JPH07287456A - Color image forming method and device used therefor - Google Patents

Abstract

PURPOSE:To transfer a toner image onto a transferred material without color smear in a color image and a deterioration in image quality caused by a transfer, further, to make the preservation stability of a color copy excellent and to repeatedly use a photoreceptor. CONSTITUTION:The color image forming method and the device used therefor are for forming the toner images 25 of one or more colors on the photoreceptor 11 having a peelable surface in an electrophotographic process and providing a peelable transfer layer 12 on the toner images 25, to transfer them to a primary receptor 20 and further, a final transferred material 21 together with the transfer layer 12 and the photoreceptor 11 having the peelable surface can be simply and easily obtained by supplying a releasing compound to the photoreceptor 11.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color image forming method such as an electrophotographic color copying machine, a color printer, a color proofer, and a color checker, and an apparatus used therefor.

[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 the photoconductor in advance, a wet toner image is formed on the film by an electrophotographic process, and then the film is peeled from the photoconductor and attached to plain paper to 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. In addition, Japanese Patent Fair 2-4
Japanese Patent No. 3185 discloses a method of exposing a transparent electrophotographic photosensitive member from the rear side to form an overlapping color separation image on a dielectric support and transferring the support together with the support onto a material to be transferred. There is. 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 Unexamined Patent Publication Nos. 1-112264 and 1-
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 thereon. Proposals have been made to transfer the transfer layer to 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 disadvantage in terms of cost cannot be avoided.

On the other hand, Japanese Patent Application 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 and JP-A-4-9087 propose a method of obtaining a good final color image even with a wet toner by using a special transfer medium.

[0006]

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 the toner image can be directly transferred to the primary intermediate transfer medium, Since the image is transferred onto the final transfer material, the resulting color image has a missing toner image or uneven image density, and in particular, fine image defects such as fine lines and fine characters are observed. Further, the toner image remains on the surface of the photoconductor after the transfer of the toner image. This means that when the photoconductor is repeatedly used, it becomes necessary to clean the surface of the photoconductor, and further, setting of an apparatus for that purpose and damage to the surface of the photoconductor due to the cleaning become problems.

As described above, in the conventional color image forming method using the intermediate transfer medium, a sufficiently satisfactory color image cannot be obtained, and the properties of the intermediate medium change when it is repeatedly used, and stable performance is maintained for a long time. There are various problems that it is difficult to maintain, a disposable member is generated to maintain the performance, and it is necessary to use a special transfer medium.

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 a final transfer material. A novel electrophotographic color image forming method using a transfer layer as a medium and an apparatus used therefor. Furthermore, the transfer layer is easily formed and peeled off, and the transfer device having a simple structure is used in the electrophotographic apparatus to form the transfer layer on the photoconductor each time after the color image is formed, and the photoconductor is repeatedly used. It is possible to reduce the running cost. Further, it is a further object to make it possible to further reduce the running cost by using a general-purpose electrophotographic photoreceptor.

[0009]

The above object of the present invention is to form a toner image of one or more colors on an electrophotographic photosensitive member having a releasable surface by an electrophotographic process, and to form a releasable transfer layer on the toner image. A color image formed on a photoreceptor having a toner, the toner image is transferred to a primary receptor together with a transfer layer, and then the toner image on the primary receptor is transferred to a final transfer material together with the transfer layer. It has been found to be achieved by the method of formation.

The color image forming method of the present invention uses an ordinary electrophotographic process on an electrophotographic photosensitive member 11 composed of at least a support 1 and a photosensitive layer 2 as shown in FIG. To form a toner image 25 of one or more colors, and a peelable transfer layer 12 is provided on the photoconductor 11 having the toner image 25. Transcribe to receptor 20. Further, the toner image 25 is transferred to the final transfer material 21 together with the transfer layer 12 to form a color copy.

According to the present invention, a releasable transfer layer is provided on the photoreceptor on which the toner image is formed, and the toner transfer is carried out together with the transfer layer, so that the toner image can be easily and completely transferred. Also,
A transfer device with a simple structure is sufficient, and a color image can be formed regardless of the final transfer material.

Further, since the transfer layer is formed on the color image and transferred together with the transfer layer, it is possible to easily and stably obtain a high-definition and high-quality color image without color shift. Furthermore, the transfer layer protects the surface of the photosensitive layer, and since the final transfer material does not directly touch the surface of the photosensitive layer because it is once transferred onto the primary receptor, the damage to the surface of the electrophotographic photosensitive member is reduced,
The photoreceptor can be used repeatedly and for a long period of time.

Further, by forming the transfer layer in the same apparatus as the electrophotographic process and the transfer process, the electrophotographic photosensitive member can be repeatedly used in the apparatus, and the running cost can be reduced. One preferable embodiment of the present invention is a color image forming method characterized in that the following steps (i) to (iv) are performed in the same apparatus. (I) a step of forming a toner image of one or more colors on the electrophotographic photoreceptor by an electrophotographic process, (ii) a step of forming a peelable transfer layer on the photoreceptor having the toner image, (ii)
i) a step of transferring the toner image together with the transfer layer to a primary receptor, and (iv) a step of transferring the toner image together with the transfer layer onto a final transfer material.

The present invention further comprises means for forming a toner image of at least one color on an electrophotographic photosensitive member by an electrophotographic process, means for providing a peelable transfer layer on the photosensitive member having the toner image, and a primary Provided is a color image forming apparatus having at least means for transferring the toner image together with a transfer layer onto a receptor and means for transferring the toner image together with the transfer layer from a primary receptor onto a final transfer material.

In the present invention, the peelable transfer layer is preferably formed on the photosensitive member by at least one of a hot melt coating method, an electrodeposition coating method and a transfer method.

Further, the electrophotographic photoreceptor having a releasable surface used in the present invention can be manufactured according to JIS Z0237-1980, "Adhesive tape.
Adhesive strength according to "Adhesive sheet test method" is 100 grams / forc
e (g · f) or less, more preferably 50 g · f or less, particularly preferably 30 g · f or less, and the adhesive force of the surface of the primary receptor is larger than the adhesive force of the surface of the photoreceptor. , Especially 10g ・ f or more, further 30g
-It is preferable that it is larger than f.

The adhesive force on the surface of the primary receptor is 200 g · f at the maximum, and particularly preferably 180 g · f or less. As a result, the peelability between the photoreceptor and the transfer layer can be exhibited, and the transfer of the toner image for each transfer layer from the photoreceptor to the primary receptor and from the primary receptor to the final transfer material can be easily achieved. If further added, it is preferable that at least the adhesive force between the surface of the primary receptor and the surface of the final transfer material is smaller than that of the latter.

The adhesive strength is measured according to JIS Z 0237-1980 "Adhesive tape / adhesive sheet test method" described in 18 of 8.3.1.
Follow the 0-degree peeling method with the following modifications. An electrophotographic photosensitive member on which a transfer layer is to be formed is used as a "test plate". As the “test piece”, an adhesive tape having a width of 6 mm and manufactured according to JIS C 2338-1984 is used. Peel at a speed of 120 mm / min using a constant speed tension type tensile tester. That is, with the adhesive surface of the test piece facing down, the roller is reciprocated once over the test piece at a speed of about 300 mm / min 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 time it is peeled off by 20 mm, and a total of 4 times is read. The test is performed on three test pieces, and an average value of twelve pieces measured from the three test pieces is obtained, and the average value is proportionally converted per 10 mm width. When measuring the adhesive force of the primary receptor and the final transfer material, these are used as test plates and the same procedure as above is performed.

The transfer layer used in the present invention will be described in detail below. The transfer layer of the present invention is made of a peelable resin (hereinafter referred to as resin (A)), is light-transmissive, and transmits at least a part of wavelength light in the spectral sensitivity region of the electrophotographic photosensitive member. It is not particularly limited as long as it has properties, and it may be colored. When the image transferred to the final transfer material is a color image (particularly a full-color image), a colorless and transparent transfer layer is usually used.

The resin (A) has a temperature of 180 ° C. or lower or 2
A resin that can be peeled off under a transfer condition of a pressure of 0 kgf / cm ² or less is preferable. If this value is exceeded, it is necessary to increase the size of the transfer device to maintain the heat capacity and pressure of the transfer device in order to separate and transfer the transfer layer from the surface of the photoconductor, or the transfer device will only release under transfer conditions that exceed these conditions. The use of a resin is not preferable because it causes a practically difficult problem such that the transfer speed must be extremely slowed down in order to perform the transfer sufficiently. The lower limit is not particularly limited, but a resin that can be peeled off under a transfer condition of usually room temperature or higher or pressure of 100 gf / cm ² or higher is preferable.

Any resin can be used as the resin (A) as long as it can be peeled off under the above-mentioned transfer conditions, but as its thermophysical property, a resin having a glass transition point of 140 ° C. or lower or a softening point of 180 ° C. or lower is preferable, and further glass transition. A resin having a point of 100 ° C. or lower or a softening point of 150 ° C. or lower is preferable.

In the present invention, it is preferable to use at least two kinds of resins having different glass transition points or softening points in combination.
In particular, a resin having a glass transition point of 30 ° C. or higher or a softening point of 35 ° C. or higher (hereinafter referred to as a resin (AH)) and a resin having a glass transition point or a softening point of 2 ° C. or higher, particularly 5 ° C. or higher than a resin (AH) {hereinafter: Resin (AL)} is preferably used in combination. Further, the resin (AL) has a glass transition point of -50 ° C.
The softening point is preferably from + 40 ° C or from -10 ° C to + 45 ° C. Here, the resin (AH) or the resin (AL) is 2
The difference in the glass transition point or the softening point in the case of containing more than one species is the one having the lowest glass transition point or the softening point in the resin (AH) and the highest glass transition point or the softening point in the resin (AL). It is the difference from the thing. Resin (A
H) / resin (AL) abundance ratio (weight ratio) is 5 to 90
It is preferably / 95 to 10, particularly preferably 10 to 70/90 to 30. If the abundance ratio of resin (AH) / resin (AL) deviates from the above range, the effect of the combined use decreases.

Further, the transfer layer of the present invention is a first layer of a resin (AL) having a low glass transition point on the surface of the photoreceptor and a second layer of a resin (AH) having a high glass transition point thereon. Thus, it is preferable that the layers are formed in multiple layers. As a result, the transferability from the primary receptor to the final transfer material is further improved, the latitude of the transfer conditions (heating temperature, pressure, transport speed, etc.) is increased, and the final transfer that becomes a color image copy is made. It is not affected by the type of material, and can be easily transferred. Further, since the surface side of the transfer layer finally transferred to the final transfer material is composed of a resin (AH) having a high glass transition point, the transfer layer is peeled off even if it is put in various sheets and stacked and filed. The storage stability of the copy is further improved, such as the occurrence of no such phenomenon (appropriate filing). Further, by selecting the type of the resin (AH), it becomes possible to impart the writing property and the imprinting property similar to those of plain paper.

Specific examples of the resin (A) that can be used in the transfer layer include thermoplastic resins, resins known as adhesives or pressure-sensitive adhesives, such as olefin polymers and copolymers, and vinyl chloride. Copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, polymers and copolymers of styrene and its derivatives, olefin-styrene copolymers, olefins -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 ester copolymer, styrene-methacrylic acid ester copolymer, itaconic acid diester copolymer Body and copolymers, maleic anhydride copolymers, acrylamide copolymers, methacrylamide copolymers, hydroxy group-modified silicone resins, polycarbonate resins, ketone resins, polyester resins, silicone resins,
Amide resin, hydroxyl group- and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin,
Cyclized rubber-methacrylic acid ester copolymer, cyclized rubber-
Acrylic ester copolymer, copolymer containing a heterocycle (for example, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, a benzofuran ring, a benzothiophene ring, 1,3- Dioxetane ring, etc.), cellulose resin,
Examples thereof include fatty acid-modified cellulose-based resins and epoxy resins.

[0025] For example, "Plastic Material Lecture Series" Vol. 1 to 18 (1981) published by Nikkan Kogyo Shimbun, "Polyvinyl chloride" edited by Kinki Chemical Association Vinyl Section, published by Nikkan Kogyo Shimbun (1988), Hide Omori Three "Functional Acrylic Resins" Techno System Co., Ltd. (1985), Eiichiro Takiyama "Polyester Resin Handbook" Nikkan Kogyosha (1988), Kazuo Yuki "Saturated Polyester Resin Handbook" Nikkan Kogyo Shimbun (1989) ), "Polymer Data Handbook <Applications>" edited by The Polymer Society of Japan, Chapter 1 Baifukan (1986), Yuji Harazaki "Latest Binder Technology Handbook" 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 Hattond Book 2nd Edition" edited by Adhesion Association, Nikkan Kogyo Shimbun (1980
Years) and the like.

Resin (A) for use in the transfer layer of the present invention
Further contains a polymer component (F) containing a fluorine atom- and / or silicon atom-containing substituent having the effect of improving the releasability of the resin (A) itself, as the polymer component in the resin. May be. As a result, the releasability of the releasable surface from the electrophotographic photosensitive member is further improved, and as a result, the transferability is improved. The content thereof is preferably 3 to 40% by weight in 100 parts by weight of all polymer components of the resin (A),
It is 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) is contained as a block in the resin (A).

Further, as described above, when the resin (A) constituting the transfer layer is composed of two or more kinds of resins having different glass transition points or softening points, these fluorine atom and / or silicon atom containing polymer components ( F) may be contained in both the high glass transition point resin (AH) and the low glass transition point resin (AL).

The polymer component (F) which has the function of improving the releasability of the resin (A) itself and which may be contained in the polymer will be described below. Examples of the substituent containing a fluorine atom include the following monovalent or divalent organic residues.

[0029]

[Chemical 1]

[0030]

[Chemical 2]

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

[0032]

[Chemical 3]

However, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different and each may be an optionally substituted hydrocarbon group or an —OR ⁶ group (R ⁶ is substituted. Represents a good hydrocarbon group).

Specific examples of the hydrocarbon group represented by R ^{1 to} R ⁶ include alkyl groups having 1 to 18 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group,
Hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 2-cyanoethyl group, 3,3,3-trifluoropropyl group Ethyl group,
2-methoxyethyl group, 3-bromopropyl group, 2-methoxycarbonylethyl group, 2,2,2,2 ', 2',
2'-hexafluoroisopropyl group, etc., 4 to 4 carbon atoms
18 optionally substituted alkenyl groups (for example, 2-methyl-1-propenyl, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2- A hexenyl group, a 4-methyl-2-hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group, a phenethyl group, a 3-phenylpropyl group, a naphthylmethyl group, 2
-Naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic group having 5 to 8 carbon atoms Groups (eg cyclohexyl group, 2-cyclohexyl group, 2
-Cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group,
Butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl Group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group,
A propioamidophenyl group, a dodecyloylamidophenyl group, etc.).

The organic residue containing a fluorine atom and / or a silicon atom may be constituted in combination, in which case it may be directly bonded or further via another linking group. May be combined together. Specific examples of the linking group include a divalent organic residue, for example, -O.
-, - S -, - N (d 1) -, - CO -, - SO -, - S
_{O 2 -, - COO -,} - OCO -, - CONHCO-,
^{-NHCONH -, - CON (d 1} ) -, - SO 2 N (d 1)
Examples thereof include a divalent aliphatic group or a divalent aromatic group which may have a bonding group selected from the group such as-, and an organic residue constituted by a combination of these divalent residues. Here, d ¹ represents the same content as R ¹ .

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

[0037]

[Chemical 4]

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

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

Specific examples of the repeating unit having a substituent containing a fluorine atom and / or a silicon atom as described above are shown below. However, the scope of the present invention is not limited to these. In each of the following (F-1) to (F-32), R _f represents any one of the following (1) to (11), and b represents a hydrogen atom or a methyl group.

[0041]

[Chemical 5]

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

[0043]

[Chemical 6]

[0044]

[Chemical 7]

[0045]

[Chemical 8]

[0046]

[Chemical 9]

[0047]

[Chemical 10]

Preferred embodiments as a so-called block copolymer in the resin (A) of the present invention will be described below. In the block copolymer, any polymer may be used as long as the polymer component (F) containing a fluorine atom and / or a silicon atom is composed of a block in the copolymer. Here, being composed of blocks means that the fluorine atom and / or the silicon atom is 70
It means having a polymer segment contained in an amount of not less than wt% in the copolymer. For example, the following AB type block, ABA type block, BAB type block, A graft type block or a star type block may be used.

[0049]

[Chemical 11]

These various block copolymers can be synthesized by a conventionally known polymerization method. For example,
WJ Burlant, AS Hoffman `` Block and Graft poly
mers ”(1986, Reuhold), RJ Cevesa“ Block and
Graft Copolymers "(1962, Butterworths), DC A
llport, WH James "Block Copolymers" (1972, A
ppliedSci), A. Noshay, JE McGrath `` Block Copoly
mers "(1977, Academics Press.), G. Huvterg, D.
J. Wilson, G. Riess, NATO ASIser. SerE. 1985 , 14
9, V. Perces, Applide. Polymer Sci. 285, 95 (1985).

For example, regarding an ionic polymerization reaction using an organic metal compound (eg, alkyllithium, lithium diisopropylamide, alkali metal alcoholates, alkylmagnesium halides, alkylaluminum halides) as a polymerization initiator, TE Hogeu- Esc
h, J. Smid `` Recent Advances in Anion Polymerizatio
n '' (1987, Elsevier New York), Okamoto Yoshio, Polymer, 38 , 912 (1989), Sawamoto Mitsuo, Polymer, 38 , 1018 (198)
9), Tadashi Narita, Polymer, 37 , 252 (1988), BC Anderson
et al., Macromolecules 14 , 1601 (1981), S. Aoshima,
T. Higashimura, Macromolecules 22 , 1099 (1989) and the like.

Regarding the ionic polymerization reaction with hydrogen iodide / iodine system, etc., see T. Higashimura at al., Macro.
mol. Chem., Macromol. Symp ., 13/14, 457 (1988), Higashimura Satoshinobe, Mitsuo Sawamoto, by Kobunshi Ronbunshu 46, 189 (1989) and the like. For the group transfer polymerization reaction, see D.
Y. Sogah et al., Macromolecules, 20 , 1473 (1987),
OW Webster, DY Sogah, Polymer, 36 , 808 (198
7), MT Reetg et al., Qngew. Chem. Int. Ed. Eng
25 , 9108 (1986), JP-A-63-97609 and the like.

For living polymerization reaction using a metalloporphyrin complex, see T. Yasuda, T. Aida, S. Inoue, Mac.
romolecules, 17 , 2217 (1984), M. Kuroki, T. Aida,
S. Inoue, T. Ann. Chem. Soc. 109, 4737 (1987), M. K.
uroki et al., Macromolecules, 21 , 3155 (1988), M.K.
uroki, I. Inoue, Synthetic Organic Chemistry, 47 , 1017 (1989).

Further, regarding ring-opening polymerization reaction of cyclic compounds, S. Kobayasi, T. Saegusa "Ring Opening Polyme
rization ”(1984, Applied Science Publishers Lt.
d.), W. Seeliger et al., Angew. Chem. Int. Ed. Eng
l. 5, 875 (1966), S. Kobayasi et al., Poly. Bull. 1
3 , 447 (1985), Y. Chujo et al., Macromolecules, 2
2 , 1074 (1989) and the like.

Further, regarding the living photopolymerization reaction using a dithiocarbamate compound, a xanthate compound or the like as an initiator, Takayuki Otsu, Kogaku, 37 , 248 (1988),
Shunichi Hinomori, Ryuichi Otsu, Polym. Rep. Jap. 37 , 3508 (198
8), JP-A 64-111, and JP-A 64-26619.
No., M. Niwa, Macromolecules, 189, 2187 (1988) and the like.

[0056] On the other hand, a method of synthesizing a block copolymer by radical polymerization reaction to polymeric initiator containing an azo group or a peroxide group, Ueda Akirato, polymer Collected Papers, 3
3 , 931 (1976), Akira Ueda, Osaka City Research Institute Report 84 (198)
9), O. Nuyken et al., Macromol. Chem., Rapid. Comm.
un. 9, 671 (1988), Yasuo Moriya et al. "Reinforced plastic" 2
9 , 907, Ryohei Oda, "Science and Industry" 61 , 43 (1987).

Regarding the synthesis of the graft type block copolymer, in addition to the above-mentioned books and reviews, Fumio Ide “Graft polymerization and its applications” (1977, Polymer Society of Japan), Polymer Society, “Polymer”・ Alloy ”(1981, Tokyo Kagaku Dojin). For example, a method of grafting a polymer chain with a polymerization initiator, a chemical actinic ray (radiation, electron beam, etc.), a mechanochemical reaction in mechanical application, etc., a polymer chain and a functional group of the polymer chain Utilizing such a method, there is known a method of chemically bonding (so-called interpolymer reaction) and grafting, a method of polymerizing a macromonomer and grafting.

As a method of grafting using a polymer, specifically, T. Shota et al., J. Appl. Polym. S
ci. 13 , 2447 (1969), WH Buck, Rubber Chemistry a
nd Technology, 50 , 109 (1976), Takeshi Endo, Tsutomu Uezawa, Journal of Japan Adhesion Society, 24 , 323 (1988), Takeshi Endo, ibid. 25 , 409 (1)
989) etc.

As a method of carrying out a polymerization reaction and grafting using a macromonomer, specifically, P. Dreyfuss
& RP Quirk, Encycl. Polym. Sci. Eng., 7, 551 (1
987), PF Rempp, E. Franta, Adv. Polym. Sci., 5
8 , 1 (1984), V. Percec, Appl. Poly. Sci., 285, 95
(1984), R. Asami, M. Takari, Macromol. Chem. Supp.
l., 12 , 163 (1985), P. Rempp et al., Macromol. Che
m. Suppl., 8, 3 (1985), Yusuke Kawakami, Chemical Industry, 38 , 56 (1)
987), Yuya Yamashita, Polymer, 31 , 988 (1982), Shiro Kobayashi,
Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of Japan Adhesion Society, 1
8 , 536 (1982), Koichi Ito, Polymer processing, 35 , 262 (198
6), Takashiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No.10, 5, edited by Yuya Yamashita, "Chemistry and Industry of Macromonomers" (1989,
"PC Design Co., Ltd.", edited by Takeshi Endo, "Molecular Design of New Functional Polymers" Chapter 4 (1991, CMC Co., Ltd.), Y. Yam
ashita et al., Polym. Bull. 5, 361 (1981) and the like.

The synthesis method of the star type block copolymer is as follows:
For example, MT Reetz, Angew. Chem. Int. Ed. Engl.,
27 , 1373 (1988), M. Sgwarc `` Carbanions, Living Poly
mersand Electron Transfer Processes '' (1968, Wile
y. New York), B. Gordon et al., Polym. Bull. 11 , 34
9 (1984), RB Bates et al., J. Org. Chem. 44 , 3800.
(1979), Y. Sogah, ACS Polym. Rapr. 1988 , No.
2, 3, JW Mays. Polym. Bull. 23 , 247 (1990), IM
Khan et al., Macromolecules, 21 , 2684 (1988), A. M
orikawa, Macromolecules, 24 , 3469 (1991), Akira Ueda,
Toru Nagai, Polymer, 39 , 202 (1990), T. Otsu, Polym. Bul
L. 11 , 135 (1984) etc. However,
The method for synthesizing the block copolymer is not limited to these methods.

The amount of the block copolymer is preferably 70% by weight or more, more preferably 90% by weight, based on the total amount of the entire composition of the transfer layer.
It is preferably used in a proportion of not less than wt%. These copolymers may be used alone or in combination of two or more kinds.

If necessary, other additives may be added to the transfer layer in order to improve various physical properties such as adhesiveness, film-forming property and film strength. For example, polybutene, DOP, DBP, low-molecular-weight styrene resin, 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 total thickness of the transfer layer is 0.1 to 20 μm.
m is suitable, and preferably 0.5 to 10 μm.
If the film thickness is too thin, transfer defects are likely to occur, and if it is too thick, problems in the electrophotographic process are likely to occur, sufficient image density cannot be obtained, and image quality is likely to deteriorate. To form the transfer layer on the surface of the photoconductor, a hot melt coating method, an electrodeposition coating method or a transfer method is preferably used as described below.

Next, the electrophotographic photosensitive member used in the present invention will be described. As the electrophotographic photoreceptor, any conventionally known one can be used. What is important is that the surface of the photoreceptor has releasability before the toner image is formed so that the transfer layer provided on the surface of the photoreceptor can be easily peeled off together with the toner image. In the present invention, as described above, the adhesive strength of the surface of the photoreceptor before forming a toner image according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method” is 100 g · f or less, further 50 g · f
It is preferably f or less, and particularly preferably 30 g · f or less.

In order to obtain a photoreceptor having a releasable surface, specifically, a method of using a photoreceptor having a releasable surface in advance or a releasing compound (S) on the surface of a commonly used electrophotographic photoreceptor is used. A method of imparting releasability to the surface of the photoconductor by adsorbing or adhering).

Examples of the former photosensitive body having a peelable surface include those using amorphous silicon as a photoconductor, and an electrophotographic photosensitive body containing at least one of a silicon atom and a fluorine atom near the surface thereof. Examples thereof include a polymer containing a polymer component (containing a silicon atom and / or a fluorine atom). Here, the vicinity of the surface of the electrophotographic photosensitive member means the uppermost layer of the photosensitive member, and includes the overcoat layer and the uppermost photoconductive layer provided on the photoconductive layer. That is, an overcoat layer is provided as the uppermost layer of the photoconductor having a photoconductive layer, and the polymer is added to the overcoat layer to impart releasability, or a photoconductive layer (photoconductive single layer and photoconductive layer The above-mentioned polymer may be contained in the uppermost layer of any of the body laminates), and the surface thereof may be modified to a state in which releasability is exhibited. By using such a photoconductor, the toner image is easily and completely transferred together with the transfer layer onto the primary receptor because the surface thereof has a good releasability.

In order to impart releasability to the overcoat layer or the uppermost photoconductive layer, a polymer containing a silicon atom and / or a fluorine atom may be used as the binder resin of the layer. Alternatively, a small amount of a block copolymer (surface unevenly distributed copolymer) containing a polymer segment composed of a polymer component containing a silicon atom and / or a fluorine atom as described in detail below is used together with another binder resin. Is also preferable. Further, the resin containing silicon atoms and / or fluorine atoms may be used in the form of particles. Above all, over
When the coating layer is provided, the method of using the above-mentioned surface unevenly distributed copolymer in combination with the binder resin of the layer is preferable because the adhesion between the photoconductive layer and the overcoat layer can be sufficiently maintained.
The surface unevenly distributed copolymer can be used in combination with another binder resin in a proportion of usually 0.1 to 20 parts by weight based on 100 parts by weight of the total composition of the overcoat layer.

As such an overcoat layer, specifically, in a PPC photosensitive member using a dry toner,
A protective layer used for providing a surface layer on the photoconductor to protect the photoconductor is known as one means for keeping durability of the photoconductor surface against repeated use of the photoconductor.

For example, a technique relating to a protective layer using a silicone block copolymer is disclosed in JP-A-61-95.
358, JP-A-55-83049, JP-A-62-8.
7971, JP-A-61-189559, JP-A-62.
-75461, JP-A-62-75461, JP-A-6
Examples thereof include those described in JP-A No. 1-139556, JP-A No. 62-139557, JP-A No. 62-208055 and the like. Further, as the protective layer using a fluorine-based block copolymer, there are JP-A-61-116362, JP-A-61-117563, and JP-A-61-270768.
And JP-A No. 62-14657 and the like. Further, as a protective layer in which a resin containing a fluorine atom-containing polymer component is also used in the form of particles, JP-A-63-249152 and JP-A-63-22135 can be used.
Those described in each publication of No. 5 are mentioned.

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

Further, in order to strengthen the uneven distribution of the surface, as a binder resin for the overcoat layer or the photoconductive layer, a polymer segment containing a fluorine atom and / or a silicon atom, and a heat and / or photocurable resin are used. It is possible to use a block copolymer obtained by bonding at least one kind of polymer segment containing a functional group-containing component in blocks. Examples of the polymer segment containing such a heat- and / or photo-curable group-containing component include the same as those described in JP-A-5-197169. Also,
A light and / or thermosetting resin may be used in combination with the fluorine atom and / or silicon atom containing resin according to the present invention.

In the electrophotographic photosensitive member having a peelable surface in advance, in addition to the electrophotographic photosensitive member mainly containing amorphous silicon, the fluorine atom of the present invention effective for modifying the photosensitive member surface by the above-mentioned method. And / or the polymer containing the polymer component containing a silicon atom is composed of resin {hereinafter referred to as resin (P)} or resin particles {hereinafter referred to as resin particle (PL)}.

When the polymer containing a polymer component containing a fluorine atom and / or a silicon atom used in the present invention is a random copolymer, a polymer component containing a fluorine atom and / or a silicon atom is used. Is 6 out of all polymer components
It is preferably 0% by weight or more, more preferably 8
It is 0% by weight or more. More preferably, a polymer segment (α) containing 50% by weight or more of a polymer component containing a fluorine atom and / or a silicon atom, and a polymer segment containing 0 to 20% by weight of a polymer component containing a fluorine and / or silicon atom. It is a block copolymer in which united segments (β) are linked by blocks. More preferably, the block copolymer contains at least one polymer component containing at least one photo- and / or thermosetting functional group in the segment (β) of the block copolymer. is there. In these block copolymers, the segment (β) preferably contains no fluorine atom and / or silicon atom-containing polymer component.

In the above polymer, the block copolymer (surface unevenly distributed copolymer) containing the polymer segment (α) and the segment (β) is used, so that the surface of the polymer is better than that of the random copolymer. The improvement of the peelability itself, and further, the maintenance of the peelability is maintained. That is, when a small amount of the resin (P), which is a block copolymer containing a fluorine atom and / or a silicon atom of the present invention, is allowed to coexist to form a coating film, these are easily formed by the end of the drying step after coating. Secondly, it is transferred to and concentrated on the surface portion of the film and is modified so that the film surface can exhibit peeling property.

As described above, when the polymer segment (α) containing a fluorine atom and / or a silicon atom is blocked, the other polymer segment (β) (fluorine atom and / or silicon atom) is Since the compatibility with the binder resin for forming the film is good, the resin does not sufficiently interact with the binder resin for forming the film, and when the transfer layer is formed, these resins are Further transfer to the transfer layer is suppressed or eliminated, and the interface between the transfer layer and the electrophotographic photosensitive member can be clearly formed and maintained (that is, the anchor effect). By using a polymer containing a light- and / or thermosetting group in the segment (β) of the block copolymer to crosslink the polymers during film formation, it is possible to further improve the interface between the photoreceptor and the transfer layer. The effect of clearly maintaining peelability is exhibited.

As described above, the polymer is a resin particle (P
L) may be used. Preferred resin particles are resin particles dispersed in a non-aqueous solvent. Such resin particles include a polymer component containing a fluorine atom and / or a silicon atom-containing polymer component, which is insoluble in the non-aqueous solvent, and a polymer component containing a fluorine atom and / or a silicon atom. It is preferable that the polymer segment (β) which is soluble in the non-aqueous solvent and is contained in an amount of 20% or less is bonded. In the case of resin particles, by the action of the insolubilized polymer segment, migration and concentration to the surface is performed, further, the polymer segment soluble in the non-aqueous solvent bound to the particles, the case of the resin Similarly, it acts as an anchor by interacting with the binder resin. Furthermore, by containing a light and / or thermosetting group, transfer to the transfer layer is eliminated.

The polymer component containing a substituent containing a fluorine atom and / or a silicon atom contained in the resin (P) and the resin particles (PL) is the resin (A) constituting the transfer layer.
The same as those described in the polymer component (F) which may be contained in the above can be mentioned.

In the resin (P) and resin particles (PL) containing a silicon atom and / or a fluorine atom of the present invention,
In the case of a so-called surface uneven distribution type copolymer, in the segment (α) containing the polymer component containing the silicon atom and / or the fluorine atom, the polymer component is contained in the total amount of the segment (α), It is at least 50% by weight, preferably 70% by weight or more, more preferably 80% by weight or more. In the segment (β), the content of the fluorine atom- and / or silicon atom-containing polymer component is 20% by weight or less, preferably 0% by weight, of the total amount of the segment (β). Segment (α) and segment (β)
The weight ratio of 1-95 to 5-99, preferably 5-90.
The pair is 10 to 95. If it deviates from this range, the concentration effect and the anchor effect on the surface of the photoconductive layer or the overcoat layer portion will be reduced for both the resin (P) and the resin particles (PL).

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

Preferred embodiments of the so-called surface unevenly distributed copolymer in the resin (P) will be described below. In the resin (P), any one may be used as long as the polymer component containing a fluorine atom and / or a silicon atom is composed of a block. Here, being composed of a block means having a polymer segment (α) containing 50% by weight or more of a fluorine atom and / or a silicon atom in the copolymer,
For example, as described in the resin (A) for the transfer layer,
AB type block, ABA type block, BAB
Examples include mold blocks, graft blocks, star blocks and the like. These various block copolymers (P) are
It can be synthesized by a conventionally known polymerization method, and specifically, it is the same as the content described in the resin (A).

Next, a preferred embodiment of the resin particles (PL) will be described. As mentioned above, resin particles (PL)
Is preferably a fluorine atom and / or insoluble in a non-aqueous solvent.
Alternatively, it comprises a polymer segment (α) containing a silicon atom and a polymer segment (β) soluble in the solvent and containing almost no fluorine atom and / or silicon atom. Furthermore, the polymer segment (α) part constituting the insoluble part of the resin particles may form a crosslinked structure.

As a preferred method for producing the resin particles (PL), there is a non-aqueous dispersion polymerization method which will be described later with respect to the production of the non-aqueous dispersion resin particles. By synthesizing dispersed resin particles in a non-aqueous solvent system by a dispersion polymerization method, the average particle size of the resin particles can easily be 1 μm or less, and the particle size distribution can be made extremely narrow and monodisperse particles. .

Specifically, the monomer (a) and the segment (β) corresponding to the polymer component constituting the segment (α)
And a monomer (b) corresponding to the polymer component that constitutes The polymerization may be carried out by heating in the presence of a polymerization initiator such as lauroyl oxide), an azobis compound (eg, azobisisobutyronitrile, azobisisovaleronitrile, etc.), an organometallic compound (eg, butyllithium, etc.). Alternatively, the monomer (a) and the polymer (PB) composed of the segment (β) may be polymerized in the same manner as above.

Further, the inside of the insolubilized polymer particles of the resin particles (PL) may have a crosslinked structure. Any conventionally known method can be used to form these crosslinked structures. That is, a method of crosslinking a polymer containing a polymer segment (α) with various crosslinking agents or curing agents, and a polymerization reaction is carried out by containing at least a monomer (a) corresponding to the polymer segment (α). At this time, by allowing a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups to coexist,
It can be carried out by a method of forming a network structure between molecules, a method of crosslinking the polymer segment (α) with a polymer containing a component containing a reactive group by a polymerization reaction or a polymer reaction, and the like.

As the cross-linking agent in the above method, compounds usually used as cross-linking agents can be mentioned. Specifically, "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko.
The compounds described in Taiseisha (1981), "Polymer Data Handbook, Basic Edition", edited by The Polymer Society of Japan, Baifukan (1986), etc. can be used. For example, organic silane compounds (for example, silane coupling agents such as vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane). Etc.), polyisocyanate compounds (for example, toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high molecular polyisocyanate) Nato, etc.), a polyol compound (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxyethylene glycol,
1,1,1-trimethylolpropane, etc.), polyamine compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine,
Modified aliphatic polyamines, etc.), titanate coupling compounds (eg tetrabutoxy titanate, tetrapropoxy titanate, 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 (for example, "New Epoxy Resin" by Hiroshi Kakiuchi Shokoido (1985), Kuniyuki Hashimoto "Epoxy Resin" Nikkan Kogyo Shimbun (1969) ) Etc.), melamine resin (for example, Ichiro Miwa,
"Uria Melamine Resin" edited by Hideo Matsunaga, compounds listed in Nikkan Kogyo Shimbun (1969), poly (meta)
Crylate compounds (eg Shin Okawara, Takeo Saegusa, Toshinobu Higashimura, "Oligomer" Kodansha (1976), Eizo Omori "Functional Acrylic Resin" Techno System (1985)
And the like).

Further, a polymerizable functional group of a polyfunctional monomer (also referred to as a polyfunctional monomer (c)) or a polyfunctional oligomer containing two or more polymerizable functional groups coexisting by the above method. Specifically, CH ₂ ═CHCH
_{2 -, CH 2 = CHCOO-,} CH 2 = CH-, CH 2 = C
_{(CH 3) COO-, CH (} CH 3) = CHCOO-, CH
_{2 = CHCONH-, CH 2 = C} (CH 3) CONH-, C
_{H (CH 3) = CHCONH-,} CH 2 = CHOCO-,
_{CH 2 = C (CH 3)} OCO-, CH 2 = CHCH 2 OCO
_{-, CH 2 = CHNHCO-, CH} 2 = CHCH 2 NHC
_{O-, CH 2 = CHSO 2 -} , CH 2 = CHCO-, CH 2
= CHO-, can be mentioned CH ₂ = CHS-like. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, styrene derivatives such as divinylbenzene and trivinylbenzene, and polyhydric alcohols as monomers or oligomers having the same polymerizable functional group. (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 polyhydroxyphenols (eg hydroquinone,
Methacrylic acid, acrylic acid or crotonic acid esters of resorcin, catechol and their derivatives, 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, vinylamides or allylamides, polyamines (eg ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and carvone containing vinyl groups. Acid (eg,
Methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.) and the like.

Examples of the monomers or oligomers having different polymerizable functional groups include vinyl group-containing carboxylic acids (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid). , Itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic acid anhydride, etc.) and a reaction product of an alcohol or amine (for example, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.) ) Etc. containing a vinyl group-containing ester derivative or amide derivative (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate,
Allyl methacrylate, allyl acrylate, allyl itaconic acid, methacryloyl vinyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate,
Methacrylic acid vinyloxycarbonyl methyl ester,
Acrylic acid vinyloxycarbonylmethyloxycarbonyl ethylene ester, N-allyl acrylamide, N
-Allylmethacrylamide, N-allylitaconic acid amide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (for example, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol) and vinyl Examples thereof include a condensation product with a carboxylic acid containing a group.

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is the same as the above-mentioned monomer (a) and another monomer coexisting with the monomer (a). It is used in an amount of 10 mol% or less, preferably 5 mol% or less, and polymerized to form a resin.

Furthermore, in the case of forming a chemical bond by the reaction of reactive groups between polymers and bridging between the polymers in the above-mentioned method, it is carried out in the same manner as the reaction of a normal organic low molecular compound. be able to.

In the dispersion polymerization, monodisperse particles having a uniform particle size can be obtained, and fine particles of 0.5 μm or less can be easily obtained. The method using a monomer is preferable. That is, by carrying out the polymerization granulation reaction in the coexistence of the above-mentioned monomer (a), monomer (b) and / or polymer (PB) and, if necessary, a polyfunctional monomer (c). Can be synthesized. Furthermore, when the polymer (PB) composed of the above-mentioned segment (β) is used, the monomer (a) is attached to a side chain in the polymer main chain of the polymer (PB) or one end of the main chain.
A polymer (PB ') having a polymerizable double bond group copolymerizable with is preferred.

The polymerizable double bond group may be any as long as it has copolymerizability with the monomer (a) as described above, but a specific example thereof is CH ₂ ═C (p)- COO-, C
_{(CH 3) H = CH-} COO-, CH 2 = C (CH 2 COO
_{H) -COO-, CH 2 = C} (p) -CONH-, CH 2
= C (p) -CONHCOO-, CH 2 = C (p) -C
_{ONHCONH-, C (CH 3) H} = CH-CONH-,
_{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 — and the like {p is —H or —CH
Represents ₃ }.

These polymerizable groups may be directly bonded to the polymer chain or may be bonded via another divalent organic residue. Specific embodiments of these polymers are described in, for example, JP-A 61-43757, JP-A 1-257969,
No. 2-74956, No. 1-282566, No. 2-1
No. 73667, No. 3-15862, No. 4-70669.
No. etc.

The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 parts by weight, relative to 100 parts by weight of the non-aqueous solvent.
˜50 parts by weight. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compounds. The polymerization temperature is 3
The temperature is about 0 to 180 ° C, preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours.

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

The polymer component containing at least one photocurable and / or thermosetting group contained in these polymers is 1 part by weight per 100 parts by weight of the polymer segment (β) of the block copolymer (P). To 95 parts by weight, preferably 10 to 70 parts by weight. Furthermore, it is preferable to contain 5 to 40 parts by weight in 100 parts by weight of the total amount of the polymer components of the whole copolymer (P). When the content is less than the lower limit, the curing after the film formation of the photoconductive layer does not proceed sufficiently, and the effect of holding the film interface with the surface of the electrophotographic photoreceptor during coating of the transfer layer decreases. On the other hand, when the content is more than the upper limit, the electrophotographic characteristics of the photoconductive layer as the binder resin may be deteriorated, the original reproducibility of the copied image may be deteriorated, and the background fog in the non-image area may occur. Occurs. The block copolymer (P) containing a light and / or thermosetting group is preferably used in an amount of 40% by weight or less based on 100 parts by weight of the total binder resin. If the amount of the resin (P) exceeds 40% by weight, electrophotographic characteristics tend to deteriorate.

Further, the light and / or thermosetting resin (D) may be used together with the fluorine atom and / or silicon atom containing resin. As the light and / or thermosetting resin (D),
Any conventionally known curable resin may be used, and examples thereof include a resin containing a curable group as described in the block copolymer (P) of the present invention.

As described above, as one embodiment of the pre-peeling photoreceptor of the present invention, the uppermost layer of the photoreceptor, for example, the overcoat layer or the photoconductive layer, is a resin containing a silicon atom and / or a fluorine atom. And, if necessary, other binder resin is contained, and it is preferable that a small amount of the photo- and / or thermosetting resin (D) and / or the cross-linking agent is coexistent in order to improve the curing of the film. The amount used is 0.01 to 20% by weight, preferably 0.1 to 15% by weight, based on 100 parts by weight of the total binder resin. The amount used is 0.01
If it is less than wt%, the effect of improving the hardening of the film is diminished.
On the other hand, if it exceeds 20% by weight, electrophotographic characteristics are adversely affected, which is not preferable.

Further, it is preferable to use a crosslinking agent in combination,
The compound normally used as a crosslinking agent can be used. Specifically, compounds described in "Crosslinking Agent Handbook" edited by Fuzo Yamashita and Tosuke Kaneko, published by Taisei Co., Ltd. (1981); Can be used. For example, the compounds described as the cross-linking agent may be mentioned, and further, a monomer having a polyfunctional polymerizable group (for example, vinyl methacrylate, acryl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate,
Divinyl succinic acid ester, divinyl adipate, diacrylic succinic acid ester, 2-methylvinyl methacrylate, trimethylolpropane trimethacrylate, divinylbenzene, pentaerythritol polyacrylate and the like).

Top layer of the present invention (layer adjacent to transfer layer)
Is preferably cured after film formation. The binder resin (B), the block copolymer (P), the curable resin (D) and the cross-linking agent to be provided are preferably used in a combination of functional groups in which polymers are easily chemically bonded. For example, well-known ones are generally well known as a polymer reaction by a combination of functional groups, and specifically, a combination of a functional group of group A and a functional group of group B as shown in the table below is exemplified. However, it is not limited to this.

[0101]

[Table 1]

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

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

As a method of curing the specific functional group in the resin of the present invention by irradiation with light, a step of irradiation with chemically active light may be included. The chemical actinic ray used in the present invention may be any of visible ray, ultraviolet ray, far ultraviolet ray, electron beam, X ray, γ ray, α ray, and the like, and preferably ultraviolet ray. More preferably, it is a light ray having a wavelength of 310 nm to a wavelength of 500 nm. Generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp or the like is used. The light irradiation treatment can usually be performed sufficiently by irradiation for 10 seconds to 10 minutes from a distance of 5 cm to 50 cm.

Next, a releasing compound (S) is adsorbed or attached to the surface of an ordinary electrophotographic photosensitive member before forming a toner image, which is a second method for obtaining a photosensitive member having a peelable surface. A method of imparting releasability to the surface of the photoconductor will be described.

Examples of the releasing 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 releasability of the surface of the electrophotographic photosensitive member. It may be any of low molecular weight compounds, oligomers and polymers. In the case of an oligomer or a polymer, the substituent containing a fluorine atom and / or a silicon atom may be incorporated in the main chain of the polymer or may be present as a substituent of the side chain of the polymer. Preferred oligomers and polymers include those in which the repeating unit containing the substituent is contained in a block, and these exhibit particularly excellent adsorbability and releasability on the electrophotographic photoreceptor surface.

The substituents containing a fluorine atom and / or a silicon atom are the same as those described in relation to the resin (A) used in the transfer layer.

Specific examples of the compound (S) containing a fluorine atom and / or a silicon atom used in the present invention include:
Toshiyuki Yoshida et al., "New Edition Surfactant Handbook," published by Engineering Book Co., Ltd. (1987), supervised by Takao Karime, "Latest Surfactant Application Technology," CMC Co., Ltd. (1990), Kunio Ito "Silicone Handbook", published by Nikkan Kogyo Shimbun (19
90), "Special Function Surfactant" supervised by Takao Karimei C.
MC (1986), AM Schwartz et al. "Surface Act"
ive Agents and Detergents vol. II ”and the like, and fluorine-based and / or silicon-based organic compounds. Furthermore, Nobuo Ishikawa “Synthesis and Function of Fluorine Compounds” CM
C. (1987), edited by Jiro Hirano, “Fluorine-Containing Organic Compounds-Synthesis and Applications-”, Technical Information Institute Co., Ltd. (1991), Mitsuo Ishikawa, “Organic Silicon Strategy Data” Chapter 3, Science Co., Ltd. The compound (S) of the present invention satisfying the above physical properties can be synthesized by utilizing the synthetic method described in the literature such as Forum (1991).

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

When the compound (S) of the present invention 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, being composed of blocks means that the polymer has a polymer segment containing 70% by weight or more of a component having a fluorine atom and / or a silicon atom, for example, as described in the resin (A). Similar examples include AB type blocks, ABA type blocks, BAB type blocks, graft type blocks, star type blocks and the like. These can be synthesized by the same method as described above.

In order to adsorb or adhere the compound (S) as described above to the surface of the electrophotographic photosensitive member, any conventionally known method may be applied, and the compound (S) may be appropriately incorporated into the apparatus used in the present invention. It is preferable to use. For example, Yuji Harazaki "Coating Engineering" Asakura Shoten Co., Ltd. (19
71), Yuji Harazaki "Coating Method" Maki Shoten (1979
(Annual), Hiroshi Fukada "Practice of Hot Melt Adhesion" published by Kobunshi Kogyo Kaisha (1979), etc. Air doctor coater, blade coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater , A gravure coater, a kiss roll coater, a spray coater, a curtain coater, a calendar coater and the like.

Also, cloth, paper impregnated with the compound (S),
A method in which a felt or the like is brought into close contact with the photoconductor, a method in which a curable resin impregnated with the compound (S) is brought into pressure contact with the photoconductor, and the photoconductor is wetted with a non-aqueous solvent in which the compound (S) is dissolved, and then the solvent is removed. Examples thereof include a method of drying, a method of causing a non-aqueous solvent in which the compound (S) is dispersed to undergo electrophoresis in the same manner as the wet electrodeposition method described below, and adhering it to the photoreceptor.

Furthermore, the non-aqueous solution of the compound (S) can be uniformly wetted on the surface of the photoreceptor by the ink jet method and then dried to be adsorbed or attached.
The ink jet method is described in, for example, Shin Ohno, “Non-Impact Printing”, CMC (1986).
It is achieved by the principles and means described in the annual publication. For example, continuous injection type Sweet method, Hertz method, intermittent injection type Wins
Examples include a ton method, an ink-on-demand type pulse jet method, a bubble jet method, and an ink mist type mist method.

In each case, the compound (S) is used instead of the ink directly or after being diluted with a solvent and filled in the ink tank and / or the ink head cartridge portion. Normal ink viscosity is 1-10cP, surface tension is 30-60dyne /
If necessary, a surfactant or the like may be added, and the ink may be heated. In conventional ink jet printers, the orifice system of the head is 3
It is about 0 to 100 μm, and the particle diameter of the flying ink is about the same, but in the present invention, it may be larger than this. In this case, the amount of ink discharged increases, so that the time required for coating can be shortened. Further, the use of multiple nozzles is also extremely effective for shortening the coating time.

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

In the present invention, these methods are not particularly limited, and various methods are selected depending on the state of the compound (S) to be used (liquid, waxy substance, solid), and if necessary, a heating medium is used in combination. It is also possible to adjust the fluidity of the compound (S) to be used. In the present invention, the compound (S) is adsorbed or adhered on the electrophotographic photosensitive member to impart releasability to the surface before the formation of the toner image by the electrophotographic process, and the adhesive force of the surface is preferably 100 g. It suffices that it be not more than f, and it is not necessary to repeat this step in the color image forming step of the present invention. It may be appropriately carried out according to the combination of the photoreceptor used and the ability to maintain the releasability due to the adsorption or adhesion of the compound (S) and its means.

The amount of the compound (S) adsorbed or adhered to the surface of the photoconductor is not particularly limited, and the adverse effect on the electrophotographic characteristics of the photoconductor should not be a practical problem. Usually, a coating film thickness of 1 μm or less is sufficient, and the adhesive strength of the present invention is expressed by “Weakboundary Layer” (Bikerman “The Scien”
The state of "ce of Adhesive Joints" Academic Press (defined in 1961) is sufficient.

In the present invention, the releasability is improved by using the simple method of adsorbing or adhering the compound (S) containing at least a fluorine atom and / or a silicon atom on the surface of the electrophotographic photoreceptor as described above. It can be a photoreceptor having a surface. As described above, by using a means for imparting releasability to a photoconductor, a photoconductor having a releasable surface can be simply used by using a general-purpose electrophotographic photoconductor without considering the releasability of the surface of the electrophotographic photoconductor itself. You can get the body.

The photoconductor used in the electrophotographic photoreceptor provided in the present invention may be any conventionally known photoconductor and is not limited. For example, "Basics and Applications of Electrophotographic Technology" edited by The Electrophotographic Society of Japan (Corona Publishing, 1988), Hiroshi Komon, "Recent Development and Practical Use of Photoconductive Materials and Photoconductors" (Japan Science Information Co., Ltd.) 1985) 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. The dispersed photoconductive layer may be a single layer type or a laminated type. Good. The photoconductive compound used in the present invention may be either an inorganic compound or an organic compound.

Examples of the inorganic compound used as the photoconductive compound of the present invention include amorphous silicon,
Conventionally known inorganic photoconductive compounds such as zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, selenium, selenium-tellurium, and lead sulfide can be used. When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used as the photoconductive compound, the binder resin is in a ratio of 10 to 100 parts by weight, preferably 15 to 100 parts by weight of the inorganic photoconductive compound. Used at a rate of -40 parts by weight.

On the other hand, the photoconductive layer using an organic compound may be any of the conventionally known ones, specifically, Japanese Patent Publication No.
7-17162, 62-51462, JP-A-52
-24437, 54-19803, 56-1072.
46, JP-A-57-161863, etc., a photo-conductive layer mainly composed of an organic photo-conductive compound, a sensitizing dye and a binder resin, JP-A-56-146145 and JP-A-60-146145.
17751, 60-17752, 60-177
No. 60, No. 60-254142, No. 62-54266
JP-A-60-230, and a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent and a binder resin as described in JP-A-60-230.
No. 147, No. 60-230148, No. 60-2388.
A photoconductive layer having a two-layer structure containing a charge generating agent and a charge transporting agent in separate layers as described in JP-A-53, etc. can be mentioned. The electrophotographic photoreceptor of the present invention may have any form of a photoconductive layer.

Examples of the organic photoconductive compound in the present invention include (a) triazole derivatives described in US Pat. No. 3,112,197 and (b) US Pat. No. 3,18.
Oxadiazole derivatives described in Japanese Patent No. 9,447, (c) imidazole derivatives described in Japanese Patent Publication No. 37-16096, (d) US Pat. No. 3,615,402.
Nos. 3,820,989, 3,542,544, and Japanese Patent Publication Nos. 45-555 and 51-10983.
JP-A Nos. 51-93224 and 55-108.
No. 667, No. 55-156953, No. 56-3665.
No. 6, the polyarylalkane derivative described in each publication,
(E) U.S. Pat. Nos. 3,180,729 and 4,27.
8,746, each specification, JP-A-55-88064, JP-A-55-88065, JP-A-49-105537, and JP-A-55.
-51086, 56-80051, 56-88
No. 141, No. 57-45545, No. 54-11263.
7, the pyrazoline derivatives and the pyrazolone derivatives described in JP-A-55-74546, (f) US Pat.
No. 615,404, Japanese Patent Publication No. 51-10105,
Phenylenediamine derivatives described in JP-A-46-3712, JP-A-47-28336, JP-A-54-83435, JP-A-54-110836, JP-A-54-119925 and the like, (g) US Patent No. 3 , 567,450,
Nos. 3,180,703, 3,240,597, 3,658,520, 4,232,103, 4,175,961 and 4,012,376, respectively. , JP-B-49-35702, West German patent (DA
S) No. 1,110,518, JP-B-39-27
577, JP-A-55-144250 and JP-A-56-11.
No. 9132, No. 56-22437, etc., arylamine derivatives,

(H) Amino-substituted chalcone derivatives described in US Pat. No. 3,526,501, etc., (i) N, N-described in US Pat. No. 3,542,546, etc.
Bicarbazyl derivative, (j) US Pat. No. 3,257,2
No. 03 specification, etc., (k) styrylanthracene derivative described in JP-A-56-46234, etc., (l) fluorenone derivative described in JP-A-54-110837, (m) U.S. Pat. No. 3,7
17,462, JP-A-54-59143 (corresponding to US Pat. No. 4,150,987), JP-A-55-52063, 55-52064 and 5
No. 5-46760, No. 55-85495, No. 57-1
No. 1350, No. 57-148749, No. 57-104
144, hydrazone derivatives described in each publication,
(N) U.S. Pat. Nos. 4,047,948 and 4,04
7,949, 4,265,990 and 4,27
3,846, 4,299,897, 4,30
No. 6,008, benzidine derivatives described in each specification,
(O) JP-A-58-190953 and 59-9554
0, 59-97148, 59-195658.
Nos. 62-36674 and the like, stilbene derivatives described in JP-B No. 34-10966 and (p) polyvinylcarbazole and derivatives thereof, (q)
Polyvinyl pyrene, polyvinyl anthracene described in JP-B Nos. 43-18674 and 43-19192,
Vinyl polymers such as poly-2-vinyl-4- (4'-dimethylaminophenyl) -5-phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole, (r) described in JP-B-43-19193. Polyacenaphthylene,
Polyindene, polymers such as copolymers of acenaphthylene and styrene, (s) condensation resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin described in JP-B-56-13940, (t) ) JP-A-56-9083
There are various triphenylmethane polymers described in JP-A Nos. 3 and 56-161550.

In the present invention, the organic photoconductive compound is not limited to the compounds listed in (a) to (t),
All known organic photoconductive compounds can be used. These organic photoconductive compounds may optionally be 2
It is possible to use more than one type together.

As the sensitizing dye contained in the photoconductive layer,
Conventionally known sensitizing dyes used for electrophotographic photoreceptors can be used. These are "Electronic photography" 12 , 9 (1973),
“Organic Synthetic Chemistry” 24 (11), 1010 (1966) and the like. For example, U.S. Pat. Nos. 3,141,770 and 4,2
83,475, Japanese Patent Application Laid-Open No. 48-25658, Japanese Patent Application Laid-Open No. 62-71965, etc., Applied Optics Supplement 350 (1969), Japanese Patent Application Laid-Open No. 50-39548, etc. And the cyanyl dyes described in U.S. Pat. No. 3,597,196, and the styryls described in JP-A Nos. 60-163047, 59-164588, and 60-252517. Based dyes 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 shown in the following (1) to (9) can be used. (1) U.S. Pat. Nos. 4,436,800 and 4,4
39,506, JP-A-47-37543,
58-123541, 58-192042, 58-219263, 59-78356, 60.
-179746, 61-148453, 61-
No. 238063, Japanese Patent Publication No. 60-5941, No. 6
Azo pigments such as monoazo, bisazo, and trisazo pigments described in JP-A Nos. 0-45664, (2) U.S. Pat. Nos. 3,397,086, 4,666,802, and JP-A-51. No. 90827 and No. 52-55643, phthalocyanine pigments such as metal-free or metal phthalocyanines, (3) US Pat. No. 3,371,8
No. 84, Japanese Patent Application Laid-Open No. 47-30330, and the like, (4) British Patent No. 2,237,68
No. 0, JP-A 47-30331, etc., indigo and thioindigo derivatives, (5) British Patent No. 2,
Quinaclindone pigments described in JP-A-237,679, JP-A-47-30332, etc. (6) British Patent No. 2,237,678, JP-A-59-184348, JP-A-62-28738 Issue No. 47
No. 18544, polycyclic quinone pigments described in each publication,
(7) JP-A 47-30331 and 47-18543
No. bisbenzimidazole pigments described in each publication,
(8) U.S. Pat. Nos. 4,396,610 and 4,64
4,082 Squalium salt-based pigments described in each specification, (9) JP-A-59-53850 and JP-A-61-212.
The azurenium salt-based pigments described in JP-A No. 542 and the like. These may be used alone or in combination of two or more.

The mixing ratio of the organic photoconductive compound and the binder resin is such that 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 the amount exceeds the upper limit. Is not preferable because crystallization of the organic photoconductive compound occurs. 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 organic photoconductive compounds may be used alone or in combination of two or more.

The binder resin that may be used in the photoconductor of the present invention (hereinafter sometimes referred to as the binder resin (B)) may be any of the resins used in conventionally known electrophotographic photoconductors. The molecular weight is preferably 5 × 10 ³ to 1 × 1
0 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10 ⁵ . The glass transition point of the binder resin is preferably -40.
C. to 200.degree. C., more preferably -10.degree. C. to 140.degree. Examples of the binder resin for these conventionally known electrophotographic photosensitive layers include, for example, Ryuji Shibata, Jiro Ishiwata, Polymer, Volume 17,
Page 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No.8), Koichi Nakamura, "Practical Technology of Binders for Recording Materials," Chapter 10, CMC Publishing (1985), Electrophotographic Society of Japan Edited by "Present Symposium on Organic Photoreceptors for Electrophotography" (1985), Hiroshi Komon "Edited Photoconductive Materials and Photoconductors, Development and Practical Use", Japan Science Information Co., Ltd. (1986), Electronics Chapter 5 "Basics and Applications of Electrophotographic Technology" edited by the Photographic Society, Corona Co., Ltd. (1988), D. Tatt, SCHeidecker, Tappi, 49
(No.10), 439 (1966), ESBaltazzi, RG Blanclott
eet al., Phot. Sci. Eng. 16 (No.5), 354 (1972), Nguyen Chan Kae, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography 18 (No.2), 22 (1980) Compounds and the like described in the publications and reviews of the above are cited.

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, isobrene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers. Polymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, itaconic acid diester polymers and copolymers , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymer, hydroxyl group modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl group and carboxyl group modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, ring Rubber-acrylic acid ester copolymer, a copolymer containing a nitrogen atom-free 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.), epoxy resin and the like.

More concretely, Takeshi Endo "Refinement of thermosetting polymer" (CMC Co., Ltd., published in 1986), Yuji Harasaki "Handbook of latest binder technology", Chapter II-1 (General Technology Center 1985)
Annual publication), Takayuki Otsu "Synthesis and design of acrylic resin and new application development" (published by Chubu Business Development Center in 1985), Eizo Omori "Functional acrylic resin" (Technosystem published in 1985), etc. A conventionally known resin is used.

In particular, as the binder resin (B) for the photoconductor,
The electrostatic characteristics can be improved by using a resin having a relatively low molecular weight (about 10 ³ to 10 ⁴ ) containing an acidic group such as a carboxyl group, a sulfo group, and a phosphono group together. For example, a resin in which the acidic group-containing polymerization component described in JP-A-63-217354 is randomly present in the polymer main chain, and an acidic group is added to one end of the polymer main chain described in JP-A-64-70761. Resin formed by bonding, JP-A-2-67563, 2
-2365651, 2-238458, 2-23
No. 6562 and No. 2-247656, etc., a resin having an acidic group bonded to the main chain end of the graft copolymer, or a resin containing an acidic group in the graft portion of the graft copolymer, JP The AB type block copolymer containing the acidic group in a block as described in JP-A-3-181948 can be mentioned.

Further, in order to make the mechanical strength of the photoconductive layer sufficient by using only these low molecular weight resins,
It is preferable to use another resin having a medium to high molecular weight together. For example, a thermosetting resin forming a crosslinked structure between polymers described in JP-A-2-68561, JP-A-2-68562.
Part of the resin described in JP-A No. 2-6 has a crosslinked structure.
The resin etc. which connect the acidic group of 9759 to the main chain terminal of a graft type copolymer are mentioned. Further, by using a specific medium to high molecular weight resin, stable performance can be maintained even when the environment is significantly changed. For example, JP-A-3-29954, JP-A-3-77954, and JP-A-3-77954. Nos. 92861 and 3-53257, a resin for binding an acidic group to the end of the graft portion of the graft copolymer or a resin containing an acidic group in the graft portion of the graft copolymer, JP-A-3-206464. No. and 3-22
Examples thereof include a graft type copolymer containing an AB block type copolymer consisting of an acidic group-containing A block and an acidic group-free B block described in No. 3762 in a graft portion. By using these specific resins, it is possible to uniformly disperse the photoconductor and form a photoconductive layer with good smoothness. In addition, a scanning exposure method using a change in environment or a semiconductor laser beam was used. Even in this case, excellent electrostatic characteristics can be maintained.

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

In the present invention, various dyes can be used as a spectral sensitizer depending on the type of light source such as visible light exposure or semiconductor laser light exposure. For example, Harumi Miyamoto, Hidehiko Takei; Imaging 1973 (No.8) No. 12
Page, CJ Young et al .: RCA Review 15 , 469 pages (1954
), Kyohei Kiyota: Transactions of the Institute of Electrical Communication, J63-C ( No.
2), p. 97 (1980), Yuji Harasaki et al., Journal of Industrial Chemistry 66 , 78.
And 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35 , 208.
Carbon dioxide dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.) ), A phthalocyanine dye (which may contain a metal), and the like.

More specifically, as those mainly containing carbonium type dyes, triphenylmethane type dyes, xanthene type dyes and phthalein type dyes, Japanese Patent Publication No. 51-45.
2, JP-A-50-90334 and JP-A-50-11422.
No. 7, No. 53-39130, No. 53-82353, U.S. Pat. Nos. 3,052,540 and 4,05.
4,450, each specification, JP-A-57-16456, etc. are mentioned. Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes are FM Hamer “The Cyanine Dye
and related compounds "can be used, and more specifically, US Pat. No. 3,047,3 can be used.
No. 84, No. 3,110,591, No. 3,121,00
No. 8, No. 3,125,447, No. 3,128,179
Nos. 3,132,942, 3,622,317, British Patents 1,226,892, 1,3
Nos. 09,274, 1,405,898, Japanese Patent Publication Nos. 48-7814 and 55-18892, and the like.

Further, as a polymethine dye for spectrally sensitizing a near-infrared region to an infrared region having a long wavelength of 700 nm or more, JP-A No. 4/1992 has been proposed.
No. 7-840, No. 47-44180, and Japanese Patent Publication No. 51-4
1061, JP-A-49-5034, and JP-A-49-451.
No. 22, No. 57-46245, No. 56-35141.
No. 57-157254, No. 61-26044,
No. 61-27551, U.S. Pat. No. 3,619,
Nos. 154 and 4,175,956, "Resear"
ch Disclosure ”, 1982, 216, pp. 117-118.

Furthermore, if necessary, various conventionally known additives for electrophotographic photoreceptors can be used in combination. These additives include chemical sensitizers for improving electrophotographic sensitivity, various plasticizers for improving film properties, surfactants and the like. Examples of the chemical sensitizer include halogen, benzoquinone, chloranil, fluoranyl, bromanil, dinitrobenzene, anthraquinone,
2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, 2,3-dichloro-5,6-
Electron-withdrawing compounds such as dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone, and tetracyanoethylene, Hiroshi Komon et al. "Recent Developments and Practical Applications of Photoconductive Materials and Photoconductors" Chapters 4 to 6: Japanese Scientific Information A review of the publication department (1986) Polyarylalkane compounds,
Examples thereof include hindered phenol compounds and p-phenylenediamine compounds. Also, JP-A-58-65439
No. 58-102239, No. 58-129439.
And compounds disclosed in JP-A Nos. 62-71965 and the like. Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl glycolate, and dimethyl glycol phthalate. It can be added to improve the flexibility of the conductive layer. These plasticizers can be contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer. The addition amount of these various additives is not particularly limited, but is usually 0.001 to 2.0 parts by weight with respect to 100 parts by weight of the photoconductor.

The photoconductive layer of the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, a substrate such as metal, paper, plastic sheet or the like is impregnated with a low resistance substance as in the conventional case. Those which have been subjected to a conductive treatment by, for example, those which are 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 for preventing curling, Having a water-resistant adhesive layer on its surface, having at least one precoat layer on the surface layer of the support, if necessary, and laminating a conductive electroconductive plastic substrate on which Al or the like is deposited on paper Etc. can be used. Specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14 (No.1), pp. 2-11 (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry," Polymer Publication Meeting (1975),
MF Hoover, J. Macromol. Sci. Chem. A-4 (6), 1327
Up to 1417 (published in 1970), etc. are used.

As described above, the electrophotographic photosensitive member of the present invention preferably has good releasability on the surface which comes into contact with the transfer layer before the formation of the toner image. Whether or not the releasability is good can be judged by the adhesive strength according to the JIS Z0237-1980 “Adhesive tape / adhesive sheet test method”. The electrophotographic photoreceptor having a releasable surface of the present invention preferably has an adhesive force of 100 g · f or less, more preferably 50 g · f or less, and particularly preferably 30 g · f or less as measured by the above test method.

In the present invention, a toner image is formed on a photoreceptor having a releasable surface through a usual electrophotographic process. That is, each process of charging-exposure-developing-fixing is performed by a conventionally known method.

The developer used in the present invention may be a conventionally known developer for electrostatic photography, and may be either a dry developer for electrostatic photography or a liquid developer. For example, “Basics and Applications of Electrophotographic Technology”, pages 497 to 505, “Development and Practical Use of Toner Material” supervised by Koichi Nakamura, Chapter 3 (1985, published by Nihon Kagaku Information Co., Ltd.), “Machida Gen. Photosensitive resin "10
Specific embodiments are shown in pages 7 to 127 (1983), Academic Society Publishing Center, Electrophotographic Society, "Imaging No. 2 to 5: Development, fixing, charging and transfer of electrophotography". As the dry developer, a one-component magnetic toner, a two-component toner, a one-component non-magnetic toner, a capsule toner and the like have been put into practical use, and any of these can be used.

The combination of the scanning exposure method using laser light which is exposed based on digital information and the developing method using a liquid developer is an effective process because a high-definition image can be formed. An example is shown below. First, the photosensitive member is positioned on the flat bed by the register pin method, and then sucked and fixed by air suction from the back surface. Then, for example, “Basics and Applications of Electrophotographic Technology” (edited by the Institute of Electrophotography, Corona Publishing Co., 1988, 6).
Charge the photoconductor using the charging device on and after page 212. The corotron or scorotron system is generally used. At this time, it is also preferable to control the charging condition by giving feedback so that the surface potential is always within a predetermined range based on the information from the charging potential detecting means of the photoconductor.

Thereafter, for example, scanning exposure is performed by a laser light source using the method described in the above-cited reference materials, pp. 254 et seq. First, an image corresponding to yellow in a color image divided into four colors is converted into a dot pattern and exposed. Next, toner development is performed using a liquid developer. The photoconductor charged and exposed on a flat bed can be removed from the photoconductor, and the direct wet development method shown on page 275 and after of the above cited document 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 above is used to apply a developing bias voltage so that the toner is electrodeposited on the exposed portion. The details of the principle are explained on pages 157 and after of the above cited material. After development, in order to remove the excess developer, squeeze as shown on page 283 of the same document is performed, and then dried. It is also preferable to rinse only with the carrier liquid of the developer before squeezing. By repeating the above process for each color of magenta, cyan, and black, a full-color image of four colors can be obtained on the photoconductor.

Further, as the basic constitution of the material of the concrete wet developer, an electrically insulating organic solvent {for example, isoparaffin aliphatic hydrocarbon: Ansoper H, Isopar G (manufactured by Esso Co.) Shelsol 70, Shelsol 71 (Manufactured by Shell Co., IP-solvent 1620 (manufactured by Idemitsu Petrochemical Co., Ltd.), etc.) as a dispersion medium, an inorganic or organic pigment or dye as a colorant, an alkyd resin, an acrylic resin, a polyester resin, a styrene-butadiene resin, a rosin, etc. Dispersion stability, fixing property, and resin for imparting chargeability are dispersed,
In addition, various additives are added, if desired, in order to enhance the charging characteristics or improve the image characteristics.

Known dyes and pigments can be arbitrarily selected as the colorant, and examples thereof include benzidine type, azo type,
Examples include dyes or pigments such as azomethine-based, xanthene-based, anthraquinone-based, phthalocyanine-based (including metal-containing), titanium white, nigrosine, aniline black and carbon black. Further, as other additives, those specifically described in Yuji Harazaki, "Electrophotography" Vol. 16, No. 2, p. 44 are used. For example, di-2-
Ethylhexyl sulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, alkylbenzene sulfonic acid metal salt, alkyl phosphoric acid metal salt, lecithin, poly (vinylpyrrolidone), copolymer containing semi-maleic acid amide component, coumarone indene Examples thereof include resins, higher alcohols, polyethers, polysiloxanes and waxes. However, it is not limited to these.

The amounts of the main components of these wet type developers are usually as follows. Toner particles composed mainly of a resin (and optionally a coloring agent) are
0.5 to 50 parts by weight is preferable for 1000 parts by weight of the carrier liquid. If it is less than 0.5 parts by weight, the image density will be insufficient, and if it exceeds 50 parts by weight, fog will easily occur in the non-image area. Further, the carrier liquid-soluble resin for stabilizing the dispersion is also used as necessary, and can be added in an amount of about 0.5 to 100 parts by weight with respect to 1000 parts by weight of the carrier liquid. The charge control agent as described above is preferably 0.001 to 1.0 parts by weight with respect to 1000 parts by weight of the carrier liquid. If desired, various additives may be added, and the upper limit of the total amount of these additives is restricted by the electric resistance of the liquid developer. That is, if the electric resistance of the liquid developer with the toner particles removed is lower than 10 ⁹ Ω · cm, it becomes difficult to obtain a good continuous tone image. Therefore, the amount of each additive added should be controlled within this limit. Has been done.

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 Japanese Patent Laid-Open No. 57-4.
As described in No. 8738, there is a method of dyeing a dispersed resin with a preferable dye. Further, as another method, as described in JP-A-53-54029,
When a dispersion resin and a dye are chemically bonded, or as described in Japanese Examined Patent Publication No. 44-22955, when a polymerization granulation method is used, a monomer containing a dye is used in advance,
There is a method of using a dye-containing copolymer.

In the present invention, the transfer layer is formed on the photoreceptor having the toner image of one or more colors formed as described above. The transfer layer may be formed separately from the electrophotographic process and the transfer process, but these steps are preferably performed in the same apparatus. As a method for forming the transfer layer on the surface of the photoreceptor, as described above, the hot melt coating method, the electrodeposition coating method or the transfer method is preferably used. These methods are preferable because a transfer layer can be easily formed on the surface of the photoconductor in the apparatus.

Each method will be described in detail below.
The hot melt coating method is a method in which a transfer layer composition is hot melt coated on a photoreceptor by a known method, and for this purpose, a solventless coating machine, for example, 197 to 2 of "the actual practice of hot melt adhesion" is used.
The mechanism of the hot melt coating apparatus for hot melt adhesives (hot melt coater) described on page 15 can be diverted to the photoreceptor drum coating specifications. Examples thereof include a direct roll coater, an offset gravure roll coater, a lot coater, an extrusion coater, a slot orifice coater and a curtain coater.

The melting temperature of the thermoplastic resin at the time of coating is optimized depending on the component composition of the thermoplastic resin used, but it is usually in the range of 50 to 180 ° C. It is desirable that the temperature be raised to an appropriate temperature in a short time at the position where it is applied to the photoconductor after it is melted in advance by using a preheating device having a closed automatic temperature control means. By doing so, it is possible to prevent deterioration and coating unevenness of the thermoplastic resin due to thermal oxidation. The coating speed depends on the fluidity of the thermoplastic resin at the time of heat melting, the coater method, the coating amount, etc., but 1 to 100 mm / sec is suitable, and preferably 5 to 40 mm / sec.

Next, the electrodeposition coating method will be described. In this method, the thermoplastic resin is electrostatically adhered or electrodeposited (hereinafter also simply referred to as electrodeposition) on the surface of the photoconductor in the form of resin particles, and then a uniform thin film is formed, for example, by heating. To form a transfer layer. Therefore, it is necessary that the thermoplastic resin particles have either a positive charge or a negative charge, and the detection property thereof is arbitrarily determined by the chargeability of the electrophotographic photosensitive member to be combined. .

The resin particles are in the range satisfying the above-mentioned physical properties, and usually have an average particle diameter of 0.01 μm to 1 μm.
5 μm, preferably 0.05 μm to 5 μm,
The range is more preferably 0.1 μm to 1 μm. The particles may be in the form of particle powder (dry electrodeposition) at the time of electrodeposition or resin particles dispersed in a non-aqueous system (wet electrodeposition). Preferred are non-aqueous dispersed resin particles, which can easily adjust the thickness of the transfer layer to a thin film with a uniform thickness.

The resin particles used in the present invention can be produced by a conventionally known mechanical pulverization method or polymerization granulation method. In these production methods, particles of either dry electrodeposition or wet electrodeposition can be used.

In the case of producing a particle powder used in the dry electrodeposition method, the mechanical pulverization method is a method of directly pulverizing with a conventionally known pulverizer to obtain fine particles (eg,
A method using a ball mill, a paint shaker, a jet mill, etc.) may be mentioned, and if necessary, the materials to be resin particles are mixed, and the mixture is melted and kneaded to be pulverized, or after pulverization, classification for equalizing particle diameters or A post-treatment for treating the surface of the particles can be appropriately combined and performed. A spray dry method is also known. Specifically, "Granulation Handbook", Part II (edited by Ohmsha, 1991), edited by Japan Powder Industrial Technology Association, Kanagawa Business Development Center, "Actual state of the latest granulation technology" (Published by Kanagawa Business Development Center) Department, 1984
Ed.), Arakawa Masafumi et al., “Latest powder design technology”, Technosystem Co., Ltd., 1988), etc., and can be easily manufactured by appropriately using the methods described in detail in the textbooks.

As the polymerization granulation method, conventionally known methods such as an emulsion polymerization reaction carried out in an aqueous system, a seed polymerization reaction, a suspension polymerization reaction and a dispersion polymerization reaction carried out in a non-aqueous solvent system are known. Specifically, Soichi Muroi "Chemistry of Polymer Latex" Polymer Publishing (1970), Taira Okuda, Hiroshi Inagaki "Synthetic Resin Emulsion" Polymer Publishing (1978), Soichi Muroi "Polymer Latex""Introduction" Kobunsha (1983), I.
Piirma, PC Wang "Emulsion Polymerization", I.
Piirma and JL Gavdon, ACS symp. Sev. 24, P34 (1
974), Fumio Kitahara et al. "Chemistry of Dispersion Emulsion System" Engineering Book (1
979), Soichi Muroi supervised "Cutting-edge technology of ultrafine particle polymer" CMC Publishing (1991), after granulating by the method described in the textbook, as described in the textbook on the mechanical method. It can be manufactured by collecting and pulverizing by various various methods.

As a method of dry electrodeposition of the obtained fine particle powder, a conventionally known coating method of electrostatic powder or a developing method of dry electrostatic photographic developer can be used. Specifically, as described in "Electrostatic Powder Coating" by JF Hughes (Translated by Hideo Nagasaka and Machiko Midorikawa), corona charging, friction charging,
Electrodeposition of fine particles charged by induction charging, ionic wind charging, reverse ionization, etc., Koichi Nakamura, "Development and practical application of recent electrophotographic development systems and toner materials", Chapter 1 (Japanese Science) Information Co., Ltd. (1985), etc., and development methods such as cascade method, magnetic brush method, fur brush method, electrostatic method, induction method, touchdown method, powder cloud method, etc. are used. Can be performed as appropriate.

In the case of producing the non-aqueous dispersion resin particles used in the wet electrodeposition method, either the mechanical pulverization method or the polymerization granulation method can be produced as described above. Examples of the mechanical pulverization method include a method in which a dispersion polymer is used in combination and further dispersed by a wet disperser (for example, a ball mill / paint shaker, Keddy mill, Dynomill, etc.), a material serving as a resin particle component, and a dispersion auxiliary polymer ( Alternatively, a method may be mentioned in which a coating polymer) is kneaded in advance to obtain a kneaded product, which is then pulverized, and then a dispersed polymer is allowed to coexist and dispersed. Specifically, it is possible to use a method for producing a paint or a developer for electrostatic photography. For example, Kenji Ueki, "Flow of Paint and Dispersion of Paint," Kyoritsu Shuppan (1971), "Solomon, Science of Paint". , `` Paint and Surface Coating Th
eory and Practice ", Yuji Harasaki" Coating Engineering "Asakura Shoten (1971), Yuji Harazaki" Basic Science of Coating "Maki Shoten (1977), etc.

Further, as the polymerization granulation method, a conventionally known non-aqueous dispersion polymerization method can be mentioned, and specifically, the above-mentioned "state of the art of ultrafine particle polymer", Chapter 2, "Recent electrophotographic development system" can be mentioned. And development and practical application of toner materials ”No. 3
Chapter, KEJ Barvettic “Dispersion Polymerization
In Organic Media "John Wiley (1975) and other books.

The non-aqueous solvent used in the above non-aqueous dispersion polymerization method may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or in combination of two or more. Specific examples of such an organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, and benzyl alcohol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diethyl ketone, ethers such as diethyl ether, tetrahydrofuran, and dioxane. , Carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate, aliphatic hydrocarbons having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane and cyclooctane, benzene, Aromatic hydrocarbons such as toluene, xylene, chlorobenzene,
Examples thereof include halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane and trichloroethane. However, it is not limited to the above-mentioned compound examples. By synthesizing dispersed resin particles in these non-aqueous solvent systems by the dispersion polymerization method, the average particle size of the resin particles easily becomes 1 μm or less, and the particle size distribution is very narrow and monodisperse particles. You can

Since these non-aqueous dispersion resin particles are subjected to a wet electrostatic photography development method or a method of electrophoresing in a pressure field of an electric field, the dispersion medium used at the time of electrodeposition has an electric resistance. It is adjusted to a non-aqueous solvent system having a dielectric constant of 3.5 or less and 10 ⁸ Ω · cm or more. This method of supplying particles mainly containing a thermoplastic resin dispersed in an electrically insulating solvent having an electric resistance of 10 ⁸ Ω · cm or more and a relative dielectric constant of 3.5 or less is It is preferable because it can be prepared uniformly and thinly and easily.

As the insulating solvent, specifically, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, and halogen-substituted products thereof can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L
(Isopar; trade name of Exxon), Shersol 7
0, Shersol 71 (Shellsol; trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco; trade name of American Mineral Spirits Co., Ltd.) and the like can be used alone or in combination.

Here, the above-mentioned insulating organic solvent is preferably used from the beginning as the non-aqueous solvent used for the polymerization and granulation of the non-aqueous dispersion resin particles, but after granulation with a solvent other than these solvents, the dispersion is carried out. It can also be prepared by substituting the medium.

In order to electrophoretically disperse the dispersed particles in the dispersion medium, the particles must be positively-charged or negatively-charged electro-detectable particles. This can be achieved by appropriately using the technique of wet electrostatic developer. Specifically, "Recent Development and Practical Use of Electrophotographic Development Systems and Toner Materials" 139-148, "Basics and Applications of Electrophotographic Technology" edited by The Institute of Electrophotography, 497-505 (Corona Publishing Co., 1988 Annual), Yuji Harasaki "Electronic Photography" 16 (No.2),
It is carried out by using the electroscopic material and other additives described on page 44 (1977). Specifically, for example, British Patent Nos. 893,429, 934,038, U.S. Pat. Nos. 1,122,397, 3,900,412, 4,606,989, and JP-A No. 60-179751,
No. 60-185963, JP-A-2-13965 and the like.

The composition of the non-aqueous resin particle dispersion (latex) to be subjected to electrodeposition is usually 0.1 to 20 g of particles containing mainly a thermoplastic resin in at least 1 liter of an electrically insulating dispersion medium, Dispersion stabilizing resin is 0.0
1 to 50 g, the charge control agent added if necessary is 0.0
It is in the range of 001 to 10 g.

The thermoplastic resin particles which have been made into fine particles, imparted with a charge and dispersed in the electrically insulating liquid in this manner, exhibit the same behavior as an electrophotographic wet developer. For example, the developing device described in "Basics and Applications of Electrophotographic Technology", pages 275 to 285, such as the slit developing electrode device, can be used for electrophoresis on the surface of the photoreceptor. That is, particles mainly containing a thermoplastic resin are supplied between the counter electrodes installed to face the electrophotographic photosensitive member, and are electrophoresed according to a potential gradient applied from an external power source to adhere to the electrophotographic photosensitive member. Alternatively, it is electrodeposited to form a film. Generally, when the particles are positively charged, a voltage is applied from an external power source between the conductive support of the photoconductor and the development electrode of the development device so that the photoconductor side has a negative potential, Is electrostatically deposited on the surface of the photoconductor.

It is also possible to perform electrodeposition by wet toner development by a usual electrophotographic process. That is, as shown on the premise "Basics and Applications of Electrophotographic Technology", pages 46 to 79, so-called burn-off is performed in which the photosensitive member is uniformly charged and then not exposed or only unnecessary areas are exposed. Perform normal wet toner development.

The amount of the thermoplastic resin particles deposited on the photoconductor can be arbitrarily adjusted by the applied voltage of the external bias, the charging potential of the photoconductor, the developing time and the like. After electrodeposition, the developer is wiped off by a squeeze using a known rubber roller, gap roller, reverse roller or the like. Known methods such as corona squeeze and air squeeze can also be used. Next, it is dried with cold air or warm air, or with an infrared lamp or the like, and preferably thermoplastic resin particles are formed into a film to form a transfer layer.

Next, the formation of the transfer layer by the transfer method will be described. In this method, a transfer layer held on a releasable support typified by release paper (hereinafter referred to as release paper) is transferred onto the surface of the electrophotographic photosensitive member. The release paper on which the transfer layer is formed is roll-shaped or sheet-shaped and can be easily supplied to the transfer device.

As the release paper to be used in the present invention, any conventionally known release paper can be used. For example, "new technology of adhesive (adhesive) and its application / development material of various applied products"(issued;
Business Development Center Publishing Department, May 20, 1978), "All Paper Guide Paper Encyclopedia, Volume 1, Culture Industry Edition"
(Published by Paper Industry Times Co., December 1, 1983) and the like described in the publications. Specifically, release paper is made by applying a release agent mainly composed of silicone to unbleached Clupak paper laminated with polyethylene resin, high-grade paper precoated with solvent-resistant resin, kraft paper, or undercoat. It is a PET base coated with or coated directly on glassine paper. In general, a solvent type silicone is used, and the silicone is applied and dried at a concentration of 3 to 7% on a gravure roll, a reverse roll, a wire bar or the like, and then heat treated at 150 ° C. or higher to be cured. The coating amount is about 1 g / m ² .

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

To form a transfer layer on a release paper, a transfer layer composition containing a thermoplastic resin as a main component is prepared by a conventional method.
It can be easily performed by applying a film by bar coating, spin coating, spray coating, or the like.

In order to thermally transfer the transfer layer on the release paper onto the electrophotographic photosensitive member, a usual thermal transfer method can be used. That is,
The release paper holding the transfer layer may be pressure-bonded to the electrophotographic photosensitive member to thermally transfer the transfer layer. The conditions for transferring the transfer layer from the release paper to the photoreceptor surface are preferably as follows. The roller nip pressure is 0.1 to 10 kgf / cm ² , more preferably 0.2 to 8 kgf / cm ² , and the transfer temperature is 25.
C. to 100.degree. C., more preferably 40.degree. C. to 80.degree.
The transport speed is 0.5 to 100 mm / sec, more preferably 3 to 50 mm / sec, which may be different in each of the electrophotographic process and the thermal transfer process to the primary intermediate receptor 20.

Next, the primary receptor of the present invention will be described. The primary receptor is such that the toner image and the transfer layer are closely peeled and transferred from the surface of the photoconductor under heating and / or pressure, and further, the toner image and the transfer layer are similarly peeled and transferred onto the final transfer target material and finally transferred. It forms a color image.

Therefore, it is important that the releasability of the surface of the primary selector is lower than that of the surface of the photoconductor and that the releasability for peeling and transferring to the final transfer material is maintained, and it is preferable that it is larger than the adhesive force of the surface of the photoconductor. , Preferably 10 g · f or more, more preferably 20 g · f or more.
In addition, the maximum adhesion of the primary receptor surface is 200g.
f is more preferable, and 180 g · f is more preferable.
It is the following.

The nip pressure in transfer is 0.2 to 20 kg.
The pressure is f / cm ² , more preferably 0.5 to 15 kgf / cm ² , and as a roller pressing means, a spring or an air cylinder using compressed air at both ends of the roller shaft can be used. The transport speed is in the range of 0.1 to 300 mm / sec, more preferably 0.5 to 200 mm / sec, and may be different in the electrophotographic process and the thermal transfer process.

The transfer from the photoconductor to the primary receptor and the transfer from the primary receptor to the final transfer material may be simultaneous within one screen, or after the transfer of the entire one screen to the primary receptor is finished, You may transfer to a to-be-transferred material. Further, this thermal transfer step can be incorporated in a series of electrophotographic process apparatuses as appropriate.

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 photoreceptor to the primary receptor include a drum method and an endless belt method that 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, but in a preferred embodiment, an elastic layer and / or a laminated structure including 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.

Examples of the elastic body include conventionally known natural resins and synthetic resins, and these may be used alone or in combination of two or more kinds 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 ",
Various resins are described in Hanser Publishers (published in 1989), plastic material structure, 18 volumes, Nikkan Kogyo Shimbun, etc. For example, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, cyclized rubber,
Examples include, but are not limited to, chloroprene rubber, ethylene-propylene rubber, butyl rubber, chlorosulfonated polyethylene rubber, silicone rubber, fluororubber, polysulfide rubber, natural rubber, isoprene rubber, and urethane rubber. It can be arbitrarily selected in consideration of releasability from the layer, durability and the like. Further, the adhesion of the receptor surface can be easily adjusted by the same method as that described for the easily peelable photoreceptor.

As the reinforcing layer for the elastic layer, cloth, glass fiber, resin-impregnated special paper, aluminum, stainless steel or the like is used. A sponge-like rubber layer may be provided 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.

In the endless belt system, a known belt type primary receptor member can be used. For example, US Pat. Nos. 3,839,761 and 46,842 are used.
No. 38, No. 469039, etc. are mentioned. 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 described in JP-A-4-503265 is known.

In the present invention, a known method and apparatus can be used to thermally transfer the toner image together with the transfer layer to the final transfer material.

The final transfer material used in the present invention is as follows:
The material is not particularly limited, and is a reflective material such as high-quality paper, coated paper, natural paper such as art paper, synthetic paper support, metal support such as aluminum, iron, SUS, etc., or polyester, polyolefin, polyvinyl chloride. Any transparent material such as a resin film (plastic film) such as polyacetate may be used.

The thermal transfer behavior on the final transfer target material is estimated as follows. That is, when the transfer layer softened to some extent is heated, the tackiness increases, and the transfer layer adheres to the final transfer material. Then, after passing under the peeling roller, the temperature is lowered, the fluidity and the tackiness are reduced, and the toner is peeled off from the surface of the primary receptor while being adhered to the final transfer material together with the toner. Therefore, the conditions should be set so that such a state is realized.

The toner image on the final transfer material is eventually overcoated by the transfer layer, so that the toner image can be protected from scratches and stains.

Specific embodiments of the color image forming method of the present invention will be described below with reference to the drawings.

FIG. 2 has a means for applying the compound (S),
A general outline of the method and apparatus of the present invention is shown when a wet development method is used as the developing method, an electrodeposition method is used as the method for forming the transfer layer 12, and a drum method is used as the transfer method to the primary receptor 20. is there. The means (10) for applying the compound (S) is
It can be appropriately omitted depending on the surface releasability of the photoconductor used.

On the wet developing unit set 14, 11 drums of electrophotographic photosensitive member, 20 drums of primary receptor,
The final transferred material 21 is arranged. For drum and transfer
A temperature adjusting means 17 is provided in each of the peeling backup rollers. During image formation by the electrophotographic process, the primary receptor 20 drum and the final transfer material 21 are not in contact with each other as shown in the figure.

As described above, when the electrophotographic photosensitive member 11 whose surface is modified to have the peeling property in advance is used, the toner image 25 is formed on the photosensitive member 11 as it is. If the releasability of the surface of the photoreceptor 11 is insufficient, the toner image 25
By adsorbing or adhering the compound (S) before the formation of, the 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) supply unit 10 of the present invention using any one of the above-described specific modes. Supply unit 10 for adsorbing or adhering the compound (S) on the surface of the photoreceptor 11.
May be fixed or movable.

As described above, the development in the present invention may be carried out with either a dry developer or a wet developer, but a copy image obtained by the method using a wet developer gives a higher resolution image. Therefore, the case where the developing unit is a wet developing unit will be described below as an example. The wet developing unit set 14 is movable. The unit set 14 further includes a liquid developing unit 14 containing yellow, magenta, cyan, and black wet developers, respectively.
y, 14m, 14c, 14k, and a thermoplastic resin particle electrodeposition unit 50 for forming the transfer layer 12 by an electrodeposition coating method when the transfer layer 12 is formed by an electrodeposition method. Each may be provided with a pre-bath, a rinse, and a squeeze means for the purpose of preventing the non-image area from being soiled, if necessary. A wet developer carrier liquid is usually used as the pre-bath and rinse liquid.

The electrophotographic process will be described with reference to FIG. FIG. 3 is a diagram showing a step of forming a toner image 25 on the electrophotographic photosensitive member 11 by an electrophotographic process in the overall view shown in FIG.

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

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 the bias power source and electric connection not shown.
The yellow wet developer is supplied to the surface of the photoconductor 11 while applying a developing bias voltage between the developing electrode 1 and the developing electrode. At this time, the bias voltage 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 incorporated 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 obtain a color toner image on the photoconductor 11.

Then, a peelable transfer layer 12 is formed on the electrophotographic photosensitive member 11 having the toner image 25. The means is shown in FIGS. 4 is a transfer layer forming method by an electrodeposition coating method, FIG. 5 is a transfer layer forming method by a transfer method, and FIG.
FIG. 3 is a schematic partial view for explaining each transfer layer forming method by hot melt coating.

A case where the transfer layer 12 is formed by the electrodeposition coating method will be described with reference to FIG. The thermoplastic resin (A), which is the transfer layer material, is made into fine particles and charged to give a thermoplastic resin particle dispersion liquid 12a. This is put into the electrodeposition unit 50, and after the development process is completed, the wet developing unit set 14 is brought close to the photoconductor 11 and fixed so that the distance from the developing electrode of the unit set 14 is 1 mm. A particle dispersion liquid is supplied from the electrodeposition unit 50 into this gap and rotated while applying a voltage from the outside so that the particles are adsorbed on the entire surface of the photoreceptor 11. If necessary, the squeeze means built in the developing unit set 14 removes the particle dispersion adhering to the surface of the photoconductor 11, and then the resin particles are thermally melted by a heating means to form a film. Can be obtained. After that, if necessary, the photoconductor 11 is cooled by a cooling device similar to the intake / exhaust unit.
From the outside or from the inside of the photoconductor 11 drum, it is cooled to a predetermined temperature. The developing unit set 14 is moved to the standby position, and the process of forming the transfer layer 12 is completed.

The transfer layer 12 is formed by the transfer method or the hot melt coating method.
In the case of forming the above structure, instead of using the electrodeposition unit 50 shown in FIG. 4, the apparatus shown in FIGS. 5 and 6 can be easily applied to the overall view shown in FIG.

The transfer layer 12 is formed on the photoreceptor 1 by using a release paper.
As a device which can be easily prepared on the device 1, a device having a schematic partial view shown in FIG. That is, the release paper 40 provided with the transfer layer 12 is heated and pressed by the heating roller 122 to transfer the transfer layer 12 to the surface of the photoconductor 11. Release paper 40
Is cooled by the cooling roller 123 and collected. If necessary, the photoconductor 11 itself may be heated by the preheating means 16 to improve the transferability of the transfer layer 12 by thermocompression bonding. The position where the device shown in FIG. 5 is incorporated is not particularly limited.

For the hot melt coating method, an apparatus as shown in FIG. 6 can be used. In FIG. 6, yellow (14
y), magenta (14 m), cyan (14 c), and black (14 k) liquid developing unit set 14 including a developing unit is moved, and a toner image 25 is formed by the electrophotographic process as described above. . After the liquid developing unit 14 moves to the standby position, the hot melt coater 30 is moved from the standby position 30a to that position. The transfer layer 12 is a hot melt coater 30.
As a result, the surface of the photoconductor 11 on the peripheral surface of the drum is coated, and it is cooled to a predetermined temperature by passing under the air intake / exhaust unit 15 to form the transfer layer 12.

Next, the transfer process to the primary receptor will be described with reference to FIG. When the photoreceptor 11 on which the toner image 25 and the transfer layer 12 are located as shown in FIG. 7a and the primary receptor 20 drum are brought into contact with each other and heated and pressed, the toner image 25 is transferred to the transfer layer as shown in FIG. 7b. The data 12 is transferred from the photoconductor 11 onto the primary receptor 20 drum.
That is, after the transfer layer 12 is formed, predetermined heating is performed by the heating means 16 and / or 17 for thermal transfer of the photosensitive drum, and if necessary, the primary receptor 20 is also heated by the heating means 16 and / or 17. The toner image 25 is transferred together with the transfer layer 12 by pressure contact with the primary receptor 20 by performing predetermined preheating.

As the heating means 16, it is preferable to use a non-contact type infrared line heater or a flash heater, and the heating surface temperature of the photosensitive layer at the time of thermal transfer is 40 to 150 ° C., particularly preferably 50 to 120 ° C. .

Transfer to the final transfer material 21 will be described with reference to FIG. The toner image 25 completely transferred onto the primary receptor 20 is pressed against the final transfer target material (coated paper etc.) 21 together with the transfer layer 12 to perform thermal transfer. Primary receptor 20
Predetermined heating by the heating means 16 and / or 17 of
Further, the material to be transferred 21 is preheated to a predetermined level by the transfer backup roller 22. Then, the transferred material 21 in the position shown in FIG. 2 is pressed against the primary receptor 20 drum by the transfer and peeling backup rollers 22 and 23, and the transfer layer 12 and the toner image 25 are transferred as shown in FIG. After transferring to the final transfer material 21, the transfer layer 1 is transferred onto the transfer material 21 while being cooled by the peeling back roller 23.
The toner image 25 is peeled off and transferred for every 2 and a series of steps is completed.

Also, when the endless belt system is applied as the primary receptor 20, transfer to the final transfer material 21 can be completed by the same operating method and conditions as the drum system, and the series of steps can be completed.

In the color image forming method of the present invention, the respective condition settings for transferring the toner image 25 and the transfer layer 12 are set such that the photoconductor 11 (photosensitive layer and support) used, the physical properties of the primary receptor 20 surface, It is natural that the transfer layer 12 and the material to be transferred 21 are optimized depending on the physical properties of the material. In particular, the temperature condition in the thermal transfer step needs to be determined in consideration of factors such as the glass transition point of the transfer layer, the softening temperature, the fluidity, the tackiness, the film property, and the film thickness. That is, the transfer layer, which has been softened to some extent by the preheating means, passes under the heating roller to increase the tackiness and adhere to the material to be transferred. Then, after passing under the cooling roller, the conditions should be set so that the temperature is lowered, the fluidity and the tackiness are reduced, and the toner as a film is peeled off while being adhered to the transfer layer together with the toner.

The material of the cooling roller is, for example, a heat conductive metal such as aluminum or copper coated with silicone rubber,
It is desirable to radiate heat by using a cooling means inside the roller or on the outer peripheral portion that does not contact the transfer paper. It is preferable to use a cooling fan, a cooling medium circulation device, an electronic cooling element, or the like as the cooling means, and to keep it in a predetermined temperature range in combination with a temperature controller.

[0207]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[Production Example of Resin Particles for Transfer Layer] Production Example 1: Resin Particles (AL) 1: (AL-1) 10 g of a dispersion stabilizing resin (Q-1) having the following structure, vinyl acetate
A mixed solution of 100 g and Isopar H (384 g) was heated to a temperature of 70 ° C. with stirring under a nitrogen stream. 2, as a polymerization initiator
2'-azobis (isovaleronitrile) (abbreviation AIVN) 0.
8g was added and reacted for 3 hours. Twenty minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88 ° C. Further, 0.5 g of the initiator was added and reacted for 2 hours, then the temperature was raised to 100 ° C. and stirred for 2 hours to distill off unreacted vinyl acetate. After cooling
The white dispersion obtained through a 200-mesh nylon cloth was a latex having a polymerization rate of 90% and an average particle size of 0.23 μm and good monodispersity. The particle size is CAPA-500 (Horiba Ltd.)
Manufactured). A part of the white dispersion was subjected to a centrifuge (rotation speed 1 × 10 ⁴ rpm, rotation time 60 minutes) to collect and dry the precipitated resin particle component. The weight average molecular weight (Mw: polystyrene equivalent GPC value) of the resin particles was 2 × 10 ⁵ , and the glass transition point (Tg) was 38 ° C.

[0209]

[Chemical 12]

Production Example 2 of Resin Particles (AL): (AL-
2) 15 g of dispersion stabilizing resin (Q-2) having the following structure, 7.5 g of benzyl methacrylate, 25 g of methyl acrylate, 1.3 g of methyl 3-mercaptopropionate and 552 g of Isopar H.
The mixed solution of was heated to a temperature of 50 ° C. while stirring under a nitrogen stream. 1 g of 2,2'-azobis (2-cyclopropylpropionitrile) (abbreviation ACPP) was added as a polymerization initiator,
Reacted for 2 hours. Further, 0.8 g of ACPP was added and after reacting for 2 hours, 0.8 g of AIVN as an initiator was added, and then the reaction set temperature was set to 75 ° C. and the reaction was conducted for 3 hours. Next, the mixture was heated to a temperature of 90 ° C., the unreacted monomer was distilled off under a reduced pressure of 20 to 30 mmHg, and then cooled, passed through a nylon cloth of 200 mesh, and the obtained white dispersion had a polymerization rate of 98%. It was a latex with an average particle size of 0.20 μm and good monodispersity. Mw of resin particles is 2.8 x 1
0 ⁴ , Tg was 55 ° C.

[0211]

[Chemical 13]

Production Example of Resin Particles (AL): (AL-3) A mixed solution of 14 g of the dispersion stabilizing resin (Q-3) having the following structure and 382 g of Isopar G was stirred at a temperature of nitrogen while flowing.
Warmed to 50 ° C. To this, benzyl methacrylate 80
g, 20 g of vinyltoluene, and 0.8 g of ACPP were added dropwise at a dropping time of 1 hour, and the reaction was continued for another 1 hour. Add 0.8g ACPP and react for 2 hours, then AI
Add 0.8 g of VN and heat to 80 ℃ for 2 hours, then AI
VN 0.5g was added and reaction was performed for 2 hours. Then the temperature
After heating to 100 ° C and distilling off unreacted monomers under a reduced pressure of 10 to 20 mmHg, cooling and passing a 200 mesh nylon cloth,
The obtained white dispersion was a latex having a polymerization rate of 90% and an average particle size of 0.17 μm and good monodispersity. Mw of resin particles
Was 1 × 10 ⁵ and Tg was 55 ° C.

[0213]

[Chemical 14]

Production Example 4 of Resin Particles (AL): (AL-
4) 14 g of a dispersion stabilizing resin (Q-4) having the following structure, a macromonomer of dimethylsiloxane (M-1) (FM-072
5, manufactured by Chisso Corp., Mw: 1 × 10 ⁴ ) 10 g and a mixed solution of Isopar H 553 g were stirred at a temperature of 50 under a nitrogen stream.
Warmed to ° C. To this, a mixture of 70 g of methyl methacrylate, 20 g of ethyl acrylate, 1.3 g of methyl 3-mercaptopropionate and 1.0 g of ACPP was added dropwise for 30 minutes, and the reaction was continued for another 1.5 hours. Furthermore, AC
0.8 g of PP was added and reacted for 2 hours, then 0.8 g of AIVN was added and the temperature was set to 80 ° C. for 2 hours, and 0.5 g of ACPP was further added and reacted for 2 hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having a polymerization rate of 99% and an average particle size of 0.15 μm and good monodispersity.
The resin particles had Mw of 3 × 10 ⁴ and Tg of 50 ° C.

[0215]

[Chemical 15]

Production Examples 5-9 of Resin Particles (AL): (AL
-5) to (AL-9) In Production Example 4 of resin particles (AL), instead of 10 g of the macromonomer (M-1), each macromonomer shown in Table A below (Mw is 8 × 10 ³ to 1) was used. Each resin particle was synthesized in the same manner as in Production Example 4 except that the range of × 10 ⁴ ) was used.
The degree of polymerization of each particle was 98 to 99%, the average particle diameter of the particles was within the range of 0.15 to 0.25 μm, the particle size distribution was narrow, and the monodispersity was good. Mw of the resin particles is 2.5 × 10 ⁴
~4 × 10 ^4, Tg ranged 40 ° C. to 70 ° C..

[0217]

[Table 2]

[0218]

[Table 3]

Production Example 10 of Resin Particles (AL): (AL-1
0) Styrene-butadiene copolymer [(48/52) weight ratio] having a softening point of 45 ° C as the thermoplastic resin (A) (Sorprene 30
3, the solid content of Asahi Kasei Co., Ltd. was roughly pulverized by a pulverizer trio blender, and 5 g of this pulverized product, 4 g of a resin for stabilizing dispersion (Sorprene 1205, Asahi Kasei Co., Ltd.) and Isopar H 5
1 g was placed in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) with glass beads having a diameter of about 4 mm as a media, and preliminarily dispersed for 20 minutes. This pre-dispersion was used at 6500 at 4,500 rpm using Dynomill KDL type (manufactured by Shinmaru Enterprises Co., Ltd.) having glass beads of 0.75 to 1 mm in diameter as media.
Wet-dispersed for an hour. The white dispersion obtained by passing these through a 200-mesh nylon cloth was a latex having an average particle size of 0.4 μm.

Production Examples of Resin Particles (AL) 11 to 16: (AL
-11) to (AL-16) Production Example 10 for resin particles (AL) was the same as Production Example 10 except that each compound shown in Table B below was used instead of Sorprene 303 as the resin (A). A dispersion was prepared by the same wet dispersion method. White dispersion has an average particle size of 0.3-0.6 μm
The softening point of the obtained resin particles is 40 ° C to 10 ° C.
It was within the range of 0 ° C.

[0221]

[Table 4]

Production Example 17 of resin particles (AL): (AL-1
7) 12 g of the dispersion stabilizing resin (Q-1), 70 g of vinyl acetate,
A mixture of 30 g of vinyl butyrate and 388 g of Isopar H was heated to a temperature of 80 ° C. with stirring under a nitrogen stream. To this, 1.5 g of AIBN was added as an initiator and reacted for 2 hours.
IBN 0.8 g was 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 0.18 μm and good monodispersity. Mw of resin particles is 8 × 10 ⁴ ,
Tg was 18 ° C.

Production Example 18 of Resin Particles (AL): (AL-1
8) 18 g of the dispersion stabilizing resin (Q-3) and Isopar H 5
49 g of the mixture was heated to 55 ° C. with stirring under a stream of nitrogen. 70 g of benzyl methacrylate, 30 g of methyl acrylate, and methyl 3-mercaptopropionate 2.
A mixture of 6 g and AIVN 1.0 g was added dropwise at a dropping time of 1 hour, and the reaction was continued for another 1 hour. After adding AIVN 0.8g, set the temperature to 75 ℃ and continue for 2 hours.
g was added and the reaction was carried out for 3 hours. After cooling, the white dispersion obtained through a 200 mesh nylon cloth has a polymerization rate of 98%.
It was a latex having an average particle size of 0.18 μm. The resin particles had Mw of 3 × 10 ⁴ and Tg of 18 ° C.

Production Examples of Resin Particles (AL) 19 to 28: (AL
-19) to (AL-28) In Production Example 18 of resin particles (AL), except that 70 g of benzyl methacrylate and 30 g of methyl acrylate were used instead of the monomers shown in Table C below, Production Example 18 Each resin particle (AL) was synthesized in the same manner as in. Each of the white dispersions was a latex having a polymerization rate of 90 to 99% and an average particle size of 0.13 to 0.20 μm and good monodispersity. T for each resin particle
The g ranged from 10 ° C to 25 ° C.

[0225]

[Table 5]

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

[0227]

[Chemical 16]

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

[0229]

[Table 6]

[0230]

[Table 7]

Synthesis Example 10 of Resin (P): (P-10) 60 g of 2,2,3,4,4-hexafluorobutylmethacrylate, macromonomer of methyl methacrylate (A)
A-6) (manufactured by Toagosei Kagaku Co., Ltd., Mw 1 × 10 ⁴ ) 40 g,
A mixed solution of 200 g of benzotrifluoride was heated to a temperature of 75 ° C under a nitrogen stream. AIBN (1.0 g) was added and reacted for 4 hours, and AIBN (0.5 g) was further added and reacted for 4 hours. The Mw of the obtained copolymer was 6.5 × 10 ⁴ .

[0232]

[Chemical 17]

Synthesis Examples 11 to 15 of Resin (P): (P-11) to
(P-15) Instead of the monomer and macromonomer used in Synthesis Example 10 of resin (P), each monomer and each macromonomer corresponding to the polymer component shown in Table E below were used. The other is
Each copolymer was synthesized in the same manner as in Synthesis Example 10. The Mw of the obtained copolymer was in the range of 4.5 × 10 ^{4 to} 6.5 × 10 ⁴ .

[0234]

[Table 8]

[0235]

[Table 9]

[0236]

[Table 10]

Synthesis Example 16 of Resin (P): (P-16) 67 g of methyl methacrylate, 22 g of methyl acrylate,
A mixed solution of 1 g of methacrylic acid and 200 g of toluene was heated to a temperature of 80 ° C under a nitrogen stream. To this, 10 g of a polymeric azobis initiator (PI-1) having the following structure was added and reacted for 8 hours. After the reaction was completed, the precipitate was reprecipitated in 1.5 liter of methanol, and the obtained precipitate was collected and dried to give a yield of 75 g and Mw.
A 3 × 10 ⁴ copolymer was obtained.

[0238]

[Chemical 18]

Synthesis Example 17 of Resin (P): (P-17) 70 g of methyl methacrylate and 200 g of tetrahydrofuran
The mixed solution of 1 was thoroughly degassed under a nitrogen stream and cooled to -20 ° C. 0.8 g of 1,1-diphenylbutyllithium was added and reacted for 12 hours. Furthermore, the following monomer (m
-1) A mixed solution of 30 g and tetrahydrofuran 60 g,
After sufficiently degassing under a nitrogen stream, the mixture was added and reacted for 8 hours. After this mixture was heated to 0 ° C., 10 ml of methanol was added and the mixture was reacted for 30 minutes to terminate the polymerization. The obtained polymer solution was heated to a temperature of 30 ° C. with stirring, 3 ml of a 30% hydrogen chloride ethanol solution was added thereto, and the mixture was stirred for 1 hour. Then, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation in 1 liter of petroleum ether. The Mw of the polymer obtained by collecting the precipitate and drying under reduced pressure was 6.8 × 10 ⁴ ,
The yield was 76 g.

[0240]

[Chemical 19]

Synthesis Example 18 of Resin (P): (P-18) Methyl Methacrylate 52.5 g, Methyl Acrylate 22.5
A mixed solution of g, 0.5 g of (tetraphenylporphinato) aluminum methyl and 200 g of methylene chloride was heated to 30 ° C. under a nitrogen stream. This is irradiated with 300 W-xenon lamp light through a glass filter from a distance of 25 cm, and 20
Reacted for hours. This mixture was further mixed with the following monomer (m-
2) After adding 25 g and irradiating for 12 hours in the same manner, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction. The reaction mixture was then reprecipitated in 1.5 liters of methanol, the precipitate was collected and dried. The yield of the obtained polymer was 78 g, and the Mw was 7 × 10 ⁴ .

[0242]

[Chemical 20]

Synthesis Example 19 of Resin (P): (P-19) Ethyl Methacrylate 50 g, Glycidyl Methacrylate
10 g and benzyl N, N-diethyldithiocarbamate 4.
8 g of the mixture was sealed in a container under a nitrogen stream and heated to a temperature of 50 ° C. This was irradiated with light from a high pressure mercury lamp of 400 W at a distance of 10 cm from a glass filter for 6 hours for photopolymerization. This was dissolved in 100 g of tetrahydrofuran, 40 g of the following monomer (m-3) was added, the atmosphere was replaced with nitrogen, and the amount was again 10
Irradiated for hours. The obtained reaction product was reprecipitated in 1 liter of methanol, collected, and dried. The polymer obtained has a yield of 73.
The Mw was 4.8 × 10 ⁴ in g.

[0244]

[Chemical 21]

Synthesis Example 20 of Resin (P): (P-20) Methyl Methacrylate 50 g, Ethyl Methacrylate 25 g
And a mixture of benzyl isopropyl xanthate 1.0 g,
The container was sealed under a nitrogen stream and heated to a temperature of 50 ° C. This was irradiated with light from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 6 hours to perform photopolymerization. To this, 25 g of the monomer (m-1) was added, and the atmosphere was replaced with nitrogen, and light was again irradiated for 10 hours. The obtained reaction product was reprecipitated in 2 liters of methanol, collected, and dried to obtain a polymer having a yield of 63 g and a Mw of 6 × 10 6.
^{Was 4} .

[0246]

[Chemical formula 22]

Synthesis Examples 21 to 27 of Resin (P): (P-21) to
(P-27) In the same manner as in Synthesis Example 19 of Resin (P), each copolymer shown in Table F below was synthesized. The Mw of the obtained polymer was 3.5 × 10 ⁴ to
The range was 6 × 10 ⁴ .

[0248]

[Table 11]

[0249]

[Table 12]

Synthesis Example 28 of Resin (P): (P-28) In Synthesis Example 19 of Resin (P), 18 g of an initiator (I-1) having the following structure was used instead of benzyl N, N-diethyldithiocarbamate. Was synthesized in the same manner as in Synthesis Example 19 except that was used to obtain a copolymer having Mw of 4.5 × 10 ⁴ .

[0251]

[Chemical formula 23]

Synthesis Example 29 of Resin (P): (P-29) In Synthesis Example 20 of Resin (P), 0.8 g of an initiator (I-2) having the following structure was used instead of benzyl isopropyl xanthate.
Except that the above reaction was carried out in the same manner as in Synthesis Example 20, Mw 2.5 × 1
A copolymer of 0 ⁴ was obtained.

[0253]

[Chemical formula 24]

Synthesis Example 30 of Resin (P): (P-30) 68 g of methyl methacrylate, 22 g of methyl acrylate,
A mixed solution of 10 g of glycidyl methacrylate, 17.5 g of the initiator (I-3) having the following structure, and 150 g of tetrahydrofuran was heated to a temperature of 50 ° C. under a nitrogen stream. 400W for this solution
Photopolymerization was carried out by irradiating with light from a high pressure mercury lamp at a distance of 10 cm through a glass filter for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried,
A polymer having a yield of 72 g and Mw of 4.0 × 10 ⁴ was obtained. This polymer 70
g, 30 g of the monomer (m-2) and tetrahydrofuran
100 g of the mixed solution was heated to a temperature of 50 ° C. under a nitrogen stream and irradiated with light under the same conditions as above for 13 hours. Next, this reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried to obtain a copolymer of Mw 6 × 10 ⁴ with a yield of 78 g.

[0255]

[Chemical 25]

Synthesis Examples 31 to 38 of Resin (P): (P-31) to
(P-38) In Synthesis Example 30 of Resin (P), the initiator (I-3) 17.5
The same conditions as in Synthesis Example 30 were used except that 0.031 mol of the initiator (I) shown in Table G below was used instead of g. The yield of each polymer obtained was 70 to 80 g, and Mw was ⁴ × 10 ^{4 to} 6 × 10 ⁴ .

[0257]

[Table 13]

[0258]

[Table 14]

[0259]

[Table 15]

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

[0261]

[Chemical formula 26]

Synthesis Example 2 of Resin Particles (PL): (PL-
2) As a dispersion stabilizing resin (AB-6) (manufactured by Toagosei Co., Ltd .:
5 g of a monofunctional macromonomer consisting of butyl acrylate units) and 140 g of methyl ethyl ketone
The mixture was heated to a temperature of 60 ° C while stirring under a nitrogen stream. To this, a mixed solution of 40 g of a monomer (LM-2) having the following structure, 1.5 g of ethylene glycol diacrylate, 0.2 g of AIVN and 40 g of methyl ethyl ketone was added dropwise over 1 hour. After reacting for 2 hours as it was, 0.1 g of AIVN was further added and reacted for 3 hours to obtain a white dispersion. After cooling, the average particle size of the dispersion obtained through a 200 mesh nylon cloth is 0.35μ.
It was m.

[0263]

[Chemical 27]

Synthesis Examples 3 to 11 of Resin Particles (PL): (PL
-3) to (PL-11) In Synthesis Example 1 of resin particles (PL), the monomer (LM-
Resin particles were produced in the same manner as in Synthesis Example 1 except that 1), ethylene glycol dimethacrylate, and methyl ethyl ketone were replaced with the compounds shown in Table H below. The average particle size of the obtained resin particles was in the range of 0.15 to 0.30 μm.

[0265]

[Table 16]

[0266]

[Table 17]

Synthesis Examples 12 to 17 of Resin Particles (PL): (PL
-12) to (PL-17) In Synthesis Example 2 of resin particles (PL), 5 g of the dispersion stabilizing resin (AB-6) was used instead of the resin (PL) shown in Table I below.
Each resin particle was synthesized in the same manner as in Synthesis Example 2 except that The average particle size of the obtained particles was in the range of 0.10 to 0.25 μm.

[0268]

[Table 18]

[0269]

[Table 19]

Synthesis Examples of Resin Particles (PL) 18 to 23: (PL
-18) to (PL-23) In Synthesis Example 2 of resin particles (PL), the monomer (LM-
2) Instead of 40 g, each monomer of the following Table-J was used, and instead of 5 g of the dispersion stabilizing resin (AB-6), the resin of the following structure (L
P-8) was used in the same manner as in Synthesis Example 2 except that 6 g was used,
Each resin particle was synthesized. The average particle size of the obtained particles is 0.
It was in the range of 05 to 0.20 μm.

[0271]

[Chemical 28]

[0272]

[Table 20]

[0273]

[Table 21]

Example 1 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 2
g, 10 g of a binder resin (B-1) having the following structure, the resin (P
-1) A mixture of 0.3 g, 0.15 g of the compound (A) having the following structure and 80 g of tetrahydrofuran was put in a 500 ml glass container together with glass beads and dispersed for 60 minutes with a paint shaker (manufactured by Toyo Seiki Seisakusho), and then the glass beads were filtered. Separately, a photosensitive layer dispersion liquid was obtained.

[0275]

[Chemical 29]

Then, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, with a wire bar, and was dried by touching with a finger, and then dried at 110 ° C. in a circulating oven at 20 ° C. Heated for seconds. The thickness of the obtained photoreceptor is 8
It was μm. When the adhesive strength of the photoconductor was measured by "Adhesive tape / adhesive sheet test method" of JIS Z0237-1980, the value was 15 gf.

On the other hand, the resin (P-
1) Except that 0.3 g was removed, the adhesive force of the surface of the photosensitive member made of the photosensitive layer prepared in exactly the same manner was 450 g · f or more, and no peelability was exhibited when the transfer layer was formed.

The above-mentioned photoconductor having an easily peelable surface was mounted as an electrophotographic photoconductor 11 on the apparatus shown in FIG. 2 (however, the compound (S) applying means 10 was not provided). Then an electrophotographic process was performed. Corona charging device 1 for photoconductor 11 in the dark
After passing under 8, and corona charging to + 450V,
Read the original in advance with a color scanner,
After separating the colors and applying some corrections related to system-specific color reproduction, about the yellow among the yellow, magenta, cyan, and black colors that were stored in the hard disk in the system as digital image data. Based on the information, in the negative image mode, the semiconductor laser drawing device 19 was used to perform exposure with light of 788 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 diluted 75 times with Isopar H (manufactured by Esso Standard Petroleum) and supplied to the yellow liquid developing unit 14y.
A bias voltage of +350 V is applied to the side to perform reversal development so that the toner is electrodeposited on the exposed area, and then a bath of Isopar H alone is rinsed to remove stains on the non-image area, and then the intake / exhaust unit 15 And, it was passed under 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 25.

Next, on this, resin particles (AL-1) 8
g (as solid content), positive charge control agent (CD-1)
{(Octadecyl vinyl ether / semi-maleic acid dodecylamide) copolymer} 0.02 g and branched tetradecyl alcohol (FOC-1400, Nissan Chemical Co., Ltd.) 10 g were added to 1 liter of Isopar G (Esso Corp.). The dispersion for electrodeposition (L-1) prepared as above was supplied by the method and apparatus shown in FIG.

The peripheral speed of the drum of the photosensitive member 11 was rotated at 10 mm / sec, and the dispersion liquid 12 was formed on the surface of the photosensitive member by using the electrodeposition unit 50 which diverted the developing unit used for developing the color toner.
While supplying a, the photoreceptor 11 side was grounded, and a voltage of +200 V was applied to the electrode side of the electrodeposition unit 50 to electrodeposit the resin particles. Then, the dispersion liquid was removed by an air squeeze using an intake / exhaust unit 15, and the infrared line heater of the preheating means 16 melted and made a film to form the thermoplastic resin transfer layer 12. The film thickness at this time was 3 μm.

Also, as a primary receptor 20, a blanket for offset printing 9600-A (adhesive force 80 g · f / 10 mm)
Width, overall thickness 1.6 mm, made from Meiji Rubber) 1 drum
It was heated to 20 ° C. On the other hand, if the surface temperature of the photoconductor 11 is
It heated using the preheating means 16 and the temperature control means 17 so that it might become 60 degreeC. Next, the drum 11 of the photoreceptor and the drum 20 of the primary receptor were brought into contact with each other and heated and pressed under the conditions of a nip pressure of 3 kgf / cm ² and a drum peripheral speed of 5 mm / sec. Transfer layer 1 on top
All 2 were transferred.

Then, the surface temperature is adjusted to 60 ° C. by the temperature adjusting means 17.
Between the primary receptor 20 drum set at 10 ° C., the transfer backup roller 22 set at 130 ° C., and the peeling backup roller 23 set at 10 ° C. Then, when the nip pressure was 5 kgf / cm ² and the drum peripheral speed was 10 mm / sec and heating and pressurization were performed, the color toner image 25 was completely transferred onto the coated paper 21 and a high-quality clear color image was obtained. was gotten.

On the other hand, a color image is formed on coated paper in the same manner except that the toner image is directly transferred to the primary receptor 20 without providing the transfer layer 12 on the photoreceptor 11 after the toner image 25 is formed. Compared to the invention. The color image of the obtained coated paper was found to have a missing toner image or uneven image density. Finer lines,
Visual inspection of fine characters and other parts with a 20x magnifier revealed a fine lack of images. Further, when the surface of the photoconductor was observed, residual toner image areas were observed. This means that, in the method of repeatedly using the photoconductor, cleaning of the photoconductor surface for removing the residual toner, setting of an apparatus therefor or damage to the photoconductor surface due to cleaning or the like becomes a problem.

On the other hand, in the present invention, the toner image is sufficiently peeled from the photosensitive member, and the primary receptor is easily and sufficiently transferred to the final transfer material, so that the above problems do not occur. Moreover, since the toner image is protected by the transfer layer, the stability of the obtained color copy is excellent.

Example 2 An electrophotographic photosensitive member obtained by surface-modifying an amorphous silicon photosensitive member with tridecylfluorooxyltrimethoxysilane was used (the adhesive force on the surface of the photosensitive member was 80 g · f), and Example 1 was used. In the same manner as described above, the device shown in FIG.
Compound (S) providing means 10 was not provided).

After the photoreceptor 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, using a semiconductor laser, light of 780 nm was used. Plate exposure is 25erg / c
It was exposed to m ² . Residual potential of exposed area is + 120V
Met. Subsequently, yellow toner for Versatec 3000 (Xerox color electrostatic plotter) was diluted with 50 times Isopar H (Esso Standard Petroleum) and used.
A developing device having a pair of flat plate developing electrodes applies a bias voltage of +300 V to the electrodes on the photoconductor surface side to perform reversal development so that toner is electrodeposited on the exposed area, and then rinses in an Isopar H single bath. The stain on the non-image area was removed.
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. To confirm the reproducibility of the copied image before transfer, copy the image (fogging, image quality) to 20
It was visually evaluated with a 0-fold optical microscope. The image quality of the toner image portion 25 on the photoreceptor 11 is clear in the high-definition image portion of thin lines, fine characters, and halftone dots of continuous gradation, and the image density of the solid portion is 1.2.
The above results were good, and no fog was observed in the non-image area.

The surface temperature of the photoconductor was set to 60 ° C., and the peripheral speed of the drum of the photoconductor 11 was rotated at 10 mm / sec in the same manner as in Example 1, and the surface of the photoconductor 11 was rotated by using a slit electrodeposition apparatus.
4 g of thermoplastic resin particles (AL-17) (as solid content), 4 g of thermoplastic resin particles (AL-4) (as solid content), charge control agent (CD-2) ([1-tetradecene /
Half maleic acid decylamide] copolymer) 0.015 g and branched octadecyl alcohol (FOC-1800, Nissan Chemical Co., Ltd.)
(Supplied) 10 g of the positively charged resin particle dispersion liquid (L-2) adjusted with Isopar G so that the total amount becomes 1 liter, while the photoreceptor side is grounded and the electrode side of the slit electrodeposition apparatus is
A voltage of 100 V was applied to electrodeposit and fix the resin particles to form a layer having a thickness of 2 μm.

In addition, Example 1 was used as the primary receptor 20.
On the roll surface of the blanket 9600-A used in 1., 5 parts by weight of the resin (P-2) and 0.001 g of phthalic anhydride were applied to 100 parts by weight of isoprene rubber to form a film having a thickness of 10 μm.
The thing which formed the cured film by heating at 140 degreeC for 2 hours was used (the adhesive force of this surface was 130 gf). Otherwise, the same operation as in Example 1 was carried out to transfer the color image 25 onto the coated paper 21.

The color image obtained was clear, and the transfer layer had sufficient strength in the image area and a sufficient film-thickness strength, and was not scraped off. Further, the writing property and the marking property with a pencil hardness HB were also good.

Example 3 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 2
g, a mixture of 10 g of the binder resin (B-2) having the following structure, 0.15 g of the compound (B) having the following structure, and 80 g of tetrahydrofuran together with glass beads in a 500 ml glass container, and using a paint shaker (Toyo Seiki Seisakusho) After dispersing for 60 minutes, 2 g of the resin (P-35) of the present invention, 0.1 g of gluconic anhydride and 0.002 g of o-chlorophenol were added and dispersed for 10 minutes, and then the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0292]

[Chemical 30]

Then, this dispersion was applied to an aluminum support with a wire bar, dried by touching with a finger, and then heated in a 110 ° C. circulation type oven for 20 seconds, and further heated at 140 ° C. for 2 hours to carry out a curing treatment. went. The thickness of the obtained photoconductor is 8μ.
It was m. The adhesive strength of the photoconductor measured by JIS Z0237-1980 “Adhesive tape / adhesive sheet test method” was 5 g · f. On the other hand, in the above photosensitive layer, resin (P-35) 2
The adhesive force of the surface of the photosensitive member made of the photosensitive layer prepared in the same manner except that g was removed was 450 gf or more, and no peelability was exhibited even when the transfer layer was formed.

The obtained photoreceptor was attached to the apparatus shown in FIG. 6 applied to the apparatus shown in FIG. 2 (however, without the compound (S) applying means 10). After forming a color image on the photoconductor 11 in the same manner as in Example 1, the transfer layer 12 was formed by the hot melt coating method as described below. That is, an ethylene-vinyl acetate copolymer (vinyl acetate content 20% by weight, softening point 90 ° C. by ring and ball method) is used as a thermoplastic resin for the transfer layer, and the surface of the photoreceptor 11 is adjusted by a hot melt coater 30 set at 120 ° C. Was coated at a speed of 20 mm / sec, and cooling air was blown from the intake / exhaust unit 15 to cool it, and then the surface temperature of the photoreceptor was kept at 30 ° C. The thickness of the transfer layer 12 at this time was 3 μm.

Subsequently, the transfer to the primary receptor 20 and the transfer to the coated paper 21 were performed in the same manner as in Example 1 to form a color image on the coated paper 21. The color image on the obtained coated paper was clear, and the toner was completely covered with the thermoplastic resin as the transfer layer on the coated paper, so that it did not rub off.

Example 4 The same operation as in Example 3 was carried out except that the transfer layer forming method by the hot melt coating method was changed to the transfer method from release paper according to the following contents. , A color image copy was obtained. That is, the photoreceptor 11 is attached to a device in which the device shown in FIG. 5 is applied to the device shown in FIG. 2 (however, the compound (S) applying means 10 is not provided), and the release paper 40 is a separate paper (Oji Paper Co., Ltd.). Manufactured by K.K.), and a coating film is formed thereon with a film thickness of 3 μm consisting of poly (vinyl acetate) and a (5/5) weight ratio of [methyl methacrylate / methyl acrylate (6/4) weight ratio] copolymer. The prepared paper is attached to the device shown in the schematic diagram of FIG. 5, and the pressure between rollers is 3 kgf / c.
m ² , surface temperature of 80 ℃, and passage speed of 10 mm / sec,
The transfer layer 1 is formed on the photoconductor 11 on which the toner image 25 is formed.
2 was transferred and formed. The color image of the obtained coated paper was a good image without fog, and the image strength was sufficient, as in Example 3. In addition, the writing and stamping properties were good.

Examples 5 to 14 In place of 8 g of the resin particles (AL-1) in the dispersion liquid (L-1) of the resin (A) in Example 1, each resin particle (AL) shown in Table K below (total amount). In the same manner as in Example 1 except that 8 g) was used, a color image was formed.

[0298]

[Table 22]

The color copy thus obtained had a clear image quality without background stains. That is, the toner image formed on the photoconductor has good image reproducibility and good image pick-up that no fog in the non-image area is observed, and transfer of each transfer layer to coated paper causes uneven transfer. Was completely transferred without causing Further, it was possible to add or stamp the copy paper in the same manner as the case of plain paper.

Examples 15 to 30 Same as Example 3 except that each resin shown in Table L below was used in place of the ethylene-vinyl acetate copolymer used for forming the transfer layer 12 in Example 3. When a transfer image forming operation was performed by using the above, the same results as in Example 2 were obtained.

[0301]

[Table 23]

Examples 31 to 37 In Example 4, instead of the separate paper 40 provided with a transfer layer, a release paper: Sun release (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) having a film thickness of 3.5 μm was used. A color image was prepared in the same manner as in Example 4, except that the resin (A) of M was used.

[0303]

[Table 24]

[0304]

[Table 25]

The obtained color image was a clear image without background fog, and almost no deterioration of the image image was recognized as compared with the original. This means that after toner image formation,
Even if the transfer layer is formed on the photoconductor using a release paper and then transferred to the coated paper, the transfer layer at each transfer is transferred uniformly and completely without causing a bad influence on the image deterioration. Shows.

Example 38 As an organic photoconductive substance, 4,4'-bis (diethylamino) -2,2'-dimethyltriphenylmethane (5 g), a binder resin (B-3) having the following structure (4 g), and the above resin ( P-27) 0.
4 g, 40 mg of dye (D-1) having the following structural formula, and 0.2 g of anilide compound (C) having the following structural formula as a chemical sensitizer were dissolved in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride to prepare a photosensitive layer dispersion liquid. And

[0307]

[Chemical 31]

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, a surface resistance of 10 ³ Ω) using a wire round rod. Thus, an organic thin film having a photosensitive layer with a thickness of about 4 μm was obtained. Adhesive force on the photoreceptor surface is 8
It was gf. 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 coated paper after transfer was clear without background fog, and the image strength was good in durability.

Example 39 Example 39 was carried out in the same manner as in Example 2 except that as the electrophotographic photosensitive member 11, a photosensitive member provided with a peelable surface layer having a film thickness of 1.5 μm on an amorphous silicon photosensitive member as described below was used. A color copy paper was prepared in the same manner as in Example 2.

<Formation of easily peelable surface layer> Resin (P-12)
A coating solution was formed on an amorphous silicon photoconductor to a thickness of 1.5 μm using a toluene solution of 1.0 g, a binder resin (B-4) having the following structure, 0.03 g of phthalic anhydride and 100 g of toluene. After that, dry it by touching it, and add 1 at 130 ℃.
The film was cured by heating for a period of time. The adhesive force on the surface of the amorphous silicon photoconductor provided with the surface layer was 8 g · f.

[0311]

[Chemical 32]

The image pick-up property and the transfer property were examined in the same manner as in Example 2. The copied image formed on the photoconductor is good,
Next, the copied image transferred to the coated paper was also a good one that almost reproduced the original, and no transfer unevenness was observed. In addition, the filing suitability was good, and the adhesion and peeling of the sheet did not occur. Further, the imprintability was also good.

Example 40 5 g of bisazo pigment having the following structure and 95 g of tetrahydrofuran
And polyester resin Byron 200 (manufactured by Toyobo Co., Ltd.)
5 g of the mixture was thoroughly ground in a ball mill. Next, this mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was applied onto the conductive transparent support used in Example 38 using a wire round rod to form a charge generation layer having a thickness of about 0.7 μm.

[0314]

[Chemical 33]

Next, a hydrazone compound of the following structural formula 20
g, polycarbonate resin (GE company, trade name Lexan
121) A mixed solution of 20 g and tetrahydrofuran 160 g is applied onto the above charge generation layer using a wire round rod, dried at 60 ° C. for 30 seconds, and further heated at 100 ° C. for 20 seconds to obtain a charge transport layer of about 18 μm. Was formed to obtain an electrophotographic photosensitive member having a photosensitive layer composed of two layers.

[0316]

[Chemical 34]

Further, in order to form a surface layer for imparting releasability on this photosensitive layer, the following resin (P-39) 13
g, phthalic anhydride 0.2g, o-chlorophenol 0.002g
A mixed solution of 100 g of toluene and 100 g of toluene was applied using a wire round rod to a film thickness of 1 μm, dried by touch, and further heated at 120 ° C. for 1 hour. The adhesive force on the surface of the obtained photoreceptor was 5 g · f.

[0318]

[Chemical 35]

The surface potential of this light-sensitive material was +500 V in the dark.
On the photoconductor, except that it was exposed to light of 633 nm with a He-Ne laser so that the exposure amount on the plate surface would be 30 erg / cm ² after being charged. A color toner image was formed. Furthermore, in order to form a transfer layer on this, 4.5 g of resin particles (AL-17) and resin particles (AL-17)
-10) Using 2 g, the film thickness is 4.5 μm in the same manner as in Example 1.
To form a transfer layer. In the same manner as in Example 1, a full-color image was formed on the coated paper. The copy paper obtained is
Similar to Example 1, it showed good performance.

Example 41 100 g of photoconductive zinc oxide, a binder resin (B-
5) 15 g, 5 g of the binder resin (B-6) having the following structure, 2 g of the resin (P-28), 0.01 g of the dye (D-2) having the following structure,
A mixture of 0.1 g of salicylic acid and 150 g of toluene was placed in a ball mill and dispersed for 2 hours to prepare a photosensitive layer dispersion liquid.

[0321]

[Chemical 36]

Next, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, with a wire bar, and was dried by touching with a finger, and then in a 110 ° C. circulation type oven for 20 seconds. Heated. Further, it was allowed to stand for 24 hours in the dark under the condition of (25 ° C., 65% RH). The adhesive force on the surface of the photoconductor was 12 g · f.

Next, this photoreceptor 11 was corona charged to -600 V in a dark place, and then the same digital image data as in Example 1 was used. First, based on the information about yellow, this time in the positive mirror image mode. , Using semiconductor laser 19
Exposure was performed with 0 nm light so that the plate surface exposure amount was 25 erg / cm ² . The residual potential of the exposed portion was -120V. Then, the yellow toner for Versatec 3000 (Xerox color electrostatic plotter) was diluted with 50 times Isopar H (made by Esso Standard Petroleum) and used, and a developing device having a pair of flat plate developing electrodes was used for the electrodes on the photoconductor surface side. A bias voltage of -200 V was applied to perform positive development in which the toner was electrodeposited on the unexposed area, and then rinsed in a bath of Isopar H alone to remove stains on the non-image area. The above process was repeated for each color of magenta, cyan and black.

Subsequently, the transfer layer 12 was formed by the same operation as in Example 1, and the transfer layer 12 was transferred to the primary receptor 20 and further to the coated paper 21 to form the color image 25 on the coated paper 21. . The obtained color image was a copy having a clear image quality without background fog, and the strength of the image area was sufficient.

Examples 42 to 61 In Example 1, except that each resin (P) and / or resin particles (PL) of the following Table-N was used in place of 0.3 g of the resin (P-1), Each light-sensitive material was prepared in the same manner as in 1. Next, these light-sensitive materials were operated in a dark place in the same manner as in Example 1 to examine the image pickup property and the transfer property. The obtained color copied images of the coated paper after transfer were clear without background fog, and the image strength was good in durability.

[0326]

[Table 26]

Examples 62 to 72 A mixture of 3.5 g of X-type metal-free phthalocyanine, 10 g of a binder resin (B-7) having the following structure and 80 g of tetrahydrofuran was added.
Put the glass beads together with glass beads in a 500 ml glass container, disperse for 60 minutes with a paint shaker (manufactured by Toyo Seiki Seisakusho), further add resin (P) or resin particles (PL) and crosslinking compound shown in the following Table-O, and then for 10 minutes. After the dispersion, the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0328]

[Chemical 37]

[0329]

[Table 27]

Then, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate which had been subjected to a conductive treatment and a solvent resistance treatment with a wire bar, and was dried by touching with a finger, and then dried in a circulating oven at 110 ° C. for 30 seconds. After drying, it was heated at 140 ° C. for 1 hour. A transfer image was formed in the same manner as in Example 3 except that this photosensitive member was used instead of the photosensitive member used in Example 3.
The obtained color copied image of the coated paper after transfer was clear without background fog and the image strength was good in durability.

Example 73 Amorphous silicon photoconductor (manufactured by Kyocera Corp.) 11 was loaded in the apparatus shown in FIG. As means 10 for imparting releasability to the surface of the photoconductor, the photoconductor 11 was brought into contact with a solution prepared by dissolving 1 g of the compound (S-1) (polyether-modified silicone oil) having the following structure in 1 liter of Isopar G, Speed 30
After rotating at a rotation speed of mm / sec for 10 seconds, squeeze roll was used to squeeze, followed by drying by preheating means. As a result, the photoconductor having an adhesive force of 203 g · f has an adhesive force of 8 g · f.

[0332]

[Chemical 38]

Next, the peelable amorphous silicon photoconductor 11 is corona charged to +700 V in a dark place, and then read from a document by a color scanner in advance and color-separated to reproduce some system-specific color. After the correction related to, yellow stored in the hard disk in the system as digital image data,
Among the colors of magenta, cyan, and black, first, exposure was performed with light of 780 nm using a semiconductor laser in a negative image mode based on information about yellow. The potential of the exposed part is +2
At 20V, the unexposed area was + 600V. Next, the Isopar H
After making a pre-bath at (made by Esso Standard Oil),
Isopar H with 50 times the positively charged yellow toner for Versatec 3000 (Xerox color electrostatic plotter)
The wet type developer 14y diluted with was supplied from the developing unit 14 to the surface of the photoconductor 11. +50 to the development unit side at this time
A developing bias voltage of 0 V was applied to carry out reversal development so that the toner was electrodeposited on the yellow unexposed portion. Then, the bath was rinsed in a bath containing Isopar H alone to remove stains on the non-image area, and dried in an intake / exhaust unit. The above process was repeated for each color of magenta, cyan and black.

Next, the same electrodeposition dispersion liquid (L-1) as that used in Example 1 was supplied thereon by the method and apparatus shown in FIG. The peripheral speed of the photosensitive drum 11 is 10mm /
The electrode 11 side of the electrodeposition unit 50 is grounded while the dispersion liquid 12a is supplied by using the electrodeposition unit 50 in which the developing unit used for color toner development is diverted to the surface of the photoconductor. A voltage of + 200v was applied to the resin particles to electrodeposit the resin particles. Then, the dispersion liquid was removed by an air squeeze using an intake / exhaust unit 15, and the infrared line heater of the preheating means 16 melted and made a film to form the thermoplastic resin transfer layer 12. The film thickness at this time was 5 μm.

Further, as a primary receptor 20, a blanket for offset printing 9600-A (adhesive force 80 g · f / 10 mm)
Width, overall thickness 1.6 mm, made from Meiji Rubber) 1 drum
It was heated to 20 ° C. On the other hand, if the surface temperature of the photoconductor 11 is
It heated using the preheating means 16 and the temperature control means 17 so that it might become 60 degreeC. Next, the drum 11 of the photoreceptor and the drum 20 of the primary receptor were brought into contact with each other and heated and pressed under the conditions of a nip pressure of 3 kgf / cm ² and a drum peripheral speed of 5 mm / sec. Transfer layer 1 on top
All 2 were transferred.

Next, between the primary receptor 20 drum whose surface temperature is set to 60 ° C. by the temperature adjusting means, the transfer backup roller 22 set to 130 ° C. and the peeling backup roller 23 set to 10 ° C. Then, the coated paper 21, which is the final printing material, which is the final transfer material, was introduced, and the color toner image 25 was coated with the coated paper 21 with the nip pressure of 5 kgf / cm ² and the drum peripheral speed of 10 mm / sec. Two
All were transferred onto No. 1 and a high-quality clear color image was obtained.

On the other hand, the toner image 25 is formed on the photoconductor 11 without applying the compound (S), and the transfer layer 12 is further formed.
A color image was formed on the coated paper by the method of transferring the image to the primary receptor 20 by providing the above and compared with the present invention. The color image of the obtained coated paper was at a level at which it did not form a body as a copy at all, because transfer failure was remarkable. When the surface of the photoconductor at this time was observed, a large amount of the toner image and the transfer layer remained irregularly. This is because the releasability of the surface of the photoreceptor is insufficient. On the other hand, in the present invention, the toner image is sufficiently peeled from the photoconductor, and the toner image is easily and sufficiently transferred from the primary receptor to the final transfer material. A color copy was obtained. It can be seen that the supply of the compound (S) provided the photoreceptor with sufficient releasability in forming and transferring the toner image and the transfer layer.

Examples 74 to 94 In Example 73, as a means for imparting the surface releasability of the amorphous silicon photoreceptor, instead of the compound (S-1), a predetermined amount of each compound (S) shown in the following Table-P was used as an isopar. G
Example 73, except using a solution dissolved in 1 liter
The same operation was performed. The photoconductor 1 is treated with each compound (S).
The adhesive strength of each surface was in the range of 3 to 20 gf. The color image on the obtained coated paper was a good image without fog as in Example 73, and the image strength was also sufficient.

[0339]

[Table 28]

[0340]

[Table 29]

[0341]

[Table 30]

[0342]

[Table 31]

[0343]

[Table 32]

[0344]

[Table 33]

Example 95 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 2
g, a binder resin (B-8) of the following structure 8.5 g, a binder resin (B-9) of the following structure 1.5 g, and a compound (D) of the following structure 0.15 g
A mixture of 80 g of tetrahydrofuran and 80 g of tetrahydrofuran was put together with glass beads in a 500 ml glass container, dispersed for 60 minutes with a paint shaker (manufactured by Toyo Seiki Seisakusho), and the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0346]

[Chemical Formula 39]

Then, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, with a wire bar, and was dried by touching with a finger, and then dried in a 120 ° C. circulation type oven for 2 minutes. Heated for hours. The thickness of the obtained photoreceptor is 8
It was μm.

The photoconductor 11 was loaded into the apparatus shown in FIG. 2, and the compound (S-23) for imparting releasability to the photoconductor 11 was provided.
(Carboxy-modified silicone oil TSF4446: manufactured by Toshiba Silicon Co., Ltd.) A metalling roll having a silicone rubber layer on the outermost surface in contact with a bath containing oil was brought into contact with the photoconductor 11 and rotated at a peripheral speed of 15 mm / sec. Both drums at speed
It was rotated for 20 seconds. With this treatment, the adhesive force on the surface of the photoconductor 11 was 400 g · f or more before the treatment,
It became gf.

Also, the same result as above can be obtained by processing through a transfer roll having a styrene-butadiene rubber layer on the outermost surface between the metering roll immersed in the silicone oil bath and the photoconductor. It was Furthermore, in the method using the above-mentioned metering roll / transfer roll, as shown in the partial schematic view of the compound (S) supply device of FIG. 9, the compound (S-23) is added between the metering roll 112 and the transfer roll 111. Similarly good results were obtained with the method of supplying 113 as well.

Next, an electrophotographic process was performed. Pass the photoconductor under corona charging device 18 in the dark, and
After corona charging to 0v, the original was read in advance by a color scanner, color separation was performed, and some corrections related to system-specific 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 yellow, magenta, cyan, and black, the exposure amount on the photoconductor is 30 erg / cm ² in the negative image mode with the semiconductor laser drawing device 19 and the light of 788 nm. Exposed.
Subsequently, the positively charged yellow toner for the signature system (made by Kodak) is diluted 75 times with Isopar H (made by Esso Standard Petroleum) and the yellow liquid developing unit 14
Y is supplied, a bias voltage of +350 V is applied to the developing unit side, and reversal development is performed so that toner is electrodeposited on the exposed portion, and then a rinse of Isopar H alone bath is performed to remove stains on the non-image area. After that, it was passed under 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.

Photoconductor 11 on which this toner image 25 is formed
The transfer layer 12 having a laminated structure was formed thereon as follows.

First, 8 g (as solid content) of resin particles (AL-4) and the charge control compound (CD-3) {(1-
Wet electrodeposition unit 50, which is a transfer layer forming apparatus, is a resin dispersion (L-3) prepared by adjusting the amount of tetradecene / t-octylmaleic acid half amide) copolymer} 0.03 g with Isopar H so that the total amount becomes 1 liter. And a first transfer layer was formed by a wet electrodeposition method. That is, the surface temperature of the photoreceptor 11 is 60
Heating was performed using the preheating means 16 and the temperature control means 17 so that the temperature became ℃. The photoconductor drum is rotated at a peripheral speed of 10 mm / sec, the dispersion liquid 12a is supplied to the surface of the photoconductor 11 on which the toner image 25 is formed by using a slit electrodeposition device, the photoconductor side is grounded, and an electrode of the slit electrodeposition device is formed. The resin particles were electrodeposited by applying a voltage of -130 V to the side. Next, the dispersion liquid was removed by an air squeeze using the air intake / exhaust unit 15, and further melted and filmed by the infrared line heater of the preheating means 16 to form the first thermoplastic resin transfer layer 12. The film thickness at this time was 2 μm.

Furthermore, on top of this, the above resin dispersion (L-3)
In the above, the same resin dispersion (L-4) was used except that 8 g of resin particles (AL-18) (as solid content) were used instead of 8 g of resin particles (AL-4), and the electrodeposition applied voltage was −
At 250 V, the second transfer layer 12 having a film thickness of 3 μm was formed in the same manner as above.

Next, 20 drums of the primary receptor are heated at a temperature of
The photoreceptor 11 drum having the transfer layer 12 on the toner image 25 is brought into contact with the primary receptor 20 by heating to 100 ° C.,
Under the conditions of a nip pressure of 4 kgf / cm ² and a drum peripheral speed of 5 mm / sec, the entire toner image 25 was transferred onto the primary receptor 20 together with the transfer layer 12. Here, as the primary receptor 20, 7 parts by weight of resin (P-2) and 0.001 g of phthalic anhydride were used on the roll surface of the blanket 9600-A used in Example 1 for 100 parts by weight of isoprene rubber. A coating film having a thickness of 10 μm and heated at 140 ° C. for 2 hours to form a cured film was used (the adhesive strength of the surface was 80 g · f).

Next, between the primary receptor 20 drum whose surface temperature is set to 60 ° C. by the temperature adjusting means, the transfer backup roller 22 set to 130 ° C. and the peeling backup roller 23 set to 10 ° C. Then, the coated paper 21, which is the final printing material, which is the final transfer material, was introduced, and the color toner image 25 was coated with the coated paper 21 with the nip pressure of 5 kgf / cm ² and the drum peripheral speed of 10 mm / sec. Two
All were transferred onto No. 1 and a high-quality clear color image was obtained.

On the other hand, the toner image 25 is formed on the photoconductor 11 without supplying the compound (S-23) to the photoconductor 11, and the transfer layer 12 is further provided to transfer the toner image 25 to the primary receptor 20. Image 25 was formed on coated paper 21 and compared to the present invention. The color image of the obtained coated paper was at a level at which it did not form a body as a copy at all, because transfer failure was remarkable. When the surface of the photoconductor at this time was observed, a large amount of the toner image and the transfer layer remained irregularly. This is because the releasability of the surface of the photoreceptor is insufficient. On the other hand, in the present invention, the toner image is sufficiently peeled from the photoconductor, and the toner image is easily and sufficiently transferred from the primary receptor to the final transfer material. A color copy was obtained. It can be seen that the supply of the compound (S) provided the photoreceptor with sufficient releasability in forming and transferring the toner image and the transfer layer.

Example 96 A color image was formed on the coated paper 21 in the same manner as in Example 95 except that the means for imparting releasability of the photoconductor 11 was changed to the following contents. A rubber roller with a built-in heating means was wrapped with a cloth impregnated with compound (S-24): Fluorosurfactant Surflon (S-141; manufactured by Asahi Glass Co., Ltd.). After heating, the photoconductor 11 is contacted and both drums are rotated at a peripheral speed of 20 mm /
It was rotated for 30 seconds at a rotation speed of 2 seconds. The adhesive force on the surface of the photoconductor 11 became 12 g · f. The final color image obtained had the same results as in Example 95.

Example 97 A color image was formed on the coated paper 21 in the same manner as in Example 95 except that the releasing property imparting means for the photoconductor 11 was changed to the following contents. Silicon rubber roller in which silicone rubber is wrapped around a metal core roller (Co., Ltd.)
(Kinyo Co., Ltd.) on the surface of the photoconductor 11 with a nip pressure of 500 gf / cm ²
, And rotated for 10 seconds at a rotational speed of 15 mm / sec.
As a result, the adhesive force on the surface of the photoconductor 11 was reduced to 15 g · f. The obtained final color image showed the same performance as that of Example 95.

Examples 98 to 115 In Example 95, instead of 8 g of the resin particles (AL-4) in the resin dispersion liquid (L-3), the resin particles (AL) of the following Table-Q (total amount of 8 g). A color image was formed in the same manner as in Example 95 except that was used.

[0360]

[Table 34]

The color copy thus obtained had a clear image quality without background stains. That is, the toner image formed on the photoconductor has good image reproducibility and good image pick-up with no fog in the non-image area, and transfer of each transfer layer to coated paper Transferred completely without unevenness. Further, even if the copy paper is added or stamped,
The procedure was the same as for plain paper.

Example 116 The procedure of Example 73 was repeated, except that the transfer layer forming method by the hot melt coating method according to the following contents was used instead of the transfer layer forming method by the electrodeposition method. A color image copy was obtained. That is, the photoconductor 11 was mounted on the device in which the device shown in FIG. 6 is applied to the device shown in FIG. After forming a color image on the photoreceptor 11 in the same manner as in Example 73, an ethylene-vinyl acetate copolymer (vinyl acetate content 20% by weight, softening by the ring and ball method as the thermoplastic resin (A) for the transfer layer is formed. (Point 90 ° C.), a hot melt coater 30 of 120 ° C. is applied to the surface of the photoconductor 22 at a speed of 20 mm / sec, and cooling air is blown from the intake / exhaust unit 15 to cool the surface of the photoconductor 11. It was kept at 30 ° C. The thickness of the transfer layer 12 at this time was 5 μm.

The color image obtained on the coated paper 21 was clear, and the toner was completely covered with the thermoplastic resin as the transfer layer on the coated paper, so that it did not rub off.

Example 117 A color toner was prepared in the same manner as in Example 73 except that the transfer layer forming method by the electrodeposition method was changed to the transfer layer forming method by the following method. An image copy was obtained. That is, the photoconductor 11 is attached to the device in which the device shown in FIG. 5 is applied to the device shown in FIG. 2, and a separate paper (manufactured by Oji Paper Co., Ltd.) is used as the release paper 40. Vinyl) and [methyl methacrylate /
Methyl acrylate (6/4) weight ratio] (5
/ 5) Paper coated with a film thickness of 4 μm in a weight ratio was mounted on the device shown in the partial schematic view of FIG. 5, the pressure between rollers was 3 kgf / cm ² , the surface temperature was 80 ° C., and the passing speed was 10 mm /
Under the condition of seconds, the transfer layer 12 was transferred and formed on the photoconductor 11 on which the toner image 25 was formed.

The color image of the obtained coated paper 21 was a good image without fog, and the image strength was sufficient, as in Example 73. In addition, the writing and stamping properties were good.

Example 118 Ethylene used in the transfer layer 12 in Example 116
Instead of the vinyl acetate copolymer, each resin similar to that used in Examples 15 to 30 in Table L above was used,
When a transfer image forming operation was performed in the same manner as in Example 116, the same result as in Example 116 was obtained.

Example 119 In Example 117, in place of the separate paper provided with the transfer layer 12, a release paper: Sun release (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) having a film thickness of 4 μm was used. A color image was prepared in the same manner as in Example 117, except that a paper provided with each resin (A) similar to that used in Nos. 31 to 37 was used. The color image obtained was a clear image without background fog, and almost no deterioration of the image image was recognized as compared with the original. This means that even after the toner image is formed, the transfer layer is formed on the photoconductor using release paper and then transferred to the coated paper, so that the transfer layer at each transfer is transferred uniformly and completely. It indicates that no adverse effect on deterioration occurs.

Example 120 In Example 95, 5 g of 4,4′-bis (diethylamino) -2,2′-dimethyltriphenylmethane was used as an organic photoconductive material instead of the X-type metal-free phthalocyanine photoconductor. And the binder resin (B
-3) 4 g, 40 mg of the dye (D-1) used in Example 38 and 0.2 g of the anilide compound (C) used in Example 38 as a chemical sensitizer were added to a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride. It was dissolved to obtain a photosensitive layer dispersion liquid. This photosensitive layer dispersion is applied to a conductive transparent support (a polyethylene terephthalate support having a thickness of 100 μm and a vapor deposition film of indium oxide, a surface resistance of 10 ³ Ω) using a wire round rod, and then applied. An organic thin film having a photosensitive layer having a thickness of 4 μm was obtained.

A transferred image was formed in the same manner as in Example 73 except that this photosensitive member 11 was used in place of the photosensitive member used in Example 73. The color copied image of the obtained coated paper after transfer was clear without background fog and had good image strength and durability.

Example 121 The photoreceptor used in Example 40 and having a two-layered photosensitive layer (but not having a surface layer for imparting releasability) was charged to a surface potential of +500 V in a dark place. After making it He
A color toner image was formed on the photoconductor by the same operation as in Example 73 except that the exposure was performed with a 633 nm light using a —Ne laser so that the exposure amount on the plate surface was 30 erg / cm ² . Further, in order to form the transfer layer 12 thereon, 4.5 g of the resin particles (AL-17) and 2 g of the resin particles (AL-10) were used, and the transfer layer 12 having a thickness of 4.5 μm was formed in the same manner as in Example 1.
Was formed. In the same manner as in Example 73, a full-color image was formed on the coated paper 21. The obtained copy paper showed good performance as in Example 73.

Example 122 100 g of photoconductive zinc oxide, 15 g of the binder resin (B-5) used in Example 41, and the binder resin (B- used in Example 41
6) A mixture of 5 g, the following resin (P-40) 2 g, the dye (D-2) 0.01 g used in Example 41, salicylic acid 0.1 g and toluene 150 g was placed in a ball mill and dispersed for 2 hours to obtain a photosensitive layer dispersion liquid. did.

[0372]

[Chemical 40]

Next, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, with a wire bar, and was dried by touching with a finger, and then in a 110 ° C. circulation type oven for 20 seconds. The mixture was heated and further left under the condition of (50 ° C., 80% RH) for 8 hours. Next, it was left to stand in the dark for 24 hours under the condition of (25 ° C., 65% RH). The adhesive strength of this photoreceptor surface
It was 12 g · f. In order to further improve the releasability of the surface of this photoreceptor, a releasing compound (S-23) was attached in the same manner as in Example 95. As a result, the adhesive force on the surface of the photoreceptor 11 became 1 g · f or less.

Next, after corona-charging this photosensitive member to -600 V in a dark place, using the same digital image data as in Example 73, first, based on the information about yellow, this time in the positive mirror image mode, 780n using semiconductor laser 19
The plate surface was exposed to light of m at a dose of 25 erg / cm ² .
The residual potential of the exposed portion was -120V. Subsequently, yellow toner for Versatec 3000 (Xerox color electrostatic plotter) was diluted with 50 times Isopar H (Esso Standard Petroleum) and used, and a developing device having a pair of flat plate developing electrodes was used for the photoreceptor 11 surface side. A bias voltage of -200 V was applied to the electrodes to perform positive development so that the toner was electrodeposited on the unexposed areas, and then rinsed in a bath of Isopar H alone to remove stains on the non-image areas. The above process was repeated for each color of magenta, cyan and black.

Subsequently, the transfer layer 12 was formed by the same operation as in Example 1, and the transfer layer 12 was transferred to the primary receptor 20 and further to the coated paper 21 to form a color image on the coated paper 21. The obtained color image was a copy having a clear image quality without background fog, and the strength of the image area was sufficient.

[0376]

According to the present invention, by using a transfer layer in an electrophotographic color image forming method using an intermediate medium, a color image of high definition and high quality can be easily and stably obtained without color shift. be able to. Further, the obtained color copy is excellent in storage stability. Further, by taking into consideration the surface releasability of the photoreceptor or the intermediate medium (primary receptor), the components of the transfer layer, and the like, the releasability of the transfer layer can be further improved, and a more excellent image can be obtained.

Further, by devising the transfer layer, the transferability is further improved, the latitude at the time of transfer is expanded, and an excellent color image can be reproduced without selecting the final transfer target material. It is also possible to give the obtained color copy a writing property and a marking property similar to those of plain paper. Further, by forming the transfer layer on the photoconductor in the electrophotographic apparatus each time after the toner image is formed, the photoconductor can be repeatedly used, and the running cost can be reduced. Further, this can be implemented by a color image forming apparatus having a simple structure.

Further, by adsorbing or adhering the specific releasing compound (S) to the photoreceptor before the toner image formation,
It is possible to easily obtain a surface-releasing photoreceptor, which makes it possible to use a general-purpose electrophotographic photoreceptor and further reduce the running cost.

[Brief description of drawings]

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

FIG. 2 is a schematic view showing the method of the present invention and the entire apparatus.

FIG. 3 is a schematic partial view showing a step of forming a toner image on an electrophotographic photosensitive member by an electrophotographic process.

FIG. 4 is a schematic partial view for explaining a transfer layer forming method by an electrodeposition coating method.

FIG. 5 is a schematic partial view for explaining a transfer layer forming method by a transfer method.

FIG. 6 is a schematic partial view for explaining a transfer layer forming method by a hot melt coating method.

FIG. 7 is a schematic partial view showing a process of transferring a toner image together with a transfer layer to a primary receptor.

FIG. 8 is a schematic partial view showing a process of transferring a toner image on a primary receptor together with a transfer layer onto a final transfer material.

FIG. 9 is a schematic partial view of a device for supplying a compound (S).

[Explanation of symbols]

 1 Support 2 Photosensitive Layer 10 Compound (S) Applying Device 11 Electrophotographic Photosensitive Member 12 Transfer Layer (Thermoplastic Resin Layer) 12a Thermoplastic Resin Particle Dispersion 12b Thermoplastic Resin Film 12c Thermoplastic Resin Melt 14 Wet Development Unit Set 14y Yellow liquid developing unit 14m Magenta liquid developing unit 14c Cyan liquid developing unit 14k Black liquid developing unit 15 Intake / exhaust unit 15a Intake part 15b Exhaust part 16 Preheating means 17 Temperature adjusting means 18 Corona charging device 19 Semiconductor laser drawing device 20 Primary receptor 21 Transferred material 22 Backup roller for transfer 23 Backup roller for peeling 25 Toner image 30 Hot melt coater 30a Hot melt coater standby position 40 Release paper 50 Thermoplastic resin particle electrodeposition unit 111 Transfer roll 112 Metering roll 113 Compound (S) 122 Heating roller 123 Cooling roller

Claims (6)

[Claims] 1. A toner image of one or more colors is formed on an electrophotographic photosensitive member having a releasable surface by an electrophotographic process, and a peelable transfer layer is formed on the photosensitive member having the toner image. A color image forming method comprising: transferring a toner image together with a transfer layer to a primary receptor, and then transferring the toner image on the primary receptor together with a transfer layer onto a final transfer material. 2. An electrophotographic photosensitive member having a releasable surface by adsorbing or adhering a compound (S) containing at least a fluorine atom and / or a silicon atom on the surface of the electrophotographic photosensitive member. A toner image of one or more colors by an electrophotographic process, a releasable transfer layer is formed on a photoreceptor having the toner image, the toner image is transferred to a primary receptor together with the transfer layer, and then the primary image is transferred. A method for forming a color image, which comprises transferring the toner image on a receptor together with a transfer layer to a final transfer target material. 3. The surface of the electrophotographic photoreceptor having the releasable surface has an adhesive force of 100 gram · force or less according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method”, and the surface of the primary receptor. 3. The color image forming method according to claim 1 or 2, wherein the adhesive strength of is larger than the adhesive strength of the surface of the photoconductive layer. 4. The peelable transfer layer is formed by a hot melt coating method,
3. The color image forming method according to claim 1, wherein the color image forming method is formed by at least one of an electrodeposition coating method and a transfer method. 5. A means for forming a toner image of at least one color on an electrophotographic photoreceptor by an electrophotographic process, a means for providing a peelable transfer layer on the photoreceptor having the toner image, and a means for forming a toner image on a primary receptor. A color image forming apparatus comprising at least means for transferring a toner image together with a transfer layer and means for transferring the toner image together with the transfer layer from a primary receptor onto a final transfer material. 6. The color image forming apparatus according to claim 5, further comprising means for adsorbing or adhering the compound (S) containing at least a fluorine atom and / or a silicon atom on the surface of the electrophotographic photosensitive member.