.
The reverse development was carried out by applying the bias voltage of No. 1 to the toner so that the toner was electrodeposited on the exposed portion, and then rinsed in a bath of Isopar H alone to remove stains on the non-image portion. The above image forming process was repeated for each color of magenta, cyan and black.

Next, the temperature of the photosensitive drum on which the toner image is provided on the transfer layer is adjusted to 60 ° C., and the surface temperature is 120 ° C.
The high-quality paper was passed between the transfer rubber roller set at 1 and the transfer speed of 100 mm / sec at a nip pressure of 4 kgf / cm ² . After passing, the high-quality paper was peeled off from the photoconductor, and the toner image was transferred onto the high-quality paper together with the transfer layer. The copied image thus formed on the high-quality paper was visually observed using a 200 × optical microscope. No background stains on the non-image area were observed, and the toner image and transfer layer were all transferred onto high-quality paper without being left untransferred on the photoconductor, and there was a lack of high-resolution areas such as fine lines and fine characters, and disturbances. No loss or disorder of halftone dots was observed in the high-definition image area in the halftone portion, and it was a very good copy image. The image strength was also sufficient. Furthermore, the writing and stamping properties were also good.

Example 3 In Example 1, instead of the method of forming the second transfer layer (T ₂ ) by the electrodeposition coating method, the following hot melt coating method (see FIG. 3) was used.
A color copy was prepared in the same manner except that the second transfer layer (T ₂ ) was formed by using the reference material. Second transfer layer (T ₂₎ of forming the resin (AL ₂₎ as the following structure of the resin by a hot-melt coater 13c of the (AL ₂ -1) Temperature 110 ° C. set to 12T ₁ surface to the first transfer layer of 20 mm / sec Coating was performed at a speed, cooling air was blown from the intake / exhaust unit 15 to cool, and then the surface temperature was maintained at 30 ° C. Second at this time
The thickness of the transfer layer (T ₂ ) was 2.0 μm.

[0193]

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The copy image thus formed on the coated paper was visually observed using a 200 × optical microscope.
No background stains on the non-image area were observed, and the toner image and transfer layer were all transferred onto the coated paper without being left untransferred on the photoconductor, and there was a lack of high-resolution areas such as thin lines and fine characters, and disturbances. No loss or disorder of halftone dots was observed in the high-definition image area in the halftone portion, and it was a very good copy image.

Examples 4 to 13 The same as Example 1 except that the resin particles used in the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ) were replaced with the resin particles shown in Table F below. A color copy was made by operating the.

[0196]

[Table 6]

The color copy obtained had clear image quality without background stains. That is, the toner image formed on the light-sensitive material showed good image reproducibility and good image pickup property with no fog in the non-image area. Also, the transfer of each transfer layer onto the coated paper was completed without causing any inconvenience such as uneven transfer. Further, the color copy can be added or stamped in the same manner as in the case of plain paper. Examples 14 to 16 In Example 2, the release paper Sun Release (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) was used instead of the separate paper provided with the transfer layer.
A color copy was prepared in the same manner as above except that each resin layer having the film thickness of 1.0 [mu] m shown in Table G below was provided.

[0198]

[Table 7]

The obtained color copy had a clear image quality without background stain, and almost no image deterioration was recognized as compared with the original. This means that the transfer layer is uniformly and completely transferred at each transfer even when the second transfer layer (T ₂ ) is formed by a transfer method using a release paper and transferred to a high-quality paper.
It indicates that adverse effects such as image deterioration do not occur.

[0200] In Example 17-19 Example 3, except for using each of the resin in the following Table -H in place of the resin (AL ₂ -1) used to form the second transfer layer (T ₂₎ is in the same manner Transfer image formation.

[0201]

[Table 8]

The obtained color image had a clear image quality without background stain, and almost no deterioration of the image was recognized as compared with the original. This indicates that the transfer layer is uniformly and completely transferred even when the second transfer layer is formed by using the hot melt coating method and then transferred to the coated paper, and adverse effects such as image deterioration do not occur. There is. Example 20 2 g of X-type metal-free phthalocyanine, 14 g of a binder resin (B-3) having the structure shown below, and a releasability-imparting resin having the structure shown below (P-
1) Add 50 g of a mixture of 4 g and 80 g of tetrahydrofuran.
It was put together with glass beads in a 0 ml glass container, and dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho) for 60 minutes.
After adding 0.02 g of phthalic anhydride and 0.005 g of acetylacetone zirconium salt to the dispersion, they were dispersed again for 1 minute and the glass beads were filtered to obtain a dispersion liquid for a photosensitive layer.

[0203]

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This dispersion was applied to a degreased 0.2 mm thick aluminum plate with a wire bar, dried by touch with a finger, and then heated in a circulating oven at 110 ° C. for 20 seconds and further heated at 140 ° C. for 1 hour. did. The thickness of the obtained photosensitive layer is 8
μm. The adhesive strength of the surface of this photoreceptor was 1 g · f. On the other hand, the adhesive force of the surface of the photoreceptor prepared in the same manner without adding the resin (P-1) was 400 g · f or more, showing no releasability at all. Using the above photoreceptor, the same operation as in Example 1 was carried out to prepare a color copy. The color copy obtained had a clear image quality with no background stain, and no transfer layer or toner image remained on the photoreceptor. Example 21 4,4′-bis (diethylamino) -2,2′-dimethyltriphenylmethane (5 g), a binder resin (B-4) having the following structure (4 g), and a resin having the following structure (P
-2) 1.2 g, 40 mg of the dye (D-1) having the following structural formula,
Anilide compound (B) having the following structural formula as a chemical sensitizer
0.2 g was dissolved in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride to prepare a photosensitive layer dispersion liquid.

[0205]

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This photosensitive layer dispersion was applied to a conductive transparent support (having a vapor-deposited film of indium oxide on a polyethylene terephthalate support having a thickness of 100 μm, surface resistance 10 ³ Ω) using a wire round rod. After touch-drying, it was heated at a temperature of 80 ° C. for 1 hour. The thickness of the obtained photosensitive layer was 6 μm, and the adhesive force on the surface of the photoreceptor was 2 g · f. A copied image was formed in the same manner as in Example 1 except that this photoreceptor and plain paper were used. The color image of the obtained plain paper was clear without scumming and the image strength was good. Further, when 2 g of the resin particles (PL-1) was used instead of 1.2 g of the resin (P-2) and the other operations were performed in the same manner as described above, similarly good results were obtained. Examples 22 to 24 5 g of bisazo pigment having the following structure, tetrahydrofuran 95
g of polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) was sufficiently pulverized in a ball mill. This mixture was taken out and 520 g of tetrahydrofuran was added with stirring. This dispersion was coated on the same conductive transparent support as used in Example 21 using a wire round rod to form a charge generation layer of about 0.7 μm.

[0207]

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Next, the hydrazone compound 20 of the following structural formula
g, 20 g of polycarbonate resin (trade name: Lexan 121, manufactured by GE), and 160 g of tetrahydrofuran are applied onto the charge generation layer using a wire round rod, dried at 60 ° C. for 30 seconds, and further heated at a temperature of 10
It was heated at 0 ° C. for 20 seconds to form a charge transport layer having a thickness of about 18 μm to obtain an electrophotographic photoreceptor having a photosensitive layer composed of two layers.

[0209]

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Further, in order to form a surface layer for imparting releasability on this photosensitive layer, 13 g of resin (P) shown in Table I below, 0.2 g of glutaric anhydride, 0-chlorophenol 0 A mixed solution of 0.002 g and 100 g of toluene was applied using a wire round rod so as to have a film thickness of 1 μm, dried by touch with a finger, and further heated at 140 ° C. for 1 hour.
The adhesive force on the surface of each of the obtained photoreceptors was 2 g · f or less. Example 1 except that each of the light-sensitive materials was charged to a surface potential of -500 V in the dark and then exposed to a light of 633 nm with a He-Ne laser so that the exposure amount on the surface was 30 erg / cm ^2. A color copy was obtained in the same manner as in. Each of the obtained copies showed good performance as in Example 1.

[0211]

[Table 9]

Example 25 100 g of photoconductive zinc oxide, a binder resin (B-
5) 24 g, 5 g of the binder resin (B-6) having the following structure, 3 g of resin (P-6) having the following structure, and resin particles (PL-2) 1
g, 0.01 g of the dye (D-2) having the following structure, 0.1 g of salicylic acid, and 150 g of toluene were used with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to rotate at 1 × 10 ⁴ rp.
Dispersion was carried out for 15 minutes at m. to obtain a photosensitive layer dispersion liquid.

[0213]

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[0214]

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This dispersion was used as an ELP-system (Fuji Photo
Used for EPL-II type photosensitive material used in Film Co., Ltd.
25g coating with a wire bar on the EPL-II support
/ M ^TwoSo that the coating becomes
Heated in a rotary oven for 20 seconds. 30 ℃, 80%
It was allowed to stand for 1 week in the dark under the condition of RH. This photoconductor surface
Had an adhesive force of 2 g · f.

Using this photoreceptor, a color copy was prepared in the same manner as in Example 1. However, the toner image was formed as follows. That is, after corona charging this photoreceptor to −600 V in a dark place, using the same digital image data as in Example 1, first, based on the information about yellow, a semiconductor laser was used to emit light of 780 nm. It was exposed so that the surface exposure amount was 25 erg / cm ² . The residual potential of the exposed portion was -120V. Subsequently, a yellow toner for Versatec 3000 (Xerox color electrostatic plotter) was diluted with 50 times Isopar G (made by Esso Standard Petroleum) and used, and a bias voltage of 200 V was applied to the developing electrode to apply toner to the unexposed area. Was developed so as to be electrodeposited, and then rinsed in a bath of Isopar H alone to remove stains on the non-image area. The above image forming process was repeated for each color of magenta, cyan and black. In the obtained copy, the toner image was completely transferred onto the coated paper together with the transfer layer. In addition, the image strength was sufficient, and it was possible to write or imprint on copy paper in the same manner as for plain paper.

Examples 26 to 31 Amorphous silicon photoconductors (manufactured by Kyocera Corp.) are shown in FIG.
The device was loaded as shown in. In order to impart releasability to the surface of the photoconductor 11, as the compound (S) application unit 10, the photoconductor is brought into contact with a solution prepared by dissolving each compound (S) shown in the following Table-J in 1 liter of Isopar G, and the Speed 30mm /
After rotating at a rotation speed of 10 seconds for 10 seconds, it was squeezed by a squeeze roll and dried by a heating means 17a. This gives 2
The adhesive force on the surface of the photoreceptor, which was 30 gf, is 3 to 10 each.
It became gf. Thereafter, in the same manner as in Example 2, a transfer layer was formed, a toner image was formed by an electrophotographic process, and transfer to high-quality paper was performed. The color copy obtained on the high-quality paper had a clear image quality without scumming similar to that in Example 2 and had sufficient image strength.

[0218]

[Table 10]

[0219]

[Table 11]

[0220]

According to the present invention, it is possible to easily and stably obtain a high-definition and high-quality color image without color shift. Further, it is possible to transfer at a low transfer temperature and a high speed, and a good color copy can be obtained regardless of the material to be transferred. The color copy obtained is also good in writing property, imprinting property and filing property. Further, by using the compound (S), a general-purpose electrophotographic photoreceptor can be used.

[Brief description of the drawings]

FIG. 1 is a schematic diagram for explaining a method of the present invention.

FIG. 2 is a schematic view showing an example of an apparatus for carrying out the method of the present invention using an electrodeposition coating method as a method for forming a second transfer layer (T ₂ ).

FIG. 3 is a schematic view showing an example of an apparatus for carrying out the method of the present invention using a hot melt coating method as a method for forming a second transfer layer (T ₂ ).

FIG. 4 is a schematic view showing an example of an apparatus for carrying out the method of the present invention using a transfer method as a method for forming a second transfer layer (T ₂ ).

[Explanation of symbols]

1 Support 2 Photosensitive Layer 3 Toner Image 10 Compound (S) Application Unit 11 Electrophotographic Photosensitive Body 12 Transfer Layer 12T ₁ First Transfer Layer 12T ₂ Second Transfer Layer 12a Thermoplastic Resin Particle Dispersion Liquid 12b Thermoplastic Resin Particle Dispersion Liquid 12c Thermoplastic resin 13a Electrodeposition unit 13b Electrodeposition unit 13c Hot melt coater 14 Liquid developing unit set 14Y Yellow liquid developing unit 14M Magenta liquid developing unit 14C Cyan liquid developing unit 14B Black liquid developing unit 14R Rinse unit 15 Intake / exhaust unit 15a Intake Part 15b Exhaust part 16 Transfer material 17 Transfer unit to transfer material 17a Heating means 17b Transfer backup roller 17c Separation backup roller 18 Corona charging device 19 Exposure device 20 Release paper 117 Transfer unit 117b heating roller 117c cooling roller to light body

Claims (3)

[Claims] 1. A peelable transfer layer is formed on the surface of an electrophotographic photosensitive member, a toner image of one or more colors is formed on the transfer layer by an electrophotographic process, and the toner image is transferred together with the transfer layer onto a transfer material. In the electrophotographic color image forming method, the transfer layer comprises a resin (AH) having a glass transition point of 20 ° C. to 140 ° C. or a softening point of 30 ° C. to 180 ° C. and a glass transition point-
Resin (AL ₁ ) with 40 ° C to 40 ° C or softening point 0 ° C to 60 ° C
And thermoplastic resin particles (AR) containing at least two kinds of resins in which the glass transition point or softening point of the resin (AH) is higher than that of the resin (AL ₁ ) by 2 ° C. or more in the same particle.
The first transfer layer (T
₁ ) and a glass transition point of −40 ° C. provided on this layer
An electrophotographic color image forming method having a laminated structure composed of a second transfer layer (T ₂ ) mainly containing a resin (AL ₂ ) having a softening point of 0 ° C. to 45 ° C. at 35 ° C. 2. The electrophotographic color according to claim 1, wherein the second transfer layer (T ₂ ) is formed by any one of an electrodeposition coating method, a hot melt coating method and a transfer method. Image forming method. 3. The surface of the electrophotographic photosensitive member is a first transfer layer (T
₁ ) The electrophotographic color image forming method according to claim 1, which has a surface releasability of 100 gram · force or less according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method” at the time of formation.