JPH096154A - Electrophotographic color image forming method - Google Patents

Abstract

PURPOSE: To easily and stably obtain a color image of high definition and high quality without causing color slurring by transferring a toner image formed on a photoreceptor onto a material to be transferred provided with a transfer layer mainly containing a specified thermoplastic resin. CONSTITUTION: The peelable transfer layer (To) 12' is arranged on the surface of the electrophotographic photoreceptor 11, and the toner image 3 is formed on the transfer layer (To) 12' by an electrophotographic process, then, the toner image 3 is transfer together with the transfer layer (To) 12' onto the material 16 provided with a transfer layer (T) 12. The transfer layer (To) 12' formed on the photoreceptor 11 is light-transmissible, and also, it is preferable for the layer (To) 12' to provide a transmissibility with reference to at least a part of wavelength light in the spectral sensitivity area of the photoreceptor 11. Besides, as for the transfer layer (T) 12 which is formed on the surface of the material 16 on which the toner image 3 is formed, it is suitable for the layer to be mainly constituted of the thermoplastic resin (A) having a glass transition point <=140 deg.C, or a softening point <=180 deg.C.

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, and an apparatus used therefor. 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 directly on the surface of an electrophotographic photosensitive member to form a multicolored color image, which is then transferred to a transfer material such as a printing paper at a time. 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 Publication 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-2-115865 and 2
In No. 115866, after a transparent film is laminated on the surface of the photoconductor in advance, a wet toner image is formed on the film by an electrophotographic process, and then the film is peeled from the photoconductor and attached to plain paper to transfer the image. A method of doing so is disclosed. However, in this case, the film to be laminated is 9 μm
Is suitable, 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, Japanese Patent Publication No. 2-43185 discloses that
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,
A method is disclosed in which color separation images are overlapped and formed on a dielectric support, and the support is transferred 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 peelable transfer layer made of a thermoplastic resin is provided on a photoreceptor having a peelable surface as a color image forming method using a wet toner capable of repeatedly using the photoreceptor. A method is described in which a toner image is formed thereon by an electrophotographic process, and then the toner image is transferred together with a transfer layer onto a final transfer target material.
According to these methods, even when a wet toner is used,
By transferring the toner image together with the transfer layer, it can be completely transferred to the final transfer target material without degrading the toner image, and the transfer layer is formed on the photosensitive member in the electrophotographic apparatus so that the photosensitive member can be repeatedly used. It is possible to realize low cost. However, even in these technologies, the transfer layer must be designed so as not to adversely affect the electrophotographic process, or a toner image is formed on the transfer layer, so that the transfer material is not sufficiently mixed with the final transfer material during transfer. Since they must be brought into close contact with each other and peeled off, they are susceptible to the influence of the toner image portion or the surface condition of the final transfer material, 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 an intermediate transfer medium, a sufficiently satisfactory color image cannot be obtained. There are various problems such as difficulty in maintaining the performance over a long period of time, occurrence of disposable members for maintaining the performance, and necessity of using a special transfer medium. On the other hand, the color image forming method in which the transfer layer is provided on the photoreceptor still has problems to be solved, such as difficulty in obtaining a stable and high-definition image regardless of the type of the toner and the type of the final transfer receiving material. Exists.

The present invention solves the above-mentioned problems of the conventional electrophotographic color image forming method.
An object of the present invention is to provide a transfer layer capable of easily and stably obtaining a high-definition, high-quality color image without color shift and reproducing an excellent color image regardless of a final transfer-receiving material. An object of the present invention is to provide an electrophotographic color image forming method used. 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 final transfer material.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrophotographic process on an electrophotographic photoreceptor having a releasable surface.
A transfer layer (T) mainly containing a thermoplastic resin (A) having a glass transition point of 140 ° C. or lower or a softening point of 180 ° C. or lower after forming a toner image of a color or more
It has been found that this can be achieved by an electrophotographic color image forming method, which is characterized in that it is transferred onto a transfer material having As shown in FIG. 1, the electrophotographic color image forming method of the present invention has at least the surface of an electrophotographic photoreceptor 11 composed of at least a support 1 and a photosensitive layer 2 in a usual electrophotographic process, as shown in FIG. The toner image 3 of one color is formed, and then the toner image 3 is transferred onto the transfer material 16 having the transfer layer (T) 12 to obtain a color copy.

According to the method of the present invention, the toner image formed on the photoconductor is transferred onto the transfer material having the transfer layer (T), so that it is affected by the surface shape and composition of the transfer material. The toner image can be completely transferred without using. Further, since the surface of the photosensitive layer does not directly contact the material to be transferred, damage to the surface of the electrophotographic photosensitive member is reduced, and the photosensitive member can be used repeatedly or for a long time. In the electrophotographic color image forming method described above, the present invention further provides a release containing a thermoplastic resin (A) as a main component on an electrophotographic photoreceptor having a releasable surface before forming one or more toner images by an electrophotographic process. Included is an embodiment characterized in that a possible transfer layer (T ₀ ) is provided. In this embodiment, as shown in the outline of the process, a transfer layer (T ₀ ) 12 'is provided on the surface of the electrophotographic photosensitive member 11, and then the toner image 13 is transferred through the process similar to the above. The (T ₀ ) 12 'is transferred together to form a color copy.

According to this aspect, after the peelable transfer layer (T ₀ ) is provided on the surface of the photosensitive member, the toner image is formed thereon, and the toner image is transferred together with the transfer layer (T ₀ ). Therefore, it is possible to easily and stably obtain a high-definition and high-quality color image with no color shift. In the transfer process, the transfer temperature can be lowered, the transfer pressure can be lowered, and the transfer speed can be improved, and a transfer device with a simple structure can be used. Further, instead of using an electrophotographic photosensitive member having a transfer layer (T ₀ ) on the surface in advance, the transfer layer (T ₀ ) is peeled off by forming the transfer layer on the photosensitive member in the apparatus each time. Since the photoconductor can be repeatedly used after
The electrophotographic process can be continuously performed without disposing the photoreceptor.

The present invention will be described in more detail below. The electrophotographic color image forming method of the present invention is characterized in that the transfer material to which the toner image formed by the electrophotographic process is transferred has a transfer layer (T) on its surface. It is desired that the transfer layer (T) enables good transfer of the toner image in the thermal transfer process and has sufficient mechanical strength. For this purpose, the glass transition point 14
Thermoplastic resin (A) having a softening point of 0 ° C or lower or a softening point of 180 ° C or lower
Layers consisting essentially of are suitable. The resin (A) used in the transfer layer (T) preferably has a glass transition point of 100 ° C.
Or less or a softening point of 120 ° C. or less, more preferably a glass transition point of 60 ° C. or less or a softening point of 100 ° C. or less.

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 copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, polymers and copolymers of styrene and its derivatives, olefin-styrene copolymers Coal, olefin-unsaturated carboxylic acid ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer, acrylic acid ester polymer and copolymer, methacrylic acid ester polymer and copolymer , Styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, itaconic acid Polymers and copolymers, maleic anhydride copolymers, acrylamide copolymers, methacrylamide copolymers, hydroxyl-modified silicone resins, polycarbonate resins, ketone resins, polyester resins, silicone resins, amide resins, hydroxyl groups and carboxyl groups Modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, cyclized rubber-acrylic acid ester copolymer, copolymer containing a heterocycle (for example, a furan ring, a 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.

[0015] For example, "Plastic Materials Course Series" Vol. 1 to 18 (1981) published by Nikkan Kogyo Shimbun, "Polyvinyl chloride" edited by Kinki Chemical Society 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 Volume 20, Extra Number" Adhesive "" Polymer Publishing Association (Published in 1976), Keiji Fukuzawa "Adhesive Technology" Polymer Publishing Association (Published in 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 transfer layer (T) of the present invention may contain two or more kinds of the resin (A). Further, other resins and additives may be included in order to adjust various physical properties such as adhesiveness, film formability, and film strength. For example, polybutene, DOP, DBP, low-molecular-weight styrene resin, low-molecular-weight polyethylene wax, microcrystalline wax, as a plasticizer and a softening agent for improving film-forming property and lowering melt viscosity, such as rosin and petroleum resin for adjusting adhesiveness. Polymeric hindered polyhydric phenols, triazine derivatives and the like can be added as antioxidants such as paraffin wax. For details, see “Actual Hot Melt Adhesion” (Hiroshi Fukada, Kobunshi Kogakukai, published in 1983), pages 29 to 107. The total thickness of the transfer layer (T) is suitably 0.1 to 20 μm, preferably 0.5 to 10 μm, more preferably 1 to 5 μm. The transfer layer (T) may be preliminarily provided on the material to be transferred, or may be formed on the material to be transferred each time in an apparatus for performing an electrophotographic process (hereinafter referred to as an electrophotographic apparatus). To provide the transfer layer (T) on the material to be transferred, a known layer forming method can be used. For example, a solution or dispersion of the transfer layer composition may be applied by a conventional method. In particular, a hot melt coating method, an electrodeposition coating method or a transfer method, which will be described in detail later, is preferably used. These methods are advantageous in that the transfer layer (T) can be uniformly and easily formed on the transfer material in the electrophotographic apparatus.

The material to be transferred used in the present invention is not particularly limited, and a conventionally known reflection type or transmission type material is used. For example, paper such as high-quality paper, coated paper, art paper, and synthetic paper, metal such as aluminum, iron, and stainless steel, and plastic film such as polyester, polyolefin, polyvinyl chloride, and polyacetate can be used alone or in combination. In order to enhance the adhesion with the transfer layer (T), the material to be transferred may be subjected to a surface treatment or an undercoat layer may be provided, if necessary.

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 a releasability at the time of forming the toner image or the transfer layer (T ₀ ) so that the toner image or the transfer layer (T ₀ ) formed on the photoconductor can be easily peeled off later. To have.

That is, in the present invention, when at least a toner image or a transfer layer (T ₀ ) is formed, the adhesive force of the surface of the electrophotographic photosensitive member according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method” is 100 gr.
It is desirable that the value is not more than am · force (gf).
Thereby, the peeling property between the photoconductor and the toner image or the transfer layer (T ₀ ) can be exhibited more favorably,
The toner image or the transfer layer (T ₀ ) can be easily transferred to the transfer material.

The measurement of the adhesive strength by the above-mentioned JIS Z 0237-1980 "Adhesive tape / adhesive sheet test method" is carried out according to the 180 degree peeling method of 83.1 with the following modifications. An electrophotographic photoreceptor is used as the "test plate". JIS C 2338-with 6 mm width as "test piece"
An adhesive tape manufactured according to 1984 is used. Peel at a speed of 120 mm / min using a constant speed tension type tensile tester. That is, with the adhesive surface of the test plate piece facing down, a roller is reciprocated once over the test piece at a speed of about 300 mm / min and pressure-bonded to the test plate. After peeling about 25 mm using a constant-speed tension type tensile tester for 20 to 40 minutes after crimping, 1
Peel off at a speed of 20 mm / min. The force is read every 20 mm peeling and a total of 4 times. The test is performed on three test pieces, and an average value of twelve pieces measured from the three test pieces is obtained, and the average value is proportionally converted per 10 mm width.

The adhesive force on the surface of the electrophotographic photosensitive member is more preferably 50 gf or less, and particularly preferably 30 gf or less. As a method for obtaining a photoreceptor having releasability on the surface, a method using a photoreceptor having a releasability on the surface itself (first method) and a compound (S) expressing releasability are used as a toner image or a transfer layer. (T ₀ ) A method (second method) of applying it to the surface of the photoconductor before formation is mentioned. Also,
Any of these methods can be used in combination.

An example of a photoconductor having a releasable surface that can be used in the first method is a photoconductor having a surface of amorphous silicon modified to have releasability. In the electrophotographic photosensitive member, as a method of modifying the surface of the electrophotographic photosensitive member mainly containing amorphous silicon to have releasability, a coupling agent containing a fluorine atom and / or a silicon atom (silane coupling agent, titanium There is a method of treating the surface of the amorphous silicon photoconductor with a coupling agent or the like).
844, JP-A-4-231318, JP-A-60-1.
70860, 59-102244, 60-17.
No. 750, etc. Further, as another method, a releasing agent (S) described later, particularly a releasing agent containing a component containing a fluorine atom and / or a silicon atom in a block (for example, polyether modification, carboxylic acid, amino group, A modified polydialkyl silicones such as carbinol can be adsorbed and fixed. 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 toner image or the transfer layer (T ₀ ) can be 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 a silicon atom and / or a fluorine atom 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 silicon atom-containing resin and / or fluorine atom-containing resin may be used in the form of particles. Among them, when the overcoat layer is provided, the method of using the surface unevenly distributed copolymer in combination with another binder resin is preferable because the adhesion between the photoconductive layer and the overcoat layer can be sufficiently maintained. The above-mentioned surface unevenly distributed copolymer is usually the entire composition 1 of the overcoat layer.
It can be used in a proportion of 0.1 to 20 parts by weight in 00 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 photoreceptor which uses at least a photoconductor and a binder resin. 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.

In order 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 No. 51-97169. Alternatively, a light and / or thermosetting resin may be used together with a resin containing a fluorine atom and / or a silicon atom.

The 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 toner image or transfer layer (T ₀ ) is suppressed or eliminated, and the interface between the toner image or transfer layer (T ₀ ) and the electrophotographic photoreceptor can be clearly formed and maintained. (Ie 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. .

As described above, the polymer is a resin particle (PL).
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, by containing a curable group in the polymer or the binder resin, transfer to the toner image or the transfer layer (T ₀ ) is eliminated.

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

[0033]

Embedded image

[0034]

Embedded image

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

[0036]

Embedded image

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, and in that case, they may be directly bonded or further combined via another connecting 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 -, - COO
-, -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
Represents the same contents as R ³¹ .

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

[0040]

Embedded image

Here, e ¹ and e ² may be the same or different from each other, and each is a hydrogen atom or a halogen atom (for example,
Chlorine atom, bromine atom, etc.) or C1-C12 alkyl group (for example, methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc. ) Is represented. Q is -O
-, - S- or -N (d ²⁾ - represents, d ² is 1 to the number of carbon atoms
4 represents an alkyl group of 4, —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 represented by the following (1) to (1
It represents any one of the groups 1), and b represents a hydrogen atom or a methyl group.

[0044]

Embedded image

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.

[0046]

[Chemical 6]

[0047]

[Chemical 7]

[0048]

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[0049]

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[0050]

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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 is used. 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 , and more preferably 1 × 10 ⁴ to.
It is 5 × 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, being 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.

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These various block copolymers can be synthesized by a conventionally known polymerization method. For example,
W. J. Burrant, A.A. S. Hoffman "Block and G
raft Polymers "(1986, Reuhold), R.P. J. Ceve
sa "Block and Craft Copolymers" 1962, Butt
erworths), D.E. C. Allport, W.A. H. James "Blo
ck Copo1ymers "(1972, App1ied Sci), A.K. Nosh
ay, J. E. FIG. McGrath "Block Copolymers" (1977
Year, Academis Press), G. Huvterg, D.M. J. Wil
son, G.I. Riess, NATO ASIser. Ser E., 1
985 , 149, V.I. Perces, Applide Polymer
Sci., 285 , 95 (1985), T.S. E. FIG. Hogeu-Esc
h, J. Smid "Recent Advances in Anion Polym
erization "(1987, Elsevier New York), S.W. K
obayashi, T. Saegusa "Ring Oping Po1ymeriz
ation ”(1984, Applied Science Publishers Lt.
d.), Fumio Ide "Graft Polymerization and Its Application" (1977)
, Kobunshi Kogyokai) 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. 310754, No. 5-197169, 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. 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 thereof include halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane and trichloroethane. However, it is not limited to the above-mentioned compound examples.

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 a 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 photo- 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 promote a crosslinking reaction in the photosensitive layer film. In the case of a reaction mode in which a crosslinking reaction forms a chemical bond between functional groups, 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 (acetylacetonato zirconium salt, acetylacetone zirconium salt, acetylacetocobalt salt, dibutoxytin dilaurate, etc.), dithiocarbamic acid compounds (diethyldithiocarbamate, etc.) ), Thiuram disulfide compounds (such as tetramethylthiuram disulfide), carboxylic anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butylsuccinic anhydride, 3,
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 prepared by applying the photosensitive layer-forming material,
It is preferably light and / or heat cured. 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 ℃ ~
Process at 150 ° C. 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 for curing a specific functional group in the resin by irradiation with light, a step of irradiating with a chemically active ray 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, a peeling compound (S) is formed on an ordinary electrophotographic photoreceptor before forming a toner image or a transfer layer (T ₀ ), which is a second method for obtaining a photoreceptor having a peelable surface.
A method of making the surface of the photoreceptor releasable 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 photosensitive member means supplying the compound (S) to the surface of the electrophotographic photosensitive member to form a state in which the compound (S) is adsorbed or attached to the surface of the photosensitive member. 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 wetted 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 electrodeposition coating method described below. 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). For example, continuous jet Sweet method, Hertz method,
The intermittent jet type Winston method, the ink-on-demand type pulse jet method, the bubble jet method, the ink mist type mist method and the like can be mentioned.

In each case, the compound (S) is used instead of the ink directly or after being diluted with a solvent 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 may 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) to be 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, when the toner image or the transfer layer (T ₀ ) is formed, the compound (S)
Is adsorbed or adhered on the electrophotographic photosensitive member and imparts releasability to the surface thereof, preferably the surface adhesive force is 100 gf or less, and in the method of the present invention, it is not always necessary to repeat this step.

For example, "Basics and Applications of Electrophotographic Technology" edited by The Institute of Electrophotography (published by Corona Publishing Co., Ltd. (1988)), Hiroshi Komon, "Recent Developments and Practical Uses of Photoconductive Materials and Photoconductors" (Japanese Scientific Information) (Published in 1985), Ryuji Shibata, Jiro Ishiwatari, Kogaku, Vol. 17, p. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 , (No.8), The Institute of Electrophotography. Ed. "Present Symposium on Current Situation of Organic Photoreceptors for Electrophotography" (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, etc. 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 of the printer 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. Examples thereof include imidazole-based pigments, squalium salt-based pigments, and azurenium salt-based pigments, which may be used alone or in combination of two or more.

Examples of the charge transfer agent include 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. The organic photoconductive compounds may be used alone or in combination of two or more.

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 Kay, Isamu Shimizu, Eiichi Inoue, The Electrophotographic Society of Japan, 18 (No. 2), 22 (1980) and the like.

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 the 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-3-29954.
No. 3-77954, No. 3-92961 and No. 3
-53257, a resin having an acidic group bonded to the end of the graft portion of the graft copolymer, or a resin having an acidic group in the glide portion of the graft copolymer, JP-A-3-2-3.
Graft copolymers containing an AB block copolymer comprising an acidic group-containing A block and an acidic group-free B block described in JP-A-066464 and JP-A-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 in combination as a spectral sensitizer depending on the type 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 Disclosur".
e ”1982, 216 pages 117-118, FM Hamer
Carbonium dyes, diphenylmethane dyes described in reviews such as "The Cyanine Dyes and Related Compounds",
Examples thereof include triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes) and phthalocyanine dyes (which may contain a metal). 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 of forming a toner image on the electrophotographic photosensitive member of the present invention will be described.

A toner image is formed on the electrophotographic photosensitive member having a releasable surface by a usual electrophotographic process. That is, each step of charging-exposure-developing-fixing is performed by a conventionally known method. When the releasability of the surface is insufficient, a releasable photoreceptor can be obtained by applying the compound (S) to the surface of the photoreceptor before such a normal electrophotographic process.

The developer used in the development 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
~ 127 pages (1983), Academic Publishing Center, The Institute of Electrophotography "Imagen No. 2-5 Development and fixing of electrophotography
There is a specific description in "Electrification / transfer". As the dry developer, a one-component magnetic toner, a two-component toner, a one-component non-magnetic toner, a capsule toner and the like have been put into practical use, and any of these can be used.

On the other hand, the basic constitution of the liquid developer is well known, and an electrically insulating organic solvent {for example, isoparaffin aliphatic hydrocarbon: Ansoper H, Isopar G (manufactured by Esso Co.) Shell Sol 70, Shell Sol 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 the other additives, 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.

Particularly, the 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 photoconductor is then transferred to a transfer material having a 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 photoconductor with a heating roller, for example, a metal roller having a built-in heating element coated with rubber, and then passed through a cooling roller. If necessary, the photoreceptor or 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 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 transfer paper. 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.

The surface temperature of the heating roller at the time of thermal transfer is preferably 30 to 150 ° C, more preferably 35 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 15 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. The conveying speed is preferably 0.1 to 300 mm / sec, more preferably 10 to 2
The range is 00 mm / sec. The transport speed may be different in the electrophotographic process and the thermal transfer process.

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 photoconductor (photosensitive layer and support), the transfer layer, the material to be transferred, etc. used. It is natural to make it. The temperature condition in the thermal transfer step is 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.

According to a preferred embodiment of the present invention, a peelable transfer layer (T ₀ ) is provided on the surface of the electrophotographic photosensitive member, a toner image is formed thereon by an electrophotographic process, and the toner image is transferred to the transfer layer. The entire (T ₀ ) is transferred onto the transfer material having the transfer layer (T). The transfer layer (T ₀ ) provided on the electrophotographic photosensitive member is light transmissive,
Further, it is not particularly limited as long as it is transparent to at least a part of the wavelength light in the spectral sensitivity region of the electrophotographic photosensitive member, and may be colored. A colorless and transparent transfer layer is used for usual purposes.

The transfer layer (T ₀ ) has a temperature of 180 ° C. or lower and / or a pressure of 30 kgf / cm ² or lower, preferably 160.
It is preferable that the transfer can be carried out under the conditions of a temperature of not more than 0 ° C. and / or a pressure of not more than 20 kgf / cm ² . If this condition is exceeded, the size of the apparatus tends to increase in order to maintain the heat capacity and pressure for peeling / transferring the transfer layer from the surface of the photoreceptor, and the transfer speed tends to be extremely slow. The above conditions are preferably a temperature of room temperature or higher and / or a pressure of 0.1 kgf / cm ² or higher. The transfer layer (T ₀ ) is mainly composed of the thermoplastic resin (A) as described above.
The resin (A) used for the transfer layer (T ₀ ) is
₀ ) Deterioration of electrophotographic characteristics (chargeability, dark charge retention rate, photosensitivity, etc.) because a toner image is formed on it by an electrophotographic process and it becomes the uppermost layer on the surface side of the transfer material in a color copy. It is desirable not to do so and to maintain the film strength to protect the toner image.

The resin (A) constituting the transfer layer (T ₀ ) is
A glass transition point of -50 ° C to 120 ° C or a softening point of -40 ° C to 160 ° C is preferable, and a glass transition point of -50 ° C to 90 ° C or a softening point of -40 ° C to 12 is more preferable.
0 ° C. Resin (A) used for transfer layer (T ₀ ).
Is preferably higher in glass transition point or softening point by 2 ° C. or more than the resin (A) used in the transfer layer (T). More preferably, it is 5 ° C. or higher. When two or more resins (A) are used in the transfer layer (T) and / or the transfer layer (T ₀ ), the difference in the glass transition point or the softening point is the highest among the resins (A) in the transfer layer (T). The difference between the glass transition point or the softening point is the highest and the resin (A) in the transfer layer (T ₀ ) is the lowest in the glass transition point or the softening point.

The transfer layer (T ₀ ) on the photoreceptor is a resin having a glass transition point of 30 ° C. to 140 ° C. or a softening point of 35 ° C. to 180 ° C. (hereinafter sometimes referred to as resin A ₀ H) and a glass transition point of 40 ° C. Resin having a softening point of 45 ° C. or lower (hereinafter, resin A
₀ L), and the difference in glass transition point or softening point between the resin (A ₀ H) and the resin (A ₀ L) is preferably 2 ° C. or more. These resins may be mixed to form a single layer. You may take the laminated structure which each consists of an independent layer. In the latter case, it is preferable to use a resin (A ₀ H) having a high glass transition point or softening point in the layer in contact with the photoreceptor. Resin (A
₀ H) preferably has a glass transition point of 30 ° C to 120 ° C or a softening point of 38 ° C to 160 ° C, more preferably a glass transition point of 35 ° C to 90 ° C or a softening point of 40 ° C to 120 ° C. The resin (A ₀ L) preferably has a glass transition point of −50 ° C. to 38 ° C.
C. or softening point -30.degree. C. to 40.degree. C., more preferably glass transition point -20.degree. C. to 33.degree. C. or softening point 0.degree. C. to 35.degree. More preferably, the glass transition point or softening point of the resin (A ₀ L) is lower than that of the resin (A ₀ H) by 5 ° C. or more.

The difference in glass transition point or softening point in the case where two or more kinds of resin (A ₀ H) or resin (A ₀ L) are contained in the transfer layer (T ₀ ) is the difference in the resin (A ₀ H). The one with the lowest glass transition point or softening point and the resin (A
₀ L) is the difference from the one having the highest glass transition point or softening point. In the transfer layer (T ₀ ), the resin (A
₀ H) and the resin (A ₀ L) are present in a proportion of 5 to 90/95.
-10 (weight ratio) is preferable. A more preferable ratio of the resin (A ₀ H) / resin (A ₀ L) is 20 to 70/8.
0 to 30. Further, in a color copy, the surface side of the transfer layer transferred to the material to be transferred can be made of a resin having a high glass transition point, so that the transfer layer is peeled off even if it is put into various sheets and piled up. The storage stability of the copy is further improved, such as no occurrence of damage (good filing suitability). Further, by selecting the type of resin, it becomes possible to impart the writing property and the imprinting property close to those of plain paper.

The resin (A) used in the transfer layer (T ₀ ) of the present invention contains a substituent containing a fluorine atom and / or a silicon atom, which has the effect of improving the releasability of the resin (A) itself. It may further contain a polymer component. As a result, the releasability from the electrophotographic photoreceptor surface is further improved, and as a result, the transferability is further improved. As the polymer component containing a substituent containing a fluorine atom and / or a silicon atom, the polymer component (F) described for the photoreceptor is preferably used. The content thereof is preferably 3 to 40 parts by weight, more preferably 5 to 25 parts by weight in 100 parts by weight of the total polymer component of the resin (A). The substituent containing a fluorine atom and / or a silicon atom may be incorporated into the polymer main chain of the polymer, or may be present as a substituent on the side chain of the polymer. More preferably, the polymer component (F) is contained as a block in the resin (A).

As described above, when the resin (A) constituting the transfer layer (T ₀ ) is composed of two or more kinds of resins having different glass transition points or softening points, these fluorine atom and / or silicon atom containing polymers are used. The component is a resin (A
₀ H) or a resin having a low glass transition point (A ₀ L). When the transfer layer (T ₀ ) has a laminated structure, it is preferable to use a fluorine atom- and / or silicon atom-containing resin, particularly a fluorine atom- and / or silicon atom-containing block copolymer for the layer in contact with the photoreceptor. This makes it easier to separate the surface of the photoconductor from the transfer layer (T ₀ ), thus improving transferability. Regarding the block copolymer containing a fluorine atom and / or a silicon atom used in the resin (A) and a method for synthesizing the block copolymer, the description on the block copolymer described in connection with the electrophotographic photoreceptor can be incorporated.

The transfer layer (T ₀ ) may contain other compounds in order to adjust various physical properties such as adhesiveness, film-forming property and film strength. For example, polybutene, DOP, DBP, low-molecular-weight styrene resin, low-molecular weight styrene resin, low-molecular weight resin such as rosin, petroleum resin, silicone oil, etc. for adjusting adhesion Polyethylene wax, microcrystalline wax,
Polymeric hindered polyphenols, triazine derivatives and the like can be added as antioxidants such as paraffin wax. For details, see “Actual Hot Melt Adhesion” (Hiroshi Fukada, Kobunshi Kogakukai, published in 1983), pages 29 to 107. The film thickness of the transfer layer (T ₀ ) is 0.
1 to 20 μm is suitable, and 0.3 to 10 is preferable.
μm, and more preferably 0.5 to 5 μm. If the film thickness is too large, inconvenience may occur in the electrophotographic process, and a sufficient image density may not be obtained or the image quality may be deteriorated.

The transfer layer (T ₀ ) is formed on the surface of the electrophotographic photosensitive member by a usual coating film forming method. For example, a solution or dispersion containing the transfer layer composition may be applied to the surface of the photoreceptor by a known method. The method for forming the transfer layer (T ₀ ) may be the same as or different from the method for forming the transfer layer (T). The transfer layer (T ₀ ) is preferably formed on the photoconductor in each case in the electrophotographic apparatus. As a result, the electrophotographic photosensitive member can be repeatedly used in the electrophotographic apparatus, and the electrophotographic process can be continuously performed without disposing the photosensitive member. As a result, there is an advantage that the cost of the printing plate produced can be significantly reduced.
In order to form the transfer layer (T ₀ ) on the surface of the photoconductor in the electrophotographic apparatus, the hot melt coating method, the electrodeposition coating method or the transfer method is effective.

The hot melt coating method, electrodeposition coating method and transfer method will be described in detail below. Here, the material to be coated includes a material to be transferred on which the transfer layer (T) is formed and an electrophotographic photosensitive member on which the transfer layer (T ₀ ) is formed. The hot melt coating method is
A transfer layer composition is hot-melt coated by a known method, and a solventless coating machine, for example, a hot-melt coating apparatus for hot-melt adhesives described on pages 197 to 215 of the above-mentioned document "Practice of Hot Melt Adhesion". A (hot melt coater) mechanism can be used by making it a specification for coating an object to be coated. Examples include direct roll coaters, offset gravure roll coaters, lot coaters, extrusion coaters, slot orifice coaters, curtain coaters, and the like.

The melting temperature of the thermoplastic resin at the time of coating is optimized depending on the component composition of the thermoplastic resin used, but it is usually in the range of 50 to 180 ° C. It is desirable that the temperature be raised to an appropriate temperature in a short time at the position where it is applied to the object to be coated after it is melted in advance using a closed preheating device having an automatic temperature control means. By doing so, it is possible to prevent deterioration and coating unevenness due to thermal oxidation of the thermoplastic resin. The coating speed depends on the fluidity of the thermoplastic resin at the time of heat melting, the coater method, the coating amount, etc., but 1 to 200 mm / sec is suitable, and more preferably 5 to 150 mm / sec.

In the electrodeposition coating method, the above-mentioned thermoplastic resin (A) is electrodeposited or adhered (hereinafter also simply referred to as electrodeposition) on the surface of the object to be coated in the form of resin particles, and the resin is uniformly applied by, for example, heating. A thin film is formed as a transfer layer. Therefore, it is necessary that the thermoplastic resin particles [hereinafter also referred to as resin particles (AR)] have either a positive charge or a negative charge, and the electroscopic property thereof depends on the combination of It is arbitrarily determined by the chargeability of the coating material.

The resin particles (AR) are in a range satisfying the above-mentioned physical properties, and the average particle diameter thereof is usually 0.01.
μm to 15 μm, preferably 0.05 μm
To 5 μm, more preferably 0.1 μm to 1 μm. The particles are either powdered particles (dry type) or resin particles dispersed in a non-aqueous system (wet type), or resin particles dispersed in an electrically insulating organic substance which is solid at room temperature and becomes liquid by heating (pseudo-wet type). It may be in a state. Preferably, non-aqueous dispersed resin particles that can easily and uniformly adjust the thickness of the transfer layer are used.

Particularly, at least two kinds of resins having different glass transition points (preferably the above-mentioned resins having a high glass transition point (A
₀ H) and the resin having a low glass transition point (A ₀ L)) in the same particle [hereinafter referred to as resin particle (AR
W) may be used]. In the present invention, the resin particles (ARW) can be obtained by arbitrarily selecting the resin (A ₀ H) and the resin (A ₀ L) whose glass transition point or softening point falls within the above range. This improves the transferability, increases the durability of the transfer layer, and improves the strength of the copied image.

In the resin (ARW), the ratio of resin (A ₀ H) / resin (A ₀ L) is 10/90 to 95/5 (weight ratio), particularly 30/70 to 90/10 (weight ratio). It is preferably contained. When the ratio of the resin (A ₀ H) is 10% by weight or more, even if a color copy is put in various sheets and overlapped for filing, peeling of the transfer layer does not occur (filing suitability is good). Storage stability is further improved, which is preferable. Further, when the content ratio of the resin (A ₀ L) is 5% by weight or more, the transferability of the transfer layer is more excellently exhibited.

At least two kinds of resins (A ₀ H) and resins (A ₀ L) contained in the resin particles (ARW) are in a state of being arbitrarily mixed in the particles or a portion where the resin (A ₀ H) is the main part. And the resin (A ₀ L) may form a separate layer structure in the main part (that is, particles having a core-shell structure), and in the case of a core-shell structure, a part serving as a core Is a resin (A ₀ H), a resin (A ₀ L)
However, it is not particularly limited.

The fine resin particles can be produced by a conventionally known mechanical grinding method or polymerization granulation method.
In these production methods, particles of either dry electrodeposition or wet electrodeposition can be used. In the case of producing fine particles used in the dry electrodeposition method, as a mechanical pulverizing method, a method of directly pulverizing with a conventionally known pulverizer to obtain fine particles (for example, ball mill, paint shaker,
A method using a jet mill, etc.) can be mentioned, and if necessary, materials for resin particles are mixed, pulverized through melting and kneading, or after pulverization, classification or surface treatment of particles to make the particle diameter uniform The post-treatment and the like can be appropriately combined and performed. A spray dry method is also known. For example, "Granulation Handbook", Part II (edited by Ohmsha, 1991) edited by The Japan Powder Industry Technology Association, "Actual state of latest granulation technology", Kanagawa Business Development Center (Kanagawa Business Development Center Publishing 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, there are known methods such as an emulsion polymerization reaction carried out in a water system, a seed polymerization reaction, a suspension polymerization reaction and a dispersion polymerization reaction carried out in a non-aqueous solvent system. Specifically, Soichi Muroi "Chemistry of Polymer Latex" Polymer Publishing Society (1970), Taira Okuda, Hiroshi Inagaki "Synthetic Resin Emulsion" Polymer Publishing Society (1978), Soichi Muroi "Polymer Latex""Introduction" Kobunsha (1983), I. Piirm
a, PC Wang "Emulsion Polymerization", I. Piirma
& JL Gardon, ACS symp. Sev. 24, p.34 (1974
Fumio Kitahara et al. "Chemistry of Dispersed Emulsion Systems" Engineering Book (1979)
), Soichi Muroi's supervision, "Cutting-edge technology of ultrafine polymer"
It can be produced by granulating by the method described in the textbook such as CMC (1991), then collecting and pulverizing by various methods as described in the textbook on the above mechanical method. .

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 photographic 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,
Electrodeposition of charged fine particles by methods such as induction charging, ionic wind charging, and reverse ionization phenomenon, edited by Koichi Nakamura "Recent development of electrophotographic development systems and toner materials.
Practical use ”, as described in the publications such as Chapter 1 (Japan Science Information Co., Ltd., 1985), cascade method, magnetic brush method, fur brush method, electrostatic method, induction method, touchdown method, It can be appropriately performed using a developing method such as a powder cloud method.

When the non-aqueous latex used in the wet electrodeposition method is produced, either the mechanical method or the polymerization granulation method can be used as described above. For example, a method in which a dispersion polymer is used in combination and further dispersed by a wet disperser (for example, a ball mill / paint shaker, Keddy mill, Dynomill, etc.), a material to be a resin particle component and a dispersion assisting polymer (or coating polymer) are kneaded in advance. And the like, and then pulverized, and then a dispersing polymer is coexisted and dispersed. Specifically, a method for producing a paint or a developer for electrostatic photography can be used.
), "Solomon, Science of Paint", "Paint and Surfac
e Coating Theory and Practice ”, Yuji Harasaki“ Coating Engineering ”Asakura Shoten (1971), and Yuji Harasaki“ Basic Science of Coating ”(1977).

As the polymerization granulation method, a seed polymerization method can be used for easy production. Specifically, the above-mentioned “Latest Technology of Ultrafine Particle Polymer”, Chapter 2, “Recent Electrophotographic Development System and Development and Practical Use of Toner Material”
Chapter 3, KEJ Barvett "Dispersion Polymerizatio
n in Organic Media, "John Wiley (1975) and other publications.

In the above-mentioned polymerization granulation method, in order to introduce the polymer component (F) for improving the releasability into the resin (A), it is soluble in an organic solvent which becomes a thermoplastic resin and is polymerized. The resin (A) is obtained by carrying out a polymerization reaction in the presence of a monomer corresponding to the polymer component (F) together with the insoluble monomer.
The resin particles (AR) of the random copolymer are easily copolymerized therein.

Further, in order to introduce the polymer component (F) in blocks, a method of using at least a block copolymer containing the polymer component (F) in blocks as a dispersion stabilizing resin, or the polymer component (F ) As a main repeating unit, and 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 ) coexistent. A block copolymer can be easily obtained by the method of copolymerization. As another method, by using a polymer initiator (azobis polymer initiator or peroxide polymer initiator) containing the polymer component (F) as a main repeating unit, a block copolymer resin is similarly obtained. Particles can be obtained.

Further, in order to obtain resin particles (ARW) having a core-shell structure containing at least two kinds of resins having different glass transition points in the same particle, for example, it is easy to produce by using a seed polymerization method. You can Specifically, fine particles are first synthesized by the above-mentioned conventionally known non-aqueous dispersion polymerization method, and then the fine particles are used as seeds in the same manner as described above to obtain a single amount corresponding to the seed particles and the resin (A) having a different glass transition point. It can be produced by feeding and polymerizing the body.

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 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, methyl propionate, hexane, octane,
Decane, dodecane, tridecane, cyclohexane, cyclooctane and other aliphatic hydrocarbons having 6 to 14 carbon atoms, benzene, toluene, xylene, chlorobenzene and other aromatic hydrocarbons, methylene chloride, dichloroethane, tetrachloroethane, chloroform, methyl Examples thereof include halogenated hydrocarbons such as chloroform, dichloropropane and trichloroethane. However, it is not limited to the compounds described above. By synthesizing dispersed resin particles in these non-aqueous solvent systems by a dispersion polymerization method, the average particle diameter of the resin particles easily becomes 1 μm or less, and the particle diameter distribution is very narrow and monodisperse particles are obtained. You can

Since the non-aqueous dispersion resin particles are used in a wet electrostatic photography development method or a method in which they are electrophoresed by electrophoresing in a pressure field of an electric field, the dispersion medium used in the electrodeposition is an electric resistance. 10 ⁸ Ω · cm or more and relative permittivity 3.5
It is preferable to adjust to the following non-aqueous solvent system. Particles mainly containing thermoplastic resin have an electric resistance of 10 ⁸ Ω · cm.
The above method in which the transfer layer is dispersed and supplied in an electrically insulating solvent having a relative dielectric constant of 3.5 or less is preferable in that the film thickness of the transfer layer can be uniform and thin and easily adjusted.

As the insulating solvent, 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), Shersol 7
0, Shelsol 71 (Shelsol; trade name of Shell Oil), Amsco OMS, Amsco 460 solvent (Amsco; trade name of American Mineral Spirits) or the like can be used alone or in combination.

Here, it is preferable to use the above-mentioned insulating organic solvent from the beginning as the non-aqueous solvent used at the time of polymerization granulation of the non-aqueous dispersion resin particles, but after granulating with a solvent other than these solvents, the dispersion medium is replaced. Can also be prepared.

As another method for synthesizing the non-aqueous latex, a polymer component soluble in a non-aqueous solvent having an electric resistance of 10 ⁸ Ω · cm or more and a dielectric constant of 3.5 or less and an insoluble substance in this solvent are used. The block copolymer composed of the following polymer component can be wet-dispersed in this solvent to be provided as fine resin particles. That is, a block copolymer consisting of a soluble polymer component and an insoluble polymer component is polymerized in advance in an organic solvent in which the block copolymer is dissolved by using the block polymer synthesis method described above, and then electrocoating. This is a method of dispersing in a non-aqueous solvent.

As described above, in order to electrophoretically disperse the dispersed particles in the dispersion medium, the resin particles (AR) are positively-charged or negatively-charged detectable particles, and the resin particles (AR) are detected. The technology of imparting electrical conductivity can be achieved by appropriately utilizing the technology of the developer for wet electrostatic photography. Specifically, "Recent Development and Practical Use of Electrophotographic Development System and Toner Material" pp. 139-148, "Basics and Applications of Electrophotographic Technology" edited by The Institute of Electrophotography, pp. 497-505, Lonasha, 1988 ), Yuji Harasaki, “Electrophotography” 16 (No. 2), page 44 (1977), etc., and the use of the electrophotographic material and other additives. Further, for example, British Patents 893,429 and 934,038, US Patents 1,122,397 and 3,900,412.
No. 4,606,989, JP-A-60-17975.
No. 1, 60-185963, JP-A-2-13965.
What is described in the No. etc. is used.

The composition of the non-aqueous resin particle dispersion (latex) to be subjected to electrodeposition is usually 0.1 to 30 g of particles mainly containing a thermoplastic resin in at least 1 liter of an electrically insulating dispersion medium, Dispersion stabilizing resin is 0.0
1 to 100 g, and the charge control agent to be added as needed is 0.1 g.
The range is from 0001 to 10 g.

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, when the electric resistance is lower than 10 ⁸ Ωcm, it becomes difficult to obtain a sufficient amount of the thermoplastic resin particles, and the amount of each additive is controlled within this limit.

The thermoplastic resin particles which have been microparticulated and imparted with a charge and dispersed in the electrically insulating liquid in this manner behave like an electrophotographic wet developer. Therefore, for example, it is possible to perform electrophoresis on the surface of an object to be coated by using a developing device, for example, a slip developing electrode device described in "Basics and Applications of Electrophotographic Technology" on pages 275 to 285. That is, the particles (AR) mainly containing the thermoplastic resin (A) are supplied between the counter electrodes placed facing the object to be coated, and electrophoresed according to a potential gradient applied from an external power source. A film is formed by electrodeposition on the coated object.

Generally, when the particles are positively charged, a voltage is applied between the object to be coated and the developing electrode of the developing device from an external power source so that the object to be coated has a negative potential. Is electrostatically electrodeposited on the surface. When the object to be coated is an electrophotographic photoreceptor, it can be electrodeposited by wet toner development by a usual electrophotographic process.
That is, as shown on the premise "Basics and Applications of Electrophotographic Technology" on pages 46 to 79, so-called burn-off is performed in which the photosensitive member is uniformly charged and then is not exposed or is exposed only to unnecessary areas, Wet toner development may be performed.

On the other hand, a preferable medium used when resin particles dispersed in a medium which is liquefied by heating is solid at room temperature and has a heating temperature of 30 to 80 ° C., preferably 4
It is an electrically insulating organic compound that becomes a liquid at 0 to 70 ° C. Suitable compounds include paraffins and waxes having a freezing point of 30 to 80 ° C., low molecular weight polypropylene having a freezing point of 20 to 80 ° C., beef tallow having a freezing point of 20 to 50 ° C., and a freezing point of 30.
Hardened oils at -80 ° C and the like can be used, and 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, the resin particles used in this pseudo-wet method are so-called core-shaped particles in which 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. By using shell-type particles (a resin with a low Tg in the core part and a resin with a high Tg in the shell part), it is possible to maintain a stable dispersed state without the fused resin particles being fused by heating. Becomes

The amount of the thermoplastic resin particles deposited on the article to be coated can be arbitrarily adjusted by the applied voltage of the external bias, the charging potential of the article to be coated, the processing time, and the like. After electrodeposition, the treatment liquid is wiped off by a squeeze using a known rubber roller, gap roller, reverse roller or the like. Moreover, methods such as corona squeeze and air squeeze are also used. Further, it is dried with cold air or hot air, or with an infrared lamp or the like to form thermoplastic resin particles into a film to form a transfer layer. The wet electrodeposition method is particularly preferable because the apparatus can be simplified and a uniform thin film can be formed stably and easily.

Next, the formation of the transfer layer by the transfer method will be described. The transfer method is a method in which a transfer layer is previously formed on a peelable support represented by a release paper by an ordinary method, and then the transfer layer is transferred from the peelable support onto an object to be coated. The releasable support (release paper) on which the transfer layer is formed is usually roll-shaped or sheet-shaped and can be easily supplied to the electrophotographic apparatus. Any conventionally known release paper can be used for this method. For example, "new technology of adhesive (adhesive) and its use / development materials of various applied products" (published by Management Development Center Publishing Department) , May 20, 1978), "Encyclopedia of All Paper Guide Paper", Volume 1, Culture Industry Edition (Published;
Examples include those described in papers such as Paper Industry Times Co., Ltd., December 1, 1983). Specifically, release paper is made by applying a release agent mainly composed of silicone to unbleached Clupak paper laminated with polyethylene resin, high-grade paper precoated with solvent-resistant resin, kraft paper, or undercoat. It is a PET base that has been subjected to the above, or one that is directly applied to glassine paper. Generally, a solvent type silicone is used, and the silicone is applied onto the above substrate at a concentration of 3 to 7% with a gravure roll, a reverse roll, a wire bar, or the like.
After drying, it is heat-treated and cured at 150 ° C. or higher. The application 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.)
And NK High Release (manufactured by Nippon Kaishi Paper Co., Ltd.). To form a transfer layer on a release paper, it is easy to form a transfer layer composition containing a thermoplastic resin (A) as a main component by bar coating, spin coating, spray coating, etc. according to a conventional method to form a film. To be done. Furthermore, hot melt coating and electrodeposition coating are also used.

In order to thermally transfer the transfer layer on the release paper onto the article to be coated, a usual thermal transfer method can be used. That is, the release paper holding the transfer layer may be pressure-bonded to the object to be coated to thermally transfer the transfer layer. The conditions for transferring the transfer layer from the release paper onto the coated object are preferably as follows. The nip pressure of the roller is preferably 0.1 to 10 kgf / cm ² , more preferably 0.2 to 8 kgf / cm ² , and the temperature during transfer is preferably 25 to 100 ° C., more preferably 40 ° C. to 80 ° C. Is. The transport speed is preferably 0.5 to 200 mm / sec,
More preferably, it is 10 to 150 mm / sec.

The transfer layer (T ₀ ) is formed on the electrophotographic photosensitive member whose surface has been modified to be peelable, prior to the step of forming a toner image by the electrophotographic process. When the releasability of the surface of the photoconductor is insufficient, the releasable photoconductor can be obtained by applying the compound (S) to the surface of the photoconductor as described above. In the present invention, when the transfer layer (T ₀ ) is formed by an electrodeposition coating method, the compound (S ′) exhibiting releasability is coexisted in the dispersion liquid containing the resin particles (AR) used. can do. That is, the surface of the photoconductor exhibits releasability by electrocoating a conventionally known electrophotographic photoconductor with the electrocoating dispersion containing the compound (S ′).

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 form a transfer layer (T ₀ ) which can be separated. The compound (S ') contained in the electrodeposition dispersion liquid for forming the transfer layer (T ₀ ) is adsorbed on the photoreceptor before the dispersed resin particles (AR) are electrophoresed and electrodeposited on the photoreceptor surface. Alternatively, since it adheres, it results in a photoreceptor having releasability before the formation of the transfer layer (T ₀ ).

The compound (S ') may be the same 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 in resistance, decrease in viscosity). It is added to the extent that it does not increase). It is preferably about 0.05 g / liter to 20 g / liter.

After the transfer layer (T ₀ ) is provided on the electrophotographic photosensitive member, a toner image is formed on the transfer layer (T ₀ ), and the transfer layer (T) for each transfer layer (T ₀ ) of the toner image is formed. The transfer is carried out to the material to be transferred, but these steps are substantially the same as those described above. However, since the transfer is performed for each transfer layer (T ₀ ), the conditions for the transfer step to the transfer target material are set by the photoconductor (that is, the photoconductive layer and the support) used by the transfer layer (T
₀ ), the transfer layer (T) and the physical properties of the material to be transferred are naturally optimized. In particular, the preheating, roller heating, and cooling conditions in the thermal transfer step are preferably determined in consideration of factors such as the glass transition point of each transfer layer, the softening temperature, the fluidity, the tackiness, the film property, and the film thickness. That is, the transfer layer softened to some extent by the preheating means passes under the heating roller to increase the tackiness, and the toner image and the transfer layer (T ₀ ) are sufficiently adhered to the transfer layer (T) on the transfer material.

Then, after passing under the cooling roller,
Conditions should be set so that the transfer layer (T ₀ ) is peeled off from the surface of the photoconductor as it is a film by lowering the temperature, reducing the fluidity and the tackiness. Further, by stopping the electrophotographic apparatus with the transfer layer (T ₀ ) formed, the electrophotographic process can be started immediately when the next apparatus is in operation, and the transfer layer (T ₀ ) protects the surface of the photosensitive layer. It is possible to prevent characteristic deterioration due to the influence of the physical environment.

Specific embodiments of the electrophotographic color image forming method of the present invention and the apparatus used therefor will be described below with reference to the drawings. FIG. 3 is a schematic view of the entire method and apparatus of the present invention, which has a transfer layer (T) forming means, a transfer layer (T ₀ ) forming means, and a compound (S) applying means and uses a wet development method as a developing method. Is shown. The transfer layer (T) forming means 21, the transfer layer (T ₀ ) forming means 22 and the compound (S) applying means 10 can be appropriately omitted.

On the liquid developing unit set 14, the electrophotographic photosensitive member 11 drum and the transferred material 16 are arranged. It is preferable that temperature adjusting means is provided in each of the drum, the transfer backup roller 17b, and the peeling backup roller 17c. When the toner image is formed by the electrophotographic process, the transfer material 16 is separated from the photosensitive drum as shown in the figure.

As described above, when the electrophotographic photosensitive member 11 whose surface is previously modified to be peelable is used, a toner image is directly formed on the photosensitive member 11 by an electrophotographic process. When the releasability of the surface of the photoconductor 11 is insufficient, the desired releasability can be imparted to the surface of the photoconductor 11 by applying the compound (S) before forming the toner image. That is, the compound (S) is supplied to the surface of the photoconductor 11 by the compound (S) applying means 10 using the above-described embodiment. The compound (S) applying means 10 may be either a fixed type or a movable type. When the transfer layer (T ₀ ) is provided on the electrophotographic photosensitive member 11, the transfer layer (T ₀ ) is formed by the transfer layer (T ₀ ) forming means 22 prior to the formation of the toner image.
₀ ) to form.

The liquid developing unit set 14 is movable. The unit set 14 includes liquid developing units 14Y, 14M, 14C and 14B containing liquid developers of yellow, magenta, cyan and black, respectively. Further, if necessary, a pre-bath, rinsing, and squeezing means may be provided in order to prevent the non-image portion from being stained. It is generally preferable to use a carrier liquid of a liquid developer for the prebath and the rinsing liquid.

First, the electrophotographic process will be described. After the photoconductor 11 is uniformly charged positively by the corona charging device 18, for example, an image is first exposed by the exposure device (for example, a semiconductor laser) 19 based on the image information of yellow, the potential of the exposed part is reduced, and the unexposed part is exposed. A potential contrast is obtained during the period. 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 set 14 and the gap is set to 1
mm and 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 rinsing means built in the developing unit set, and subsequently, the rinsing solution adhering to the surface of the photosensitive member is removed by the squeeze means, and then it is passed under the intake / exhaust unit 15 to be dried. The above steps are repeated for magenta, cyan, and black to form a color toner image on the photoconductor 11. Next, if necessary, preheating means 17a for thermal transfer performs a predetermined preheating, and then a heat generating body having a temperature control means is built in via a transfer material 16 coated with a transfer layer (T) on the surface. The rubber roller 17b is pressed and further passed under the cooling roller 17c to be cooled, and the toner on the surface of the photoconductor is thermally transferred to the transfer material 16 having the transfer layer (T), and a series of steps is completed. The transfer layer (T) can be formed on the surface of the material to be transferred in the electrophotographic apparatus in the manner as described above.

FIG. 4 shows a general outline of the method and apparatus of the present invention when the electrodeposition coating method is used to form the transfer layer (T ₀ ). The electrodeposition units 13a and 13b are used as the transfer layer (T ₀ ) forming means, and the liquid developing unit set 14 is used.
Equipped inside. Furthermore, the rinse unit 14R is also equipped. The thermoplastic resin particles (A
R) is charged to form a thermoplastic resin particle dispersion liquid 12a, which is put into the electrodeposition unit 13a, and the liquid developing unit set 14 is brought close to the photoconductor 11, and the distance from the developing electrode of the electrodeposition unit 13a is increased. Is fixed to be 1 mm. The particle dispersion is supplied from the electrodeposition unit 13a between the gaps and rotated while applying a voltage from the outside, so that the particles are adsorbed on the entire surface of the photoconductor 11. If necessary, the liquid is used to remove the particle dispersion adhering to the surface of the photoconductor 11 by a squeeze means incorporated in the developing unit set, and then the resin particles are thermally melted by a heating means to form a transfer layer ( T ₀ ) 12 'is formed. Then, if necessary, from the outside of the photoconductor 11 or the inside of the drum of the photoconductor 11 with a cooling device similar to the intake and exhaust unit,
Cool to the desired temperature. Liquid developing unit set 14
Is moved to the standby position, and the step of forming the transfer layer (T ₀ ) 12 'is completed. At this time, the suction and exhaust unit 15 provided for the electrophotographic process of the electrophotographic photosensitive member can be used to exhaust the dispersion solvent of the dispersion. It is preferable to use an ordinary carrier of a liquid developer for the rinsing liquid. The electrodeposition unit 13a may be installed in the liquid developing unit set 14 as shown in FIG. 4, or may be installed separately from the developing unit set.

Further, as shown in FIG. 4, the electrodeposition unit 13b
May be provided and a thermoplastic resin particle dispersion liquid 12b different from the thermoplastic resin particle dispersion liquid 12a may be supplied for forming the transfer layer (T ₀ ). FIG. 5 is a schematic diagram of an apparatus in the case of using the hot melt coating method for forming the transfer layer (T ₀ ). The thermoplastic resin 12c is applied to the surface of the photoconductor 11 on the peripheral surface of the drum by the hot melt coater 13c.
It is cooled to a predetermined temperature by passing under 5.
After the hot melt coater 13c has moved to the standby position, the liquid developing unit set 14 is moved to that position to enter the electrophotographic process. The subsequent steps are substantially the same as those described with reference to FIG.

The transfer layer (T
_As an apparatus for easily producing ( ₀ ) on the photoconductor, for example, the one shown in the schematic view of FIG. That is, the release paper 20 provided with the transfer layer (T ₀ ) 12 ′ is attached to the heating roller 1
The transfer layer (T ₀ ) 12 ′ is transferred onto the surface of the photoreceptor 11 by thermocompression bonding at 17 b. The release paper 20 is cooled by the cooling roller 117c and collected. If necessary, the photoconductor 11 itself is heated by the preheating means 17a to transfer the transfer layer (T ₀ ).
Transferability may be improved by thermocompression bonding of 12 '.

The apparatus shown in FIG. 6 has basically the same structure as the apparatus using the hot melt coating method (FIG. 5) except for the transfer layer (T ₀ ) forming apparatus 117. The transfer layer (T ₀ ) forming device 117, as shown in FIG.
After the transfer layer 12 ′ is transferred onto the photoconductor 11 by 0, it is replaced with the transfer means 17 for transferring the transfer material 16. In this way, the means 117 for transferring the transfer layer 12 ′ onto the photoreceptor 11 by the release paper 20 and the transfer layer 1 together with the toner image.
Both of the means 17 for transferring 2'to the material 16 to be transferred may be incorporated in the apparatus. Alternatively, the transfer layer 12 ′ is removed from the release paper 20 by the transfer layer (T ₀ ) forming device 117.
1 and then the transfer material 16 is supplied using the same means in place of the release paper to form the toner image and the transfer layer 1.
2'may be transferred to the transfer material.

[0160]

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

[Production Example of Resin Particles for Transfer Layer] Production Example 1: Resin Particles (AR) 1: (AR-1) 10 g of dispersion stabilizing resin (Q-1) having the following structure, 70 g of vinyl acetate, 30 g of vinyl propionate. And Isopar H
While stirring 384 g of the mixed solution under a nitrogen stream, the temperature was adjusted to 7
Warmed to 0 ° C. As a polymerization initiator, 2,2'-azobis (isovaleronitrile) (abbreviation AIVN) 0.
8 g was added and reacted for 3 hours. Twenty minutes after addition of the initiator, cloudiness occurred and the reaction temperature rose to 88 ° C. Furthermore,
After adding 0.5 g of an initiator and reacting for 2 hours, the temperature was raised to 10
The temperature was raised to 0 ° C. and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a degree of polymerization of 90% and an average particle size of 0.23 μm and having good monodispersity. Particle size is CAPA-
It was measured with 500 (manufactured by HORIBA, Ltd.) (the same applies hereinafter). A part of the white dispersion is centrifuged (rotation speed 1
The resin particles that had settled were collected and dried at x10 ⁴ rpm and a rotation time of 60 minutes. The resin particles had a weight average molecular weight (Mw: polystyrene equivalent GPC value; the same applies hereinafter) of 8 × 10 ⁴ and a glass transition point (Tg) of 28 ° C.

[0162]

[Chemical 12]

Production Example 2 of Resin Particles (AR): (AR-
2) A mixed solution of 20 g of a dispersion stabilizing resin (Q-2) having the following structure and 382 g of Isopar G was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. 30 g of methyl methacrylate, 70 g of ethyl acrylate, 0.6 g of methyl 3-mercaptopropionate, A. I. V. N 1.0
g and Isopar G (400 g) were added dropwise at a dropping time of 1 hour, and the reaction was continued for another 1 hour. Furthermore, A. I.
V. 0.8 g of N was added and reacted for 2 hours, then 2,2'-azobis (isobutyronitrile) (AIBN) was added and heated to a temperature of 80 ° C. for 2 hours, and A.N. I. B. N.
0.5g was added and reaction was performed for 2 hours. Then temperature 1
After heating to 00 ° C and distilling off unreacted monomer under a reduced pressure of 10 to 20 mmHg, cooling and passing through a 200 mesh nylon cloth, the obtained white dispersion has a polymerization rate of 98% and an average particle size of The latex had a good monodispersity of 0.17 μm. The resin particles had Mw of 8 × 10 ⁴ and Tg of 16 ° C.

[0164]

Embedded image

Production Example 3 of Resin Particles (AR): (AR-
3) 10 g of a dispersion stabilizing resin (Q-3) having the following structure, macromonomer (M-1) (macromonomer FM-0725 of dimethylsiloxane, manufactured by Chisso Corporation, Mw: 1 × 1)
A mixed solution of 10 g of O ⁴ ) and 533 g of Isopar H was heated to a temperature of 50 ° C. with stirring under a nitrogen stream. 50 g of methyl methacrylate, 50 g of methyl acrylate, 1.3 g of methyl 3-mercaptopropionate,
A mixture of 1.0 g of 2,2'-azobis (2-cyclopropylpropionitrile (abbreviation: A.C.P.P.)) and 400 g of Isopar H was added dropwise for 30 minutes, and the reaction was continued for another 1.5 hours. In addition, A.C.P.P.
0.8 g was added and the mixture was reacted for 2 hours. I. V. N
0.8 g was added and the temperature was set to 80 ° C. to react for 2 hours. C. P. P 0.5g was added and reaction was performed for 2 hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth had a polymerization rate of 99% and an average particle size of 0.19 μm.
Was a latex having good monodispersibility. M of resin particles
The w was 3 × 10 ⁴ and the Tg was 35 ° C.

[0166]

Embedded image

Production Examples 4-14 of Resin Particles (AR): (A
R-4) to (AR-14) In Production Example 2 of the resin particles (AR), the following Table-A was used instead of methyl methacrylate and ethyl acrylate.
Each resin particle (AR) was synthesized in the same manner as in Production Example 2 except that each of the monomers was used. Each white dispersion is
Polymerization rate 90-99%, average particle size 0.13-0.20 μm
Was a latex having good monodispersibility.

[0168]

[Table 1]

Production Examples 15-19 of Resin Particles (AR):
(AR-15) to (AR-19) In Production Example 3 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). Each resin particle was synthesized in the same manner as in Production Example 3, except that the resin particles were used in the range of 1 × 10 ⁴ ). The polymerization rate of each particle was 98 to 99%, the average particle size of the particles was in the range of 0.15 to 0.25 μm, the particle size distribution was narrow, and the monodispersity was good. Mw of the resin particles is in the range of 2 × 10 ^{4 to} 3.5 × 10 ⁴ , and Tg is 30 ° C. to 3
It was in the range of 5 ° C.

[0170]

[Table 2]

Synthesis Example of Resin Particles (ARW) 1: (ARW)
-1) 12 g of the following dispersion stabilizing resin (Q-4), vinyl acetate 7
A mixture of 0 g, vinyl butyrate 30 g and Isopar H 388 g was heated to a temperature of 80 ° C. while stirring under a nitrogen stream. To this, A. I. B. N. 1.5 g was added and 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. A part of the white dispersion was centrifuged (rotation speed 1 × 10 ⁴ rpm, rotation time 60 minutes),
The precipitated resin particles are collected and dried, and the resin particles M
When w and Tg were measured, Mw was 8 × 10 ⁴ , and Tg was 18 ° C. The resin particles obtained here are (ARL-
1).

This resin particle dispersion (that is, seed particles)
And a mixed solution of 10 g of a dispersion stabilizing resin (Q-5) having the following structure was heated to a temperature of 60 ° C. while stirring under a nitrogen stream.
To this, methyl methacrylate (60 g), methyl acrylate (40 g), methyl 3-mercaptopropionate 2.0
g, A. I. V. N. 0.8g and Isopar G 4
00 g of the mixture 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, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a degree of polymerization of 98% and an average particle size of 0.25 μm and having good monodispersity.

[0173]

Embedded image

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 (ARL-1) (Tg 18 ° C.) and the following resin particles (ARL-2) (Tg 45 ° C.) each composed of two kinds of resins (copolymers) constituting the particles of the present invention. ), And dispersed resin particles obtained by mixing these two types of resin particles in a 1/1 weight ratio.

Production of Resin Particles (ARL-2) 18 g of the dispersion stabilizing resin (Q-5) 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, 2.0 g of methyl 3-mercaptopropionate, A.I. C. P. P. A mixture of 1.0 g and 400 g of Isopar G was added dropwise at a dropping time of 30 minutes, and the reaction was continued for another 1.5 hours. Furthermore, A. C.
P. P. 0.8 g was added and reacted for 2 hours, and then the initiator A. I. V. N. 0.8 g was added and the temperature was set to 80 ° C. for 2 hours. C. P. P. Add 0.5g 2
A time reaction was performed. 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.

The sample consisting of the resin particles (ARL-1) had a temperature of 20 although the unheated sample was in a particle state.
No particle state was observed at 0 ° C, and the particles of the resin particles (ARL-2) became invisible at a temperature of 50 ° C. Further, when a sample composed of mixed particles was examined for a sample not heated and a sample at a temperature of 20 ° C., it was confirmed that the particles at a temperature of 20 ° C. were invisible in comparison with an unheated sample.

As described above, as a result of visual observation of the thermal behavior of the particles, 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.

Synthesis Examples 2-8 of Resin Particles (ARW): (A
RW-2) to (ARW-8) Resin particles obtained by operating in exactly the same manner as in Synthesis Example 1 except that the monomers shown in Table-C below were used in Synthesis Example 1 of resin particles (ARW). (ARW-2) to (ARW-8) were produced. The polymerization rate of each obtained latex particle is 95 to 99.
%, The average particle size was in the range of 0.20 to 0.30 μm, and the monodispersity was good.

[0179]

[Table 3]

Synthesis Example 9 of Resin Particles (ARW): (ARW)
-9) 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 10-14 of Resin Particles (ARW):
(ARW-10) to (ARW-14) Synthesis Example 9 except that each of the compounds in Table-D below was used in place of the two resins (A) used in Synthesis Example 9 of the resin particles (ARW). A dispersion was prepared by the same wet dispersion method. The obtained white dispersion has an average particle size of 0.3 to 0.6 μ.
It was in the range of m.

[0182]

[Table 4]

[Synthesis Example of Resin (P)] Synthesis Example 1: Resin (P) 1: (P-1) 80 g of methyl methacrylate, macromonomer (M-
1) A mixed solution of 20 g and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. A. I. B. N.
1.0 g was added and reacted for 4 hours. I. B. N.
0.7 g was added and reacted for 4 hours. The Mw of the obtained copolymer was 5.8 × 10 ⁴ .

[0184]

Embedded image

Synthesis Examples 2 to 9 of Resin (P): (P-2) to
(P-9) In Synthesis Example 1 of Resin (P), instead of methyl methacrylate and macromonomer (M-1), the following Table-E was used.
Other than using each monomer corresponding to the polymer component described in,
Each polymer was synthesized in the same manner as in Synthesis Example 1. The Mw of each polymer obtained was in the range of 4.5 × 10 ^{4 to} 6 × 10 ⁴ .

[0186]

[Table 5]

[0187]

[Table 6]

Synthesis Example 10 of Resin (P): (P-10) 60 g of 2,2,3,4,4,4-hexafluorobutyl methacrylate, macromonomer of methyl methacrylate (AA-6 Toa Gosei Kagaku Co., Ltd.) Made, Mw1 × 10 ⁴ )
A mixed solution of 40 g and 200 g of benzotrifluoride was heated to a temperature of 75 ° C. under a nitrogen stream. A. I. B.
N. 1.0 g was added and the reaction was carried out for 4 hours. I. B.
0.5 g of N was added and reacted for 4 hours. The Mw of the obtained copolymer was 6.5 × 10 ⁴ . Synthesis Examples 11 to 12 of Resin (P): (P-11), (P-
12) In place of the monomer and macromonomer used in Synthesis Example 10 of resin (P), each monomer and each macromonomer corresponding to the polymer component shown in Table F below was used, Each copolymer was synthesized in the same manner as in Synthesis Example 10.
Mw of the obtained copolymer was 4.5 × 10 ^{4 to} 6.5 × 1.
It was in the range of 0 ⁴ .

[0189]

[Table 7]

Synthesis example 13 of resin (P): (P-13) methyl methacrylate 67 g, methyl acrylate 22
A mixed solution of g, methacrylic acid 1 g and toluene 200 g was heated to a temperature of 80 ° C. under a nitrogen stream. To this, 10 g of a polymeric azobis initiator (PI-1) having the following structure was added and reacted for 8 hours. After the reaction was completed, the precipitate was reprecipitated in 1.5 liter of methanol, and the obtained precipitate was collected and dried to obtain a copolymer having an Mw of 3 × 10 ^{4 in} a yield of 75 g.

[0191]

Embedded image

Synthesis Example 14 of Resin (P): (P-14) A mixture of 50 g of ethyl methacrylate, 10 g of glycidyl methacrylate and 4.8 g of benzyl N, N-diethyldithiocarbamate was sealed in a container under a nitrogen stream,
The temperature was raised to 50 g. This was irradiated with light from a high-pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 6 hours for photopolymerization. This is 100 g of tetrahydrofuran
Was added to the above solution, 40 g of the following monomer (m-1) was added, the atmosphere was replaced with nitrogen, and light was again irradiated for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, collected, and dried. The obtained polymer had a yield of 73 g and an Mw of 4.8 × 10 ⁴ .

[0193]

Embedded image

Synthesis Examples 15 to 18 of Resin (P): (P-1
5) to (P-18) In the same manner as in Synthesis Example 14 of resin (P), each copolymer shown in Table G below was synthesized. Mw of the obtained polymer is 3.5 ×
It was in the range of 10 ^{4 to} 6 × 10 ⁴ .

[0195]

[Table 8]

Synthesis Example 19 of Resin (P): (P-19) In Synthesis Example 14 of Resin (P), 18 g of an initiator (I-1) having the following structure was used instead of benzyl N, N-diethyldithiocarbamate. Was synthesized in the same manner as in Synthesis Example 14 except that was used to obtain a copolymer having Mw of 4.5 × 10 ⁴ .

[0197]

Embedded image

Synthesis Example 20 of Resin (P): (P-20) 68 g of methyl methacrylate, 22 of methyl acrylate
g, 10 g of glycidyl methacrylate, 17.5 g of an initiator (I-2) having the structure below, and tetrahydrofuran 15
0 g of the mixed solution was heated to a temperature of 50 ° C. under a nitrogen stream.
This solution was irradiated with light from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 10 hours to perform photopolymerization.
The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to give a yield of 72 g and a Mw of 4.0 × 10.
A polymer of ⁴ was obtained.

70 g of this polymer, 30 g of monomer (m-2)
A mixed solution of g and tetrahydrofuran (100 g) was irradiated with light under a nitrogen stream at a temperature of 50 ° C. under the same conditions as above for 13 hours. Next, the reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried to obtain a yield of 78 g and a Mw of 6 g.
A copolymer of × 10 ⁴ was obtained.

[0200]

Embedded image

Synthesis Examples 21 to 25 of Resin (P): (P-2
1) to (P-25) In Synthesis Example 20 of Resin (P), Initiator (I-2) 1
Instead of 7.5 g, the initiator (I) of Table H below 0.0
It operated on the same conditions as the synthesis example 20 except having used 31 mol. The yield of each polymer obtained was 70 to 80 g and Mw4.
It was x10 ^{4 to} 6x10 ⁴ .

[0202]

[Table 9]

[0203]

[Table 10]

[Synthesis Example of Resin Particles (PL)] Synthesis Example 1: Resin Particles (PL) 1: (PL-1) 40 g of the monomer (LM-1) having the following structure, 2 g of ethylene glycol dimethacrylate, and the following structure Dispersion stabilizing resin (LP-1) 4.0 g and methyl ethyl ketone 180 g
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. In addition, A. I. V. N 0.1g was added and it reacted for 4 hours. After cooling, a 20 mesh nylon cloth was passed through to obtain a white dispersion. It was a latex having an average particle size of 0.25 μm.

[0205]

[Chemical 21]

Synthesis Example 2 of Resin Particles (PL): (PL-
2) Monofunctional macromonomer consisting of butyl acrylate unit as a dispersion stabilizing resin (AB-6 manufactured by Toagosei Co., Ltd.)
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.

[0207]

Embedded image

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 as in Synthesis Example 1 except that the compounds shown in Table I below were 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.

[0209]

[Table 11]

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 following structure, 3.6 g of the resin resin (B-2) having the following structure, 0.15 g of the compound (A) having the following structure, and 80 g of tetrahydrofuran were mixed with 500 ml of glass. Put it in a 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.

[0211]

Embedded image

Next, this dispersion was subjected to desorption treatment to 0.2 mm
It was applied on a thick aluminum plate with a wire bar, dried by touch, and heated in a circulating oven at 110 ° C. for 20 seconds. The thickness of the obtained photoreceptor was 8 μm. A releasable surface layer having the following contents was provided on this photoreceptor. Formation of releasable surface layer 10 g of silicone resin having the following structure, crosslinking agent 1 having the following structure
g, 0.2 g of a crosslinking control agent having the following structure, and 0.1 g of a crosslinking catalyst platinum in 100 g of n-hexane were applied to a film thickness of 1.5 μm using a wire round rod. After being touch-dried, it was further heated at 120 ° C. for 10 minutes. The adhesive strength of the obtained surface was 1 g · f or less.

[0213]

Embedded image

The electrophotographic photosensitive member having a peelable surface obtained as described above was mounted in an apparatus as shown in FIG. First, a toner image was formed on the photoreceptor by an electrophotographic process. That is, the photoreceptor 11 is placed in the dark and the corona charging device 1 is used.
After passing under 8 and corona charging to + 450V, read the original with a color scanner, color-separate it, and add some corrections related to system-specific color reproduction. Based on the information about yellow among the colors of yellow, magenta, cyan, and black stored in the hard disk, using a semiconductor laser drawing device as the exposure device 19, the exposure amount on the photoconductor with light of 788 nm. Is 30
It was exposed to erg / cm ² . Next, add 75% positively charged yellow toner for the signature system (manufactured by Kodak).
It is diluted twice with Isopar H (made by Esso Standard Petroleum) and supplied to the yellow liquid developing unit 14Y, and a bias voltage of + 350V is applied to the developing unit 14Y side.
The exposed portion is subjected to reversal development so that the toner is electrodeposited, and then a bath of Isopar H alone is rinsed to remove stains on the non-image portion, and then it is passed through the intake / exhaust unit 15 and the preheating means 17a and dried. did. The above toner developing process was repeated for each of the colors magenta, cyan, and black to obtain four color toner images. On the other hand, plain paper as a material to be transferred was loaded on a drum, and a transfer layer (T) was formed by an electrodeposition coating method using a dispersion liquid (L-1) of a resin (A) having the following content.

Dispersion liquid (L-1) of resin (A) Resin particles (AR-4) 20 g (as solid content) Charge adjusting compound (D-1) 0.08 g Octadecyl vinyl ether / t-octyl maleic acid half amide ( (1/1 molar ratio) Copolymer Charge control auxiliary agent (AD-1) 2 g Dodecyl methacrylate / methacrylic acid (95/5 weight ratio) copolymer was adjusted with Isopar G so that the total amount was 1 liter.

The surface temperature of the material to be transferred is set to 60 ° C. by an infrared line heater, and the peripheral speed of the drum of the material to be transferred is set to 10
While rotating at 0 mm / sec, while supplying the dispersion liquid to the surface of the transferred material using a slit electrodeposition device, the transferred material side is grounded and a voltage of 130 V is applied to the electrode side of the slit electrodeposition device to form resin particles. Was electrodeposited. Then, while removing the dispersion by air squeeze using an intake / exhaust unit, the resin particles were melted and formed into a film to form a transfer layer (T) made of a thermoplastic resin. At this time, the film thickness was 1.5 μm. Next, the surface temperature 7
Between the photoconductor drum provided with the toner image of 0 ° C., the transfer backup roller 17 b set at 120 ° C. and the peeling backup roller 17 c not adjusted in temperature, the transfer layer (T ) Is provided, the nip pressure is 5 kgf / cm ² , and the drum peripheral speed is 1
Heating and pressurization were performed at a rate of 00 mm / sec. The color toner images were all transferred onto plain paper to obtain a multicolor image. The copy image thus formed on the plain paper is
It was visually observed using an optical microscope with a magnification of 00. No background stains on the non-image area are observed, and the toner image is all transferred onto plain paper, and the high resolution areas such as fine lines and characters are missing / disturbed and the halftone dots in the high-definition image area are missing. -No turbulence was observed and it was a very good copy image. No transfer residue of the toner image was observed on the surface of the photoreceptor.

On the other hand, a color image was formed on plain paper in the same manner except that the toner image was transferred on plain paper without providing the transfer layer (T), and the result was compared with the present invention. In the obtained color image on the plain paper, a part where the toner image was missing or the image density was uneven was found. Further, when fine lines, fine characters, and the like were visually observed with a magnifying glass of 20 times, fine image loss was recognized. Further, when the surface of the photoconductor was observed, residual toner image was observed. This means that when the photoconductor is repeatedly used, it is necessary to clean the surface of the photoconductor in order to remove the residual toner, and setting of an apparatus for that purpose or damage to the surface of the photoconductor due to the cleaning becomes a problem. .

On the other hand, in the present invention, the toner image is sufficiently peeled from the photosensitive member, the above problems do not occur, and the toner image is sufficiently adhered to the transfer layer, so that a color copy obtained. The stability of the product is also excellent. In addition, there was no problem in that the writing property of the copy by a pencil or a ballpoint pen, the sealability, and the filing property of a film file such as a vinyl chloride sheet were almost the same as those of plain paper, and did not cause any problem. Further, in place of plain paper as the material to be transferred, coated paper, high-quality paper, copy paper for PPC, recycled paper, and PET film were used to similarly create a color image,
All showed exactly the same performance as in Example 1. In this way, even if the transferred material with different surface smoothness and composition is used,
In all cases, stable and good color copies could be easily obtained.

Example 2 The X-type metal-free phthalocyanine photoconductor provided with the releasable surface layer used in Example 1 was mounted in a device as shown in FIG. A transfer layer (T ₀ ) was formed on this photosensitive drum by the electrodeposition coating method under the following conditions. The surface temperature of the photoconductor is 50 ℃
Then, the peripheral speed of the photosensitive drum is rotated at 100 mm / sec, and while supplying the dispersion liquid (L-2) of the resin (A) having the following content to the surface of the photosensitive member using the slit electrodeposition device, Was grounded, and a voltage of 150 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit and fix the resin particles to form a first transfer layer (T ₀ ) having a film thickness of 2 μm. Resin (A) dispersion liquid (L-2) Resin particles (AR-8) 10 g (as solid content) Resin particles (AR-14) 10 g (as solid content) Charge adjusting compound (D-2) 0.08 g

[0220]

Embedded image

Branched tetradecyl alcohol: 10 g of FOC-1400 (manufactured by Nissan Chemical Industries, Ltd.) was adjusted with Isopar G so that the total amount became 1 liter. In the same manner as in Example 1, a color image was formed on this photoconductor by an electrophotographic process. Next, between the photosensitive drum provided with the toner image having a surface temperature of 50 ° C., the transfer backup roller 17b set at 80 ° C. and the peeling backup roller 17c set at 20 ° C., as a transfer target material, As the resin (A), a resin (A-
Guide the OHP film coated with 1) in a thickness of 1 μm, nip pressure 4 kgf / cm ² , drum peripheral speed 100 m.
Heating / pressurizing was performed at m / sec. Color toner image is O
All were transferred onto a HP film to obtain a multicolor image.

[0222]

[Chemical formula 26]

The copied image thus formed on the OHP film was visually observed using a 200 × optical microscope. No scumming of the toner in the non-image area is observed, and the toner image and transfer layer are all transferred onto the film, so high-definition image areas in high-definition areas such as thin lines and fine characters lacking or disturbing the high-resolution area No missing or disorder of halftone dots was observed and it was a very good copy image. In addition, the ability to write on a copy with a pencil, a ballpoint pen, etc., the imprintability, and the filing property on a file made of a film such as a vinyl chloride sheet were almost the same as those of coated paper and did not cause any problems.

Example 3 Amorphous silicon photoconductor (manufactured by Kyocera Corp.) as an electrophotographic photoconductor (adhesive force of the photoconductor surface is 230 g · f)
Was loaded into a device as shown in FIG. The release property was imparted to the photoconductor by immersing it in a solution in which the compound (S) of the present invention was dissolved in the same device (immersion method). That is, the photoreceptor was rotated at a peripheral speed of 10 mm / sec in a bath containing a solution prepared by dissolving 1.0 g of the following compound (S-1) in 1 liter of Isopar G (manufactured by Esso Corporation). It was treated by touching for 2 seconds and dried by air squeeze.
When the adhesive strength of the surface of the photoconductor thus obtained was measured, it was found to be 3 g · f, indicating good peelability.

[0225]

Embedded image

Then, in the same manner as in Example 2, a dispersion layer (L-3) of resin (A) having the following contents was used to apply a voltage of 110 V to form a transfer layer (T ₀ ) having a film thickness of 1 μm. It was Dispersion (L-3) of resin (A) Resin particles (ARW-1) 20 g (as solid content) Charge adjusting compound (D-2) 0.08 g Branched tetradecyl alcohol FOC1400 10 g makes the total amount 1 liter. Was adjusted with Isopar G. After the photoconductor 11 was corona-charged to +700 V, the same digital image data as in Example 1 was used. First, based on the information about yellow, a semiconductor laser was used.
It was exposed to light of 80 nm so that the surface exposure amount was 25 erg / cm ² . The residual potential of the exposed part was + 120V. Next, the yellow toner for Versatec 3000 (Xerox color electrostatic plotter) is 50 times Isopar H.
Diluted with (Esso Standard Petroleum), applied a bias voltage of +300 V to the developing electrode, and performed reversal development so that the toner was electrodeposited on the exposed area, and then rinsed in a bath of Isopar H alone. The stain on the non-image area was removed. The above toner developing process was repeated for each of the colors magenta, cyan, and black. On the other hand, the transfer layer (T) was formed on the plain paper, which is the material to be transferred, by the hot melt coating method as follows. That is, a saturated polyester resin (Chemit R-185 Toray Co., Ltd.) is used as the thermoplastic resin for the transfer layer.
Was applied to the surface of the material to be transferred at a speed of 50 mm / sec by a hot melt coater, and the surface temperature was kept at 50 ° C. after cooling by blowing cooling air from. The thickness of the transfer layer (T) at this time was 1.5 μm.

Next, between the photosensitive drum provided with the toner image and the transfer rubber roller whose surface temperature is set at 120 ° C., the plain paper is nipped at a pressure of 4 kgf / cm ² and a conveying speed of 1
It was passed at a rate of 00 mm / sec, the plain paper after passing was peeled off from the photoconductor, and the toner image was transferred onto the plain paper together with the transfer layer. A copy image formed on plain paper in this way is
It was visually observed using a 0 × optical microscope. No background stain on the non-image area was observed. In addition, the toner image and the transfer layer are all transferred onto plain paper without being left untransferred on the photoconductor, and the high resolution image area in the halftone area is missing or disturbed in the high resolution area such as fine lines and fine characters. No missing or irregular dots were found, and the image was very good as a copied image.

Example 4 A color copy was prepared in the same manner as in Example 3 except that the transfer method from release paper according to the following contents was used instead of the transfer layer formation by the hot melt coating method. Obtained. That is, separate paper (manufactured by Oji Paper Co., Ltd.) was used as the release paper, and polyvinyl acetate and methyl methacrylate / methyl acrylate (6/4 weight ratio) copolymer 5
/ 5 weight ratio paper with a coating film of 3 μm thickness is pressed against the OHP film, and the pressure between rollers is 3 kgf / c.
Transfer layer (T) on the OHP film, which is the material to be transferred, under the conditions of m ² , surface temperature of 80 ° C, and passing speed of 50 mm / sec.
Was transferred and formed. The obtained color image on the OHP film was a good image without fog similarly to Example 3, and the image intensity was sufficient. Further, the writing property and the marking property were also good.

Examples 5 to 20 In Example 1, instead of the resin particles (AR-4) in the dispersion liquid (L-1) of the resin (A), each resin particle (AR) and / or each of the following Table-J was used. A color image was formed in the same manner as in Example 1 except that (ARW) (total amount of 20 g) was used.

[0230]

[Table 12]

The color copy thus obtained had a clear image quality without background stains. In other words, the toner image formed on the photoconductor has good image reproducibility and good image pick-up with no fog in the non-image area, and the transfer to plain paper does not cause uneven transfer. Made in. Furthermore, the obtained copy paper could be added or imprinted in the same manner as on plain paper.

Examples 21 to 28 In the same manner as in Example 2 except that each resin shown in Table K below was used in place of the resin (A-1) used for forming the transfer layer (T). When a transfer image forming operation was performed by using the above, the same results as in Example 2 were obtained.

[0233]

[Table 13]

Examples 29 to 33 In Example 4, a release paper (manufactured by Sunrelease Sanyo Kokusaku Pulp Co., Ltd.) was used instead of the separate paper provided with the transfer layer.
A color image was prepared in the same manner as in Example 4 except that the transfer layer having the film thickness of 1.0 μm and comprising the resin (A) shown in Table L below was provided.

[0235]

[Table 14]

The obtained color image was a clear image without background fog, and almost no deterioration of the image was recognized as compared with the original. Example 34 As an organic photoconductive substance, 5 g of 4,4′-bis (diethylamino) -2,2′-dimethyltriphenylmethane,
4 g of binder resin (B-3) having the following structure, resin (P-3)
0.6 g, 40 mg of the dye (D-1) having the following structural formula, and 0.2 g of the anilide compound (C) having the following structural formula as a chemical sensitizer.
30 ml of methylene chloride and 3 of ethylene chloride
It was dissolved in a mixture with 0 ml to obtain a photosensitive layer dispersion liquid.

[0237]

Embedded image

This photosensitive layer dispersion was applied onto a conductive transparent support (a polyethylene terephthalate support having a thickness of 100 μm and a vapor deposition film of indium oxide, a surface resistance of 10 ³ Ω) using a wire round rod. Then about 4
An organic thin film having a photosensitive layer with a thickness of μm was obtained. The adhesive force on the surface of the photoconductor was 4 g · f. A copied image was formed in the same manner as in Example 1 except that this photosensitive member was used instead of the photosensitive member used in Example 1. The color copy image of the obtained plain paper was clear without any fog and the image strength was good.

Examples 35 to 42 5 g of bisazo pigment having the following structure, and tetrahydrofuran 95
and 5 g of polyester resin (Vylon 200 Toyobo Co., Ltd.) were sufficiently pulverized in a ball mill. Next, this mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was applied onto the conductive transparent support used in Example 34 using a wire round rod to form a charge generation layer having a thickness of about 0.7 μm.

[0240]

[Chemical 29]

Next, the hydrazone compound 20 of the following structural formula
g, 20 g of a 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 to a temperature of 100.
The film was heated at 20 ° 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.

[0242]

Embedded image

Further, in order to form a surface layer for imparting releasability on this photosensitive layer, resin (P) and resin particles (PL) shown in Table M below, 0.2 g of phthalic anhydride,
0.002 g of o-chlorophenol and 100 of toluene
1 g of mixed solution of g using wire round rod
It was coated so as to have a thickness of μm, dried by touch with a finger, and further heated at 120 ° C. for 1 hour. The surface of the obtained photoreceptor has an adhesive force of 2 g · f
Met. This photosensitive material was charged to a surface potential of -500 V in a dark place, and then exposed to light of 633 nm using a He-Ne laser so that the exposure amount on the surface was 30 erg / cm ² . Thereafter, the same operation as in Example 1 was performed to form a color toner image on the photoconductor. The obtained copy showed good performance as in Example 1.

[0244]

[Table 15]

Example 43 100 g of photoconductive zinc oxide, a binder resin (B-
4) 25 g, binder resin (B-5) 5 g having the following structure, resin (P-6) 3 g, dye (D-2) 0.01 having the following structure
A mixture of g, 0.1 g of salicylic acid and 150 g of toluene was dispersed for 15 minutes at a rotation speed of 1 × 10 ² rpm using a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain a photosensitive layer dispersion liquid.

[0246]

[Chemical 31]

Next, this dispersion is applied to an ELP-II type light-sensitive material used in an ELP-system.
After applying it to the support for the wire with a wire bar and touch-drying it, 1
Heated for 20 seconds in a 10 ° C circulating oven. 30 more
The plate was left to stand in the dark for 1 week under the conditions of ° C and 80% RH. The adhesive force on the surface of the photoconductor was 2 g · f. A transfer layer (T ₀ ) having a film thickness of 1.5 μm was formed on the photoconductor by the same method as in Example 2 using the following dispersion liquid (L-4) of resin (A). Dispersion (L-4) of resin (A) Resin particles (ARW-3) 16 g (as solid content) Resin particles (AR-9) 4 g (as solid content) Charge adjusting compound (D-3) 0.07 g

[0248]

Embedded image

8 g of branched hexadecyl alcohol (manufactured by FOC-1600 Nissan Kagaku Co., Ltd.) was adjusted with Isopar G so that the content was 1 liter. Next, this photoreceptor was corona-charged to -600 V in a dark place, and the same digital image data as in Example 1 was used. 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. Then, the yellow toner for Versatec 3000 (color electrostatic plotter made by Xerox) was diluted with 50 times Isopar G (made by Esso Standard Petroleum) and used.
A positive voltage of 200 V was applied to the developing electrode to perform positive development so that the toner was electrodeposited on the unexposed area, and then rinsed in a bath of Isopar H alone to remove stains on the non-image area. The above toner developing process was repeated for each of the colors magenta, cyan, and black. The surface temperature of the photoconductor was adjusted to 50 ° C., and fine wood paper coated with an ethyl methacrylate / methyl acrylate (8/2 weight ratio) copolymer as a resin (A) was weighed and weighed 4 kgf / cm ² The surface temperature was kept under control at 100 ° C. under the heating rubber roller which was constantly controlled to pass at a speed of 100 mm / sec. After that, the fine paper was peeled off by passing under a cooling roller, and the toner image was completely transferred onto the fine paper. The image strength was sufficient, and writing or marking on the copy paper could be performed in the same manner as for plain paper.

Examples 44 to 53 A mixture of 3.5 g of X-type metal-free phthalocyanine, 10 g of a binder resin (B-7) having the following structure and 80 g of tetrahydrofuran was put in a 500 ml glass container together with glass beads, and a paint shaker (Toyo Seiki) was used. (Manufactured by Seisakusho Co., Ltd.) for 60 minutes, resin (P) or resin particles (PL) and a crosslinking compound shown in the following Table-N are added and dispersed for 10 minutes, and then the glass beads are filtered to obtain a photosensitive layer dispersion liquid. .

[0251]

[Chemical 33]

[0252]

[Table 16]

Then, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate with a wire bar and dried by touch with a finger, and then dried in a circulating oven at 110 ° C. for 30 seconds. It was dried and further heated at 140 ° C. for 1 hour. A transferred image was formed in the same manner as in Example 1 except that this photosensitive member was used instead of the photosensitive member used in Example 1. The color copied image obtained was clear without background fog and had good image strength.

Examples 54 to 59 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, the photoconductor is brought into contact with a solution prepared by dissolving the compound (S) shown in Table P below in 1 liter of Isopar G, and the peripheral speed is 30 mm / sec for 10 seconds. After the rotation, it was squeezed by a squeeze roll and then dried by a preheating means. As a result, the surface of the amorphous silicon photoconductor having a surface adhesive force of 203 g · f became an adhesive force of 3 to 20 g · f. Thereafter, in the same manner as in Example 3, a toner image was formed by an electrophotographic process and transferred to a transfer material. Each of the color images obtained was a color copy having the same clear image quality as that of Example 3 with no background fog, and the image intensity was also sufficient.

[0255]

[Table 17]

[0256]

[Table 18]

[0257]

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. Further, by using the compound (S), a general-purpose electrophotographic photoreceptor can be used.

[Brief description of drawings]

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

FIG. 2 is a schematic diagram for explaining another method of the present invention.

FIG. 3 is a schematic diagram showing the method and apparatus of the present invention.

FIG. 4 is a schematic diagram including a step of forming a transfer layer (T ₀ ) on an electrophotographic photosensitive member by an electrodeposition coating method.

FIG. 5 is a schematic view including a step of forming a transfer layer (T ₀ ) on a electrophotographic photosensitive member by a hot melt coating method.

FIG. 6 is a schematic diagram including a step of forming a transfer layer (T ₀ ) on an electrophotographic photosensitive member by a transfer method.

[Explanation of symbols]

1 Support 2 Photosensitive Layer 3 Toner Image 10 Compound (S) Application Means 11 Electrophotographic Photosensitive Member 12 Transfer Layer (T) 12 'Transfer Layer (T ₀ ) 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 means to transfer material 17a Preheating means 17b Transfer backup roller 17c Separation backup roller 18 Corona charging device 19 Electronic device 20 Release paper 21 Transfer layer (T) forming means 22 Transfer Layer (T ₀ ) Forming Means 117 Transfer Layer (T ₀ ) Forming Apparatus 117b Heating Roller 117c Cooling Roller

Claims (5)

[Claims] 1. After forming a toner image of one or more colors on an electrophotographic photosensitive member having a peelable surface by an electrophotographic process, the toner image on the photosensitive member has a glass transition point of 140 ° C. or lower or a softening point of 180 ° C. or lower. 6. An electrophotographic color image forming method, which comprises: transferring onto a transfer material having a transfer layer (T) mainly containing the thermoplastic resin (A). 2. In the color image forming method, a thermoplastic resin (A) is formed on an electrophotographic photoreceptor having a releasable surface before forming a toner image of one or more colors by an electrophotographic process.
The electrophotographic color image forming method according to claim 1, wherein a peelable transfer layer (T ₀ ) mainly containing is provided. 3. A resin (A) constituting the transfer layer (T ₀ ).
Has a glass transition point of 30 ° C to 140 ° C or a softening point of 35 ° C to 1
At least a resin (A ₀ H) at 80 ° C. and a resin (A ₀ L) having a glass transition point of 40 ° C. or lower or a softening point of 45 ° C. or lower, and the resin (A ₀ H) and the resin (A ₀ L) The electrophotographic color image forming method according to claim 2, wherein the difference in glass transition point or softening point is 2 ° C or more. 4. The resin (A) constituting the transfer layer (T) has a glass transition point or softening point lower by 2 ° C. or more than the resin (A) constituting the transfer layer (T ₀ ). The electrophotographic color image forming method according to claim 2. 5. The adhesive force according to JIS Z0237-1980 “adhesive tape / adhesive sheet test method” when the toner image is formed on the surface of the electrophotographic photosensitive member is 100 gram · force or less. Electrophotographic color image forming method.