JPH09146336A - Color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily and stably obtain a high-definition and high-quality color image without color slurring and to reproduce the excellent color image without selecting final material to be transferred. SOLUTION: After forming a toner image 3 of one or more colors on an electrophotographic photoreceptor 11 having a peelable surface by using liquid developer in an electrophotographic process, the toner image 3 on the photoreceptor 11 is contact-transferred on a primary receptor 20, and transferred on the material to be trasferred 30 provided with a tight contact layer (M) 5 principally containing thermoplastic resin (AM) whose glass transition point is <=80 deg.C or whose softening point is <=90 deg.C so as to form the color image (route (a)). Furthermore, it is conceivable to transfer the toner image through transfer layers (T) 7, 7' and 8 (routes (b) to (d)).

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 for a color copying machine, a color printer, a color proofer, a color checker or the like. Especially,
The present invention relates to a color image forming method for stably and repeatedly forming high quality copied images using a liquid developer.

[0002]

2. Description of the Related Art Toners of a plurality of colors are sequentially overlaid on an electrophotographic photosensitive member surface using a developer for electrostatic photography to develop a color image to form a color image, which is then transferred at a time to a transfer material such as printing paper. By doing so, a method of producing a color image printed matter, a color image 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 a dry toner, 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-2-115865 and 2-
In JP-A-115866, after a transparent film is laminated on the surface of a 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 form an image. A method of transferring is disclosed. However, in this case, the film to be laminated is 9
Although a thickness of μm is suitable, the production and handling of a film having such a thickness are extremely troublesome, and it is necessary to take measures separately for that purpose.

Further, Japanese Patent Publication No. 2-43185 discloses that
A method is disclosed in which a transparent electrophotographic photosensitive member is exposed from the rear side to form an overlapping color separation image on a dielectric support, and the whole support is transferred onto a transfer material. In this method, light is exposed from the transparent support side of the photoreceptor, and the conductive layer must be transparent, which is disadvantageous in terms of cost.

On the other hand, Japanese Patent Application Laid-Open Nos.
No. 281464 and No. 3-11347, in an electrophotographic transfer method using a so-called dry development method, a peelable transfer layer is provided in advance on the surface of a photoconductor, and a toner image is formed on the transfer layer. Proposals have been made to transfer the entire transfer layer onto the paper. However, in these techniques, when the photoreceptor is repeatedly used, a special operation is required at the time of transfer, and it is difficult to form the transfer layer. Further, in the method of using the photoconductor on which the transfer layer (or the peeling layer) is formed in advance, the photoconductor must be thrown away and the cost disadvantage cannot be avoided.

On the other hand, Japanese Patent Laid-Open No. 2-264280 describes a method of transferring a toner image on a photosensitive layer to a highly smooth primary intermediate transfer medium and then transferring it onto a final transfer material.
Further, JP-A-3-243973, JP-A-4-9087 and the like propose 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 material to be transferred, but since the toner image is directly transferred onto the primary intermediate transfer medium and further onto the final material to be transferred. In the obtained color image, a missing toner image or uneven image density is seen, and in particular, a fine image missing such as a thin line or a thin character is recognized. Further, the toner image remains on the surface of the photoconductor after the toner image is transferred. This means that when the photoconductor is repeatedly used, it becomes necessary to clean the surface of the photoconductor, and setting of an apparatus for that purpose and damage to the surface of the photoconductor due to the cleaning become problems.

Further, JP-A-5-181324 and 5-1.
No. 81325 discloses a method for forming a color image using a wet toner capable of repeatedly using a photoconductor, after providing a transfer layer made of a peelable thermoplastic resin on a photoconductor having an easily peelable surface, It has been proposed that after a toner image is formed by a photographic process, the toner image is formed on the final transfer material together with the transfer layer. According to these methods,
Even when a wet toner is used, by transferring the toner image together with the transfer layer, it is possible to completely transfer the toner image onto the final transfer target material without deteriorating the toner image, and the transfer layer is subjected to the electrophotographic process on the photoreceptor. It is described that the photoconductor can be repeatedly used by forming it on the surface, and the cost can be reduced.

However, even in these technologies,
The transfer layer must be designed so that it does not affect the electrophotographic process, and since a toner image is formed on the transfer layer, it must be sufficiently adhered to the final transfer material during transfer and peeled off. Therefore, the influence of the toner image portion or the surface condition of the final transfer material is likely to occur, and it cannot always be said that perfect transfer is always satisfied.

[0009]

As described above, according to 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 are changed and stable when repeatedly used. There are various problems such that it is difficult to maintain the above performance for a long time, a disposable member is generated to maintain the performance, and it is necessary to use a special transfer medium. Further, even in a color image forming method using a transfer layer on a photoconductor, it is difficult to obtain a stable and high-definition image when actually used, regardless of the type of toner and the final transfer material. It was

The present invention solves the problems of the conventional electrophotographic transfer image forming method as described above. An object of the present invention is to obtain a high-definition, high-quality color image without color shift easily and stably, and to reproduce an excellent color image without selecting the final transfer material. Another object of the present invention is to provide an electrophotographic color image forming method. In particular, an object of the present invention is to provide a color image forming method in which a toner image is still satisfactorily transferred to a final transfer material even if transfer conditions are relaxed and the transfer temperature or transfer speed becomes low or high, for example. To do.

[0011]

The above object of the present invention is to form a toner image of one or more colors by an electrophotographic process using a liquid developer on an electrophotographic photosensitive member having a releasable surface, and then to form the photosensitive image. The toner image on the body is contact-transferred onto the primary receptor, and further, the glass transition point is 80 ° C. or lower or the softening point is 9
It was found to be achieved by an electrophotographic color image forming method characterized by transferring onto a final transfer material provided with an adhesion layer (M) mainly containing a thermoplastic resin (AM) at 0 ° C. or lower. It was

That is, in the color image forming method of the present invention, as shown in the route (a) of FIG. 1 showing the outline of the process, the surface of the electrophotographic photosensitive member 11 comprising at least the support 1 and the photosensitive layer 2. A toner image 3 of at least one color is formed thereon by a normal electrophotographic process, then transferred onto the primary receptor 20, and then the toner image 3 is transferred onto a transfer material 30 provided with an adhesion layer (M) 5. Then, a color copy is made.

By providing the adhesion layer (M) according to the present invention, the adhesion with the toner image on the primary receptor is remarkably improved, peeling from the primary receptor becomes extremely easy, and the toner image is formed without causing image deformation. It is transferred onto the final transfer material promptly. The adhesion layer (M) provided on the transfer material may be previously coated on the transfer material, or the adhesion layer (M) may be formed on the surface of the transfer material in the same apparatus that performs an electrophotographic process. It may be formed each time.

Furthermore, in the present invention, a transfer layer can be further interposed in the above-mentioned color image forming method. For example, a releasable transfer layer (T ₀ ) mainly containing a thermoplastic resin (AT ₀ ) can be provided on an electrophotographic photoreceptor having a releasable surface before forming a toner image. That is, as shown in route (d) of FIG. 1, after the transfer layer (T ₀ ) 8 was provided on the surface of the electrophotographic photosensitive member 11, the adhesion layer (M) 5 was provided through the same process as above. The toner image 3 together with the transfer layer (T ₀ ) 8 can be transferred onto the transfer material 30 to form a color copy.

[0015] Alternatively, in the color image forming method, after providing the entire surface of the photosensitive member carrying the toner image thermoplastic resin (AT ₁₎ mainly peelable transfer layer containing (T _1), the toner image The toner image can be transferred onto the primary receptor or the toner image can be transferred onto the primary receptor provided with a transfer layer (T ₂ ) mainly containing a resin (AT ₂ ). That is, after the toner image 3 is formed on the photoconductor 11, the toner image 3 is transferred onto the surface of the primary receptor 20 provided with the transfer layer (T ₂ ) 7'as shown in the route (b) of FIG. Alternatively, as shown in route (c) in FIG. 1, a transfer layer (T ₁ ) 7 is formed on the entire surface of the photoconductor 11 on which the toner image 3 is formed, and the transfer layer is transferred together with the toner image onto the primary receptor 20. After that, the transferred material 30 provided with the adhesion layer (M) 5 is subjected to the same process as described above.
The toner image 3 can be collectively transferred together with the transfer layer (T ₁ ) 7 or (T ₂ ) 7'onto a color copy.

These transfer layers (T ₀ ), (T ₁ ) or (T ₂ ).
By setting {these transfer layers may be collectively referred to as a transfer layer (T) hereinafter}, it is possible to moderate transfer conditions, improve transfer speed, etc., and more easily transfer a toner image. Can be In particular, the adhesion layer (M)
Since the glass transition point or softening point of the resin (AM) can be adjusted to the low temperature side, the adhesiveness of the resin (AM) can be sufficiently expressed at the second transfer temperature being relatively low, and the adhesion can be improved. The transferability can be further improved.

In the present invention, the transfer layers (T ₀ ) and (T ₂ ) are
A transfer layer having a transfer layer on the photoconductor or the primary receptor in advance may be used, but the photoconductor after the transfer layer is peeled off by forming the transfer layer on the photoconductor or the primary receptor each time in the transfer device. And the primary receptor can be repeatedly used, and the electrophotographic process can be continuously performed in the electrophotographic copying machine without disposing of the photoreceptor and the primary receptor.

The adhesion layer (M) provided on the surface of the material to be transferred of the present invention satisfies the requirements of maintaining the transferability in the thermal transfer process and maintaining the mechanical strength of the film, and has a glass transition point of 8
Thermoplastic resin (AM) having a softening point of 0 ° C or lower or 90 ° C or lower
Mainly consists of.

Provide on photoreceptor surface before electrophotographic process
Transfer layer (T₀) Is the transfer layer (T ₀) On electrophotography professional
Process toner image formation and color copying
The uppermost layer on the surface side of the final material to be transferred
In addition to the above characteristics, electrophotographic characteristics (chargeability, dark
Do not deteriorate the load holding ratio, light sensitivity, etc.), toner image
It is necessary to maintain the film strength to protect the
Glass transition point 10 ° C to 80 ° C or softening point 30 ° C to 9
0 ° C thermoplastic resin (AT₀).

The transfer layer (T ₁ ) provided on the toner image of the photoreceptor and the transfer layer (T ₂ ) provided on the surface of the primary receptor are the uppermost layers on the surface of the final transfer material as a color copy. From the glass transition point 20 ° C. to 80 ° C. or the softening point 40 to 50
It mainly consists of thermoplastic resins (AT ₁ ) and (AT ₂ ) at ℃.

Further, the thermoplastic resin (AT ₀ ), (AT ₁ ), or (AT ₂ ) {hereinafter, these resins are collectively referred to as resin (AT)
The transfer layer mainly consisting of
It is preferable that it can be adhered and peeled at a temperature of 0 ° C. or lower and / or a pressure of 20 kgf / cm ² or lower, preferably at a temperature of 160 ° C. or lower and / or a pressure of 10 kgf / cm ² or lower. If the above conditions are exceeded, the apparatus for maintaining the heat capacity and pressure in the apparatus for peeling / transferring the transfer layer from the surface of the photoreceptor becomes large and the transfer speed becomes extremely slow, which is not preferable. Further, the above conditions are a temperature above room temperature and /
Alternatively, the pressure is preferably 0.1 kgf / cm ² or more.

Further, when the transfer layer is provided on the photoreceptor or the primary receptor, the thermoplastic resin (AM) which mainly constitutes the adhesion layer (M) on the material to be transferred mainly constitutes the transfer layer. The difference in glass transition point or softening point is preferably 5 ° C. or more, more preferably 8 ° C. or more lower than that of the resin (AT).

In a specific embodiment, when a transfer layer is provided, the thermoplastic resin (AM) has a glass transition point of -50 ° C.
-30 ° C or softening point -40 ° C to 38 ° C, particularly preferably glass transition point -25 ° C to 25 ° C or softening point -20 ° C to 30 ° C. As described above, resin (AM) and resin (A
By adjusting the glass transition point or softening point with T), the transferability to the transfer material is further improved, the latitude of the transfer conditions (heating temperature, pressure, transport speed, etc.) is expanded and the toner image It becomes possible to transfer the image more easily regardless of the type of the final transfer material to be a copy.

Further, the adhesion layer (M) and each transfer layer (T)
Can be repeatedly used as a photoreceptor primary receptor by forming the electrophotographic process in the same apparatus each time. Further, not only the transfer material provided with the adhesion layer (M) in advance but also an arbitrary transfer material can be used. The transfer material can be selected according to the purpose, so that the running cost can be remarkably reduced, and the usage modes can be diversified.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic photosensitive member according to the present invention will be described. As the electrophotographic photosensitive member, any conventionally known one can be used. What is important is that the surface of the photoreceptor has releasability so that the toner image or transfer formed on the photoreceptor and the toner image can be easily separated. In particular, in the present invention, it is preferable that the surface of the photoreceptor has an adhesive force of 20 g · f or less according to JIS Z 0237-1980 “Adhesive tape / adhesive sheet test method”. By adjusting the adhesive force in this manner, the toner image formed on the photoconductor can be easily and completely transferred onto the primary receptor together with the transfer layer in some cases.

The measurement of the adhesive strength of the above-mentioned photoreceptor according to JIS Z 0237-1980 "Adhesive tape / adhesive sheet test method" is 8.
In accordance with the 180-degree peeling method in 3.1, the following modifications are made. An electrophotographic photosensitive member on which a toner image is to be formed is used as a “test plate”. As a “test piece”, an adhesive tape manufactured according to JIA C 2338-1984 having a width of 6 mm is used. Peel off at a speed of 120 mm / min using a constant speed tension type tensile tester. That is, a roller is reciprocated from the top of the test piece at a speed of about 300 mm / min, with the adhesive surface of the test piece facing down, and pressure-bonded to the test plate. During 20 to 40 minutes after crimping, using a constant speed tension type tensile tester, after peeling off about 25 mm, 120
Peel off at a speed of mm / min. The force is read every 20 mm peeling, for a total of 4 readings. The test is performed on three test pieces, and an average value of twelve pieces measured from the three test pieces is obtained, and this is converted into a proportional value per 10 mm width. The adhesive force on the surface of the electrophotographic photosensitive member is preferably 20 g · f or less, more preferably 10 g · f or less.

Examples of the photoreceptor having a releasable surface used in the present invention include a photoreceptor having a releasable surface in advance. Specifically, a method of using a photoconductor obtained by modifying the surface of an electrophotographic photoreceptor mainly containing amorphous silicon to have a releasable property, at least one of a silicon atom and a fluorine atom near the surface on the photoconductive layer. A method of providing an overcoat layer containing a polymer containing a polymer component (containing a silicon atom and / or a fluorine atom) and cross-linking the polymer is included.

Such a photosensitive member has an extremely excellent releasability on its surface, wets with a carrier liquid in a developing process using a liquid developer, and further, a non-image portion in a non-image area in a heating and pressure transfer process. The releasability of the photoreceptor surface and the releasability of the primary receptor surface are not deteriorated even after repeated contact with the surface of the primary receptor, and the electrophotographic process in the above overcoat layer is performed under a heated condition. Has a characteristic that the film hardly swells even after being subjected to a wet process or when it is wet with a carrier liquid, and a toner image formed on a photoconductor is not distorted to form a high-definition copy image. be able to.

As a method for modifying the surface of the electrophotographic photosensitive member mainly containing amorphous silicon to be releasable, a coupling agent (silane coupling agent, titanium coupling agent, etc.) containing a fluorine atom and / or a silicon atom is used. ) Or the like, there is a method of treating the surface of the amorphous silicon layer with the method described in JP-A-55-89844 and JP-A-4-231.
No. 318, JP-A-60-170860 and JP-A-59-10
Nos. 2244 and 60-17750.

Further, as another method, a method of adsorbing and fixing a peeling compound (S) containing a fluorine atom and / or a silicon atom as a substituent can be mentioned. For example, the compound (S) can be adsorbed and fixed by dissolving the compound (S) in a solvent to form a solution having a concentration of about 0.1 to 5% by weight, immersing the photoreceptor in this solution, and then drying.

Examples of the strippable compound (S) include compounds containing at least a fluorine atom and / or a silicon atom, and the structure thereof is not particularly limited as long as it improves the strippability of the surface of the amorphous silicon photoreceptor. It may be a low molecular weight compound, an oligomer, or a polymer, not a substance. 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, an oligomer or a polymer containing a repeating unit containing the substituent as a block is used, and these can particularly effectively express the adsorptivity and the releasability to the surface of the amorphous silicon photoreceptor.

Specific examples of the compound (S) containing a fluorine atom and / or a silicon atom used in the present invention include:
"New edition surfactant surfactant handbook" edited by Tokiyuki Yoshida, etc., published by Kogyo Tosho Co., Ltd. (1987), supervised by Takao Karimei "Latest surfactant application technology", CMC Corporation (1990), edited by Kunio Ito "Silicone Handbook" published by Nikkan Kogyo Shimbun (19
1990), supervised by Takao Karimei "Specially Functional Surfactant" C.
MC (1986), AM Schwartz et al. "Surface Act"
ive Agents and Detergents vol. II "and the like. Furthermore, Nobuo Ishikawa "Synthesis and Function of Fluorine Compounds" CM
C. (1987), edited by Jiro Hirano et al., "Fluorine-Containing Organic Compounds-Synthesis and Application-", Technical Information Association (1991), edited by Mitsuo Ishikawa, "Organic Silicon Strategic Materials", Chapter 3 Science, Inc. Compound (S) can be synthesized using a synthesis method described in a document such as Forum (1991).

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, the term "consisting of blocks" means that the polymer has a polymer segment containing at least 70% by weight of a component having a fluorine atom and / or a silicon atom.
-B type block, ABA type block, BAB type block, graft type block or star type block. Specific compounds and embodiments of compound (S) are the same as those described in JP-A-7-5727.

In the second method, the overcoat layer provided as the uppermost layer on the surface of the photoconductor may be any one as long as the surface energy of the coating film is 30 erg.cm ^-1 or less. By adjusting the value within the above range, the adhesive force becomes 20 g · f or less, and complete transfer of the toner image layer is easily achieved. The coating surface energy is preferably 28 erg · cm ⁻¹ or less, more preferably 2 erg · cm ⁻¹ or less.
5 erg · cm ⁻¹ or less, more preferably 15 erg · cm ^{−1 to} 25
erg · cm ⁻¹ .

Specific examples of the method for adjusting the coating surface energy of the overcoat layer to the above range include a method in which a fluorine resin, a silicon resin, or the like is contained in the layer. Another feature of such a layer is that the coating forms a cured film structure.

The fluororesin is a resin mainly containing a polymer component having a substituent containing a fluorine atom. The substituent may be incorporated into the polymer main chain of the polymer, or may be contained in a substituent on the side chain of the polymer. As a substituent containing a fluorine atom, for example,-
_{C h (F) 2n + 1} (n is 1 to 22 integer), - CFH _2, -
(M is an integer _{1~17) (CF 2) m CF} 2 H, - CF
₂ -, - CFH-, such monovalent or divalent organic residues and the like.

These fluorine-atom-containing organic residues may be combined and constituted, in which case they may be directly bonded or may be combined through another linking group. Specific examples of the linking group include divalent organic residues, and include —O—, —S—, —N (d ¹ ) —, and —CO—.
-, - SO -, - SO 2 -, - COO -, - OCO-,
-CONHCO -, - NHCONH -, - CON (d 1)
A divalent aliphatic group or a divalent aromatic group, which may have a bonding group selected from —, —SO ₂ N (d ¹ ) — and the like,
Alternatively, it represents an organic residue composed of a combination of these divalent residues. Here, d ¹ represents an alkyl group having 1 to 3 carbon atoms. The fluorine-containing polymer component is preferably contained in an amount of 80 to 99 parts by weight based on 100 parts by weight of the whole polymer component of the resin.

Further, the resin contains a curable functional group, and the content thereof is 1 to 20% by weight. Examples of the contained curable functional group include those described in the below-mentioned silicon-based resin. The weight average molecular weight of the resin is
Preferably it is 5 × 10 ³ to 1 × 10 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10 ⁵ .

The silicon-based resin is a resin mainly containing a polymer component containing a substituent containing a silicon atom. In the present invention, a polymer mainly composed of a component having a repeating unit of an organosiloxane structure represented by the following general formula (I) can be mentioned as a specific example.

[0040]

Embedded image

In the above formula (I), R ₁ and R _{2, which} may be the same or different, each represents an aliphatic group, an aromatic group or a heterocyclic group.

R ₁ and R ₂ may be the same as or different from each other, and preferably have 1 carbon atoms which may be substituted.
~ 18 linear or branched alkyl group {for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Hexadecyl group,
Octadecyl, 2-fluoroethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-
Cyanoethyl group, 2-methoxycarbonylethyl group, 2
- methoxyethyl group, 3-bromopropyl group, 2-methylcarbonyl ethyl group, 2,3-dimethoxy _{propyl, - (CH 2) p C} n F 2n + 1 group (wherein p is an integer of 1 or 2, n represents an integer of _{1~12), - (CH 2)} p -
(CF ₂ ) _m —R ′ group (where p is an integer of 1 or 2, m is 1
12 integer, R 'is -CFHCF ₃ or -CFHCF ₂
H), etc., and an optionally substituted alkenyl group having 4 to 18 carbon atoms (eg, 2-methyl-1-propenyl group, 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, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group, etc.), carbon Aralkyl groups of the formulas 7 to 12 which may be substituted (for example, benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, methylbenzyl, ethyl A benzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group or the like, an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl) Group, polyfluorohexyl group, methylcyclohexyl group, meth Shi cyclohexyl group, a carbon number 6
To 12 optionally substituted aromatic groups (for example, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, Butoxyphenyl group, fluorophenyl group, chlorophenyl group, difluorophenyl group, bromophenyl group,
Cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, trifluoromethylphenyl group and the like.

Further, R ₁ and R ₂ are each a heterocyclic group which may be condensed with at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom (for example, the hetero ring is a pyran ring). , Furan ring, thiophene ring, morpholine ring, pyrrole ring, thiazole ring, oxazole ring, pyridine ring, piperidine ring, pyrrolidone ring, benzothiazole ring, benzoxazole ring, quinoline ring, tetrahydrofuran ring, etc.).

A methyl group is preferable as R ₁ and R ₂ . The total amount of organosiloxane units in the silicone resin is preferably 60% by weight or more, more preferably 75% by weight or more, of dimethylsiloxane units in which R ₁ and R ₂ are methyl groups. Thereby, the releasability is more favorably maintained, and complete transfer of the toner image layer is easily achieved.

Further, in order to sufficiently strengthen the adhesiveness between the overcoat layer and the surface of the photoreceptor, as a specific component, a substituted alkyl group (for example, a halogen atom, a cyano group substituted product) described above in the above-mentioned silicone resin, Examples thereof include a substituent R ₁ or R ₂ selected from an optionally substituted aralkyl group, an aromatic group and a heterocyclic group. Further, those containing a polar group such as a carboxyl group, a hydroxyl group, a mercapto group, a phospho group, or an amide group in the substituents of R ₁ and / or R ₂ , or a ureide group (—NHCONH
-), Thioether group (-S-), urethane group (-NH
Those containing a divalent linking group such as COO-) are also included. The organosiloxane unit containing the substituent is
It is less than 40% by weight, more preferably less than 30% by weight, based on the total amount of all organosiloxane units.

Further, it is preferable that the dimethylsiloxane unit, which is a good component for improving the peeling property, and the other organosiloxane unit, which has a good adhesiveness with the above-mentioned photoreceptor, satisfy the above-mentioned abundance ratio. May be any of a random copolymer, a block copolymer, and a star copolymer, and is not limited. This allows
It is possible to improve the adhesiveness on the photoconductor side while maintaining the peelability on the surface side.

The weight average molecular weight of the resin is preferably 5 ×
10 ³ to 1 × 10 ⁶ , more preferably 2 × 10 ⁴ to
It is 5 × 10 ⁵ . In the present invention, a resin containing both of the above-mentioned fluorine atom and silicon atom can be used as the resin for releasability.

Further, the resin layer serving as the overcoat layer used in the present invention forms a crosslinked structure and is a cured resin layer. Any conventionally known method can be used to cure the resin layer and form a crosslinked structure inside the layer. Hereinafter, a description will be given of a silicon resin as an example.

That is, the silicone resin itself is self-crosslinking, the silicone resin is crosslinked with various crosslinking agents or curing agents containing a component having a reactive group, or the silicone resin is crosslinked with various crosslinking agents. Alternatively, a method of crosslinking with a curing agent may be used. It may be some combination of these methods. Further, the reaction mode of the crosslinking reaction between the polymers of the resins may be any conventionally known chemical bonding reaction, or may be a combination of several reaction modes.

Specific examples of these reaction modes include the following reactions i) to iv). i) polyvalent metal ions (for example, Ca, Mg, Ba, Al, Zn, Fe, Sn, Zr,
Crosslinking by ionic bonding by a chelate reaction with a cation of a polyvalent metal such as Ti).

Ii) Organic reactive group (specifically, hydroxyl group, thiol group, halogen atom (for example, chlorine atom,
Bromine atom, iodine atom), carboxyl group, acid anhydride group, amino group, isocyanate group, protected isocyanate group (blotted isocyanate group), acid halide group, epoxy group, imino group, formyl group, diazo Cross-linking by a chemical bond due to an addition reaction, substitution reaction or elimination reaction between combinations of reactive groups selected from a group, an azide group and the like.

Iii) Self-coupling groups {eg --CON
Self-crosslinking with an HCH ₂ OR ₁ ′ group (R ₁ ′ represents a hydrogen atom or an alkyl group), the following groups and the like.

[0053]

Embedded image

(R ₂ ′ and R ₃ ′ may be the same or different and each represents a hydrogen atom or an alkyl group, and R ₂ ′ and R ₃ ′ may form 5 to 6 alicyclic rings. ), A cinnamoyl group, a -Si (R ₄ ′) _n (OR ₅ ′) _m group (R ₄ ′ represents an alkyl group, an alkenyl group or an aryl group, R ₅ ′ represents an alkyl group, and n is 0 or An integer from 1 to 2, m is 1
Represents an integer of ~ 3. However, n + m = 3)｝

Iv) Crosslinking by an addition polymerization reaction with a polymerizable double bond group or a triple bond group. Examples of the polymerizable double bond group include, for example, CH ₂ ＣC (p) COO— and C (CH ₃ ) H
ＣＨCHCOO—, CH ₂ （C (CH ₂ COOH) COO
_{-, CH 2 = C (p} ) CONH-, CH 2 = C (p) CO
_{NHCOO-, CH 2 = C (p} ) CONHCONH-,
_{C (CH 3) H = CHCONH-} , CH 2 = CHCO-,
_{CH 2 = CH (CH 2)} n OCO- (n is 0 or an integer of 1 to _{3), CH 2 = CHO-, CH} 2 = CH-C 6 H 4 -CH 2
= CH-S- or the like (where p is -H or-
CH ₃ ). Examples of the polymerizable triple bond group include those having the same linking group as described above.

These arbitrarily selected reactive groups can be contained at least in the polymer of the silicone resin. As the content form, specifically, the reactive group is directly attached to one or both of R _{1 and} R ₂ of the substituent of the siloxane unit represented by the repeating unit represented by the general formula (I). Substituted or contained in either or both of the substituents R ₁ or R ₂ , contained in a copolymer component of another polymer chain bonded to the polymer chain of the siloxane unit by a block. It may be bonded to the terminal of the polymer chain of the silicone resin (may be bonded via another linking group).

Further, conventionally known cross-linking reaction peculiar to the organosiloxane polymer is also an effective reaction, for example, "Silicone Handbook" edited by Kunio Ito, published by Nikkan Kogyo Shimbun (1990), supervised by Makoto Kumada and Tadashi Wada, "Latest Silicone Technology- Development and application- ", CMC Co., Ltd. (published in 1986), etc. As an example, those having the following substituents are exemplified.

[0058]

Embedded image

As described above, the curable reactive group may be contained as a random copolymer in the polymer chain together with the siloxane unit represented by the general formula (I) exhibiting peelability. It may be a so-called block copolymer in which a block that becomes releasable and a curable block are combined to form a polymer. Examples of the form of the block copolymer include forms such as a graft type, an AB type block (including an ABA type), and a star type. When provided with these block copolymers, the releasable block component preferably contains at least 30% by weight or more of all polymer components of the polymer, more preferably 5% by weight or more.
0% by weight or more.

As the cross-linking agent or curing agent capable of forming a cross-linking structure with the above-mentioned silicone resin, any of low molecular weight compounds, oligomers and polymers known as heat, light or moisture-curable compounds known in the related art can be used. These may be used alone or in combination of two or more.

Specific examples of the compound used as the crosslinking agent or the curing agent include "Crosslinking agent handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), "Polymer Data Handbook, Basic Edition" edited by The Society of Polymer Science, Japan. ”Baifukan (1986
Tsuyoshi Endo, "Precision of Thermosetting Polymer" (CMC
Ltd., 1986), Yuji Harasaki, "Handbook of Latest Binder Technologies", Chapter II-1 (General Technology Center, 1985), Takayuki Otsu, "Synthesis and Design of Acrylic Resins and Development of New Applications" (published by Chubu Business Development Center) 1985), and the compounds cited in the above-mentioned reviews such as "Silicone Handbook".

For example, an organic silane compound (for example, vinyltrimethoxysilane, vinyltriethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, vinyltrichlorosilane, vinyltris (t-butylperoxide) silane, γ-
(Β-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, silane coupling agent, etc.), polyisocyanate compounds (for example, toluylene diisocyanate, diphenylmethane) Diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.), and polyisocyanate-based polyisocyanate-protected polyisocyanates. Blocked isocyanate compounds (examples of compounds used for protecting isocyanate groups include alcohols, β-diketones,
β-ketoesters, amines, etc.), polyol compounds (eg, 1,4-butanediol, polyoxypropylene glycol, polyoxyethylene glycol,
1,1,1-trimethylolpropane, etc.), polyamine-based compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine,
Modified aliphatic polyamines, etc.), titanate coupling compounds (eg, tetrabutoxytitanate, tetrachlorooxytitanate, isopropyl tristearoyl titanate, etc.), aluminum coupling compounds (eg, aluminum butyrate, aluminum acetyl acetate, aluminum oxide octate) , Aluminum tris (acetyl acetate), etc.) polyepoxy group-containing compounds and epoxy resins (eg, "New Epoxy Resin" edited by Hiroshi Kakiuchi, Shokodo (1985), "Epoxy Resin" edited by Kuniyuki Hashimoto, Nikkan Kogyo Shimbun (1969) Compounds), poly (meth) acrylates (eg, compounds described in “Urea Melamine Resin”, edited by Ichiro Miwa, Hideo Matsunaga, Nikkan Kogyo Shimbun (1969)) and the like. Compound ( In example, Shin Okawara, Takeo Saegusa, Higashimura Satoshinobe ed., "Oligomer" Kodansha (1976 annual), Eizo Omori "functional acrylic resin" Techno System (1985
Compounds) described in the annual publication) and the like.

Specific examples of the polymerizable functional group of the polyfunctional monomer [also referred to as the polyfunctional monomer (d)] or the polyfunctional oligomer containing two or more polymerizable functional groups to be coexisted with each other. Include CH ₂ ═CHCH ₂ —, CH ₂ ═CHCOO
_{-, CH 2 = CH-, CH} 2 = C (CH 3) -COO-, C
_{H (CH 3) = CHCOO-,} CH 2 = CHCONH-,
_{CH 2 = C (CH 3)} -CONH-, CH (CH 3) = CH
_{CONH-, CH 2 = CHOCO-, CH} 2 = C (CH 3)
_{-OCO-, CH 2 = CHCH 2 OCO-} , CH 2 = CH
_{NHCO-, CH 2 = CHCH 2 NHCO-} , CH 2 = C
HSO ₂ —, CH ₂ ＣＨCHCO—, CH ₂ ＣＨCHO—, C
H ₂ = CHS- or the like can be mentioned. Any monomer or oligomer having two or more of these same or different polymerizable functional groups may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, a monomer or oligomer having the same polymerizable functional group, a styrene derivative such as divinylbenzene or trivinylbenzene: a polyhydric alcohol. (For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 20
0, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or polyhydroxyphenol (eg, hydroquinone, resorcin, catechol) And their derivatives)
Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (eg, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) Vinyl esters, allyl esters, vinyl amides or allyl amides: polyamines (eg, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and carboxylic acids containing vinyl groups (eg, methacrylic acid, acrylic Acid, crotonic acid, allyl acetic acid, etc.).

In the present invention, a reaction accelerator may be added, if necessary, in order to accelerate the crosslinking reaction of the overcoat layer. In the case of a reaction mode in which a crosslinking reaction forms a chemical bond between functional groups, for example, organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), phenols (phenol, chlorophenol, Nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc.), organometallic compounds (acetylacetonato zirconium salt, acetylacetone zirconium salt, acetylacetocobalt salt, dibutoxytin dilaurate, etc.), dithiocarbamic acid compounds (diethyldithiocarbamate, etc.) ), Thiouram disulfide compounds (such as tetramethylthiouram disulfide), carboxylic anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butyl succinic anhydride,
3,3 ', 4,4'-tetracarboxylic acid benzophenone dianhydride, trimellitic anhydride, etc.).
When the crosslinking reaction is a polymerizable reaction mode, thermal polymerization initiators (peroxides, azobis compounds, photopolymerization initiators and sensitizers (eg P. Walker, NJ Webers, et al. J. Pht
o.Sci., 18, 150 (1970), Katsumi Tokumaru, Shin Okawara, "Sensitizers" (Kodansha) (1987), etc. Organic sulfur compounds, azine-based compounds, azo compounds and the like can be mentioned.
Platinum catalysts, methylvinyltetrasiloxane, acetylene alcohols and the like can be used as a curing accelerator or a reaction control agent for silicone rubber.

As a matter of course, the curing conditions for curing these films are appropriately set according to the characteristics of the materials combined. To perform heat curing, for example, 60 ° C. to 15 ° C.
Treat at 0 ° C. for 5 to 120 minutes. When the above-mentioned reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As a method for curing a specific functional group in the resin by irradiation with light, a step of irradiating with a chemically active ray may be included. The optically active light beam may be any of visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, γ-ray, α-ray and the like, but is preferably ultraviolet light, more preferably a light ray having a wavelength 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.

The content of the above-mentioned releasing resin in the overcoat layer is preferably 60 to 100% by weight, more preferably 80 to 100% by weight.

Further, the overcoat layer used in the present invention contains another resin together with the above-mentioned releasable resin to the extent that the releasability is not impaired, and the adhesion between the surface of the photoreceptor and the releasable resin layer is improved. It is also possible to improve.

As the other resin (adhesive resin) which can be used in combination, various conventionally known resins can be used as long as they have a softening point of 35 ° C. or higher, preferably 40 ° C. or higher. Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and its derivatives, Polymers and copolymers, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene-unsaturated carboxylic acid ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer, Acrylic acid ester polymer and copolymer, methacrylic acid ester polymer and copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, itaconic acid diester polymer and copolymer, maleic anhydride Acid copolymer, acrylamide copolymer, methacrylamide copolymer, water Group modified silicone resins, polycarbonate resins, ketone resins, polyester resins, silicone resins,
Amide resin, alkyl-modified nylon resin, hydroxyl and carboxyl group-modified polyester resin, butyral resin,
Polyvinyl acetal resin, cyclized rubber-methacrylate copolymer, cellulose acetate resin, urethane resin,
Cyclic rubber-acrylic ester copolymer, copolymer containing a nitrogen-free heterocycle (for example, as a heterocycle, a furan ring, a tetrahydrofuran ring, a thiophene ring,
Dioxane ring, dioxofuran ring, lactone ring, benzofuran ring, benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy resin and the like.

The preferred proportion of these adhesion resins used in the overcoat layer is less than 80% by weight, and more preferably less than 60% by weight, based on the total resins in the layer.
In addition, a reactive group that is cured by heat, light, or moisture as described above may be contained in these adhesive resins.

As a method of compatibilizing these adhesion resins with a releasable resin so as to achieve both releasability and adhesion in the overcoat layer, for example, "Compatibilization and evaluation technology of polymers" edited by Technical Information Society (1992) Annual publication) Seiichi Nakahama, et al. "High-performance polymer alloys" edited by The Society of Polymer Science, Maruzen (published in 1991), etc. Particularly preferred examples of the adhesive resins include vinyl alkanoate polymers and copolymers, acrylic resins, methacrylic resins, vinyl chloride resins, cellulose acetate resins, urethane resins, and epoxy resins.

Further, in the film in which the peelable resin and the adhesion resin are mixed, a method may be used in which the characteristic that the peelable resin is concentrated and present on the surface side of the film is utilized. As the method, the adhesive resin is optional, and in order to further enhance the interaction between the two resins and improve the cohesive force of the film, one of the adhesive resins is a fluorine atom similar to the peelable resin. Further, a small amount of a copolymer obtained by block-bonding a polymer component containing a silicon atom can be used.

On the other hand, the overcoat layer used in the present invention may have a multilayer structure. That is, a laminated structure in which a resin layer having good adhesion (adhesion functional layer) is provided on the side in contact with the photoreceptor, and a peelable resin layer having good peelability is provided thereon.
The adhesion strength maintenance between the adhesion functional layer and the peelable resin layer having good releasability is, as described above, a polymer component having good compatibility with the resin for adhesion and a polymer component having good compatibility with the peelable resin. Is preferably made to coexist in the adhesion functional layer.

The overcoat layer as described above is preferably provided on the surface of the electrophotographic photosensitive member in a thickness of 0.1 to 5 μm. By adjusting to this range, the surface releasability of the overcoat layer is maintained without deterioration even when it is repeatedly used, and good image reproducibility is obtained by avoiding adverse effects on electrophotographic characteristics.

As the constitution and materials of the electrophotographic photosensitive member to be used in the present invention, any conventionally known one can be used,
It is not limited. For example, "Basics and Applications of Electrophotographic Technology" edited by The Institute of Electrophotography, Corona Co., Ltd. (1986),
Edited by Hiroshi Komon “Recent development and practical application of photoconductive materials and photoconductors”
Japan Science Information Co., Ltd. Publishing Department (1985), Furuji Shibata, Jiro Ishiwata, Polymer, Volume 17, 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No.8) , EM Scholars, "Present Symposium on Organic Photoreceptors for Electrophotography" Proceedings (1985), RM Schaffert, "Electrophotograph
y ”Focal Press London (1980), SWIng, MDTabak,
WEHaas “Electrophotography Fourth International
Conference "SPSE (1983), Isao Shinohara, Hidetoshi Tsuchida,
"Recording Materials and Photosensitive Resins," edited by Hideaki Kusagawa, published by the Academic Society Publishing Center (1979), Hiroshi Komon, Kagaku to Kogaku, 39 (3) 161
(1986) and the like. 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, and 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 include conventionally known inorganic photoconductive compounds such as cadmium sulfide, selenium, selenium-tellurium, amorphous silicon and lead sulfide. These may form a photoconductive layer together with a binder resin, or may be independently formed by vapor deposition or sputtering. When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used as the photoconductive compound, 10 to 100 parts by weight, preferably 15 to 40 parts by weight of the binder resin is added to 100 parts by weight of the inorganic photoconductive compound.
It is used in the proportion of parts by weight.

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.

Examples of the organic photoconductive compound used in the present invention include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives and azurenium salts. Derivatives, amino-substituted chalcone derivatives, N, N-bicarbazyl derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, benzidine derivatives, stilbene derivatives, polyvinylcarbazole and its derivatives, polyvinylpyrene, polyvinylanthracene, poly-2-vinyl -4- (4'-
(Dimethylaminophenyl) -5-phenyl-oxazole, vinyl polymers such as poly-3-vinyl-Nethylcarbazole, polyacenaphthylene, polyindene, polymers such as a copolymer of acenaphthylene and styrene, triphenylmethane polymer, Condensed resins such as a pyrene-formaldehyde resin, a bromopyrene-formaldehyde resin, and an ethylcarbazole-formaldehyde resin. Note that the organic photoconductive compound is not limited to these compounds, and all known organic photoconductive compounds can be used. These organic photoconductive compounds can be used in combination of two or more in some cases.

As the sensitizing dye contained in the photoconductive layer,
Conventionally known sensitizing dyes used for electrophotographic photoreceptors can be used. These are "electrophotography" 12 , 9 (1973),
“Synthetic Organic Chemistry” 23 (11), 1010 (1966) and the like. For example, pyrylium-based dyes described in U.S. Pat.
Applied Optics Supplement 3 50 (1969) , JP-A-50
Triazole methane dyes described in -39548 and the like;
Cyanine dyes described in U.S. Pat. No. 3,597,196 and the like;
No. 8, No. 60-252517, etc. 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. .

Examples of the organic pigment include 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, a material having good compatibility with the type of the charge generating agent used in combination is selected. Specifically, the organic photoconductive compound described above is used. A group of compounds known as

With respect to the mixing ratio of the organic photoconductive compound and the binder resin, the upper limit of the content of the organic photoconductive compound is determined by the compatibility between the organic photoconductive compound and the binder resin, and if the amount exceeds the upper limit. Crystallization of the organic 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 can be used in the photoreceptor of the present invention may be any of the resins used in conventionally known electrophotographic photoreceptors, and the weight average molecular weight is preferably 5 × 10 5.
^{It is 3} to 1 × 10 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10 ⁵ . Further, the glass transition point of the binder resin is preferably from -40C to 200C, more preferably from -10C to 14C.
0 ° C. For example, the review articles cited for the above-mentioned photoconductors, "The Actual Technology of Binders for Recording Materials", Chapter 10, edited by Koichi Nakamura,
CMC Publishing (1985), Tsuyoshi Endo "Precision of Thermosetting Polymers" CMC (1986), Yuji Harazaki "Latest Binder Technology Handbook" Chapter II-1, General Technology Center (1985),
Takayuki Otsu "Synthesis and Design of Acrylic Resin and Development of New Applications" Chubu Business Development Center Publishing Department (1985), Eizo Omori "Functional Acrylic Resin" Techno System (1985), D.Tat
t, SCHeidecker, Tappi, 49 (No.10), 439 (1966),
ESBaltazzi, RGBlanclotte et al., Phot. Sci. En
g. 16 (No.5), 354 (1972), Nguyen Chan Kae, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography 18 (No.2), 22 (198)
0) and the like, compounds and the like described in reviews.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Polymers and copolymers of the derivatives, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers. Polymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, itaconic acid diester polymers and copolymers , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymer, hydroxyl-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 copolymer, a copolymer 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, when a resin having a relatively low molecular weight (about 10 ³ to 10 ⁴ ) containing an acidic group such as a carboxyl group, a sulfo group or a phosphono group is used as a binder resin for the photoconductor, The electrical characteristics can be improved. For example, the resins described in JP-A-64-70761, JP-A-2-67563, JP-A-3-181948, and JP-A-3-249659 are exemplified. 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-3-299
No. 54, No. 3-77954, No. 3-92961, and No. 3-53257. A resin or an acidic group which binds an acidic group to the end of the graft portion of the graft copolymer. Resin contained in graft portion,
Examples of the graft type copolymer having an AB block type copolymer comprising an A block containing an acidic group and a B block not containing an acidic group described in JP-A-2064664 and JP-A-3-223762 in a graft portion. it can. By using these resins, the photoconductor is uniformly dispersed,
A photoconductive layer having good smoothness can be formed, and excellent electrostatic characteristics can be maintained even when a scanning exposure method using a semiconductor laser beam or a change in environment 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 type of light source such as visible light exposure or semiconductor laser light exposure. For example, review-literature on the electrophotographic photosensitive member described above, "electrophotographic" 12 9 (1973), "Synthetic Organic Chemistry" 24 (11),
1010 (1966), Harumiya Miyamoto, Hidehiko Takei: Imaging 1973
(No.8) p. 12, CJ Young et al .: RCA Review 15 , p. 469 (1954), Kohei Kiyota: IEICE Transactions , J63-
C (No.2), p. 97 (1980), Yuji Harazaki et al., Industrial Chemistry Magazine, 66 , 78 and 188 (1963), Tadaaki Tani, Photographic Society of Japan 35 , 208 (1972), " Research Disclosur
e '' 1982, 216 117-118, FMHamer `` The Cyanine D
yes and Related Compounds, etc., such as carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (eg, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.) ), Phthalocyanine dyes (which may contain metals) and the like.

Further, if necessary, various conventionally known additives for electrophotographic photoreceptors can be used.
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. In general, the support of the electrophotographic photosensitive layer is preferably conductive. As the conductive support, a substrate such as a metal, paper, or a plastic sheet may be impregnated with a low-resistance substance in the same manner as in the related art. And a substrate coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and further preventing curling. A substrate provided with a water-resistant adhesive layer on its surface, a substrate provided with at least one precoat layer as necessary on the surface layer of the support, a substrate obtained by laminating a base conductive plastic on which aluminum or the like is deposited on paper, or the like. 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 "Chemistry of Introductory Special Papers" Polymer Publishing Association (1975), MFHoover, J. Macromol. Sci. Chem. A-4 (6), 1
Those described on pages 327 to 1417 (published in 1970) and the like are used.

Next, the thermoplastic resin (AT ₀ ) used for the transfer layer (T ₀ ) provided on the electrophotographic photosensitive member as shown in the route (d) of FIG. 1 will be described.

The resin (AT ₀ ) satisfies the above-mentioned physical properties, and more preferably has a glass transition point of 23 ° C. to 60 ° C.
Or a softening point of 30 to 80 ° C. The resin (AT ₀ ) is at least a resin (AH) having a glass transition point of 30 ° C. to 80 ° C. or a softening point of 40 ° C. to 90 ° C. and a resin (AL) having a glass transition point of 10 to 25 ° C. or a softening point of 30 to 38 ° C. Composed,
Moreover, it is preferable that the difference in glass transition point or softening point between the resin (AH) and the resin (AL) is 2 ° C. or more.

The resin (AH) preferably has a glass transition point of 30 ° C to 60 ° C or a softening point of 40 ° C to 80 ° C. Further, the glass transition point of the resin (AL) is more preferably lower than that of the resin (AH) in the range of 5 to 10 ° C. Here, the difference in the glass transition point or the softening point in the case where two or more kinds of the resin (AH) or the resin (AL) are contained is that the resin (AH) has the lowest glass transition point or the softening point, This is the difference from the one having the highest glass transition point or softening point in AL). Resin (A
The same applies to the difference in glass transition point or softening point in the case where two or more kinds of T ₁ ), (AT ₂ ) and resin (AT ₀ ) are contained.

Here, it is preferable that the abundance ratio of the resin (AH) and the resin (AL) in the transfer layer (T ₀ ) is 5 to 90/95 to 10 (weight ratio). More preferably, resin (AH) / resin (AL) = 20 to 70/80 to 30. Within this abundance ratio, a good transferability improving effect is exhibited.

Specific examples of the resin (AT ₀ ) that can be used in the transfer layer (T ₀ ) include thermoplastic resins, resins known as adhesives or pressure-sensitive adhesives, such as olefin polymers and copolymers. Polymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, alkali alkanoate polymers and copolymers, polymers and copolymers of styrene and its derivatives, olefin-
Styrene copolymer, olefin-unsaturated carboxylic acid ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer,
Acrylic 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 Acid copolymer, acrylamide copolymer, methacrylamide copolymer, hydroxyl group modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl group and carboxyl group modified polyester resin, butyral resin, polyvinyl acetal resin , Cyclized rubber-methacrylic acid ester copolymer,
Cyclized rubber-acrylic acid ester copolymer, copolymer containing a heterocycle (as a heterocycle, for example, furan ring, tetrahydrofuran ring, thiophene ring, dioxane ring, dioxofuran ring, lactone ring, benzofuran ring, benzothiophene ring, 1,3-dioxetane ring, etc.), cellulose resin, fatty acid-modified cellulose resin, epoxy resin and the like.

For example, Volumes 1 to 18 (1981) of "Plastic Materials Course Series" published by Nikkan Kogyo Shimbun, "Polyvinyl Chloride" edited by Kinki Chemical Association Vinyl Section, published by Nikkan Kogyo Shimbun (1988), Hide Omori Three "Functional Acrylic Resins" Techno System Co., Ltd. (1985), Eiichiro Takiyama "Polyester Resin Handbook" Nikkan Kogyosha (1988), Kazuo Yuki "Saturated Polyester Resin Handbook" Nikkan Kogyo Shimbun (1989) ), "Polymer Data Handbook (Application)" edited by The Polymer Society of Japan, Chapter 1 Baifukan (1986), Yuji Harasaki "Latest Handbook of Binder Technology" Chapter 2 General Technology Center Co., Ltd. (1985), Tadashi Okuda "Polymer processing, separate volume 8 20th"
Volume special issue "Adhesive" polymer publication (1976), Keiji Fukuzawa "Adhesive technology" polymer publication (1987), Mamoru Nishiguchi "Adhesion Handbook 14th edition" polymer publication (1985), Japan "Adhesion Handbook 2nd Edition" edited by Adhesion Association, Nikkan Kogyo Shimbun (1980
Year)).

The resin (AT ₀ ) is obtained by adding the polymer component (F) containing a substituent containing a fluorine atom and / or a silicon atom, which has the effect of improving the releasability of the resin (AT ₀ ) itself, to the resin described above. You may further contain as a polymer component in. This further improves the releasability of the releasable surface from the electrophotographic photosensitive member, and as a result, the transferability becomes better. Its content is 100 parts by weight of all polymer components of the resin (AT ₀ ),
It is preferably 3 to 40% by weight, more preferably 5 to 25% by weight. The substituent may be incorporated in the polymer main chain of the polymer or may be present as a substituent of the side chain of the polymer. Preferably, the polymer component (F)
Are contained as blocks in the resin (AT ₀ ).

Further, as described above, when the resin (AT ₀ ) is composed of two or more kinds of resins having different glass transition points or softening points, the fluorine atom and / or silicon atom-containing polymer component (F) is It may be contained in either the resin (AH) or the resin (AL). Specific examples of the block copolymer component containing a fluorine atom and / or a silicon atom in the resin (AT ₀ ) include the same as those described in Japanese Patent Application No. 5-93834.

Further, in order to improve various physical properties such as adhesiveness, film-forming property and film strength, the transfer layer may optionally contain other additives. For example, polybutene, DOP, DBP, low-molecular-weight styrene resin, low-molecular-weight polyethylene as a plasticizer and a softening agent for improving wettability to a photoreceptor and lowering melt viscosity, such as rosin, petroleum resin, and silicone oil for adjusting adhesion. High molecular weight hindered polyphenols, triazine derivatives and the like can be added as antioxidants such as wax, microcrystalline wax and paraffin wax. For more information, see “Practice of Hot Melt Adhesion” (Hiroshi Fukada, Kobunshi Kogakukai, published in 1983) 29-
See page 107.

The film thickness of the transfer layer (T) is 0.1 to 0.1 as a whole.
10 μm is suitable, and preferably 0.5 to 5 μm. If the film thickness is too thick, inconvenience may occur in the electrophotographic process and sufficient image density may not be obtained,
The image quality may be deteriorated.

The transfer layer (T ₀ ) is preferably formed on the photoconductor in each case in the electrophotographic apparatus. In order to form the transfer layer (T ₀ ) on the surface of the photoconductor in the electrophotographic apparatus, the hot melt coating method, the electrodeposition coating method or the transfer method is effective. Specific embodiments of these transfer methods are described in International Publication WO93.
It can be carried out in the same manner as described in / 00179.

In particular, in the electrodeposition coating method, the above-mentioned thermoplastic resin (AT ₀ ) is electrodeposited or adhered (hereinafter also simply referred to as electrodeposition) on the surface of the object to be coated in the form of resin particles, for example, by heating. A uniform thin film is formed as a transfer layer. Therefore, the thermoplastic resin particles {hereinafter, resin particles (A
R)} is required to have either positive charge or negative charge, and its electroscopic property is arbitrarily determined by the charge property of the object to be combined, The formed transfer layer is a preferable method because a thin and uniform film can be formed and the apparatus can be simplified and downsized.

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

Particularly, resin particles containing at least two kinds of resins having different glass transition points, preferably resin (AH) and resin (AL), in the same particle {hereinafter, resin particles (ARW)
May be called}. In the present invention, a resin (AH) whose glass transition point or softening point falls within the above range
And resin (AL) are arbitrarily selected, and resin particles (AR
W). This improves the transferability, increases the durability of the transfer layer, and improves the strength of the copied image.

In the resin (ARW), the resin (AH) / resin (AL) is 10/90 to 95/5, especially 30/70 to 9
It is preferably contained in a ratio of 0/10 (weight ratio). When the ratio of the resin (AH) is 10% by weight or more, the storage stability of the copy such that the transfer layer does not peel off (good filing) even when the color copy is put on various sheets and piled up for filing. The properties are further improved, which is preferable.
When the content of the resin (AL) is 5% by weight or more, the transferability of the transfer layer is more favorably exhibited.

At least two kinds of resin (AH) and resin (AL) contained in the resin particles (ARW) are in a state of being arbitrarily mixed in the particles, or the resin (AH) main part and the resin (AL) are mixed. It may be in a state of forming a layered structure separated from the main part (that is, particles having a core-shell structure), and in the case of a core-shell structure, even if the part to be the core is the resin (AH), the resin (AL),
There is no particular limitation. Such resin particles (AR
Specific embodiments of W) are described in PCT Application No. JP94 / 005.
07.

Then, a toner image is formed by an electrophotographic process using a liquid developer on the photoconductor having a releasable surface or the transfer layer (T ₀ ) provided on the photoconductor. In particular, a combination of a scanning exposure method using laser light which is exposed 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 material is positioned on the flat bed by the register pin method and then fixed by suction from the back surface by air suction. Next, the photosensitive material is charged by the charging device described on page 212 et seq. Of, for example, "Basics and Application of Electrophotographic Technology" (edited by the Electrophotographic Society of Japan, Corona, published on June 15, 1988). The corotron or scotron system is common. At this time, it is also preferable to control the charging conditions by applying feedback so that the surface potential always falls within a predetermined range based on information from the charging potential detecting means of the photosensitive material. Thereafter, for example, scanning exposure with a laser light source is performed using the method described on page 254 and thereafter of the above-cited reference material.

Next, a toner image is formed using the liquid developer. The photosensitive material charged and exposed on the flatbed can be removed therefrom and the wet developing method described on page 275 and thereafter of the cited reference can be used. The exposure mode at this time corresponds 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 to charge the photosensitive material with the same charge polarity. The toner having the toner is used and a developing bias voltage is applied so that the toner is electrodeposited on the exposed portion. Details of the principle are described on page 157 et seq.

In order to remove the excess developer after development, a rubber roller, a Gipp roller, as shown on page 283 of the same document,
Squeeze such as reverse roller or corona squeeze,
Perform squeeze such as air squeeze. It is also preferable to rinse only the carrier liquid of the developer before squeezing. The above steps are repeated for magenta, cyan and black to form a color toner image on the photoconductor.

As the liquid developer used in the present invention, a conventionally known liquid developer for electrostatic photography can be used. For example, the above-mentioned “Basics and Applications of Electrophotographic Technology”, pages 497 to 505,
Nakamura Koichi "Development and Practical Use of Toner Materials" Chapter 3 (published by Nihon Kagaku Information Co., Ltd., 1985), Moto Machida "Recording Materials and Photosensitive Resins", pages 107-127 (1983), Academic Society of Japan Specific modes are shown in the publication center, the Electrophotographic Society of Japan "Imaging No. 2 to 5: Development, fixing, charging, and transfer of electrophotography".

The basic constitution of the material of the concrete wet developer is an electrically insulating organic solvent {for example, isoparaffin-based aliphatic hydrocarbon: Ansoper H, Isopar G (manufactured by Esso Co.) Shellsol 70, Shellsol 71 (shell Company), IP-solvent 1620 (made by Idemitsu Petrochemical)
Etc. as a dispersion medium, a resin for imparting dispersion / stability and chargeability to inorganic or organic pigments or dyes as colorants and alkyd resins, acrylic resins, polyester resins, styrene-butadiene resins, rosins, etc. Are dispersed, and various additives are added, if desired, for the purpose of enhancing charging characteristics or improving image characteristics. As the colorant, known dyes / pigments are arbitrarily selected, for example, benzidine, azo, azomethine, xanthene, anthraquinone, phthalocyanine (including metal), titanium white, nigrosine,
Examples include dyes or pigments such as aniline black and carbon black.

As other additives, for example, those specifically described in Yuji Harazaki "Electrophotography" Vol. 16, No. 2, p. 44 are used. For example, a metal salt containing a metal salt of di-2-ethylhexylsulfosuccinic acid, a metal salt of naphthenic acid, a metal salt of a higher fatty acid, a metal salt of an alkylbenzenesulfonic acid, a metal salt of an alkyl phosphate, lecithin, poly (vinylpyrrolidone), and a hemimaleamide component Polymers, coumarone indene resin, higher alcohols, polyethers,
Examples include polysiloxane and waxes. But,
It is not limited to these.

The amounts of the main components of these wet type developers are usually as follows. The toner particles mainly composed of a resin (and a coloring agent optionally used)
The amount is preferably 0.5 to 50 parts by weight based on 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. Further, the carrier liquid soluble resin for dispersion stabilization is also used as needed, and can be added in an amount of about 0.5 to 100 parts by weight based on 1000 parts by weight of the carrier liquid. The charge control agent as described above 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. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electric resistance of the 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 good continuous tone image. It is controlled.

Further, as a specific example of the method for producing a wet developer, a method for producing colored particles by mechanically dispersing a colorant and a resin using a disperser such as a sand mill, a ball mill, a jet mill or an attritor. However, for example, Japanese Patent Publication 35-
5511, Japanese Patent Publication No. 35-13424, Japanese Patent Publication No. 50-
No. 40017, Japanese Patent Publication No. 49-98634, Japanese Patent Publication No. 58
No. 129438 and JP-A No. 61-180248. As another method for producing colored particles, for example, a method of producing dispersed resin particles by a non-aqueous dispersion polymerization method that obtains fine particles having good monodispersity and coloring the resin particles can be mentioned. As one of the coloring methods, there is a method of dyeing a dispersed resin with a preferable dye as described in JP-A-57-48738. Further, as another method, as disclosed in JP-A-53-54029, a method of chemically bonding a dispersion resin and a dye, or a polymerization method as described in JP-B-44-22955 and the like. In the case of producing by a granulation method, there is a method of using a dye-containing monomer in advance to obtain a dye-containing copolymer.

[0118] Then, the toner image formed on the photosensitive member (if through the transfer layer (T ₀₎ is collectively together with the transfer layer (T ₀₎₎ make contact transferred onto the primary receptor.

The primary receptor receives the toner image formed on the surface of the photoconductor together with the transfer layer by the contact transfer method under the condition of heating and / or pressure, and further onto the final material to be transferred under the condition of heating and / or pressure. It is peeled off and transferred to the bottom. The releasability of the surface of the primary receptor is lower than that of the photoreceptor surface, and it is important to maintain the releasability of peeling and transferring to the final transfer target material, and it is necessary that it is larger than the adhesive force of the photoreceptor surface, It is preferably 10 g · f or more, and more preferably 30 g · f or more. The maximum adhesive force on the surface of the primary receptor is preferably 250 g · f, more preferably 200 g · f or less.

Known methods and devices can be used for this thermal transfer. The nip pressure in transfer is 0.1
10 kgf / cm ^2, more preferably 0.2~5kgf / cm ^2, as roller pressing means, it is possible to use air cylinder using spring or compressed air to both ends of the roller shaft. Transport speed is 10-300 mm / sec,
It is more preferably in the range of 50 to 200 mm / sec, and the heating temperature at the time of transfer is 30 ° C. to 8 ° C. on the surface of the photoreceptor.
0 ° C, more preferably 35 ° C to 60 ° C, and the primary receptor surface temperature is 40 ° C to 100 ° C, more preferably 4 ° C.
It is 5 ° C to 70 ° C.

Even if the transfer of the toner image from the photoreceptor to the primary receptor (first transfer) and the transfer of each transfer layer from the primary receptor to the final transfer material (second transfer) are performed simultaneously within one screen. Alternatively, after the transfer of the entire one screen to the primary receptor is completed, the image may be transferred to the final transfer target material.

Any material may be used as long as it is a primary receptor satisfying the above conditions. In the present invention, examples of the method used for transferring the toner image from the photoconductor to the primary receptor include a drum method and an endless belt method which can be repeatedly used.

In the drum system or the endless belt system,
The material of the primary receptor to be provided on the drum may be any material as long as it satisfies the above conditions,
As a preferred embodiment, a laminated structure including an elastic layer and / or an elastic layer and a reinforcing layer support is desirable, and the surface of the laminated structure may satisfy the above physical properties. These stacks may be provided directly on the drum, for example, or they may be removable so that they can be replaced.

As the elastic body, conventionally known natural resins,
Synthetic resins may be used, and these may be used alone or in combination of two or more to form a single layer or a plurality of layers.
For example, AD Roberts "Natural Rubber Science and
Technology "Oxford Science Publications (1988), W. Hofmann" Rubber Technology Handbook ", Ha
Various resins are described in nser Publishers (published in 1989), plastic materials course, all 18 volumes, Nikkan Kogyo Shimbun, etc.

For example, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, cyclized rubber, chloroprene rubber, ethylene-propylene rubber, butyl rubber, chlorosulfonated polyethylene rubber, silicone rubber, fluororubber, polysulfide rubber, natural rubber, Examples thereof include isoprene rubber and urethane rubber, but the present invention is not limited thereto, and can be arbitrarily selected in consideration of releasability from the transfer layer, durability and the like. Further, the adhesion of the surface of the primary receptor can be easily adjusted by the same method as described for the peelable photoreceptor.

Further, cloth, glass fiber, resin-impregnated special paper, aluminum, stainless steel or the like is used as a reinforcing layer for the elastic layer. There may be a sponge-like rubber layer between the surface elastic layer and the reinforcing layer. The average roughness of the surface of the primary receptor is preferably 0.01 mm or less, and the thickness of the surface elastic layer is preferably 0.01 mm to 10 mm. As a result, in pressure contact transfer of the lower heating layer, the pressure applied to the toner image layer is relieved by the elastic layer (cushion effect). It is possible to faithfully transfer without occurring. The elastic layer may be an elastic layer made of the following resin exhibiting elasticity, or a laminated structure including the elastic layer and a reinforcing layer support.

In the endless belt system, a known belt type primary receptor member can be used. For example, US Pat. Nos. 3,893,761 and 4,684 are used.
No. 238, No. 4,690,539 and the like. Further, a method of providing a layer serving as a heating medium in the layer of the belt carrier of the belt type primary receptor is also mentioned, and for example, the method of Japanese Patent Publication No. 4-503265 is known.

Next, in the present invention, the toner image on the primary receptor is transferred together with the transfer layer to the final transfer material by contact heat transfer. In this thermal transfer, a known method and apparatus can be used. The nip pressure between the primary receptor and the backup roller for the final material to be transferred and the conveying speed in the transfer are in the same range as the conditions in the transfer process from the photoconductor to the primary receptor. In addition, the temperature of the primary receptor is preferably the same as the temperature at the first transfer, and by making the transfer speed the same, the continuous process of the first transfer and the second transfer becomes possible, and the time is further shortened. To be done.

The surface temperatures of the transfer backup roller and the peeling backup roller, which are the backup rollers of the final transfer material, may be the same or different, and the temperature is preferably 50 ° C. to 140 ° C., more preferably It is 70 ° C to 120 ° C. Even if the temperature on the backup roller side in the second transfer is set to a high temperature, it is possible to reduce the heat load on the photoconductor by controlling the temperature on the primary receptor.

Further, in the present invention, as shown in the route (b) or (c) in FIG. 1, it is formed on the transfer layer (T ₂ ) formed on the surface of the primary receptor or on the entire surface of the photoreceptor carrying the toner image. The toner image on the photoreceptor can be transferred onto the primary receptor through the transfer layer (T ₁ ).

[0131] The transfer layer (T ₁₎ mainly configured to thermoplastic resin (AT ₁₎ or the transfer layer (T ₂₎ mainly configured to thermoplastic resin (AT ₂₎ is to satisfy each of the physical properties . Further, for the transfer layer (T ₁ ) or (T ₂ ), similarly to the transfer layer (T ₀ ), two or more kinds of resins having a difference in glass transition point or softening point of 2 ° C. or more should be used in combination. Is preferred. Specific examples include a combination of resin (AH) and resin (AL).

The film thickness of the transfer layer (T ₁ ) or (T ₂ ) is 0.1 to
10 μm is suitable, and preferably 0.5 to 5 μm. In the film within this range, the effect of improving the transfer property of the present invention is sufficiently exhibited. Specific examples of the thermoplastic resin (AT ₁ ) or (AT ₂ ) include the same as the resin (AT ₀ ).

The transfer layer (T ₀ ) can also be used as a means for forming the transfer layer (T ₁ ) or (T ₂ ) on the photoreceptor or primary receptor.
The same method as the method for forming the same can be mentioned, and resin particles (ARW) can also be used for electrodeposition coating. Further, the transfer can be performed under the same transfer conditions of pressure and heating as in the case of the transfer layer (T ₀ ).

Further, in the present invention, the transfer layer (T
₀) And a transfer layer (T₁) Or on the primary receptor
Transfer layer (T_Two) Are respectively provided to transfer the toner image to the transfer layer.
(T ₀) And transfer layer (T₁) Or (T_Two) And sandwiched composition
The method of transferring the toner image may be performed.

Next, a toner image is obtained from the primary receptor,
The final color copy is obtained by contacting and transferring onto the final transfer material provided with the adhesion layer (M).

The final transfer material used in the present invention is as follows:
It is not particularly limited, plain paper, recycled paper, high-quality paper, coated paper, natural paper such as art paper, support for synthetic paper,
Reflective materials such as aluminum, iron, metal support such as SUS,
Resin film (plastic film) of polyester, polyolefin, polyvinyl chloride, polyacetate, etc.
Any of transmissive materials such as

The present invention is characterized in that an adhesion layer (M) mainly composed of a thermoplastic resin (AM) satisfying the thermophysical properties is provided on each of the various transfer materials as described above.
The transfer material provided with the adhesion layer (M) may be the one provided with the adhesion layer (M) in advance, but it is preferably provided on the transfer material in the same apparatus of the electrophotographic process of the present invention. .
Accordingly, in the color image forming method of the present invention, it becomes possible to easily form a color image on various transfer materials.

As the method for forming the adhesion layer (M) in the same apparatus, any of the conventionally known resin layer forming methods can be used. For example, the same method as forming the transfer layer (T), for example, Yuji Harazaki "Coating Engineering" Co., Ltd.
Asakura Shoten (1971), Yuji Harasaki “Coating method”
Air doctor tarter, blade coater, knife coater, etc. described in Maki Shoten (published in 1979), Hiroshi Fukada "Practice of Hot Melt Adhesion" Co., Ltd. Polymer Publishing (published in 1979), etc.
Squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, spray coater, curtain coater, calender coater, etc. method of coating and drying a solution of resin (AM), resin by ink jet method ( The solution (AM) can be adsorbed or attached by uniformly wetting the surface of the material to be transferred and then drying.
The method using the ink jet method is described in, for example, "Non-impact Printing" edited by Shin Ohno, CMC (1986)
Annual publication). For example, a continuous jet type Sweet system, a Hertz system, an intermittent jet type Winston system, an ink-on-demand type pulse jet system, a bubble jet system, an ink mist type mist system and the like can be mentioned.

In each case, the resin (AM) is diluted with a solvent instead of the ink, and is filled in the ink tank and / or the ink head cartridge for use. Usually, the ink has a viscosity of 1 to 10 cp and a surface tension of 30 to 60 dyne / cm. If necessary, a surfactant or the like may be added, or the ink may be heated. A conventional ink jet printer has a head orifice diameter of 30 to 100 for finer character drawing.
The particle size of the flying ink is about the same, and the particle size 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 ink to be ejected increases, so that the time required for application can be reduced. Further, the use of a multi-nozzle is extremely effective for shortening the coating time.

The thickness of the adhesion layer (M) is suitably 0.05 to 5 μm, preferably 0.1 to 2 μm. If the film thickness is too thin, transfer defects are likely to occur, and if it is too thick, there is no particular problem in practice, but this is not preferable because the material is wasted.

Specific examples of the thermoplastic resin (AM) include the same resins as the above-mentioned resin (AT ₀ ),
Those satisfying the thermophysical properties of the present invention can be appropriately selected and used. These resins may be used alone or in combination of two or more.

Specific embodiments of the electrophotographic color image forming method of the present invention and the apparatus used therefor will be described below with reference to the drawings. 2 to 4 each show an example of an apparatus that can be used to carry out the method of the present invention. 2 to 4, for the purpose of explanation, FIG. 2 shows a drum system as a primary receptor, and FIG.
Shows an endless belt system, and FIG. 4 shows a drum system (however, an impression cylinder drum system as a backup of the second transfer), and the transfer layer (T ₀ ) or (T ₁ ) is formed on the photoconductor. As a method, FIG. 2 illustrates an electrodeposition coating method, FIG. 3 illustrates a hot melt coating method, and FIG. 4 illustrates a transfer method. These methods may be appropriately combined and changed, and incorporated into an apparatus. It is a thing.

Hereinafter, description will be made with reference to FIG. On the liquid developing unit set 14, the electrophotographic photoreceptor 11, the primary receptor 20, and the transfer material 30 are arranged. drum,
It is preferable that the temperature adjusting means 17 is provided in each of the transfer backup roller 31 and the peeling backup roller 32. When the toner image is formed by the electrophotographic process, the primary receptor 20 is the photoreceptor 11
Away from the drum.

As described above, when the electrophotographic photosensitive member 11 having a peelable surface in advance is used, a toner image is formed on the photosensitive member 11 by the electrophotographic process as it is. When the releasability of the surface of the photoreceptor 11 is insufficient, the compound (S) is applied before the formation of the toner image, whereby the desired releasability can be imparted to the surface of the photoreceptor 11. That is, the compound (S) is supplied to the surface of the photoconductor 11 by the compound (S) applying apparatus 10 using the above-described embodiment. The compound (S) application device 10 may be either a fixed type or a movable type.

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

After the photoconductor 11 is uniformly charged, for example, positively by the corona charging device 18, the image is first exposed by the exposure device (for example, a semiconductor laser) 19 based on the image information of yellow. A potential contrast is obtained between the exposed part and the exposed part. A yellow liquid developing unit 14Y containing a liquid developer in which a yellow pigment having a positive electrostatic charge is dispersed in an electrically insulating dispersion medium is brought close to the surface of the photoreceptor 11 from the liquid developing unit set 14 and the gap is set to 1 mm. Fix it.

First, the photoconductor 11 is pre-bused by the pre-bus means provided in the developing unit, and then the photo-conductor 1 is biased by a bias power source and electrical connection not shown in the figure.
A yellow liquid developer is supplied to the surface of the photoconductor 11 while applying a development bias voltage between 1 and the development electrode. The bias voltage at this time is connected so that the developing electrode side is positive and the photoconductor side is negative, and the applied voltage is slightly lower than the surface potential of the unexposed portion. If the applied voltage is too low, a sufficient toner image density cannot be obtained.

After that, the developing solution is washed off by the rinsing means built in the developing unit, and subsequently, the rinsing adhering to the surface of the photosensitive member is removed by the squeeze means, and then it is dried by passing under the intake / exhaust unit 15. The above steps are repeated for magenta, cyan and black to form a color toner image on the photoconductor.

Here, in the case of the route (d) in FIG. 1, the transfer layer (T ₀ ) is formed before the toner image is formed by the electrophotographic process. FIG. 2 illustrates the electrodeposition coating method, FIG. 3 illustrates the hot melt coating method, and FIG. 4 illustrates the transfer layer forming method by the transfer method.

The electrodeposition coating method will be described with reference to FIG. An electrodeposition unit 13a is provided in the liquid developing unit set 14 as a transfer layer forming means. Further, although not shown, a rinsing unit is provided. The thermoplastic resin particles forming the transfer layer are charged to form a thermoplastic resin particle dispersion liquid, which is put into the electrodeposition unit 13a, and the liquid developing unit set 14 is brought close to the photoconductor 11 to make the electrodeposition unit 13a. It is fixed so that the distance from the developing electrode is 1 mm. The particle dispersion is supplied from the electrodeposition unit 13a between the gaps and rotated while applying a voltage from the outside, so that the particles are adsorbed on the entire surface of the photoconductor 11. If necessary, the liquid dispersion liquid is removed by a squeezing means incorporated in the developing unit set to remove the particle dispersion adhered to the surface of the photoreceptor 11, and then the transfer layer formed by heating and melting the resin particles by a heating means is removed. Form. Thereafter, the photoconductor 11 is cooled to a predetermined temperature from the outside of the photoconductor 11 or from the inside of the drum of the photoconductor 11 by a cooling device similar to the air intake / exhaust unit as necessary. The liquid developing unit set 14 is moved to the standby position, and the transfer layer forming step is completed.

At this time, for exhausting the dispersion solvent of the dispersion liquid, the intake / exhaust unit 15 provided for the electrophotographic process of the electrophotographic photosensitive member can be used. It is preferable to use an ordinary carrier of a liquid developer for the rinsing liquid. The electrodeposition unit 13a may be installed in the liquid developing unit set 14 as shown in FIG. 2, or may be installed separately from the developing unit set.

FIG. 3 shows the case of using the hot melt coating method.
This will be described below. The thermoplastic resin is applied to the surface of the photoconductor 11 on the peripheral surface of the drum by the hot melt coater 13b, and is cooled to a predetermined temperature by passing under the intake / exhaust unit 15. After the hot melt coater 13b has moved to the standby position, the liquid developing unit set 14 is moved to that position, and the transfer layer forming process ends.

As an apparatus for easily forming a transfer layer on a photoconductor by a transfer method using a release paper, for example, there is an apparatus 13c shown in the schematic view of FIG. That is, the transfer layer 8
The release paper 40 provided with is heated and pressure-bonded by the heating roller 41 to transfer the transfer layer 8 to the surface of the photoconductor 11. The release paper 40 is cooled by the cooling roller 42 and collected. If necessary, the photoconductor 11 itself may be heated by the preheating means 17 to improve the transferability of the transfer layer 8 by thermocompression bonding.

After the toner image is formed, the transfer layer (T ₂ ) is applied onto the primary receptor 20 by applying the route (b) shown in FIG.
7'or when the transfer layer (T ₁ ) 7 is formed on the photoconductor 11 after the toner image is formed by applying the route (c) of FIG. 1, the electrodeposition coating method and the hot melt coating method are also used. The transfer layer can be appropriately formed on the primary receptor or on the photoreceptor in the same manner as any one of the transfer method and the transfer method. The transfer layer (T ₂ ) can be formed on the primary receptor 20 by the transfer layer forming device 13 shown by the dotted line in FIGS. 2 to 4.

On the other hand, an adhesion layer (M) is provided on the final transfer material 30. The adhesion layer (M) is the transfer target material 3 in advance.
0 may be provided on the contact layer forming unit 33.
Therefore, it may be provided on the transferred material 30 each time. The adhesion layer forming unit 33 is an apparatus for applying a method selected from a coater coating method, an ink jet method, and a method similar to the above-mentioned method of forming the transfer layer (T).

Then, as shown in FIG. 2, the photoreceptor 11 on which the toner image is formed and the primary receptor 20 drum are brought into contact with each other through the transfer layer, and heating and pressurization are carried out. The transfer layer is transferred onto the primary receptor 20 or onto the transfer layer on the primary receptor 20. That is, the heating means 16 and / or for thermal transfer of the photosensitive drum
Alternatively, the toner image is subjected to a predetermined preheating by means of 17, and if necessary, the primary receptor is further subjected to a predetermined preheating by means of heating means 16 and / or 17, and the toner image is pressed against the primary receptor 20 (optionally via a transfer layer). Heat transfer. As the heating means 16, a non-contact type, for example, an infrared line heater or a flash heater can be used.

Next, the toner image transferred on the primary receptor is pressed against the final transfer material 30 to perform thermal transfer.
When there is a transfer layer, the transfer layer is transferred to the transferred material 30. Heating means 16 and / or 17 for primary receptor 20
Is preheated to a predetermined level, and the transfer material 30 is preheated to a predetermined level by the transfer backup roller 31. Furthermore,
The transfer material 30 is pressed onto the primary receptor 20 drum by the transfer and peeling backup rollers 31 and 32, the transfer layer and the toner image are transferred onto the transfer material 30, and then the peeling backup roller 32 cools them. ,
The toner image is peeled and transferred together with the transfer layer on the transfer material 30,
A series of steps is completed.

Further, when the endless belt system is applied as the primary receptor as shown in FIG. 3 and when the impression cylinder drum system is adopted as the backup as shown in FIG. Thermal transfer can be performed on the transfer target material 30 depending on the operating method and conditions. If the backup method of FIG.
Can be transported in a plane.

[0159]

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

[Production Example of Resin Particles for Transfer Layer] Production Example 1 of Resin Particles (AR) 1: (AR-1) A mixed solution of 16 g of the dispersion-stabilizing resin (Q-1) having the following structure and 386 g of Isopar G was used as a nitrogen stream. While stirring under
The temperature was raised to 60 ° C. 80 g of benzyl methacrylate, 20 g of 2-propoxyethyl methacrylate,
2.3 g of methyl 3-mercaptopropionate and 2,
2'-azobis (isovaleronitrile) (abbreviation AIVN)
1.2 g of the mixture was added dropwise at a dropping time of 1 hour, and the reaction was continued for another 1 hour. Add 0.8 g of AIVN and react for 2 hours, then add 0.8 g of 2,2'-azobisisobutylnitrile) (abbreviation AIBN) and heat to 80 ° C for 2 hours, then add 0.5 g of AIBN. The reaction was carried out for 2 hours. Next, the temperature is raised to 100 ° C., and the degree of pressure reduction is 10 to 10.
After the unreacted monomer was distilled off under 20 mmHg, the mixture was cooled and
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. The particle size was measured by CAPA-500 (manufactured by Horiba, Ltd.) (the same applies hereinafter). A part of the white dispersion was centrifuged (rotation speed 1 × 10 ⁴ rpm, rotation time 60 minutes), and the sedimented resin particles were collected and dried. The weight average molecular weight of the resin particles (Mw: GPC value in terms of polystyrene; the same applies hereinafter) was 1.3 × 10 ⁴ glass transition point (Tg) was 40 ° C.

[0161]

Embedded image

Synthesis Example 2 of Resin Particles (AR): (AR-
2) A macromonomer having dimethylsiloxane as a repeating unit (Silaprene FM-725, Mw 1.0 × 1
A mixed solution of 0 ⁴ , 18 g of Chisso Co., Ltd., 100 g of vinyl acetate and 382 g of Isopar G was heated to 75 ° C. while stirring under a nitrogen stream. To this, AIBN1.5
g was added and reacted for 3 hours. Next, after adding 0.8 g of AIBN, immediately raise the temperature to 80 ° C for 2 hours, and then add AIBN
0.5 g was added and reacted for 2 hours. After the unreacted monomers were distilled off at a temperature of 100 ° C., the mixture was cooled and passed through a 200-mesh nylon cloth. The white dispersion obtained had a polymerization rate of 96% and an average particle size of 0.22 μm. Was latex. Mw of resin particles is 10 ⁴ and Tg is 38
° C.

Synthesis Example 3 of Resin Particles (AR): (AR-
3) A mixture solution of the following dispersion stabilizing resin (Q-2) 12 g (as solid content), vinyl acetate 65 g, vinyl valerate 30 g, crotonic acid 5 g and Isopar H275 g was added at a temperature of 80 ° C. with stirring under a nitrogen stream. Warmed. AIVN
Add 1.6g and react for 1.5 hours, AIVN 0.8g
Was added for 2 hours, and AIBN 0.5 g was further added for 4 hours. Then, the temperature was raised to 100 ° C. and the mixture was stirred for 2 hours, unreacted vinyl acetate was distilled off, then cooled and passed through a 200-mesh nylon cloth to obtain a white dispersion with a polymerization rate of 93%. It was a monodisperse latex having an average particle size of 0.25 μm. Further, the resin particles have Mw of 8 × 10 ⁴ and Tg of 24.
° C.

[0164]

Embedded image

Synthesis Examples 4 to 10 of Resin Particles (AR): (A
R-4) to (AR-10) A mixed solution of 20 g of the dispersion stabilizing resin (Q-3) having the following structure and 480 g of Isopar G was heated to 60 ° C. while stirring under a nitrogen stream. To this, a predetermined amount of each monomer shown in Table A below, methyl 3-mercaptopropionate 1.
A mixed solution of 3 g and 1.5 g of AIVN was added dropwise at a dropping time of 1 hour, and the reaction was continued for another 1 hour. Then AI
After 1.0 g of VN was added and the temperature was set to 70 ° C. and the reaction was continued for 2 hours, 0.8 g of AIBN was further added and the temperature was immediately set to 80 ° C. and the reaction was carried out for 3 hours.

[0166]

[Chemical 6]

60 g of Isopar H was added to the above reaction product,
After distilling off residual monomers at a temperature of 50 ° C. under reduced pressure of a water pump, the mixture was cooled and passed through a 200-mesh nylon cloth to obtain a white dispersion. Each of the obtained latexes had good monodispersity in the range of an average particle diameter of 0.18 to 0.25 μm. The Mw of the resin particles of each latex is 9 ×
It was in the range of 10 ^{3 to} 1.5 × 10 ⁴ . In the same manner as in Synthesis Example 1, the Tg (° C) of the sedimentation component of each particle was as shown in Table-A.

[0168]

[Table 1]

Synthesis Examples 11 to 14 of Resin Particles (AR):
(AR-11 to 14) 12 g of the dispersion stabilizing resin (Q-2) having the above structure, the following table-
A mixed solution of 12 g of B macromonomer and 402 g of Isopar H was heated to a temperature of 50 ° C. while stirring under a nitrogen stream. To this, 70g of phenethyl methacrylate, 30g of ethylene glycol propyl ether methacrylate
g, methyl 3-mercaptopropionate 0.6 g, initiator 2,2'-azobis (2-cyclopropylpropionitrile) (abbreviation ACPP) 3 g and methyl ethyl ketone 5
0 g of the mixed solution was added dropwise for 1 hour, and then 1
After reacting for an hour, 1.0 g of ACPP was further added and reacted for 2 hours. Then, immediately after adding 1.0 g of AIVN, the temperature was set to 75 ° C. and the reaction was conducted for 2 hours, and 0.8 g of AIVN was further added and the reaction was conducted for 2 hours. Next, after heating to a temperature of 100 ° C. and distilling off the solvent methyl ethyl ketone, after cooling, 200
A white dispersion was obtained through a nylon mesh cloth. The polymerization rate of each resin particle was 95 to 99%, and the average particle diameter was a latex having a narrow particle size distribution in the range of 0.20 to 0.25 μm. The Mw of the resin component of each particle is about 1.5.
× 10 ⁴ , Tg was in the range of 30 ~ 35 ℃.

[0170]

[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.) and 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 were charged into a paint shaker (manufactured by Toyo Seiki Co., Ltd.) using glass beads having a diameter of about 4 mm as media, 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 Example of Resin Particles (ARW) 1: (ARW)
-1) A mixture of 8 g of the dispersion stabilizing resin (Q-1), 70 g of vinyl acetate, 30 g of vinyl propionate and 388 g of Isopar H was heated to a temperature of 80 ° C while stirring under a nitrogen stream. To this, 1.5 g of AIBN was added as an initiator and reacted for 2 hours, and 0.8 g of AIBN was further added twice every 2 hours to carry out the reaction. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having a polymerization rate of 93% and an average particle size of 0.14 μm and good monodispersity.
A part of the white dispersion is centrifuged (rotation speed 1 × 10
^The resin particles that had settled were collected at ⁴ rpm and a rotation time of 60 minutes and dried, and the Mw of the resin particles obtained was 8 ×.
10 ⁴ and Tg were 17 ° C. The resin particles obtained here are designated as (AR-16).

A total solution of the resin particle dispersion (that is, seed particles) and a mixed solution of 10 g of the dispersion stabilizing resin (Q-2) were heated to a temperature of 60 ° C. while stirring under a nitrogen stream. To this, a mixture of 80 g of benzyl methacrylate, 20 g of 2-propoxyethyl methacrylate, 2.3 g of methyl 3-mercaptopropionate, 1.0 g of AIVN and 400 g of Isopar G was added dropwise over 2 hours, and the reaction was continued for another 2 hours. Next, add 0.8g of initiator and temperature 70 ℃
After reacting for 2 hours, 0.6 g of an initiator was further added and reacted for 3 hours. After cooling, pass a 200 mesh nylon cloth,
The obtained white dispersion has a polymerization rate of 98% and an average particle size of 0.25.
It was a latex having a good monodispersibility of μm (the resin particle component reacted here for lamination was resin particles (AR-1)).
Same as).

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 making resin particles dispersed on a PET film was heat-treated at a temperature of 30 ° C. and 60 ° C. for 5 minutes, and then each sample was processed by JEOL, JSL-T.
When observed with a Model 330 Scanning Microscope at a magnification of 20,000, a particle state was observed in the sample at a temperature of 30 ° C, but no particles were observed in the sample at a temperature of 60 ° C. That is, the particles were melted by heating. Similarly, resin particles (AR-16) each composed of two kinds of resins (copolymers) constituting the above resin particles,
The resin particles (AR-1) and dispersed resin particles obtained by mixing these two kinds of particles at a 1/1 weight ratio were examined. In the case of the resin particles (AR-16), the particle state was not already observed in the sample at a temperature of 30 ° C., while the resin particles (AR-1)
In the case of, the temperature was 30 ° C.
No particles were visible in the ° C sample. Furthermore, in the case of mixed particles, when a sample not heated and a sample at a temperature of 60 ° C were examined, the temperature was 60 ° C as compared with the sample at a temperature of 30 ° C
It was confirmed that the particles of No. 1 were invisible.

As described above, as a result of visual observation of the thermal behavior of the particles, the resin particles synthesized according to the examples of the present invention showed 2
Two kinds of resin are contained in one kind of particles, not a mixture of kinds of resin particles. In this case, high Tg
It was confirmed that the above resin was a core / shell particle in which the resin having a low Tg was distributed in the outer layer and the resin having a low Tg was distributed in the inner layer.

Synthesis Examples 2-7 of Resin Particles (ARW): (A
RW-2) to (ARW-7) In Synthesis Example 1 of the resin particles (ARW), the following Table-
Resin particles (ARW-2) to (ARW-7) were prepared in the same manner as in Synthesis Example 1 except that each monomer described in C was used.
Was manufactured. The polymerization rate of each obtained latex particle is 95.
˜99%, the average particle size was in the range of 0.22 to 0.30 μm, and the monodispersity was good.

[0177]

[Table 3]

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 resin (B-2) shown below, and 0.1 of the compound (A) having the structure shown below.
A mixture of 5 g and 80 g of tetrahydrofuran was added to 500
The mixture was placed in a glass container of ml together with the glass beads, dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho) for 60 minutes, and then the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0179]

Embedded image

Next, 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 dried in a circulating oven at 110 ° C. for 20 minutes.
Heated for seconds. The film thickness of the obtained photosensitive layer was 8 μm.

(Formation of Releasable Surface Layer) 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 platinum for crosslinking were added to 100 g of n-hexane. The contained coating material was coated using a wire round rod to a film thickness of 1.5 μm, dried by touch with a finger, and further heated at 120 ° C. for 10 minutes. The adhesive strength of the obtained surface was 1 g · f or less.

[0182]

Embedded image

The surface releasable electrophotographic photosensitive member obtained as described above was placed in an apparatus as shown in FIG.
As a primary receptor 20, a blanket for offset printing (9600-A, adhesive force 80
gf, thickness 1.6 mm, made by Meiji Rubber) was attached.

Next, a dispersion liquid (L-1) of resin (A) having the following content was supplied onto the photosensitive drum to a wet electrodeposition unit 13a which is a transfer layer forming device, and the transfer layer was formed by an electrodeposition coating method. (T
₀ ) formed. -Dispersion liquid (L-1) of resin (A) Resin particles (ARW-1) 20 g (as solid content) Charge control agent (D-1) 0.09 g (octadecyl vinyl ether / t-octyl maleic acid half imide co-weight) Was adjusted with Isopar H so that the total amount was 1 liter.

The surface temperature of the photoconductor was set to 60 ° C. by the heating means of the infrared line heater, the peripheral speed of the photoconductor drum was rotated at 100 mm / sec, and the dispersion liquid was applied to the surface of the photoconductor using a slit electrodeposition apparatus. While supplying, ground the photoreceptor side,
A voltage of −150 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit the resin particles. Then, the resin particles were melted and formed into a film while removing the dispersion by air squeezing using a suction / exhaust unit to form a thermoplastic resin transfer layer 12. The film thickness at this time was 2.0 μm.

Next, an electrophotographic process was performed. Pass the photoconductor 11 under the corona charging device 18 in the dark,
After corona charging to + 450V, the original was read by a color scanner in advance, color separation was performed, and some system-specific corrections related to color reproduction were added, and then stored as digital image data on the hard disk in the system. . Based on the information about yellow among the colors of yellow, magenta, cyan, and black, the semiconductor laser drawing device 19 is used in the negative image mode.
It was exposed to light of 8 nm so that the exposure amount on the photoconductor was 30 erg / cm ² .

Subsequently, the positively charged yellow toner for the signature system (manufactured by Kodak) is 75 times as much as Isopar H.
It is diluted with (Esso Standard Petroleum) and supplied to the yellow liquid developing unit 14Y, a bias voltage of + 350V is applied to the developing unit 14Y side, and reversal development is performed so that the toner is electrodeposited on the exposed portion. The H-only bath was rinsed to remove stains on the non-image area, and then passed through the intake / exhaust unit 15 and the preheating means 16 to be dried. The above toner development process was repeated for each color of magenta, cyan and black to obtain a color toner image.

A drum having an offset printing blanket 9600-A as the primary receptor 20 was previously heated to 90 ° C. On the other hand, the surface temperature of the photoconductor 11 was heated to 60 ° C. by using the preheating means 16 and the temperature control means 17. Next, the photoreceptor 11 drum and the primary receptor 20 drum are brought into contact with each other, and the nip pressure is 3 kgf / c.
When heat and pressure were applied under the conditions of m ² and drum peripheral speed of 150 mm / sec, the entire color toner image was transferred onto the primary receptor together with the transfer layer.

Next, as a thermoplastic resin (A-1) for the adhesive layer (M), on the high quality paper which is the final transfer material 30,
Vinyl acetate / vinyl valerate (6/4) copolymer (Tg1
Hot melt coater 13 at 70 ° C.
In step b, the surface of the photosensitive layer is coated at a speed of 150 mm / sec (film thickness is about 1 μm), and the surface temperature is adjusted by the temperature control means 1.
20 drums of the primary receptor set to 60 ° C. in 7,
Transfer backup roller 22 set at 90 ° C. and peeling backup roller 2 without temperature control
3 between, nip pressure 3kgf / cm ² , drum speed 1
When heat and pressure were applied at 50 mm / sec, the color toner image was transferred onto high-quality paper to obtain a color image.

The copied image formed on the coated paper thus obtained was visually observed with a 200 × optical microscope for the non-image area and the toner image area. No background stains on the toner in the non-image area were observed, and the toner image and the 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 fine lines and fine characters. Distortion and missing / disturbance of halftone dots in the high-definition image area in the halftone halftone area were not seen, and the image was extremely good as a copied image.

On the other hand, a color image was similarly formed on a high quality paper, except that the toner image was transferred without providing an adhesion layer (M) on the final transfer material, and the result was compared with the present invention.
The color image of the high-quality paper obtained under the transfer conditions of the present invention,
The toner image was missing or the image density was uneven. Further, when fine lines, fine characters, and the like were visually observed with a magnifying glass of 20 times, fine image loss was recognized.

When the surface of the primary receptor was observed, the toner image area and the transfer layer remained. In this comparative example, the conditions for complete transfer onto high-quality paper were examined, and when the conditions for the second transfer for transferring from the primary receptor to high-quality paper were as follows, the toner image and the transfer layer were all transferred onto high-quality paper. . Backup roller temperature for transfer 120 ° C. Backup roller temperature for peeling 20 ° C. Nip pressure 7 kgf / cm ² Drum peripheral speed 50 mm / sec However, the color image on the obtained high-quality paper was visually observed with a 200 × optical microscope. Where the thin wire is thick
Deformation of the image such as bending was seen.

On the other hand, in the present invention, the toner image is sufficiently peeled from the photoconductor and the primary receptor even under the transfer condition in which the primary transfer and the secondary transfer are continuously performed at a high speed, and the final transfer material can be easily transferred. In addition, since the transfer is sufficient, the above problems do not occur, and the toner image is sufficiently adhered to the transfer layer, so that the stability of the obtained color copy is excellent. Further, when a color copy was repeatedly prepared for 500 plates in the embodiment of the present invention, an excellent color image having no change from the first plate was obtained. Also, as the final transfer material, plain paper, recycled paper, coated paper, art paper, and OHP film were used in place of high-quality paper to create a color image. , Always the same color copy was obtained.

Example 2 Amorphous silicon photoconductor (surface adhesive force 23 g · f,
Kyocera Co., Ltd.) was added with 2.0 g of compound (S-1) (polyether-modified silicone oil) having the following structure to Isopar G1.
After being immersed in a solution dissolved in 1 liter for 30 seconds, it was washed with Isopar G and dried. By this treatment, the adhesive force of the photoconductor became 3 g · f. Further, as a primary receptor, a natural rubber (made by Kokugo Co., Ltd.) having a rubber hardness of 75 degrees and a thickness of 2 mm was mounted on a SUS plate having a thickness of 100 μm,
Furthermore, 8 parts by weight of the following resin (P-1) and 0.001 g of phthalic anhydride are added to 100 parts by weight of isoprene rubber.
Was used to form a cured film by heating at 140 ° C. for 2 hours (adhesive force on the surface was 80 g · f) and an endless belt type was prepared.

[0195]

Embedded image

The above photoreceptor and primary receptor were mounted on a device as shown in FIG. 3, and a wet electrodeposition type transfer layer forming unit was attached to the primary receptor device. After the photoconductor 11 was corona-charged to -700 V, the same digital image data as in Example 1 was used. First, based on the information about yellow, in the negative mirror image mode, the semiconductor laser was used.
The plate surface was exposed to light of 80 nm so that the plate 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.
It is diluted with (Esso Standard Petroleum) and used with a developing device having a pair of flat plate developing electrodes, and +3 is applied to the photoconductor surface side electrode.
A bias voltage of 00V was applied to carry out reversal development in which the toner was electrodeposited on the exposed portion, and then Isopar H
Rinsing was performed in a single bath to remove stains on the non-image area. The above process was repeated for each color of magenta, cyan and black.

An image was fixed on the light-sensitive material obtained as described above by a heat roll fixing method. Check the image (fogging, image quality) to confirm the reproducibility of the copied image before transfer.
It was visually evaluated with a 00-times optical microscope. Regarding the image quality of the toner image area on the photoconductor, the high-definition image area of fine lines, fine characters, and halftone dots of continuous tone is clear, and the image density of the solid area is 1.2 or more, which is good. Fog was not observed in the image area.

On the other hand, the surface temperature of the primary receptor is 60 ° C.
In addition, while rotating the primary receptor peripheral velocity at 100 mm / sec, the primary receptor side was grounded while supplying the following resin (A) dispersion (L-2) to the surface of the primary receptor using a slit electrodeposition device. Then, a voltage of -100 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit and fix the resin particles to form a transfer layer (T ₂ ) having a film thickness of 2 μm. Resin (A) dispersion (L-2) Resin particles (ARW-2) (Tg: 40 ° C and 22 ° C) 20 g (as solid content) Charge control agent (CD-2) 0.06 g (1-tetradecene / Decyl hemi-maleate) 10 g of branched octadecyl alcohol (FOC-1800, manufactured by Nissan Kagaku Co., Ltd.) was adjusted with Isopar G so that the total amount was 1 liter.

[0199] Next, the surface temperature of the photosensitive member and 60 ° C., the temperature of the primary receptor is contacted remain 60 ° C., nip pressure 4 kgf / cm ^2, under conditions of a drum peripheral speed 100 mm / sec, heat and pressure Then, the color toner image as a whole including the transfer layer was transferred onto the primary receptor. Next, a 40% Isopar E solution of a thermoplastic resin (A-2) (Tg: -8 ° C) having the following structure for the adhesive layer (M) was applied onto a fine paper as a final transfer material by a color roll coating method. The coating was dried (film thickness was about 1 μm).

[0200]

Embedded image

The surface temperature is adjusted to 6 by the temperature adjusting means 17.
20 drums of primary receptor set at 0 ℃ and 90 ℃
Between the transfer backup roller 22 and the peeling backup roller 23 whose temperature is not adjusted, the nip pressure is 3 kgf / cm ² , and the drum peripheral speed is 100 mm.
When heating and pressing were performed at a speed of 1 / sec, a color toner image was obtained on high-quality paper. The obtained color image was clear, and was coated with a transfer layer having sufficient image area strength and film thickness strength, and was not scraped off even by rubbing. Further, the writing property and the marking property with a pencil hardness HB were also good. Further, in the embodiment of the present invention, when a color copy was repeatedly prepared for 500 plates, an excellent color image having no difference from the first plate was obtained.

Example 3 In the same manner as in Example 2, a color toner image was formed on the photoconductor. Next, a transfer layer (T ₁ ) is formed on the entire surface of this toner image.
Was formed as follows. The surface temperature of the photoconductor was set to 60 ° C., the peripheral speed of the drum of the photoconductor 11 was rotated at 100 mm / sec in the same manner as in Example 1, and the following resin (A ) Dispersion (L
While supplying -3), the photoreceptor side is grounded and a voltage of -130 V is applied to the electrode side of the slit electrodeposition apparatus to electrodeposit and fix the resin particles, and a transfer layer (T ₁ ) having a film thickness of 2 μm is provided. It was Resin (A) dispersion liquid (L-3) Resin particles (AR-1) 16 g (as solid content) Resin particles (AR-2) 4 g (as solid content) Charge control agent (CD-1) 0.07 g Charge 2 g (dodecyl methacrylate / acrylic acid (95/5 weight ratio) copolymer) of the liquid preparation auxiliary agent (AD-1) was adjusted with Isopar G so that the total amount became 1 liter.

Next, in Example 2, the primary receptor was preheated to a drum surface temperature of 110 ° C. by a method in which the primary receptor was not provided with the transfer layer (T ₂ ), while the photoreceptor was provided with the transfer layer. When the surface temperature set at 60 ° C. was maintained, the photoconductor drum was brought into contact with the primary receptor drum, and heating and pressurization were performed under the conditions of a nip pressure of 3 kgf / cm ² and a drum peripheral speed of 130 mm / sec. The entire color toner image was transferred onto the primary receptor together with the transfer layer.

Subsequently, in the same manner as in Example 2, a color image and a transfer layer were collectively transferred onto a high-quality paper.
The color image on the obtained coated paper was a good image without fog as in Example 2, and the image strength was also sufficient.

Example 4 As an organic photoconductive substance, 4,4'-bis (diethylamino) -2,2'-dimethyltriphenylmethane 5 g,
4 g of a binder resin (B-3) having the following structure, 40 mg of a dye (D-1) having the following structural formula, 0.2 g of an anilide compound (B) having the following structural formula as a chemical sensitizer, and 30 methylene chloride
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.

[0206]

Embedded image

This photosensitive layer dispersion was coated on a conductive transparent support (a polyethylene terephthalate support having a thickness of 100 μm and a vapor deposition film of indium oxide having a surface resistance of 10 ³ Ω) using a wire round rod. Then about 4
An organic thin film having a photosensitive layer with a thickness of μm was obtained. Further, an overcoat layer having the following contents was provided on this photoreceptor. 5 g of the following silicone rubber base polymer and 5 g of the silicone polymer having the following structure, 400 mg of the following cross-linking agent (SV-1), catalyst X
92-1114 (manufactured by Shin-Etsu Silicon Co., Ltd.) 40 mg and 60 g of heptane were uniformly applied with a wire bar,
A silicone rubber layer was formed by heating and drying at 90 ° C. for 2 minutes and crosslinking. The thickness of the silicone rubber layer at this time is 2.
The surface adhesion at 50 μm was 1 g · f or less.

[0208]

Embedded image

A transfer image was formed in the same manner as in Example 1 except that this photosensitive member was used instead of the photosensitive member used in Example 1. The obtained color copied image of the high-quality paper after transfer was clear without background fog, and the image strength was good in durability.

Example 5 5 g of a bisazo pigment having the following structure and tetrahydrofuran 95
and 5 g of polyester resin Byron 200 (manufactured by Toyobo Co., Ltd.) were sufficiently pulverized in a ball mill. Next, the mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was applied onto the conductive transparent support used in Example 4 using a wire round rod to form a charge generation layer having a thickness of about 0.7 μm.

[0211]

Embedded image

Next, the hydrazone compound 20 of the following structural formula
g, 20 g of a polycarbonate resin (trade name: Lexan 121, manufactured by GE) and 160 g of tetrahydrofuran are applied onto the charge generation layer using a wire round rod, dried at 60 ° C. for 30 seconds, and further heated to a temperature of 100.
The film was heated at 20 ° C. for 20 seconds to form a charge transport layer of about 18 μm, and an electrophotographic photosensitive member having a photosensitive layer composed of two layers was obtained.

[0213]

Embedded image

Further, in order to form a surface layer for imparting releasability on this photosensitive layer, the following resin (B-4) 1
A mixed solution of 3 g, phthalic 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 dried at a temperature of 120 ° C. for 1 hour at 120 ° C. Heated for hours. The adhesive force on the surface of the obtained photoreceptor was 2 g · f.

[0215]

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As a primary receptor 20, a natural rubber sheet (made by Kokugo Co., Ltd.) having a rubber hardness of 75 degrees and a thickness of 4 mm was first fixed on a hollow roller, and a methoxyethyl-modified nylon copolymer (Dyamide) was placed on the sheet. MX-100,
A resin layer (manufactured by Daicel Co., Ltd.) having a thickness of 2 μm is provided, and an uppermost layer having the following composition is coated on the resin layer so that the film thickness becomes 3 μm
A film cured by heating at a temperature of 120 ° C. for 2 hours was used. The surface peeling force of this primary receptor is 120 gf
Met.

[0219]

Embedded image

First, a transfer layer (T ₀ ) was formed on a photoreceptor by a transfer method from a release paper as shown in FIG. That is, as the release paper, a separate paper (manufactured by Oji Paper Co., Ltd.) was used, and 1 / of the following resin (A-3) and resin (A-4)
A paper having a film thickness of 2.5 μm composed of two weight ratios was pressed against the same photoreceptor as in Example 1, the pressure between rollers was 3 kgf / cm ² , the surface temperature was 60 ° C., and the passing speed was 50 mm /.
A transfer layer having a film thickness of 2.5 μm was formed on the surface of the photoreceptor under the condition of seconds.

[0219]

Embedded image

This photosensitive material was charged to a surface potential of +500 V and then exposed to light of 633 nm using a He-Ne laser so that the exposure amount on the plate surface would be 30 erg / cm ^2. The same operation as in 1 was carried out to form a color toner image on the photoconductor. The color copy obtained had clear image quality without background stains. That is, the toner image formed on the photoconductor shows good image reproducibility and no fog in the non-image area, and has good image pick-up property. The transfer was also completed completely without causing uneven transfer. Furthermore,
It was possible to add or stamp on the copy paper in the same manner as for plain paper.

Example 6 In Example 5, a transfer layer (T ₀ ) was formed by the following hot melt coating method instead of forming the transfer layer by transfer from the release paper. That is, as a thermoplastic resin for the transfer layer, a saturated polyester resin Chemit R-185 (Tg;
8 ° C., manufactured by Toray Co., Ltd., is applied to the surface of the material to be transferred at a speed of 50 mm / sec by a hot melt coater, and is cooled by blowing cooling air from the surface temperature to 60 ° C.
Kept. The thickness of the transfer layer (T ₀ ) at this time was 1.5 μm. Others were operated in the same manner as in Example 5 to obtain a color copy. The toner image and transfer layer are all transferred onto high-quality paper without being left untransferred on the photoconductor and primary receptor, and there is a lack of high resolution areas such as fine lines and fine characters, disturbance, and a network of high-definition image areas in the halftone area. No missing or irregular dots were found, and the image was very good as a copied image.

Example 7 In Example 1, after a color image was formed on the electrophotographic photosensitive member by a method in which the transfer layer (T ₀ ) was not provided on the photosensitive member, the surface temperature of the photosensitive member was 80 ° C. and the primary receptor was used. After heating the surface temperature to 120 ° C., the photoreceptor and the primary receptor were heated and pressed under the conditions of a nip pressure of 5 kgf / cm ^{2 and a} drum peripheral speed of 10 mm / sec to transfer the toner image onto the primary receptor. Next, while keeping the temperature of the primary receptor at 80 ° C,
A vinyl acetate / crotonic acid (97/3 weight ratio) copolymer (Tg 43 ° C.) adhesion layer (2 μm) was pre-coated between the transfer backup roller set at 120 ° C. and the peeling backup roller set at 10 ° C. The coated paper provided was guided and heated under pressure at a nip pressure of 5 kgf / cm ² and a drum peripheral speed of 10 mm / sec to transfer the toner image onto the coated paper. The copied image transferred to the coated paper was a good reproduction of the original, and no transfer unevenness was observed. Further, the filing suitability was good, and the adhesion and peeling of the sheet did not occur. Further, the imprintability was also good.

On the other hand, when the transfer was performed on the coated paper without the adhesion layer (M), the transfer from the primary receptor was not completed. Further, various transfer conditions were examined, but no perfect transfer was obtained.

Examples 8 to 11 In Example 1, the resin particles (A) in the transfer layer (T) were used.
A color image copy was prepared in the same manner as in Example 1 except that each of the resin particles shown in Table D was used instead of 20 g of RW-1) to form a transfer layer having a film thickness of 2 μm.

[0225]

[Table 4]

Each of the color copies thus obtained exhibited the same good performance as in Example 1. For each edition, 5
When the printing plate No. 00 was repeatedly made, all were equivalent to the first plate and showed no performance deterioration.

Examples 12 to 17 In Example 3, the resin particles (AR-1) of the transfer layer (T) were used.
A color image copy was prepared in the same manner as in Example 3 except that the resin particles shown in Table E were used instead of / AR-2). Each of the color copies obtained showed good performance, which was exactly the same as in Example 3. For each edition, 500
When the plate was repeatedly made, all were equivalent to the first plate and showed no performance degradation.

[0228]

[Table 5]

Example 17 In Example 1, instead of forming the contact layer (M) on the transfer material by the hot melt coating method, the contact layer (M) was formed by the following inkjet method. Resin particles (AR
-3) 10% by weight (as solid content) of Isopar G mixture was put into an ink tank of an ink jet printer having a head orifice diameter of 40 µm and discharged, and dried to form an adhesion layer having a thickness of 0.8 µm. When the other operations were performed in the same manner as in Example 1, the same performance as in Example 1 was obtained.

Example 18 In Example 1, instead of forming the contact layer (M) on the transfer material by the hot melt coating method, the contact layer (M) was formed by the following wet electrodeposition method. That is, an OHP film was used as the material to be transferred, the surface temperature was 55 ° C., the transport speed was 100 mm / sec, and a slit electrodeposition device was used on the surface of the material to be transferred to obtain a positively charged resin particle dispersion liquid having While supplying (TL-1), the transfer target side was grounded and a voltage of +150 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit and fix the resin particles. The film thickness at this time is 1.0
μm.

Resin (A) dispersion (TL-1) Resin particles (AR-1) 20 g (as solid content) Positive charge control agent (CD-1) 0.08 g Octadecyl vinyl ether / N-hexadecyl maleic acid Half amide (1/1 weight ratio) copolymer Charge control aid (AD-1) 0.1 g Dodecylmethacrylate / methacrylic acid (94/6 weight ratio) copolymer with Isopar G to a total volume of 1.0 liter I adjusted it. When a color copy was prepared in the same manner as in Example 1 except for the above, a good copy having exactly the same performance as in Example 1 was obtained.

[0232]

According to the present invention, it is possible to easily and stably obtain a high-definition, high-quality color image free from color misregistration, and to reproduce an excellent color image regardless of the final transfer material. be able to. In particular, complete transfer can be achieved even if transfer conditions are relaxed.

[Brief description of the drawings]

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

FIG. 2 is a diagram showing an example of an apparatus for carrying out the method of the present invention, which employs an electrodeposition coating method as a transfer layer forming method and a drum system as a primary receptor.

FIG. 3 is a diagram showing an example of an apparatus for carrying out the method of the present invention, which employs a hot melt coating method as a transfer layer forming method and an endless belt method as a primary receptor.

FIG. 4 is a diagram showing an example of an apparatus for carrying out the method of the present invention, which adopts a transfer method as a transfer layer forming method, an endless belt method as a primary receptor, and an impression drum method as a backup thereof.

[Explanation of symbols]

1 Conductive Support 2 Photosensitive Layer 3 Toner Image 5 Adhesion Layer (M) 7 Transfer Layer (T ₁ ) 7 ′ Transfer Layer (T ₂ ) 8 Transfer Layer (T ₀ ) 10 Compound (S) Application Device 11 Photosensitive Member 13 Transfer layer forming device 13a Electrodeposition coating unit 13b Hot melt coater 13c Transfer method device 14 Liquid developing unit set 14Y Yellow toner image forming unit 14M Magenta toner image forming unit 14C Cyan toner image forming unit 14B Black toner image forming Unit 15 intake / exhaust unit 15a intake part 15b exhaust part 16 preheating means 17 temperature adjusting means 18 corona charging device 19 exposure device 20 primary receptor 30 final transfer material 31 transfer backup roller 32 peeling backup roller 33 adhesion layer forming unit 40 Release paper

Claims (6)

[Claims] 1. A toner image of one or more colors is formed by an electrophotographic process using a liquid developer on an electrophotographic photoreceptor having a releasable surface, and then the toner image on the photoreceptor is brought into contact with a primary receptor. Electrophotography characterized by transferring and further transferring onto a final transfer material provided with an adhesion layer (M) mainly containing a thermoplastic resin (AM) having a glass transition point of 80 ° C. or lower or a softening point of 90 ° C. or lower. Color image forming method. 2. A thermoplastic resin (AT ₀ ) is mainly contained on an electrophotographic photoreceptor having a releasable surface before forming a toner image of one or more colors by an electrophotographic process using a liquid developer. The electrophotographic color image forming method according to claim 1, wherein a transfer layer (T ₀ ) which can be peeled off is provided, and the toner image is transferred onto the primary receptor together with the transfer layer (T ₀ ). 3. A toner image of one or more colors formed by an electrophotographic process using a liquid developer is transferred onto a primary receptor via the method (i) or (ii) below. The electrophotographic color image forming method according to claim 1. (I) after primarily transferring layer containing the entire thermoplastic resin of the photosensitive member carrying the toner image (AT ₁₎ and (T ₁₎ is provided, transferring the toner image and the transfer layer (T ₁₎ on the primary receptor To do. (Ii) A toner image is transferred onto a primary receptor provided with a transfer layer (T ₂ ) mainly containing a thermoplastic resin (AT ₂ ). 4. The peelable transfer layers (T ₀ ), (T ₁ ), and (T ₂ ) are formed by any one of a hot melt coating method, an electrodeposition coating method, and a transfer method. 4. The method for forming an electrophotographic color image according to claim 3, wherein 5. A resin (AT ₀ ), (AT
₁ ) or (AT ₂ ) is a resin (AH) having a glass transition point of 30 ° C. to 80 ° C. or a softening point of 40 ° C. to 90 ° C. and a glass transition point of 4
It is composed of at least a resin (AL) having a softening point of 0 ° C. or lower or a softening point of 45 ° C. or lower, and a difference in glass transition point or softening point between the resin (AH) and the resin (AL) is 2 ° C. or more, and an adhesion layer (M 5. The electrophotographic color image forming method according to claim 2, wherein the resin (AM) constituting (1) is mainly composed of the resin (AL). 6. The surface of the electrophotographic photosensitive member is JIS Z0.
237-1980 "Adhesive tape / adhesive sheet test method"
The electrophotographic color image forming method according to any one of claims 1 to 5, wherein the adhesive force according to (4) is 20 gram · force (g · f) or less.