JPH0996926A - Electrophotographic color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an image forming method whose transfer characteristic is excellent, which does not have color slurring, by which a high-definition and high-quality color image can be easily and stably obtained, and whose transferring characteristic toward a material to be transferred is more improved by forming a first and a second transfer layers of resin respectively having specified material. SOLUTION: A color copy material can be obtained by forming the first transfer layer 12, a toner image 3 and a second transfer layer 13 on the surface of an electrophotographic photoreceptor 11 whose surface tacky power is <=20(g) force, and suceedingly transferring the toner image 3 on the material 16 to be transferred together with the layers 12 and 13. The layer 12 is formed by electrodeposition coating method by using resin particles AR which are constituted of resin AH having image transition point of 30 deg. to 80 deg.C and softening point of 35 deg. to 90 deg.C, and resin AL1 having image transition point of -30 deg. to 40 deg.C or the softening point of 0 to 60 deg.C and in which the difference of the image transition point or the softening point between the resin AH and the resin AL1 is >=2 deg.C. Furthermore, the layer 13 is mainly constituted of the resin AL2 whose image transition point is <=35 deg.C or the softening point is <=45 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. In particular, the present invention relates to an electrophotographic color image forming method that stably and repeatedly forms a high-quality copy image without color shift and without deterioration of image quality due to transfer.

[0002]

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

In order to solve this problem, Japanese Patent Laid-Open No. 2-272
Japanese Patent 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. In addition, JP-A Nos. 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 is disclosed. However, in this case, the film to be laminated preferably has a thickness of 9 μm, but the production and handling of a film having such a thickness are extremely troublesome, and it is necessary to separately take measures for that purpose.

Further, 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.

Further, in European Patent Publication No. 534479A, a transfer layer is formed on the surface of a photoreceptor having release property, and then a toner image of one or more colors is formed on the transfer layer by an electrophotographic process. A method of transferring an image together with a transfer layer onto a transfer target material is disclosed. However, this method is not sufficiently satisfactory because the latitude of the conditions (heating temperature, pressure, conveyance speed, etc.) when transferring the toner image together with the transfer layer is narrow.

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 the toner image is formed on the transfer layer, so that the final transfer material and the toner image are transferred at the time of transfer. That is, the transfer layer must be peeled off after sufficiently adhering to each other, and the transfer layer is liable to be affected by the toner image portion or the surface condition of the final transfer target material, and the complete transfer of the toner image is not always performed. There's a problem.

[0009]

As described above, in the conventional color image forming method using the intermediate transfer medium, a sufficiently satisfactory color image cannot be obtained, and the properties of the intermediate medium change when repeatedly used. There are various problems such as difficulty in maintaining stable performance for a long period of time, generation of disposable members for maintaining performance, and necessity of using a special transfer medium. On the other hand, in the color image forming method in which the transfer layer is provided on the photoreceptor, there are still problems to be solved such as difficulty in obtaining a stable and high-definition image regardless of the type of toner and the type of final transfer material. Exists.

The present invention solves the problems of the above known electrophotographic color image forming methods. Therefore, an object of the present invention is to provide a toner image with excellent transferability, without color misregistration, to obtain a high-definition and high-quality color image easily and stably, and to separate and transfer the transfer layer from the photoreceptor. It is an object of the present invention to provide an electrophotographic color image forming method which has good adhesion to a transfer material and good writing properties, imprintability, and storability of a color copy. Another object of the present invention is that the transferability to a transfer material is further improved, the latitude of transfer conditions (eg, transfer temperature, transfer speed) is expanded, and the transfer material to be used is independent of the type. The present invention provides an electrophotographic color image forming method which exhibits good transferability. A further object of the present invention is to provide an electrophotographic color image forming method capable of forming a transfer layer each time on a photoconductor in an electrophotographic apparatus, repeatedly using the photoconductor, and achieving low running cost. Is to provide.

[0011]

The object of the present invention is to provide a JIS
A first transfer layer (T ₁ ) is formed on the surface of an electrophotographic photosensitive member having an adhesive strength of 20 gram · force or less according to the “Adhesive tape / adhesive sheet test method” of Z0237-1980, and electrophotography is performed on the transfer layer. A toner image of one or more colors is formed by a process, a second transfer layer (T ₂ ) is further formed on the toner image, and then the toner image is transferred to the first transfer layer (T
₁ ) and the second transfer layer (T ₂ ), in the color image forming method of transferring to the transfer material, the first transfer layer (T ₁ ) is
Glass transition point 30 ° C to 80 ° C or softening point 35 to 90
At least one kind of resin (AH) and glass transition point at
Resin (A to 30 ° C to 40 ° C or softening point 0 ° C to 60 ° C)
L ₁ ) and at least one resin (A
H) and the resin (AL ₁ ) are formed by an electrodeposition coating method using resin particles (AR) having a glass transition point or softening point difference of 2 ° C. or more, and further, the second transfer layer (T ₂ It has been found that ( ₁ ) is mainly constituted by a resin (AL ₂ ) having a glass transition point of 35 ° C. or lower or a softening point of 45 ° C. or lower.

The outline of the electrophotographic color image forming method of the present invention will be described with reference to FIG. That is, according to the color image forming method of the present invention, the surface of the electrophotographic photosensitive member 11 including at least the support 1 and the photosensitive layer 2 (having a surface adhesive force of 2).
0 gram · force or less), a peelable first transfer layer (T ₁ ) 12 is formed by forming resin particles (AR) made of at least two kinds of thermoplastic resins by an electrodeposition coating method, and further thereon. A toner image 3 of at least one color is formed on the surface of the second transfer layer (T) by a normal electrophotographic process.
₂ ) 13 is formed, and then the toner image 3 is transferred to another substrate (transferred material) 16 together with the first transfer layer (T ₁ ) 12 and the second transfer layer (T ₂ ) 13 to form a color copy. To do.

The conventional method uses one transfer provided on the photoreceptor.
A toner image is formed on the layer, and the transfer material is transferred together with the transfer material.
Was to be transferred to. Therefore, a good color image
In order to obtain a copy, use the electrophotographic process as described above.
In the transfer process without adversely affecting the electrophotographic characteristics
Transferability (separation from the photoreceptor and close contact with the transferred material)
Property), and as a color copy, it is easy to write and print.
Wide variety of printability and filing characteristics
It was necessary to provide the conditions for one transfer layer. Against this
Then, the method of the present invention uses the transfer layer before and after toner image formation.
In two layers (T ₁And T₂), And the first transfer layer (T₁)
Resin with a relatively high glass transition point or softening point (A
H) and a resin having a relatively low glass transition point or softening point
(AL₁Electrodeposition using resin particles (AR) composed of
And the first transfer layer (T₁) On top of the
After providing the toner image by the process, the first transfer layer
(T₁) And a second transfer layer (T₂)
By providing the transfer layer as described above.
A variety of conditions are shared and fulfilled by each layer according to its function.
It was possible to add.

Further, in the present invention, the surface adhesion of the electrophotographic photosensitive member is adjusted to be 20 gram · force or less, and the first transfer layer (T ₁ ) is provided thereon,
It can be easily peeled from the surface of the electrophotographic photosensitive member, and can be excellent in adhesion to the toner image provided thereon.
That is, it is possible to adjust both the peeling property from the electrophotographic photosensitive member and the toner adhesion property in the first transfer layer (T ₁ ) in a wide range. Further, in the present invention, the toner image is sandwiched between the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ), and both transfer layers are transferred. It has a great feature that it can be used without special consideration.

Further, the second transfer layer (T ₂ ) has good adhesion to the toner image and the first transfer layer (T ₁ ) in the non-image area and to the material to be transferred. It can be easily transferred to the transfer material regardless of the type of the transfer material.
In particular, the good adhesion with the transfer material improves the peelability between the first transfer layer (T ₁ ) and the surface of the photoconductor. Also,
Since the second transfer layer (T ₂ ) is provided on the toner image after the toner image is formed, there is no restriction on the electrophotographic process.

According to the present invention, the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ) have the components and the layer structure as described above, so that the surface of the photoconductor and the first transfer layer (T) can be formed. The adhesiveness at the interface with ₁ ) can be reduced, and the transferability of the transfer layer as a whole is dramatically improved by forming the second transfer layer (T ₂ ) with good adhesiveness on the surface in contact with the material to be transferred. And the latitude of the transfer condition is expanded. That is, the transfer temperature,
It is possible to reduce transfer pressure and improve transfer speed,
As a result, the heat and pressure applied to the photoconductor is reduced, the deterioration of electrophotographic characteristics is suppressed, the repeated durability of the photoconductor is improved, and the time required for the transfer process can be shortened. Is improved. In addition, the transfer is easily performed regardless of the type of the transferred material.

Further, since the toner image is transferred together with the transfer layer, a color image of high definition and high image quality can be easily and stably obtained without color misregistration. Furthermore, since the surface of the electrophotographic photosensitive member is protected by the transfer layer and does not directly touch the material to be transferred, damage to the surface of the electrophotographic photosensitive member is reduced,
The photoreceptor can be used repeatedly and for a long period of time. Further, instead of using an electrophotographic photosensitive member having a transfer layer on the surface in advance, a transfer layer is formed on the photosensitive member in the electrophotographic apparatus each time, so that the photosensitive member after peeling the transfer layer is formed. Since it can be used repeatedly, the electrophotographic process can be continuously performed without disposing the photoconductor.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION First, the electrophotographic photosensitive member used in the present invention will be described. As an electrophotographic photoreceptor,
Any conventionally known one can be used. What is important is that the surface of the photoconductor has a desired releasability when the transfer layer is formed so that the transfer layer provided on the surface of the photoconductor can be easily peeled off together with the toner image.

That is, in the present invention, at least when the transfer layer (T ₁ ) is formed by the film formation of the resin particles (AR) by the electrodeposition coating method, the electrophotography will be adjacent to the transfer layer (T ₁ ). The adhesive strength of JIS Z0237-1980 "adhesive tape / adhesive sheet test method" on the surface of the photoreceptor is 20 gram-force (g-
f) The following. Thereby, the releasability between the photoconductor and the transfer layer can be better exhibited, and the transfer layer can be easily peeled off from the photoconductor at the time of transfer to the transfer material.

Adhesive strength is measured according to JIS Z 0237-1980 "Adhesive tape / adhesive sheet test method" described in 18 of 18.3.
Follow the 0-degree peeling method with the following modifications. An electrophotographic photosensitive member on which a transfer layer is to be formed is used as a “test plate”. An adhesive tape having a width of 6 mm and manufactured according to JIS C 2338-1984 is used as a "test piece". Peel off at a speed of 120 mm / min using a constant speed tension type tensile tester. That is, a roller is reciprocated from the top of the test piece at a speed of about 300 mm / min, with the adhesive surface of the test piece facing down, and pressure-bonded to the test plate. In a period of 20 to 40 minutes after the crimping, the film is peeled off at a speed of 120 mm / min after peeling off about 25 mm using a constant-speed tension type tensile tester. The force is read every 20 mm peeling, for a total of 4 readings. The test is performed on three test pieces, and an average value of twelve pieces measured from the three test pieces is obtained, and the average value is proportionally converted per 10 mm width.
The adhesive force on the surface of the electrophotographic photosensitive member is preferably 15 gf
It is the following. In addition, also when measuring the adhesive force of the transferred material, it can be performed in the same manner as above using the transferred material as a test plate.

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

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

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. The surface unevenly distributed copolymer is usually 0.1 to 20 in 100 parts by weight of the total composition of the uppermost layer.
It can be used in a proportion of parts by weight.

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

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

To further strengthen the surface ubiquity,
As a binder resin for the overcoat layer or the photoconductive layer, a polymer segment containing a silicon atom and / or a fluorine atom,
It is possible to use a block copolymer obtained by binding at least one kind of polymer segment containing a heat and / or photocurable group-containing component in a block. Examples of the polymer segment containing such a heat- and / or photo-curable group-containing component include those described in JP-A 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 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 the first transfer layer (T ₁ ). Even in these cases, the transfer of these resins to the transfer layer is suppressed or eliminated, and the interface between the transfer layer and the electrophotographic photoreceptor can be clearly formed and maintained (that is, the anchor effect). By using a polymer containing a curable group in the segment (β) of the block copolymer and crosslinking between the polymers at the time of film formation, an effect of further maintaining the interface with the photoreceptor clearly is exhibited. . In particular, when the photoreceptor is repeatedly used and used in combination with a liquid developer, such a crosslinked state is preferable.

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. Furthermore, migration is eliminated by containing a curable group in the polymer or the binder resin.

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 the 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.

[0032]

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[0033]

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

[0035]

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

Further, the organic residue containing a fluorine atom and / or a silicon atom may be constituted in combination, and in that case, it 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.

[0039]

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Where e¹And e²Are the same or different
May be a hydrogen atom or a halogen atom (for example,
Chlorine atom, bromine atom, etc.) or C1-C12 alkyl
Groups (eg methyl, ethyl, propyl, chloroform
Cyl group, bromomethyl group, butyl group, hexyl group, octyl group
A tyl group, a nonyl group, a decyl group, etc.). Q is -O
-, -S- or -N (d²) -Representing d²Has 1 to 1 carbon atoms
4 alkyl group, -CH ₂Cl or -CH₂Represents Br
You.

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.

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

[0043]

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

[0045]

[Chemical 6]

[0046]

[Chemical 7]

[0047]

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[0048]

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[0049]

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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 , 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, to be composed of a block means that the polymer has a polymer segment (α) containing 50% by weight or more of a fluorine atom and / or a silicon atom, for example, A-B as shown below. Examples thereof include mold blocks, ABA type blocks, BAB type blocks, graft type blocks and step type blocks.

[0053]

Embedded image

These various block copolymers can be synthesized according to conventionally known polymerization methods. For example,
W. J. Burrant, A.A. S. Hoffman "Block and G
raft Polymers "(1986, Reuhold), R.P. J. 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 Po1ymeriza
tion ”(1984, Applied Science Publishers Lt.
d.), Fumio Ide "Graft Polymerization and Its Application" (1977)
, Kobunshi Kogyokai) etc.

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

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

The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or less, and may be used alone or in combination of two or more kinds. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol and benzyl alcohol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and diethyl ketone, ethers such as diethyl ether, tetrahydrofuran and dioxane. , Carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate, aliphatic hydrocarbons having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane and cyclooctane, benzene, Aromatic hydrocarbons such as toluene, xylene, chlorobenzene,
Examples 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.

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

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

The binder resin is 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 the specific functional group in the resin by irradiation with light, a step of irradiating light 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, the peeling compound (S) is applied onto a usual electrophotographic photosensitive member before forming the first transfer layer (T ₁ ) which is the second method for obtaining a photosensitive member having a peelable surface. Then, a method for 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 photoreceptor means that the compound (S) is supplied to the surface of the electrophotographic photoreceptor to form a state in which the compound (S) is adsorbed or attached to the surface of the photoreceptor. say.

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

Further, cloth, paper impregnated with the compound (S),
A method in which a felt or the like is brought into close contact with the photoconductor, a method in which a curable resin impregnated with the compound (S) is brought into pressure contact with the photoconductor, and the photoconductor is wet with a non-aqueous solvent in which the compound (S) is dissolved, and then the solvent is dried. And a method in which a nonaqueous solvent in which the compound (S) is dispersed is electrophoresed and adhered to the photoconductor in the same manner as the above-mentioned electrodeposition coating method. Furthermore, the non-aqueous solution of the compound (S) can be uniformly applied to the surface of the photoconductor by the ink jet method, and then dried to adhere the compound (S). The ink jet method is, for example, edited by Shin Ohno, “Non-Impact Printing” Co., Ltd.
C. M. This is achieved by the principle and means described in C (published in 1986). 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)
Need only be adsorbed on or adhered to the electrophotographic photosensitive member to impart releasability to the surface thereof, and the surface adhesive force should be 20 gf or less, and it is not necessary to repeat this step in the method of the present invention.

In the present invention, the third method for imparting releasability to the photoreceptor is the resin particles (AR of the present invention used when the first transfer layer (T ₁ ) of the present invention is formed by electrodeposition coating )
The compound (S ′) containing a fluorine atom and / or a silicon atom exhibiting releasability is allowed to coexist in a dispersion liquid containing the compound. That is, a conventionally known electrophotographic photoreceptor is electrodeposited with an electrodeposition dispersion liquid containing the compound (S ′), whereby the photoreceptor surface exhibits releasability.

Specifically, the compound (S ') exhibiting releasability in an electrically insulating organic solvent having a relative dielectric constant of 3.5 or less.
Containing at least one of the resin particles of the present invention (A
The resin particles (A
R) is electrophoresed or deposited on the surface of the electrophotographic photosensitive member by electrophoresis to form a film, thereby imparting releasability to the photosensitive member by the compound (S ′) and forming a removable first transfer layer (T ₁ ). Can be formed. That is, the compound (S ′) contained in the electrodeposition dispersion liquid for forming the transfer layer is applied to the surface of the photoreceptor before the dispersed resin particles (AR) are electrophoresed and electrodeposited on the surface of the photoreceptor. Since it adheres or adheres, as a result, it becomes a photoreceptor having a peeling property before forming the transfer layer. As a result, a general-purpose electrophotographic photosensitive member can be used without providing a separate peeling property imparting means.

The compound (S ') used here is a compound similar to the above-mentioned releasable compound (S), and more specifically, it has an electric insulating property of a relative dielectric constant of 3.5 or less. At least 0.01 g or more is dissolved in 1 liter of the organic solvent (temperature: 25 ° C.). By using the compound (S ′) which dissolves at least 0.01 g in the solvent,
It is possible to always exhibit stable releasability without causing uneven adsorption on the photoreceptor.

The compound (S ') of the present invention is prepared by wetting the electrophotographic photoreceptor to be used with a solution of the compound (S') dissolved in the electrically insulating organic solvent at a concentration of 0.01 g / liter. Any compound may be used as long as it has an adhesive force of 20 g · f or less according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method” after being dried by touch. The addition amount of the compound (S ′) of the present invention in the electrically insulating organic solvent varies depending on the compound (S ′) and the electrically insulating organic solvent used and the like, but the above physical properties are satisfied and electrophoresis of resin particles is performed. Is added within a range that does not adversely affect (reduction of liquid resistance, increase of viscosity, etc.). Preferably from 0.01 g / liter
It is about 20 g / liter.

As the constitution and materials of the electrophotographic photosensitive member provided in the present invention, any conventionally known constitution can be used,
It is not limited. For example, RM Schaffert, "
Electrophotography "Focal Press London (1980), S.
W. Ing, MD Tabak, WE Haas, "Electrophotograp
hy Fourth International Conference "SPSE (1983),
"Recording Materials and Photosensitive Resins" edited by Isao Shinohara, Hidetoshi Tsuchida, Hideaki Kusakawa (1979), Hiroshi Komon, Chemistry and Industry, 39 (3), 161 (1986), Comprehensive Technology Collection of materials "Recent development and practical application of photoconductive materials and photoconductors", Japan Science Information Co., Ltd. (1986), Electrophotographic Society, "Basics and Applications of Electrophotographic Technology", Corona Publishing Co., Ltd. (1986) ,) And various photoconductors described in the review papers such as "Present Symposium on Organic Photoconductors for Electrophotography" edited by The Institute of Electrophotography (1985). That is, a single layer composed of the photoconductive compound itself or a photoconductive layer in which the photoconductive compound is dispersed in a binder resin can be mentioned. 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,
Examples of conventionally known inorganic photoconductive compounds such as cadmium sulfide, selenium, selenium-tellurium, amorphous silicon, and lead sulfide may be used to form a photoconductive layer together with a binder resin, or vapor deposition or The photoconductive layer may be formed solely by sputtering or the like. When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used, the binder resin is used in an amount of 10 to 100 parts by weight, preferably 15 to 40 parts by weight, based on 100 parts by weight of the inorganic photoconductive compound. .

On the other hand, the photoconductive layer using an organic compound may be any conventionally known one, and specifically, a photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye and a binder resin, a second Examples of the photoconductive layer include a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent, and a binder resin, and a photoconductive layer having a two-layer structure containing a charge generating agent and a charge transporting agent in separate layers.
The electrophotographic photoreceptor of the present invention may take any form of the above-described photoconductive layer. In the case of the second example, the organic photoconductive compound functions as a charge transport agent.

The organic photoconductive compound used in the present invention is not particularly limited, and known compounds can be used. For example, triazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, arylamine derivative, azurenium salt derivative, amino-substituted chalcone derivative, N, N
-Bicarbazyl derivative, oxazole derivative, styrylanthracene derivative, fluorenone derivative, hydrazone derivative, benzidine derivative, stilbene derivative, polyvinylcarbazole and its derivative, polyvinylpyrene,
Polyvinyl anthracene, poly-2-vinyl-4-
(4'-dimethylaminophenyl) -5-phenyl-oxazole, vinyl polymers such as poly-3-vinyl-N-ethylcarbazole, polyacenaphthylene, polyindene, polymers such as acenaphthylene-styrene copolymers,
Examples thereof include condensation resins such as triphenylmethane polymer, pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin. Two or more kinds of organic photoconductive compounds can be used in combination depending on the case.

As the sensitizing dye contained in the photoconductive layer,
Conventionally known sensitizing dyes used for electrophotographic photoreceptors can be used. These are "Electronic photography" 12 , 9 (1973),
“Organic Synthetic Chemistry” 24 (11), 1010 (1966) and the like. For example, U.S. Pat. Nos. 3,141,770 and 4,2.
83,475, JP-A-48-25658, and JP-A-6-
No. 2-71965, Pyrylium dye, Applie
d Optics Supplement 3 50 (1969) , JP-A-50-39
Triarylmethane dyes described in US Pat. No. 3,597,196, and cyanine dyes described in US Pat. No. 3,597,196, JP-A-60-163407, and JP-A-59-164588.
The styryl dyes described in JP-A-60-252517 and the like are advantageously used.

As the charge-generating agent contained in the photoconductive layer, various organic and inorganic charge-generating agents known in the prior art for electrophotographic photoreceptors can be used. For example, selenium, selenium-tellurium, cadmium sulfide, zinc oxide, and the organic pigments described below can be used, and these are arbitrarily selected as charge generating agents having spectral sensitivity suited to the wavelength range of the light source of the printer. .

As the organic pigment, for example, azo pigments such as monoazo, bisazo and trisazo pigments, phthalocyanine pigments such as metal-free or metal phthalocyanine, perylene pigments, indigo, thioindigo derivatives, quinacridone pigments, polycyclic quinone pigments, Examples thereof include bisbenzimidazole-based pigments, squalium salt-based pigments, and azurenium salt-based pigments, and these may be used alone or in combination of two or more.

Further, in the photoconductive layer used in combination with the charge transporting agent, one having a good compatibility with the kind of the charge generating agent used in combination is selected. The compound group known as a sex compound is mentioned.

The mixing ratio of the organic photoconductive compound and the binder resin determines the upper limit of the content of the organic photoconductive compound by the compatibility between the organic photoconductive compound and the binder resin. Crystallization of the photoconductive compound occurs, which is not preferable. Since the electrophotographic sensitivity decreases as the content of the organic photoconductive compound decreases, it is preferable to include as many organic photoconductive compounds as possible within the range where crystallization of the organic photoconductive compound does not occur. The content of the organic photoconductive compound is 5 to 120 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the binder resin.

The binder resin that may be used in the photoreceptor of the present invention (hereinafter sometimes referred to as the binder resin (B)) may be any of the resins used in conventionally known electrophotographic photoreceptors, and the weight average The molecular weight is preferably 5 × 10 ³ to 1 × 1
0 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10 ⁵ . The glass transition point of the binder resin is preferably -4.
It is 0 ° C to 200 ° C, and more preferably -10 ° C to 140 ° C. For example, Ryuji Shibata and Jiro Ishiwata, Kobunshi, Volume 17,
Page 278 (1968) Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No.8), edited by Koichi Nakamura, "Practical Technology of Binders for Recording Materials," Chapter 10, CHC Publishing (1985), The Institute of Electrophotography, "Current Symposium on Organic Photoreceptors for Electrophotography" Proceedings (1985) edited by Hiroshi Komon, "Recent Developments and Practical Applications of Photoconductive Materials and Photoreceptors" The Japan Society for Science Information (1986) The Electrophotographic Society of Japan Volume "Basics and Applications of Electrophotographic Technology" Chapter 5 Corona Co., Ltd. (1988), D. Tatt, SC Heidecker, Tappi, 49
(No.10), 439 (1966), ES Baltazzi, RG Blanclott
e et al, Phot. Sci. Eng. 16 (No.5), 354 (1972), Nguyen Chan Kay, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography
Compounds described in the books and reviews such as 18 (No. 2) and 22 (1980) can be mentioned.

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-modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylate copolymer, ring Rubber-acrylate copolymers, copolymers containing a nitrogen-free heterocycle (for example, as a heterocycle, 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, as the binder resin (B) for the photoconductor,
The electrostatic characteristics can be improved by using 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, and a phosphono group together. For example, JP-A-64-70761 and JP-A-2-67563.
No. 3,181,948, and No. 3-249659. Also, by using a specific medium to high molecular weight resin, stable performance can be maintained even when the environment fluctuates significantly. For example, JP-A-3-
29954, 3-77954, 3-92861.
No. 3 and No. 3-53257, or a resin containing an acidic group at the end of the graft portion of the graft copolymer or a resin containing an acidic group in the graft portion of the graft copolymer, JP-A-3-206464. And A block containing an acidic group and B containing no acidic group described in JP-A-3-223762.
A graft type copolymer having an AB block type copolymer composed of a block in the graft portion can be mentioned. By using these resins, it is possible to uniformly disperse the photoconductor and form a photoconductive layer having good smoothness,
In addition, excellent electrostatic characteristics can be maintained even when the environment is changed or a scanning exposure method using semiconductor laser light is used.

The thickness of the photoconductive layer is 1 to 100 μm, especially 1
0 to 50 μm is preferred. When a photoconductive layer is used as the charge generation layer of the photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm. .

In the present invention, various dyes can be used together as a spectral sensitizer depending on the kind of light source such as visible light exposure or semiconductor laser light exposure. For example, the above-mentioned review articles and documents on electrophotographic photoreceptors, "Electrophotography" 12, 9 (1973), "Organic Synthetic Chemistry" 24 (11), 1010
(1966), Harumiya Miyamoto, Hidehiko Takei; Imaging 1973 (No.8)
Page 12, CJ Young et al .: RCA Review 15, page 469 (1954
,) Kohei Kiyota: Transactions of the Institute of Electrical Communication, J63-C ( No.2)
, 97 (1980), Yuji Harasaki et al., Journal of Industrial Chemistry, 66 , 7
8 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35 , 2
08 p. (1972), "Research Discloseure", 1982, 2
16, pp. 117-118, FM Hamer `` The Cyanine Dyes and
Related compounds such as "Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes,"
Examples thereof include xanthene dyes, phthalein dyes, polymethine dyes (eg, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain a metal), and the like.

Furthermore, various conventionally known additives for electrophotographic photoreceptors can be used if necessary.
These additives include a chemical sensitizer for improving electrophotographic sensitivity, various plasticizers for improving film properties,
A surfactant and the like are included.

Examples of the chemical sensitizer include halogen, benzoquinone, chloranil, fluoranyl, bromanil,
Dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, phthalic anhydride, maleic anhydride, N-hydroxymaleimide, N-hydroxyphthalimide, 2,
Electron-withdrawing compounds such as 3-dichloro-5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone, tetracyanoethylene, nitrobenzoic acid, dinitrobenzoic acid, etc .; Development and Practical Use ”Chapters 4-6: Japan Science Information Co., Ltd.
Examples include polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are reviewed in the publication section (1986). Also, JP-A-58-65
No. 439, No. 58-102239, No. 58-1294
Compounds described in JP-A-39-62 and JP-A-62-71965 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, dimethyl glycol phthalate. Can be added to improve the flexibility of the photoconductive layer. These plasticizers are preferably contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer. The amounts of these various additives are not particularly limited, but are usually 0.1 to 100 parts by weight of the photoconductor.
001 to 2.0 parts by weight.

The electrophotographic photosensitive member can be provided on a conventionally known support. Generally, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, just as in the conventional case, for example, a substrate such as metal, paper or plastic sheet is impregnated with a low resistance substance. And conductive treatment is applied to the back surface (the surface opposite to the surface on which the photosensitive layer is provided) of the substrate, and at least one layer is coated for the purpose of preventing curling. Those provided with a water-resistant adhesive layer on the surface, those provided with at least one precoat layer as required on the surface layer of the above-mentioned support, those obtained by laminating electroconductive plastic substrate on which aluminum or the like is deposited on paper, etc. Can be used. Specifically, as an example of a conductive substrate or a conductive material,
Yukio Sakamoto, Electrophotography, 14 (No.1), pp. 2-11 (1975), Hiroyuki Moriga "Introduction to Special Paper Chemistry" Polymer Publishing (19
1975), MF Hoover, J. Macromol. Sci. Chem. A-
4 (6), pages 1327 to 1417 (published in 1970) and the like are used.

The transfer layer used in the present invention will be described in detail below. As described above, the transfer layer of the present invention comprises the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ). In the following description, the first transfer layer (T ₁ ) and the second transfer layer (T ₁ ). (T ₂ ) may be collectively referred to as a transfer layer (T). First, the first transfer layer (T ₁ ) used in the present invention will be described. The first transfer layer (T ₁ ) used in the present invention is a light-transmissive layer and is transparent to at least a part of wavelength light in the spectral sensitivity region of the electrophotographic photosensitive member, It is not particularly limited and may be colored. Usually, a colorless and transparent transfer layer is used.

The first transfer layer (T ₁ ) of the present invention preferably has a temperature of 180 ° C. or lower and / or a pressure of 30 kgf / cm ² or lower, more preferably 160 ° C. or lower and / or 20 kgf / cm ² or lower. It is preferable that peeling is possible under the transfer condition of pressure. If it is less than the above value, there is almost no need to upsize the transfer device to maintain the heat capacity and pressure of the transfer device in order to separate and transfer the transfer layer from the surface of the photoconductor, and the transfer can be sufficiently performed at an appropriate transfer speed. It can be done and there is no practical problem. The lower limit is not particularly limited,
Usually, a transfer condition of a temperature of room temperature or higher or a pressure of 100 gf / cm ² or higher is preferable. Since the toner image is formed on the first transfer layer (T ₁ ) by the electrophotographic process,
It is desirable not to deteriorate the electrophotographic characteristics (chargeability, charge retention in the dark, photosensitivity, etc.) of the photoreceptor. In addition, the first transfer layer (T ₁ ) has a thermoplastic property that is easily separated from the surface of the photoconductor in the next thermal transfer process, and further becomes the uppermost layer when transferred, so that a color copy is obtained. As a result, the storage stability of the copy should be good, for example, it does not cause any trouble even if it is written or imprinted, and it does not peel off the transfer layer even if it is put in various sheets and piled up. Is desirable.

The film thickness of the first transfer layer (T ₁ ) is 0.1 to 5 μm.
Is preferable, and more preferably 0.5 to 3 μm. As described above, the resin particles (AR) used for forming the first transfer layer (T ₁ ) of the present invention include two kinds of resin (AH) and resin (AH) having different glass transition points or softening points of 2 ° C. or more. A
L ₁ ) is contained in at least the same particle. In the present invention, the resin (AH) and the resin (AL ₁ ) whose glass transition point and softening point are within the scope of the present invention can be arbitrarily selected and provided.

The resin (AH) has a glass transition point of 30 ° C. to 80 ° C.
C. or a softening point of 35.degree. C. to 90.degree. C., preferably a glass transition point of 33.degree. C. to 60.degree. C. or a softening point of 40.degree. The resin (AL ₁ ) has a glass transition point of −30 ° C. to 40 ° C. or a softening point of 0 ° C. to 60 ° C., preferably a glass transition point of −20 ° C. to 33 ° C. or a softening point of 5 ° C. to 35 ° C. Further, the difference between the glass transition point and the softening point of the resin (AH) and the resin (AL ₁ ) is preferably 5 ° C. or higher, more preferably 10 ° C. or higher.
Here, the difference in the glass transition point or the softening point when two or more kinds of the resin (AH) or the resin (AL ₁ ) are contained is
This is the difference between the resin (AH) having the lowest glass transition point or softening point and the resin (AL ₁ ) having the highest glass transition point or softening point.

The resin (AH) and the resin (AL ₁ ) preferably have a resin (AH) / resin (AL ₁ ) ratio of 10/90 to.
When the resin particles (AR) are contained in the presence ratio of 95/5 (weight ratio), good transferability can be obtained. Also,
The resulting color copy has excellent filing properties. That is, even when a color copy is inserted into a plastic sheet or the like and filed, the transfer layer is not adhered to the plastic sheet or the like and peeled off. A more preferable usage ratio is a resin (AH) / resin (AL ₁ ) ratio of 30/70 to 90/10 (weight ratio).

At least two kinds of resin (AH) and resin (A) contained in the resin particles (AR) of the present invention.
L ₁ ) is a state in which particles are mixed arbitrarily or a resin (A
H) may be in a state of forming a layered structure in which the resin (AL ₁ ) and the resin (AL ₁ ) are separated from each other (that is, particles having a core-shell structure), and in the case of a core-shell structure, The core portion may be resin (AH) or resin (AL ₁ ) and is not particularly limited. When the resin particles (AR) having a core-shell structure in which the resin (AH) serves as a shell is used, the surface side of the transfer layer transferred to the transferred material is mainly a resin (AH) having a high glass transition point or softening point. Since it is composed, the storage stability of the copy, such as the filing characteristics described above, is further improved, and by selecting the type of resin (AH), it is possible to impart writing and imprinting properties similar to plain paper. become.

The second transfer layer (T₂) Is resin (AL
₂) Is mainly contained. Resin (AL
₂) Is preferably a glass transition point of -20 ° C to 30 ° C or soft.
20 ° C. to 45 ° C., more preferably glass transition
The point is −10 ° C. to 30 ° C. or the softening point is 25 ° C. to 45 ° C.
Second transfer layer (T₂Resin in ()₂) Is the first transfer layer
(T₁Resin in ()₁) Is the same but different
Is also good. Second transfer layer (T ₂Resin (A
L₂) Is the first transfer layer (T₁) Resin particles (A
Lower glass transition point or softening point than resin (AH) in R)
No, preferably 2 ° C or higher, more preferably 5 ° C or higher
It is desirable that it is low. Furthermore, the resin in the resin particles (AR)
(AH) has a glass transition point of 30 ° C. or higher or a softening point of 35 ° C. or higher
And the second transfer layer (T₂) Contained in resin (AL
₂) Is 1 at the glass transition point or softening point than the resin (AH)
A combination that is a low resin in the range of 0 ° C to 40 ° C is preferred.
New The second transfer layer (T₂) Is after toner image formation
Since it is provided on the first transfer layer (T₁) Different from
There are no restrictions on the electrophotographic process.

The resin used in the transfer layer of the present invention (A
The weight average molecular weights of H), (AL ₁ ) and (AL ₂ ) (hereinafter sometimes collectively referred to as resin (A)) are preferably 1 × 10 ^{3 to} 5 × 10 ⁵ , and more preferably 3 respectively. It is in the range of × 10 ³ to 8 × 10 ⁴ . Wherein the molecular weight is measured by GPC method, is obtained by polystyrene conversion, it may be abbreviated as follows M _W.

Specific examples of the resin (A) that can be used in the transfer layer of the present invention include thermoplastic resins and resins known as adhesives or pressure-sensitive adhesives.
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 olefin-unsaturated carboxylic acid ester copolymers Coal, 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 diester polymer and copolymer, maleic anhydride copolymer, acrylamide copolymer, methacrylamide copolymer, hydroxyl group-modified silicone resin, polycarbonate resin, ketone resin, polyester resin, Silicone resin, amide resin, water 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 heterocyclic ring (for example, as a heterocyclic ring , Furan ring, tetrahydrofuran ring, thiophene ring, dioxane ring, dioxofuran ring, lactone ring, benzofuran ring, benzothiophene ring, 1,3-dioxetane ring, etc.), cellulose resin,
Examples thereof include fatty acid-modified cellulose-based resins and epoxy resins.

[0109] For example, "Plastic Materials Lecture Series", Volumes 1 to 18 (1981), published by The Nikkan Kogyo Shimbun, "Polyvinyl Chloride" edited by Kinki Chemical Association Vinyl Section, published by Nikkan Kogyo Shimbun (1988), Hide Omori Three "functional acrylic resin" Co., Ltd.
Techno System (1985) Eiichiro Takiyama "Polyester Resin Handbook" Nikkan Kogyosha (1988), Kazuo Yuki "Saturated Polyester Resin Handbook" Nikkan Kogyo Shimbun (1989), Polymer Society of Japan "Polymer Data" Handbook <Application> Chapter 1 Baifukan (1986), Yuji Harazaki “Latest Handbook of Binder Technology” Chapter 2 General Technology Center Co., Ltd. (1985) Ed. Taira Okuda “Polymer Processing” Supplement 8 Two
Volume 0 Special Issue "Adhesive" Polymer Publishing (1976), Fukuzawa Keiji "Adhesive Technology" Polymer Publishing (1987), Mamoru Nishiguchi "Adhesion Handbook 14th Edition" Polymer Publishing (1985) Year),
Various resins described in “Adhesion Handbook, Second Edition” edited by Japan Adhesive Association, Nikkan Kogyo Shimbun (1980) and the like can be mentioned.

The resin (A), when used in the first transfer layer (T ₁ ), contains a substituent containing a fluorine atom and / or a silicon atom, which has a function of improving the releasability of the resin (A) itself. You may contain a polymer component (c). This improves the releasability from the electrophotographic photosensitive member, resulting in better transferability. The content of the polymer component (c) is preferably 3 to 40 parts by weight, more preferably 5 to 25 parts by weight, based on 100 parts by weight of the total polymer components of the resin (A). This fluorine atom and / or silicon atom-containing substituent may be incorporated in the polymer main chain of the polymer, or may be present as a side chain substituent of the polymer. The polymer component (c) is a resin (AH) and a resin (A
It may be included in any of L ₁ ). Preferably, the polymer component (c) is contained as a block in the resin (A).

Specific examples of the polymer component (c) are the same as those of the polymer component (F) containing a substituent containing a fluorine atom and / or a silicon atom described in relation to the electrophotographic photoreceptor. Can be mentioned.

The transfer layers (T ₁ and T ₂ ) may optionally contain other additives in order to improve various physical properties such as adhesiveness, film-forming property and film strength. For example, polybutene, DOP, DBP, low-molecular-weight styrene resin, and low-molecular-weight styrene resin Polyethylene wax, microcrystalline wax, paraffin wax, etc., such as polymeric hindered polyphenols and triazine derivatives as antioxidants can be added. For details, see “Actual Hot Melt Adhesion” (Hiroshi Fukada, Kobunshi Kogakukai, published in 1983), pages 29 to 107. Transfer layer (T ₁ and T
_{In 2} ), if the film thickness is too thin, transfer defects easily occur,
If it is too thick, the color image after transfer may be distorted due to the expansion and contraction of the resin. Therefore, the total thickness of the transfer layer is suitably 0.1 to 20 μm, preferably 0.5 to 10 μm, more preferably 1 to 5 μm. The film thickness ratio of the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ) is 99 to 5/1 to 95, preferably 95 to 30/5 to 7
0. Next, the formation of the transfer layer will be described.

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

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

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

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

As a method for 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), it is possible to use corona charging, friction charging, induction charging, ionic wind charging, reverse ionization phenomenon, etc. As described in the textbooks such as "Method of Electrodepositing Charged Fine Particles", Koichi Nakamura, "Development and Practical Use of Recent Electrophotographic Development System and Toner Material", Chapter 1 (Japan Science Information Co., Ltd., 1985). , Cascade method, magnetic brush method, fur brush method, electrostatic method, induction method,
This can be appropriately performed using a development method such as a touchdown method or a powder cloud method.

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, a paint shaker, a Keddy mill, a dyno mill, etc.), a material which becomes a resin particle component and a dispersion assisting polymer (or a 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.
), DH Solomon "The Chemistry of Organic Fil
m Formers: John Wiles & Sono (1967), Paint and
Surface Coating Theory and Practice ", Yuji Harazaki" Coating Engineering "Asakura Shoten (1971), Yuji Harazaki" Basic Science of Coating "Asakura Shoten (1977), etc.

As the polymerization granulation method, a seed polymerization method can be easily used. Specifically, the above-mentioned "state of the art of ultrafine particle polymer", Chapter 2, "Recent Electrophotography" can be used. Development and Practical Use of Development Systems and Toner Materials "Chapter 3, KEJ Barvett" Dispersion Polymerization "
In Organic Media ”John Wiley (1975) and other publications, a conventionally known non-aqueous dispersion polymerization method is used to first synthesize fine particles of resin (AH) [or resin (AL ₁ )], and then A method is preferred in which the fine particles are used as seeds and the monomers corresponding to the resin (AL ₁ ) [or resin (AH)] are fed and polymerized in the same manner as above.

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

Furthermore, in order to introduce the polymer component (c) in blocks, a method of using at least a block copolymer containing the polymer component (c) in blocks in the dispersion stabilizing resin to be used, or the polymer component ( Weight-average molecular weight of 1 × 10 ³ to 2 × 10 composed mainly of (c)
⁴ (preferably 3 × 10 ^{3 to} 1.5 × 10 ⁴ ) monofunctional macromers can be coexisted and copolymerized with the monomer to facilitate the polymerization. Further, as another method, a polymer initiator containing the polymer component (c) as a main repeating unit (azobis polymer initiator or peroxide polymer initiator) may be used to similarly obtain the block copolymer. Resin particles of can be obtained.

The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or in combination of two or more kinds. Specific examples of such organic solvents include methanol, ethanol, propanol, butanol, fluorinated alcohols, alcohols such as benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ketones such as diethyl ketone, diethyl ether,
Tetrahydrofuran, dioxane, and other ethers, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and other carboxylic acid esters, hexane, octane, decane, dodecane, tridecane, cyclohexane, cyclooctane, and other fatty acids having 6 to 14 carbon atoms Examples thereof include aromatic hydrocarbons such as group hydrocarbons, benzene, toluene, xylene, chlorobenzene, and 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 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

These non-aqueous dispersion resin particles are subjected to a wet electrostatic photography development method or a method in which they are electrophoresed by being electrophoresed in a pressure field of an electric field. Therefore, the dispersion medium used during electrodeposition is The resistance is adjusted to a non-aqueous solvent system having a resistance of 10 ⁸ Ω · cm or more and a dielectric constant of 3.5 or less. Specifically, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, and halogen-substituted products thereof can be used. For example, octane, isooctane, decane, isodecan, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L (Isoper: exon company Trade name), Shersol 70, Shersol 71 (Shellsol; trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco: trade name of American Mineral Spirits Co., Ltd.) and the like, used alone or in combination. be able to.
Therefore, preferably, as the solvent used during the polymerization granulation,
From the beginning, the insulating organic solvent is used, but it can also be prepared by granulating with a solvent other than these solvents and then substituting the dispersion medium.

In order to electrophoretically disperse dispersed particles in a dispersion medium, the particles must be positively or negatively charged electrophoretic particles. Providing the particles with an electric detecting property can be achieved by appropriately utilizing the technique of a developer for wet electrostatography. Specifically, "Development and practical application of the latest electrophotographic development system and toner material", pages 139 to 148, "Basics and applications of electrophotographic technology" edited by the Institute of Electrophotography, pages 497 to 505 (Corona, 1988 Annual), Yuji Harasaki "Electronic Photography" 16 (No.2),
It is carried out by using the electrophotographic material and other additives described on page 44 (1977). For example, British Patent No. 893,4
29, 934,038, U.S. Pat. No. 1,122,
397, 3,900,412, 4,606,9
89, JP-A-60-179751, and JP-A-60-185.
No. 963, JP-A-2-13965 and the like. The composition of the non-aqueous latex used for electrodeposition is usually at least 1 liter of the electrically insulating dispersion medium,
Particles mainly containing a thermoplastic resin are 0.1 to 20
g, 0.01 to 50 g of the dispersion stabilizing resin, and 0.0001 to 10 g of the charge control agent added if necessary.

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

The resin particles (AR) which have been made into fine particles and imparted with a charge and dispersed in the electrically insulating liquid in this manner behave like the electrophotographic liquid developer. Therefore, for example, it is possible to perform electrophoresis on the surface of the photoconductor by using the developing device described in "Basics and Applications of Electrophotographic Technology", pages 275 to 285, for example, the slit developing electrode device. That is, resin particles (AR) mainly containing a thermoplastic resin are supplied between the counter electrodes that are installed to face the electrophotographic photoreceptor, and electrophoresed according to a potential gradient applied from an external power source to perform electrophotography. A film is formed by being attached or electrodeposited on the photoconductor.

Generally, when the particles are positively charged, a voltage is applied from an external power source between the conductive support of the photoconductor and the developing electrode of the developing device so that the photoconductor side has a negative potential. Then, the particles are electrostatically electrodeposited on the surface of the photoreceptor. Electrodeposition can also be performed by wet toner development using a normal electrophotographic process. That is, as shown in the above-mentioned "Basics and Applications of Electrophotographic Technology", pages 46 to 79, so-called burn-off is performed in which the photosensitive member is uniformly charged and then not exposed or only unnecessary areas are exposed. Perform normal wet toner development.

On the other hand, when the resin particles dispersed in a medium which is liquefied by heating are used, the medium is solid at room temperature and the heating temperature is 30 to 80 ° C. (preferably 4 ° C.).
(0-70 ° C.) is an electrically insulating organic compound which becomes liquid at a freezing point of 30-80 ° C.
Paraffins, waxes, low molecular weight polypropylene having a freezing point of 30 to 80 ° C., beef tallow having a freezing point of 20 to 50 ° C., and hardened oil having a freezing point of 30 to 80 ° C., etc., 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, in the resin particles of the present invention to be subjected to this pseudo-wet method, the resin component having a high glass transition point or a high softening point which does not soften at the liquefying temperature of the medium to be used constitutes the outer shell of the particles. The so-called core-shell type particles (resin having a low glass transition point in the core portion and resin having a high glass transition point in the shell portion) are used to stably disperse the resin particles without fusion due to heating. It is possible to maintain a stable state.

The amount of the thermoplastic resin particles deposited on the photoconductor can be arbitrarily adjusted by the applied voltage of the external bias, the charging potential of the photoconductor, the developing time and the like. After electrodeposition, the developer is wiped off by a squeeze using a known rubber roller, gap roller, reverse roller or the like. Methods such as corona quiz and air squeeze are also known. In addition, cold or warm air,
Alternatively, it is dried by an infrared lamp or the like, and preferably thermoplastic resin particles are formed into a film to form the first transfer layer (T ₁ ). In the present invention, the first transfer layer (T ₁ ) may be provided in advance on the electrophotographic photosensitive member or may be formed each time. The formation of the first transfer layer (T ₁ ) may be performed by an apparatus separate from the electrophotographic process or the transfer process,
The process may be carried out on the photoconductor in the same apparatus each time. On the other hand, in order to provide the second transfer layer (T ₂ ) on the first transfer layer (T ₁ ) on which the toner image is formed, a usual method can be used. For example, a solution or dispersion containing the second transfer layer (T ₂ ) composition may be applied. The formation of the second transfer layer (T ₂ ) may be carried out in an apparatus separate from the electrophotographic process and the transfer process, but it is preferably carried out in the same apparatus as these processes each time.
As a result, the photoconductor can be repeatedly used, and there are advantages such as a reduction in running cost.

In order to form the second transfer layer (T ₂ ) on the first transfer layer (T ₁ ) carrying a toner image, the hot melt coating method, the electrodeposition coating method and the transfer method are uniform and thin layers. It is preferably used because it can be easily formed. By these methods,
It is possible to easily form the first transfer layer (T ₁ ) on the photoconductor and the second transfer layer (T ₂ ) on the toner image in the same apparatus as the electrophotographic process and the transfer process.

Hereinafter, each method will be described in detail. The hot melt coating method is one in which the transfer layer composition is hot melt coated by a known method, and for this purpose, a solventless coating machine, for example, hot melt described in "Actual of hot melt adhesion" on pages 197 to 215. The mechanism of the hot melt coating device for adhesives (hot melt coater) can be diverted to specifications for coating the first transfer layer (T ₁ ). Examples thereof include a direct roll coater offset gravure roll coater, a rod coater, an extrusion coater, a slot orifice coater and a curtain coater.

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

Next, the formation of the transfer layer by the transfer method will be described. In this method, the second transfer layer (T ₂ ) held on a releasable support typified by release paper (hereinafter simply referred to as release paper) is transferred onto the first transfer layer (T ₁ ). is there. The release paper on which the transfer layer is formed is roll-shaped or sheet-shaped and can be easily supplied to the transfer device. As the release paper used in the present invention, any conventionally known release paper can be used. For example, "New technology of adhesive (adhesive) and its use / development materials of various applied products", Management Development Center Publishing Department (Showa 53 years 5
May 20), "Encyclopedia of All Paper Guide Paper, First Volume / Culture Industry Edition", paper industry Times Co., Ltd. (December 1, 1983), and the like.

Specifically, the release paper was unbleached Kurupack paper laminated with a polyethylene resin as a release agent mainly composed of silicone, high-grade paper precoated with a solvent resistant resin, kraft paper, or undercoated. It is applied on a substrate such as PET base or glassine paper. In general, a solvent type silicone is used, and the silicone is applied and dried at a concentration of 3 to 7% on a gravure roll, a reverse roll, a wire bar or the like, and then heat treated at 150 ° C. or higher to be cured. The coating amount is about 1 g / m ² .

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

To form the second transfer layer (T ₂ ) on the release paper, a transfer layer composition containing a resin constituting the transfer layer as a main component is subjected to bar coating, spin coating, spray coating, etc. according to a conventional method. It is easily performed by applying and forming a film. The second transfer layer (T ₂ ) on the release paper is used as the first transfer layer on the electrophotographic photosensitive member.
For thermal transfer onto the transfer layer (T ₁ ), a conventional thermal transfer method can be used. That is, the release paper holding the second transfer layer (T ₂ ) is pressure-bonded to the first transfer layer (T ₁ ) on the electrophotographic photoreceptor,
The second transfer layer (T ₂ ) may be thermally transferred. The conditions for transferring the second transfer layer (T ₂ ) from the release paper onto the first transfer layer (T ₁ ) and the toner image are preferably as follows. The roller nip pressure is 0.1 to 10 kgf / cm ² , more preferably 0.2 to 8 kgf / cm ² , and the transfer temperature is 25 ° C.
To 100 ° C, more preferably 40 ° C to 80 ° C. Transport speed is 10 to 200 mm / sec, more preferably 30
~ 150 mm / sec.

The electrodeposition coating method is substantially the same as that described for forming the first transfer layer (T ₁ ). Instead of the resin particles (AR) forming the first transfer layer (T ₁ ), a thermoplastic resin (AL ₂ ) may be used as the resin particles (AL ₂ R). The formation of the second transfer layer (T ₂ ) is performed by the first transfer layer (T 2
By performing the electrodeposition coating method as in the case of ₁ ), the transfer layer forming apparatus can be made compact. Second transfer layer (T
The film thickness of ₂ ) is preferably 0.1 to 5 μm, more preferably 0.5 to ₂ μm.

Next, a method for forming a toner image of one or more colors on the electrophotographic photosensitive material having the first transfer layer (T ₁ ) will be described.

A toner image is formed on the first transfer layer (T ₁ ) provided on the electrophotographic photosensitive member by a usual electrophotographic process. That is, each step of charging-exposure-developing-fixing is performed by a conventionally known method.

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

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

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

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

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

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

In forming a toner image, a combination of a scanning exposure method using laser light based on digital information and a 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.

After that, scanning exposure with a laser light source is performed, for example, using the method described on page 254 and after 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.

After the toner image is formed on the first transfer layer (T ₁ ), the second transfer layer (T ₂ ) is provided thereon. The second transfer layer (T ₂ ) may be formed by the method described above. Next, the toner image is transferred from the photosensitive material to the transfer material together with the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ). A known method and apparatus can be used for this thermal transfer. Specifically, for example, the material to be transferred is pressure-bonded to the light-sensitive material with a heating roller, for example, a metal roller having a built-in heating element coated with rubber, and then passed under a cooling roller. If necessary, the photosensitive material and the material to be transferred may be preheated in a predetermined manner by using a heating means. The heating means is preferably a non-contact type infrared line heater or flash heater.

The 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 100 ° C, more preferably 35 to 80 ° 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 0.5.
It is about 10 kgf / cm ² . As the roller pressing means, a spring or an air cylinder using compressed air at both ends of the roller shaft can be used. The conveying speed is preferably 10 to 300 mm / sec, more preferably 50 to 250
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 materials such as the photoconductor (photosensitive layer and support), the transfer layer, the material to be transferred, etc. used. It is natural to make it. Temperature conditions such as preheating, roller heating, and cooling in the heat transfer step are determined in consideration of factors such as the glass transition point of the transfer layer, the softening temperature, the fluidity, the tackiness, the film property, and the film thickness. That is, the transfer layer that has been softened to some extent by the preheating means passes through the bottom of the heating roller to increase the tackiness and adheres to the material to be transferred, and after passing below the cooling roller, the temperature decreases and the fluidity and the tackiness are reduced. It is desirable to set the conditions so that the toner as it is as a film is peeled off from the surface of the photosensitive layer together with the toner.

The material to be transferred used in the present invention is not particularly limited, and may be natural paper such as high-quality paper, coated paper, art paper, synthetic paper, metal support such as aluminum, iron and SUS. Any of a reflective material and a transmissive material such as polyester, polyolefin, polyvinyl chloride, and a plastic film such as polyacetate may be used. In the present invention, the steps of forming the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ) are performed in the same apparatus as the electrophotographic process and the transfer process, and the transfer layer is formed each time. It is preferable that the photoconductor after peeling off these transfer layers can be repeatedly used without being thrown away, and further the electrophotographic process can be continuously carried out in the apparatus.

Therefore, one preferred embodiment of the present invention is a color image forming method in which the following steps (i) to (iv) are carried out in the same apparatus. (I) forming a first transfer layer on the surface of the electrophotographic photosensitive member (T _1), (ii) a step of forming a toner image of one or more colors by an electrophotographic process on the first transfer layer (T ₁₎ ,
(Iii) a step of forming the second transfer layer (T ₂ ) on the toner image, and (iv) the toner image on the transfer material together with the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ). The process of transferring.

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

As described above, the surface retains the desired peelability.
When using the electrophotographic photosensitive member 11
The first transfer layer (T₁) 12T₁To form
If the releasability of the surface of the photoreceptor 11 is insufficient,
As described above, the first transfer layer (T ₁) Compound before formation
A device for applying (S) is provided (second method), or
Electro-deposition containing the transfer layer-forming resin particles (AR) of the present invention
Incorporating compound (S ') into the dispersion (third party)
Method) to impart releasability to the surface of the photoreceptor 11.
Can be. In the case of the second method, the method as described above is used.
By appropriately providing the compound (S) application device 10 used
Then, the compound (S) is supplied to the surface of the photoconductor 11. Compound
(S) The application device 10 may be fixed or movable.
Yes.

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

Thereafter, if necessary, a cooling device (not shown) similar to the intake / exhaust unit 15 is used to cool the photosensitive body from the outside or the photosensitive drum to a predetermined temperature.
After lowering the electrodeposition unit 13a, the liquid developing unit set 14 is moved. The unit set 14 is composed of developing units containing liquid developers of yellow, magenta, cyan and black, respectively. If necessary, a pre-bath, a rinse, and a squeeze means may be provided for the purpose of preventing stains on the non-image area. A carrier liquid of liquid developer is usually used as the pre-bath and rinse liquid.

First transfer layer (T ₁ ) made of a thermoplastic resin
The electrophotographic photosensitive member having the surface formed thereon is then subjected to an electrophotographic process. 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 1 mm. And fix it.

The photoconductor 11 is pre-bused by a pre-bus means provided in the liquid developing unit set, and then a developing bias voltage is applied between the photo conductor 11 and the developing electrode by a bias power source and electric connection not shown. Meanwhile, the yellow liquid developer is supplied to the surface of the transfer layer (T ₁ ). 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 liquid developing unit set, and subsequently, the rinsing solution adhering to the surface of the photoconductor is removed by the squeeze means, and then it is dried by passing it under the intake / exhaust unit 15. . The above steps are repeated for magenta, cyan, and black to form a color toner image. After forming the toner image on the first transfer layer (T ₁ ), the second transfer layer (T ₂ ) is formed thereon. In FIG. 2, the second transfer layer (T
₂ ) is formed by the electrodeposition coating method. That is, it can be performed in the same manner as the formation of the first transfer layer (T ₁ ) using the second transfer layer electrodeposition unit 13b containing the dispersion liquid 12b of the thermoplastic resin particles (AL ₂ R).

Next, the toner image is thermally transferred onto the transfer material 16 by the transfer means 17 together with the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ). That is, the transfer layer holding the toner image is preheated to a predetermined level by the heating means 17a for thermal transfer, if necessary, and then the heating element having the temperature control means as the transfer backup roller 17b via the transferred material 16. A metal roller coated with a rubber is internally pressure-contacted, and further, as a backup roller 17c for peeling, a cooling roller is passed under the cooling roller to cool the toner image together with the transfer layer from the photoconductor 11 to the transfer material 16, and a series of color images are transferred. The image forming process is completed. In addition, by stopping the device with the first transfer layer (T ₁ ) formed,
The electrophotographic process can be started immediately when the next apparatus is operated, and the surface of the photosensitive layer can be protected and the characteristic deterioration due to the influence from the external environment can be prevented.

Another example of a suitable apparatus for carrying out the method of the present invention is shown in FIG. In this example, the second transfer layer (T
₂ ) is formed by the hot melt coating method. In FIG. 3, a toner image is formed by an electrophotographic process, and after the liquid developing unit set 14 moves to the standby position, the hot melt coater 13c is moved to that position. The second transfer layer thermoplastic resin 12c is a hot melt coater 13
It is coated on the first transfer layer (T ₁ ) on the photoconductor 11 and the toner image on the peripheral surface of the drum by c, and is cooled to a predetermined temperature by passing under the intake / exhaust unit 15 to be transferred to the second transfer layer (T 1). ₂ ) is formed. The subsequent process is shown in FIG.
Is substantially the same as that described with respect to.

Yet another suitable device example is shown in FIG.
You. The second transfer layer is formed according to the transfer method. FIG.
In the second transfer layer (T₂) 12T₂On the photoconductor 11
First transfer layer (T ₁) 12T₁And toner image (illustrated
The transfer layer forming device 117 can easily
Is made. That is, the second transfer layer (T₂) 12T₂Established
Heat the release paper 20 with the heating roller 117b and press it
2 transfer layers (T₂) 12T₂The first transfer layer (T₁) 12T
₁And transfer it onto the toner image. Release paper 20 is cooled
It is cooled by the roller 117c and collected. As needed
The first transfer layer and the toner image by the heating means 17a.
The second transfer layer (T₂) 12T₂Transfer by heating and pressure bonding
You may improve the property.

The position where the second transfer layer forming device 117 is incorporated is not particularly limited. As a movable type, the first transfer layer and the second transfer layer may be replaced with the transfer means 17 to transfer the toner image to the transfer material 16. Alternatively, the device 117 is first used to form the second transfer layer (T ₂ ) 12T ₂ and then the first transfer layer (T ₁ ), the toner image and the second image.
It can also be used for transferring the transfer layer (T ₂ ) to the transfer material 16. Other configurations in FIGS. 3 and 4 are essentially the same as those in FIG.

[0167]

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

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

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

[0170]

[Chemical 12]

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

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

As 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.

Production of Resin Particles (RL-2) 18 g of the dispersion stabilizing resin (Q-2) and Isopar H
553 g of the mixed solution was stirred at a temperature of 5 under a nitrogen stream.
Warmed to 5 ° C. 60g of methyl methacrylate,
40 g of methyl acrylate, 1.3 g of methyl 3-mercaptopropionate and A.I. I. V. N. 1.0 g of the mixture was added dropwise for 30 minutes, and the reaction was continued for another 1.5 hours. Furthermore, A. I. V. N. Add 0.8g 2
React for a period of time and then start initiator A. I. B. N. 0.8 g was added and the temperature was set to 80 ° C. for 2 hours. I. B.
N. 0.5g was added and reaction was performed for 2 hours. After cooling,
The white dispersion obtained through a 200-mesh nylon cloth was a latex having a polymerization rate of 99% and an average particle size of 0.15 μm and good monodispersity. The Mw of the resin particles was 1.5 × 10 ⁴ , and the Tg was 45 ° C.

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

[0176]

[Table 1]

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

[0178]

Embedded image

Synthesis Examples 10 to 14 of Resin Particles (AR):
(AR-10) to (AR-14) In Production Example 9 of resin particles (AR), instead of 10 g of the macromonomer (M-1), each macromonomer shown in Table B below (Mw is 8 × 10 ³ to). Each resin particle was synthesized in the same manner except that 1 × 10 ⁴ ) was used. The degree of polymerization of each latex particle obtained was 98 to 99%, the average particle diameter was within the range of 0.15 to 0.25 μm, the particle size distribution was narrow, and the monodispersibility was good. Mw of resin particles is 2 × 1
Tg is 30 ° C to 35 ° C in the range of 0 ^{4 to} 3.5 × 10 ^4.
Was in the range.

[0180]

[Table 2]

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

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

[0183]

[Table 3]

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

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

[0186]

Embedded image

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

[0188]

[Table 4]

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

[0190]

[Chemical 15]

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.

[0192]

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 except that each compound shown in Table E below was used instead of ethylene glycol dimethacrylate and methyl ethyl ketone. The average particle size of the obtained resin particles was in the range of 0.15 to 0.30 μm.

[0194]

[Table 5]

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

[0196]

Embedded image

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

[0198]

Embedded image

The electrophotographic photosensitive member having a releasable surface obtained as described above is loaded into an apparatus as shown in FIG. 2, and the first transfer layer (T ₁ ) is formed thereon by the electrodeposition coating method. did. That is,
The surface temperature of the photoconductor 11 was adjusted to 50 ° C., the photoconductor drum was rotated at a peripheral speed of 100 mm / sec, and the following resin particle dispersion liquid (L) was formed on the photoconductor surface using a slit electrodeposition device as the electrodeposition unit 13a. While supplying -1), the photoreceptor side was grounded and a voltage of 130 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit the resin particles. Next, the first transfer layer (T ₁ ) was formed by filming the resin particles while removing the dispersion liquid by an air squeeze using an intake / exhaust unit. The thickness of the obtained first transfer layer (T ₁ ) was 1.0 μm.

Resin particle dispersion (L-1) Resin particles (AR-1) 20 g (as solid content) Charge control agent (CD-1) 0.08 g Octadecyl vinyl ether / t-octyl maleic acid half amide (1/1) (Mole ratio) Copolymer Charge adjusting auxiliary agent (AD-1) 2 g Dodecyl methacrylate / methacrylic acid (95/5 weight ratio) A copolymer was prepared with Isopar G to a total amount of 1.0 liter.

Next, an electrophotographic process was carried out with the surface temperature of the photosensitive member kept at 50 ° C. to form a toner image. That is, the photoconductor 11 on which the transfer layer is formed is passed under the corona charging device 18 in a dark place, charged with +450 V by the corona, and then read in advance from a document by a color scanner to perform color separation. After the correction related to the color reproduction of, yellow stored in the hard disk in the system as digital image data,
Based on information about yellow among magenta, cyan, and black, a semiconductor laser drawing device is used as the exposure device 19 with light of 788 nm, a beam spot diameter of 15 μm, a pitch of 10 μm, and a scanning speed of 300 cm.
The exposure amount on the light-sensitive material was adjusted to 25 erg / m ² (2500 dpi).

Subsequently, the positively charged yellow toner for the signature system (manufactured by Kodak) is 75 times as much as Isopar H.
It is diluted with (Esso Standard Petroleum) and supplied to the yellow liquid developing unit 14Y, a bias voltage of + 350V is applied to the developing unit 14Y side, and reversal development is performed so that the toner is electrodeposited on the exposed portion. After rinsing the L-only bath to remove stains on the non-image area, the air was passed through the intake / exhaust unit 15 and dried. The above toner image forming process was repeated for each color of magenta, cyan and black to obtain four color toner images. A second transfer layer (T ₂ ) was provided on the entire surface of the first transfer layer (T ₁ ) carrying a toner image by an electrodeposition coating method. That is, with the surface temperature of the photoreceptor kept at 50 ° C., the second transfer layer (T ₂ ) Was formed. Resin particle dispersion liquid (L-2) Resin particles (AL ₂ R-1) 20 g (as solid content) Charge control agent (CD-1) 0.08 g Charge control auxiliary agent (AD-1) 2 g with Isopar G Prepared to be 1.0 liter.

Next, the coated paper which is the material 16 to be transferred is placed between the photosensitive drum having the toner image with the surface temperature kept at 50 ° C. and the transfer backup roller 17b and the peeling backup roller 17c set at the temperature of 120 ° C. The nip pressure of 5 kgf / cm ² and the drum peripheral speed of 100 mm /
Heating and pressurization were performed for seconds. The color toner images were all transferred onto coated paper to obtain a multicolor color copy. The copied image thus formed on the coated paper was visually observed using a 200 × optical microscope. No background stains on the non-image area were observed, and the toner image was transferred to the coated paper without being left untransferred on the photoconductor together with the transfer layer, and the lack of high-resolution areas such as fine lines and fine characters was recognized. However, 2 to 99% of halftone dots of 165 lines, fine lines of 10 μm and Mincho type 2 or higher grade were resolved, and there was no deformation such as bending or thickening of the image, and it was a very good copy image. On the other hand, no transfer layer remained on the surface of the photoreceptor.

Comparative Example 1 In the same manner as in Example 1, except that only the first transfer layer (T ₁ ) is provided or only the second transfer layer (T ₂ ) is provided, toner image formation and coating on coated paper are performed in the same manner. Transferred.
The color image on the obtained coated paper had many missing image portions and was not completely transferred.

Comparative Example 2 In Example 1, 10 g each of the resin particles (RL-1) and the resin particles (RL-2) were used instead of the resin (AR-1) in the resin particle dispersion liquid (L-1). The toner image formation, the second transfer layer formation, and the transfer onto the coated paper were performed in the same manner except that the photosensitive member was used as the first transfer layer having a film thickness of 1.0 μm (as the solid content). The color image on the obtained coated paper had many missing image areas and was not completely transferred.
Therefore, when the transfer conditions for complete transfer were examined, the same good color copy as in Example 1 was obtained under the following conditions.・ Surface temperature 80 ℃ ・ Backup roller temperature for transfer 120 ℃ ・ Drum peripheral speed 20mm / sec ・ Nip pressure 4kgf / cm ²

From the above results, according to the method of the present invention,
The toner image is sufficiently peeled from the photoconductor, and the problems such as the loss of the image portion as described above do not occur, and the toner image is in sufficient contact with the transfer layer, so that the stability of the color copy obtained is stable. It turns out that the property is also excellent. In addition, the ability to write on a copy with a pencil, a ballpoint pen, etc., the imprintability, and the filing property to a file made of a plastic film such as a vinyl chloride sheet were almost the same as those of plain paper and did not cause any problems. Furthermore, instead of coated paper as the material to be transferred, fine paper, copy paper for PPC, plain paper, P
When a color image was similarly prepared using the ET film, a color copy exactly the same as in Example 1 was obtained. In this way, a stable and good color copy can be easily obtained even if transfer materials having different surface smoothness and different compositions are used. The production of the above multicolor color copy according to the present invention was repeated 300 times. The 300th copy was exactly the same as the first copy. Further, the transfer layer on the surface of the photoconductor and the residual toner image were not observed at all.

Example 2 An amorphous silicon electrophotographic photosensitive member (manufactured by Kyocera Corp.) was attached to the apparatus as shown in FIG. The adhesive force on the surface of the photoconductor was 230 g · f. The release property was imparted to the photoreceptor by a method of immersing the compound (S) of the present invention in a solution in the apparatus (immersion method). That is, the photoreceptor was rotated at a peripheral speed of 10 mm / sec in a bath containing a solution prepared by dissolving 1.5 g of the following compound (S-1) in 1 liter of Isopar G (manufactured by Esso Corporation). It was touched for 7 seconds and dried by air squeeze.
The adhesive force on the surface of the photoconductor thus treated is 2 g · f
Showed good peelability.

[0208]

Embedded image

Next, after adjusting the surface temperature of the photosensitive drum to 50 ° C., the photosensitive drum was rotated at a peripheral speed of 100 mm / sec, and the following resin particle dispersion (L
While supplying -3), the photoreceptor side was grounded and a voltage of +130 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit and fix the resin particles. The film thickness of the obtained first transfer layer (T ₁ ) was 1.0 μm.

Resin particle dispersion liquid (L-3) Resin particles (AR-3) 10 g (as solid content) Charge control agent (CD-2) 0.09 g 1-hexadecene / N-decyl maleic acid half amide (1 Copolymer branched tetradecyl alcohol (FOC-1400 5 g manufactured by Nissan Kagaku Co., Ltd.) was prepared with Isopar G to a total volume of 1.0 liter.

Next, after the photoreceptor 11 having the first transfer layer (T ₁ ) formed thereon was corona charged to +700 V, the same digital image data as in Example 1 was used, and first, based on the information about yellow. The surface of the photosensitive material was exposed to light of 780 nm using a semiconductor laser so that the 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 image forming process was repeated for each color of magenta, cyan and black.

Next, the first transfer layer (T ₁ ) carrying the toner image is transferred from the release paper to the second transfer layer (T ₁ ).
₂ ) was provided. That is, separate paper (manufactured by Oji Paper Co., Ltd.) is used as the release paper 20, and vinyl acetate /
A paper coated with a vinyl propionate (75/25 weight ratio) copolymer having a film thickness of 1.5 μm was mounted on a transfer layer forming device 117, a roller pressure of 3 kgf / cm ² , a roller surface temperature of 80 ° C. and The second transfer layer (T ₂ ) was transferred and formed on the first transfer layer (T ₁ ) on which the toner image was formed under the condition of the passing speed of 50 mm / sec.

Next, the temperature of the photosensitive drum provided with the toner image and the transfer layer is adjusted to 50 ° C., a fine paper is placed between the transfer rubber roller whose surface temperature is set to 120 ° C., and the nip pressure is 4 kgf / cm. ² It was passed at a conveying speed of 100 mm / sec.
After passing, the high-quality paper was peeled off from the photoconductor, and the toner image was transferred onto the high-quality paper together with the transfer layer. The copied image thus formed on the high-quality paper was visually observed using a 200 × optical microscope. No background stains on the non-image area were observed,
In addition, the toner image and the transfer layer are all transferred onto high-quality paper without being left untransferred on the photoconductor, resulting in missing or disturbing high-resolution areas such as fine lines and fine characters, and halftone dots in the high-definition image area in the halftone area. No missing or disorder was observed, and it was a very good copy image. The image strength was also sufficient. Furthermore, the writing and stamping properties were also good.

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

[0215]

Embedded image

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

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

[0218]

[Table 6]

The color copy thus obtained had a clear image quality without background stains. That is, the toner image formed on the light-sensitive material showed good image reproducibility and good image pickup property with no fog in the non-image area. Also, the transfer of each transfer layer onto the coated paper was completed without causing any inconvenience such as uneven transfer. Further, it was possible to add or stamp a color copy in the same manner as in the case of coated paper.
In addition, 300 copies were repeatedly produced.
In all cases, the performance was exactly the same as the first version.

Example 14 2 g of X-type metal-free phthalocyanine, 14 g of a binder resin (B-3) having the following structure, and a releasability-imparting resin (P-
1) Add 50 g of a mixture of 4 g and 80 g of tetrahydrofuran.
It was put together with glass beads in a 0 ml glass container, and dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho) for 60 minutes.
After adding 0.02 g of phthalic anhydride and 0.005 g of acetylacetone zirconium salt to the dispersion, they were dispersed again for 1 minute and the glass beads were filtered to obtain a dispersion liquid for a photosensitive layer.

[0221]

[Chemical 21]

This dispersion was applied to a degreased 0.2 mm thick aluminum plate with a wire bar, dried by touch with a finger, and then heated in a circulating oven at 110 ° C. for 20 seconds and further heated at 140 ° C. for 1 hour. did. The thickness of the obtained photosensitive layer is 8
μm. The adhesive strength of the surface of this photoreceptor was 1 g · f. On the other hand, the adhesive force of the surface of the photoreceptor prepared in the same manner without adding the resin (P-1) was 400 g · f or more, showing no releasability at all. Using the above photoreceptor, the same operation as in Example 1 was carried out to prepare a color copy. The color copy obtained had a clear image quality with no background stain, and no transfer layer or toner image remained on the photoreceptor. Further, even when 4 g of the resin particles (PL-1) was used instead of 4 g of the resin (P-1), the same performance as that of Example 14 was exhibited.

Example 15 As an organic light-transmitting substance, 4,4'-bis (diethylamino) -2,2'-dimethyltriphenylmethane (5 g), a binder resin (B-4) having the following structure (5 g), and a structural formula shown below were used. Dye (D-1) 40 mg, anilide compound (B) 0.2 g having the following structural formula as a chemical sensitizer, and methylene chloride 30
It was dissolved in a mixture of 30 ml of ethylene chloride and 30 ml of ethylene chloride to obtain a photosensitive layer dispersion liquid.

[0224]

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 (surface resistance: 10 ³ Ω)) using a wire round rod. Then, it was dried by touch to the touch, and then heated for 1 hour at a temperature of 80 ° C. The thickness of the obtained photosensitive layer was 6 μm.

Furthermore, in order to form a surface layer for imparting releasability on the photosensitive layer, a resin (P-
2) A mixed solution of 13 g, glutaric anhydride 0.2 g, o-chlorophenol 0.002 g and toluene 100 g was applied to a film thickness of 1 μm using a wire round rod, and after touch-drying, further at 140 ° C. 1 Heated for hours. The adhesive force on the surface of each of the obtained photoreceptors was 2 g · f or less.

[0227]

Embedded image

A copied image was formed in the same manner as in Example 1 except that this photoreceptor and plain paper were used. The color image of the obtained plain paper was clear without scumming and the image strength was good.

Example 16 5 g of bisazo pigment having the following structure, and tetrahydrofuran 95
g of polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) was sufficiently pulverized in a ball mill. This mixture was taken out and 520 g of tetrahydrofuran was added with stirring. This dispersion was coated on the same conductive transparent support as used in Example 21 using a wire round rod to form a charge generation layer of about 0.7 μm.

[0230]

Embedded image

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

[0232]

Embedded image

On the surface of this photoreceptor, 9 g of a silicone rubber polymer having the following structure, 400 mg of a crosslinking agent having the following structure, 40 m of catalyst X92-1114 (manufactured by Shin-Etsu Silicon Co., Ltd.)
g, a mixed solution of 150 g of heptane is uniformly applied with a wire bar, heated at 90 ° C. for 2 minutes to dry and crosslink,
A peelable surface layer was formed. At this time, the thickness of the surface layer was 1.0 μm. The surface adhesive strength was 1 g · f or less.

[0234]

[Chemical formula 26]

The surface potential of this light-sensitive material was +500 V in the dark.
After being charged to 633 nm, a He-Ne laser is used.
A color copy was obtained in the same manner as in Example 1 except that the surface was exposed to the light of 30 erg / cm ² .
Each of the obtained copies showed good performance as in Example 1.

Examples 17 to 19 The same amorphous silicon photoreceptor as used in Example 2 was dipped in a solution prepared by dissolving each compound (S) shown in Table G below in 1 liter of Isopar L for 20 seconds, Rinse in Isopar L and dry. The adhesive force on the surface of each of the obtained photoreceptors was 3 g · f or less, and all showed good peelability.

[0237]

[Table 7]

In the same manner as in Example 2, the apparatus shown in FIG. 4 (however, without the compound (S) application apparatus 10) was loaded to prepare a color copy. In all cases, good results, which were exactly the same as in Example 2, were obtained.

[0239]

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 a method of the present invention.

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

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

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

[Explanation of symbols]

1 Support 2 Photosensitive Layer 3 Toner Image 10 Compound (S) Applicator 11 Electrophotographic Photosensitive Member 12T ₁ First Transfer Layer (T ₁ ) 12T ₂ Second Transfer Layer (T ₂ ) 12a Thermoplastic Resin Particle Dispersion 12b Heat Plastic 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 15 Air intake / exhaust unit 15a Intake part 15b Exhaust part 16 Transfer material 17 Transfer means to transfer material 17a Heating means 17b Transfer backup roller 17c Separation backup roller 18 Corona charging device 19 Exposure device 20 Release paper 117 Transfer layer forming device 117b Addition Roller 117c cooling roller

Claims (3)

[Claims] 1. Adhesive strength according to JIS Z0237-1980 "Adhesive tape / adhesive sheet test method" is 20 gram.
A first transfer layer (T ₁ ) is formed on the surface of the electrophotographic photosensitive member having a force of not more than a force, a toner image of one or more colors is formed on the transfer layer by an electrophotographic process, and the toner image is further formed on the toner image. In the color image forming method, after the second transfer layer (T ₂ ) is formed, the toner image is transferred to the transfer material together with the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ). The transfer layer (T ₁ ) has at least one resin (AH) having a glass transition point of 30 ° C. to 80 ° C. or a softening point of 35 to 90 ° C. and a glass transition point of −30 ° C. to 40 ° C. or a softening point of 0 ° C. to 6
Is composed of at least one resin (AL ₁ ) at 0 ° C.,
Further, it is formed by an electrodeposition coating method using resin particles (AR) having a glass transition point or a softening point difference of 2 ° C. or more between the resin (AH) and the resin (AL ₁ ), and further, the second transfer layer. (T ₂ ) has a glass transition point of 35 ° C. or lower or a softening point of 4
An electrophotographic color image forming method, which is mainly composed of a resin (AL ₂ ) at 5 ° C. or lower. 2. The peelable second transfer layer (T ₂ ) is formed by any one of a hot melt coating method, an electrodeposition coating method and a transfer method. Electrophotographic color image forming method of. 3. The following (i) to (iv) in the same device:
The method according to claim 1 or claim 2, wherein
The electrophotographic color image forming method described in any one of 1. (I) JIS Z0237-1980 "Adhesive tape
The first transfer layer (T ₁ ) is formed on the surface of the electrophotographic photosensitive member having an adhesive force of 20 gram · force or less according to the “adhesive sheet test method”.
Forming a toner image of at least one color on the first transfer layer (T ₁ ) by an electrophotographic process, (iii) forming a second transfer layer (T ₂ ) on the toner image. Step of forming, (iv) Step of transferring the toner image together with the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ) to the transfer material.