JP3365812B2 - Color image forming method and electrophotographic photosensitive member used therefor - Google Patents

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 and an electrophotographic photosensitive member used therefor. More specifically, there is no color shift in a color image, and a toner image can be completely formed without lowering the image quality due to transfer. The present invention relates to a color image forming method which can be transferred to a transfer material and has good storage stability of a color copy, and an electrophotographic photoreceptor used therefor.

[0002]

2. Description of the Related Art Conventionally, a toner for a plurality of colors is successively overlaid on a surface of an electrophotographic photosensitive member using a developer for electrostatic photography to develop a color image to form a color image. Color image prints, color image copies or color proofs (proofs for printing) by transferring to
The method of doing is known.

Such developing methods include so-called dry developing methods and wet developing methods. The color image obtained using the wet development method has no color shift of each color as compared with the case of dry toner,
This is preferable because a high-resolution color image can be obtained, but it is extremely difficult to completely transfer the wet toner image directly from the surface of the photoconductor to the main paper. In order to solve this problem, JP-A-2-
Japanese Patent No. 272469 discloses a technique of supplying a non-aqueous solvent between a material to be transferred and a photoconductor at the time of transfer and then electrostatically transferring.

Further, JP-A-2-115865 and 2-
In JP-A-115866, after a transparent film is laminated on the surface of a photoconductor in advance, a wet toner image is formed on the film by an electrophotographic process, and then the film is peeled from the photoconductor and attached to plain paper to form an image. A method of transferring is disclosed. However, in this case, the film to be laminated is 9
Although a thickness of μm is suitable, the production and handling of a film having such a thickness are extremely troublesome, and it is necessary to take measures separately for that purpose.

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

On the other hand, Japanese 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 entire transfer layer onto the paper.

[0007]

In the method of forming a color image by transferring the toner image together with the transfer layer onto the main paper, it is necessary to satisfy various conditions in order to obtain a good color image. .. First, since a toner image is formed through an electrophotographic process, the film of the transfer layer must be set uniformly in order to uniformly perform charging and exposure, and the presence of the transfer layer does not deteriorate electrophotographic characteristics. is important. Further, it is desired that the transfer is easy in the transfer step, the peeling property between the photoconductor and the transfer layer is good, and the adhesiveness between the transfer target material is good. In particular, it is preferable that the latitude of the transfer conditions (heating temperature, pressure, transport speed, etc.) is wide.

Further, there is no problem even if a color copy is added or stamped, and the storage stability of the copy is good such that the transfer layer does not peel off even if it is put in various sheets and filed. Is desirable. However, in the conventional method, these characteristics have not been sufficiently taken into consideration, and they can be sufficiently satisfied in terms of color image pick-up property, transfer layer transfer property, color copy writing / printing property, storability, etc. Was not.

On the other hand, in the prior art, when the photoconductor 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. Therefore, it is desired to develop a method that can be repeatedly used without disposing of the photoreceptor.

The present invention has been made in view of the problems of the prior art. The invention according to claim 1 is capable of easily and stably producing a high-definition and high-quality color image without color misregistration. (EN) Provided is a color image forming method in which the transfer layer has good releasability from a photoconductor and adhesion to a material to be transferred, and which has good writing / printing properties and storability of a color copy. It is intended.

According to the second aspect of the invention, the transferability to the transfer material is further improved, the latitude of the transfer condition is expanded, and good transfer performance is exhibited regardless of the type of transfer material used. In addition, the object is to improve the writing / imprinting property of the color copy. The invention according to claim 3 is intended to further improve the releasability of the transfer layer itself. It is an object of the invention according to claim 4 to provide a photoreceptor having good releasability on the surface of the photoreceptor in the color image forming method.

According to a fifth aspect of the present invention, in the color image forming method, a transfer layer can be formed on the photoconductor in the transfer device each time, and the photoconductor can be repeatedly used, so that the running cost can be reduced. The purpose is to be able to. It is an object of the invention according to claim 6 to provide an electrophotographic photoreceptor having a transfer layer according to the present invention, which is used in the color image forming method of the present invention.

[0013]

The first object of the present invention is to form a toner image of one or more colors by an electrophotographic process on a transfer layer provided on the surface of an electrophotographic photosensitive member as described in claim 1. In the color image forming method in which the toner image is formed and transferred together with the transfer layer to the transfer material, the adhesive force of the surface of the photoconductor according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method” is 200 gram · for.
ce (gf) or less, and the transfer layer mainly contains a thermoplastic resin [AH] having a glass transition point of 30 ° C. to 140 ° C. and a thermoplastic resin [AL] having a glass transition point of −20 ° C. to 40 ° C. It has been found that a color image forming method is characterized in that the difference in glass transition point between the resin [AH] and the resin [AL] is 2 ° C. or more.

That is, in the electrophotographic color image forming method of the present invention, as shown in FIG.
A transfer layer 12 mainly containing thermoplastic resins [AH] and [AL] having different glass transition points or softening points is provided on the uppermost layer of the electrophotographic photoreceptor 11 composed of at least the support 1 and the photosensitive layer 2, The toner image 3 of at least one color is formed by the electrophotographic process, and then the toner image 3 is transferred together with the transfer layer 12 to another substrate (transferred material) 16 by thermal transfer to form a color copy.

Here, the transfer layer 12 used in the present invention is
Until the toner image 3 is formed by the electrophotographic process, the electrophotographic characteristics (chargeability, charge retention ratio in the dark, photosensitivity, etc.) must not be deteriorated, and in the next thermal transfer process, the transferred image can be easily transferred regardless of the type of the transferred material. It has thermoplasticity to be transferred to the material 16, and it does not cause any trouble even if it is added or imprinted as a color copy, and the transfer layer 12 is peeled off even if it is put in various sheets and filed. It is necessary that the storage stability of the copy is good, such as the occurrence of no such phenomenon.

A thermoplastic resin [AH] having a high glass transition point according to the present invention is used as a transfer layer made of a thermoplastic resin satisfying the above-mentioned characteristics, and a glass transition temperature of 2 ° C. or more in comparison therewith.
It has been found that it is extremely effective to use in combination with a thermoplastic resin [AL] having a low point . Here, when the abundance ratio of the thermoplastic resin [AH] and the thermoplastic resin [AL] is 5 to 90/95 to 10 (weight ratio), the transferability of the transfer layer to the transfer target material becomes good. It becomes, and it is preferable.

Further, as described in claim 2, a first layer containing a thermoplastic resin [AH] having a high glass transition point on the surface of the photoreceptor, and a thermoplastic resin [AL] having a low glass transition point on the first layer. ] The transferability to the transfer material is further improved and the latitude is expanded to the transfer conditions (heating temperature, pressure, transport speed, etc.) and the color is improved. It has become possible to easily perform the transfer regardless of the type of the transfer material to be an image copy.
Further, by adopting such a laminated constitution, the outermost surface side of the transfer layer transferred to the transfer-receiving material is mainly composed of a resin [AH] having a high glass transition point, so that the above filing characteristics are further improved. 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.

Further, as described in claim 3, the thermoplastic resin [AH] and / or [AL] contains at least one of a silicon atom and a fluorine atom (hereinafter, silicon atom and / or fluorine). By containing the polymerization component (s) (containing atoms) as the copolymer component, it has the effect of further improving the releasability of the resin itself. On the other hand,
In the present invention, in order to easily peel off the transfer layer, the surface adjacent to the transfer layer of the electrophotographic photosensitive member used is JIS Z
The value measured by the adhesive strength test in “0237-1980“ Adhesive tape / adhesive sheet test method ”is 200 gram ·
force (gf) or less, preferably 150 gf or less,
More preferably, it is 100 gf or less, and peelability between the photoconductive layer and the transfer layer can be exhibited.

In the above JIS adhesion test method,
The electrophotographic photosensitive member of the present invention is used as a "test plate", and the adhesive force is measured using an adhesive tape having a peeling speed of 120 mm / min and a width of 6 mm. "Adhesive strength" represents a value converted proportionally to a width of 10 mm. The adhesive strength is 200
As the electrophotographic plate-making printing plate photoreceptor having a gf or less,
As described in claim 4, specifically, the uppermost layer of the electrophotographic photosensitive member which is adjacent to the amorphous silicon electrophotographic photosensitive member or the transfer layer or adjacent to the transfer layer is a silicon atom having a good releasability and / or Alternatively, a photoreceptor containing a resin (polymer [P]) containing a fluorine atom can be used. As a result, transfer of the transfer layer is easily and completely achieved.

Here, the layer containing a resin containing silicon atoms and / or fluorine atoms may be a layer adjacent to the transfer layer and may or may not be a photosensitive layer. A non-photosensitive layer having the releasability may be provided on the photosensitive layer (thus, between the photosensitive layer and the transfer layer) in order to impart releasability to the transfer layer. Further, in the present invention, the polymer [P] comprises a polymer segment (A) containing 50% by weight or more of a silicon atom- and / or fluorine atom-containing polymer component, and a silicon atom- and / or fluorine atom-containing polymer. A copolymer obtained by binding at least one kind of polymer segment (B) containing a united component in an amount of 0 to 20% by weight is preferable in order to further improve the releasability from the transfer layer. .

On the other hand, in the present invention, as described in claim 5, instead of using the electrophotographic photoreceptor having the transfer layer on the surface in advance, the step of forming the transfer layer on the surface of the photoreceptor is also performed, Since the photoconductor after peeling the transfer layer can be repeatedly used, the electrophotographic process can be continuously performed in the apparatus without disposing the photoconductor, which is advantageous in reducing the running cost. The transfer layer is preferably formed on the photoreceptor in the same transfer device each time.

As a method for forming a transfer layer on the surface of the photoconductor in the transfer device, the above-mentioned thermoplastic resin [A
H] and a thermoplastic resin [AL] -containing resin, and a thermoplastic resin [AH] and a thermoplastic resin [AL] formed on another supporting material (release paper or the like). ]
A method for forming a transfer layer by transferring a transfer layer containing and to the surface of the photoreceptor, on the surface of the electrophotographic photoreceptor,
Examples thereof include a method in which particles having a thermoplastic resin [AH] as a main component and particles having a thermoplastic resin [AL] as a main component are electrostatically attached or electrodeposited to form a film.

Further, in the above electrodeposition method, the particles mainly containing the thermoplastic resin are dispersed and supplied in an electrically insulating liquid having a relative dielectric constant of 3.5 or less.
The film thickness of the transfer layer for the peeling layer can be easily adjusted to a thin film with a uniform thickness. Further, particles mainly containing the thermoplastic resin are supplied between the counter electrodes installed to face the electrophotographic photoreceptor, and electrophoresed on the electrophotographic photoreceptor according to a potential gradient applied from an external power source. By depositing or electrodepositing to form a film, it becomes easy to adjust a more uniform thin layer.

The transfer layer of the present invention will be described in detail below.
The transfer layer mainly containing the thermoplastic resins [AH] and [AL] used in the present invention is transparent and transparent to 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 the following, and may be colored. When the transferred image transferred to the transferred material is a color image (particularly a full-color image), a colorless and transparent transfer layer is usually used.

The releasable transfer layer is a thermoplastic resin comprising a thermoplastic resin [AH] having a glass transition point of 30 ° C. to 140 ° C. and a thermoplastic resin [AL] having a glass transition point of −20 ° C. to 40 ° C. Mainly containing and the resin [AH]
And the resin [AL] have a glass transition point difference of 2 ° C. or more. Preferably, the resin [AL] has a glass transition point lower than that of the resin [AH] by 5 ° C. or more. Here, the difference between the glass transition points when two or more kinds of the resin [AH] or the resin [AL] are contained is as follows.
H] having the lowest glass transition point and resin [AL]
It is the difference from the one with the highest glass transition point .

Further, the glass transition point of the thermoplastic resin [AH] is preferably 30 ° C to 100 ° C, particularly 33 ° C to 80 ° C. The glass transition point of thermoplastic resin [AL] is-
The temperature is preferably 10 ° C to 35 ° C, particularly preferably 0 ° C to 30 ° C.

Further, the thermoplastic resin [A
H] and the thermoplastic resin [AL] are present in a proportion of 5 to 90 /
95-10 (weight ratio), especially 10-70 / 90-30
(Weight ratio) is preferable. If the abundance ratio deviates from the above range, the transferability of the transfer layer to the transfer material becomes insufficient in any case, which is not preferable. The resin [AH]
Preferably has a weight average molecular weight of 1 × 10 ³ to 1 × 1.
The range is 0 ⁵ , more preferably 3 × 10 ^{3 to} 5 × 10 ⁴ . The weight average molecular weight of the resin [AL] is preferably 3 × 10 ³ to 1 × 10 ⁶ , and more preferably 5 × 10.
It is in the range of ^{3 to} 5 × 10 ⁵ .

In the present invention, any thermoplastic resin satisfying the above-mentioned physical properties may be used, and specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate copolymers, etc. Polymers and copolymers, allyl alkanoate polymers and copolymers, polymers and copolymers of styrene and its derivatives, olefin-styrene olefin-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile Copolymers, alkyl vinyl ether copolymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers , Itaconic acid diester polymers and copolymers, maleic anhydride copolymers,
Acrylamide copolymer, methacrylamide copolymer,
Hydroxyl group modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl group and carboxyl group modified polyester resin,
Butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, cyclized rubber-acrylic acid ester copolymer, copolymer containing a heterocycle (for example, furan ring, tetrahydrofuran ring, thiophene as a heterocycle Ring, dioxane ring, dioxofuran ring, lactone ring, benzofuran ring, benzothiophene ring, 1,3-
Dioxetane ring, etc.), cellulose resin, fatty acid-modified cellulose resin, epoxy resin and the like.

[0029] For example, "Plastic Material Lecture Series", Volumes 1 to 18 (1981), published by The Nikkan Kogyo Shimbun, "Polyvinyl Chloride" edited by Kinki Chemical Society Vinyl Section, published by Nikkan Kogyo Shimbun (1988), Hide Omori. Three "Functional Acrylic Resins" Techno System Co., Ltd. (1985), Eiichiro Takiyama "Polyester Resin Handbook" Nikkan Kogyosha (1)
1988), "Saturated Polyester Resin Handbook" edited by Kazuo Yuki, published by The Nikkan Kogyo Shimbun (1989), "Polymer Data Handbook <Applications>" edited by The Society of Polymer Science, Chapter 1, Rofukan (1986), Yuji Harasaki. Specific examples are given in "Latest and Binder Technology Handbook", Chapter 2, General Technology Center Co., Ltd. (1985).

In the present invention, the resin [AH] and the resin [AL] whose glass transition point and softening point are within the scope of the present invention can be arbitrarily selected and provided for the present invention. Further, the thermoplastic resin [AH] or [AL] used in the transfer layer of the present invention contains a fluorine-containing and / or silicon-containing substituent having an effect of improving the releasability of the resin itself. It is preferable that the united component (s) is further contained as a copolymer component in each resin described above.

The present invention includes both the substituent incorporated into the polymer main chain of the polymer and the substituent contained in the polymer side chain in the present invention. Preferably, the polymer component (s) is contained as a block in the copolymer of the thermoplastic resin. The content thereof is preferably the resin [A] ([AH] and [AH]
L]) is 3 to 40% by weight, more preferably 5 to 25% by weight, based on the total polymer components.

The fluorine atom and / or silicon atom-containing polymer component (s) is used as a resin [AH] and a resin [A].
L], the resin [AH]
It is more effective to be contained in. As a result, the releasability from the electrophotographic photoreceptor is further improved, and as a result, the transferability is improved. Hereinafter, the polymer component (s) that can be contained in the polymer and has the action of improving the releasability of the resin [A] itself will be described.

Examples of the substituent containing a fluorine atom include a monovalent organic residue such as chemical formula 1 and a divalent organic residue such as chemical formula 2.

[0034]

[Chemical 1]

[0035]

[Chemical 2]

Examples of the substituent containing a silicon atom include a monovalent or divalent organic residue such as Chemical formula 3 and the like.

[0037]

[Chemical 3]

However, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R
^15's may be the same or different and each represents an optionally substituted hydrocarbon group or an -OR ¹⁶ group (R ¹⁶ represents the same content as the hydrocarbon group of R ¹¹ ). R ¹¹ , R ¹² , R
¹³ , R ¹⁴ and R ¹⁵ are alkyl groups having 1 to 18 carbon atoms which may be substituted (for example, 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-trifluoropropylethyl group, 2-methoxyethyl group, 3-bromopropyl group, 2-methoxycarbonylethyl group, 2,2,2,2
2 ′, 2 ′, 2′-hexafluoroisopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, 2-methyl-1-propenyl, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), carbon number 7
To 12 optionally substituted aralkyl groups (eg,
Benzyl group, phenethyl group, 3-phenylpropyl group,
Naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), substituted with 5 to 8 carbon atoms An alicyclic group (for example, a 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, ethoxy Carbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.).

In the —OR ¹⁶ group, R ¹⁶ has the same meaning as the hydrocarbon group for R ¹¹ . Further, the organic residue containing a fluorine atom and a silicon atom may be combined and configured, and in that case, they may be directly bonded or may be combined via another linking group. .. Specific examples of the linking group include a divalent organic residue, and -O
-, - S -, - N (d 1) -, - SO -, - SO 2 -,
-COO-, -OCO-, -CONHCO-, -NHC
^{ONH -, - CON (d 1} ) -, - SO 2 (d 1) - the linking group may be interposed selected from such a divalent aliphatic group or a divalent aromatic group, or these It represents an organic residue composed of a combination of divalent residues. Here, d ¹ represents the same content as R ¹¹ .

Examples of the divalent aliphatic group include the groups represented by Chemical formula 4.

[0041]

[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 represents an alkyl group having 1 to 4 carbon atoms, a -CH ₂ Cl or -CH ₂ Br.

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

Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1,3-
An oxazoline ring etc. are mentioned. Next, specific examples of the repeating unit having a substituent containing a fluorine atom and / or a silicon atom as described above are shown below. However, the scope of the present invention is not limited to these. The following (s
-1) to (s-32) in each specific example R
_f represents a group of any of (1) to (11) shown below, and b represents a hydrogen atom or a methyl group.

[0045]

[Chemical 5]

However, in the above (1) to (11), R
_{f'represents the} groups represented by the above (1) to (8), and n is 1
Shows the integer of -18, m shows the integer of 1-18, l shows the integer of 1-5.

[0047]

[Chemical 6]

[0048]

[Chemical 7]

[0049]

[Chemical 8]

[0050]

[Chemical 9]

[0051]

[Chemical 10]

The polymer component (s) is preferably contained in the resin [A] in blocks. Preferred embodiments of the so-called block type copolymer in the resin [A] will be described below. That is, any resin may be used as long as the polymer component (s) containing a fluorine atom and / or a silicon atom is composed of a block in the resin [A]. Here, "to be composed of a block" means that the polymer has a polymer segment containing 70% by weight or more of a fluorine atom and / or a silicon atom, for example, an AB type block as shown in Chemical formula 11 , A-B-A type block, B-A-B
Examples include mold blocks, graft blocks, star blocks, and the like.

[0053]

[Chemical 11]

These various block copolymers [A] are
It can be synthesized according to a conventionally known polymerization method. For example, W. J. Burrant, A.A. S. Hoffman "Block an
d Graft polymers "(1986, Reuhold), R.D.
J. Cevesa “Block and Graft Copolymers” (196
2 years, Butterworths), D.M. C. Allport, W.A. H. J
ames "Block Copolymers" (1972, Applied Sc
i), A. Noshay, J .; E. McGrath "Block Copolym
ers ”(1977, Academis Press.), G. Huvter
g, D.I. J. Wilson, G .; Riess, NATO ASI
ser. SerE. 1985 , 149, V.I. Perces,
Applid. Polymer Sci. 285 , 95 (1985) and other publications and reviews. 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,
T. E. Hogeu-Esch, J. et al. Smid "Recent Advances
in Anion Polymerization "(1987, Elsevier
(New York), Yoshio Okamoto, Kobun, 38 , 912 (19)
89), Mitsuo Sawamoto, Polymer, 38 , 1018 (198).
9), Tadashi Narita, Kogaku, 37 , 252 (1988),
B. C. Anderson, et al., Macromolecules 14 ,
1601 (1981), S.I. Aoshima, T.A. Higasimur
a, Macromolecules 22 , 1009 (1989) and the like.

Further, hydrogen iodide / iodine-based io
For the polymerization reaction, see T.W. Higasimura at al., Mak
romol. Chem., Macromol. Symp.,Thirteen/14457
(1988), Toshinobu Higashimura, Mitsuo Sawamoto, Journal of Polymer ScienceFour
6189 (1989) and the like. group
For the transfer polymerization reaction, see D. Y. Sogah et al., Ma
cromolecules,20, 1473 (1987), O.I. W.
Webster, D.M. Y. Sogah, polymer,36, 808 (1
987), M.A. T. Reetg et al., Angew. Chem. I
nt. Ed. Eugl.259108 (1986), JP-A-6
3-97609 and the like.

The living polymerization reaction using the metalloporphyrin complex is described in T.W. Yasuda, T. Aida, S. I
noue, Macromolecules, 17 , 2217 (198)
4), M.A. Kuroki, T .; Aida, S. Inoue, T .; A
nn. Chem. Soc. 109 , 4737 (1987), M.S.
Kuroki et al., Macromolecules, 21 , 3115.
(1988), M.A. Kuroki, I. Inoue, Synthetic Organic Chemistry, 47 , 1017 (1989) and the like.

Further, regarding the ring-opening polymerization reaction of the cyclic compound, S. Kobayashi, T .; Saegusa "Ring Opening
Pollymerization "(1984, Applied Scenc
e Publishers Ltd., W.M. Seeliger et al., Ange
w. Chem. Int. Ed. Engl. 5 , 875 (196
6), S. Kobayashi et al., Poly. Bull. 13 , 4
47 (1985), Y. Chujo et al., Macroromolecu
les, 22 , 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 (1)
988), Shunichi Hinomori, Ryuichi Otsu, Polym. Rep. Jap.
37 , 3508 (1988), JP-A-64-111,
Japanese Patent Laid-Open No. 64-26619, M.I. Niwa, Macroromolecu
les, 189 , 2187 (1988) and the like.

[0059] 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 (1989), O.I. Nuyken et al., Macromol.
Chem., Rapid. Commun. 9 , 671 (1988), Yasuo Moriya et al. “Reinforced Plastics” 29 , 907 (19)
), Ryohei Oda "Science and Industry" 61 , 43 (1987)
Etc.

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), edited by The Society of Polymer Science, Japan. Polymer Alloy "(1981
Year, Tokyo Kagaku Dojin) etc. For example, a method of grafting a polymer chain with a polymerization initiator, chemical actinic rays (radiation, electron beam, etc.), mechanochemical reaction in mechanical application, etc., polymer chains and functional groups of polymer chains There is known a method of grafting by utilizing a chemical bond (so-called interpolymer reaction), a method of polymerizing a macromonomer and grafting.

Specific examples of the grafting method using a polymer include T.I. Shota et al., J. Appl.Poly
m. Sci. 13 , 2447 (1969), W.M. H. Buck
, Rubber Chemistry and Technology, 50 , 1.
09 (1976), Takeshi Endo, Tsutomu Uezawa, Journal of Japan Adhesion Association,
24 , 323 (1988), Takeshi Endo, ibid. 25 , 40
9 (1989) and the like.

As a method of carrying out a polymerization reaction and grafting using a macromonomer, specifically, P. Dreyfus
s & R. P. Quirk, Encycl. Polym. Sci. En
g., 7 , 551 (1987), p. F. Rempp, E.
FraNTA, Adv. Polym. Sci., 58 , 1 (198)
4), V. Percec, Appl. Poly. Sci., 285 , 9
5 (1984), R.A. Asami, M .; Takari, Macromo
L. Chem. Suppl., 12 , 163 (1985), p. R
empp. et al., Macromol. Chem. Suppl., 8 , 3 (1
985), Yusuke Kawakami, Chemical Industry, 38 , 56 (198).
7), Yuya Yamashita, High Polymer, 31 , 988 (1982),
Kobayashi Shiro, Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of Japan Adhesion Society, 18 , 536 (1982), Koichi Ito, Polymer Processing, 35 , 262 (1986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No. 10, 5, edited by Yuya Yamashita "Chemistry and Industry of Macromonomers" (1989)
Ed., PC Corporation, edited by Takeshi Endo, "Molecular Design of New Functional Polymers", Chapter 4 (1991, CM.
C. Co., Ltd., Y. Yamashita et al., Polym. Bul
l. 5 , 361 (1981) and the like.

The synthesis method of the star block copolymer is as follows:
For example, M. T. Reetz, Angew. Chem. Int. Ed. Eng
L., 27 , 1373 (1988), M.A. Sgwarc "Car
banions, Living Polymers and Electron Transfe
r Prodesses "(1968, Wiley. New York),
B. Gordon et al., Polym. Bull. 11 , 349 (1
984), R.A. B. Bates et al., J. Org. Chem.
44 , 3800 (1979), Y. Sogah, A.A. C.
S. Polym. Rapr. 1988 , No. 2, 3, J. W. M
Alys. Polym. Bull. 23 , 247 (1990), I.S.
M. Khan et al., Macromolecules, 21 , 2684.
(1988), A. Morikawa, Macromolecules, 2
4 , 3469 (1991), Akira Ueda, Toru Nagai, Polymer,
39 , 202 (1990), T.W. Otsu, Polym. Bul
l. 11 , 135 (1984) and the like. However, the synthesis method of the block copolymer [A] of the present invention is not limited to these methods.

Further, 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, rosin, petroleum resin, silicone oil, etc. for adjusting adhesiveness, such as boribten, DOP, DBP, low molecular weight styrene resin, low molecular weight Polyethylene wax, microcrystalline wax, paraffin wax, etc., and polymeric hindered polyphenols, triazine derivatives, etc. can be added as antioxidants. For details, see “Actual Hot Melt Adhesion” (Hiroshi Fukada, Polymer Publishing, 1983) 29
~ 107 pages.

The thickness of the transfer layer according to the present invention is preferably 0.1 to 10 g / m ² , more preferably 0.5 to 7 g / m ² .
It is in the range of m ² . 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. Further, when the transfer layer has a laminated structure of the resin [AH] and the resin [AL], the first layer containing the resin [AH] and the second layer containing the resin [AL] are each at least 0. while holding 5 g / m ² or more film thickness, it is preferable that the total thickness and 1 to 10 g / m ^2. When each of the first layer and the second layer is 0.5 g / m ² or less, the effect of improving the peelability of the transfer layer is reduced.

Next, the electrophotographic photosensitive member which is an electrophotographic member to be provided with the transfer layer will be described. As a photoconductor,
Any conventionally known one can be used. What is important is that the transfer layer is provided on the photoreceptor (or the uppermost layer of the photoreceptor) to be provided, and the surface of the layer adjacent to the transfer layer is provided with peelability. Therefore,
In the present invention, as described above, the adhesive force of the surface is JIS
It is required to be 200 gf or less according to "Adhesive tape / adhesive sheet test method" of 0237-1980.

As the photosensitive member having a peelable surface, a photosensitive member using amorphous silicon as a photoconductor is first mentioned. Further, when another photoconductor is used, another layer (hereinafter referred to as an overcoat layer for convenience sake) having peelability is provided on the upper layer of the photoconductor constituting the photoconductor layer. There is a method of providing or a method of modifying the surface of the uppermost layer of the photoconductive layer (which may be either a single layer of photoconductor or a laminate of photoconductors) to a state where releasability is exhibited.

The method of imparting releasability to the overcoat layer or the uppermost photoconductive layer is to use a polymer containing a silicon atom and / or a fluorine atom as the binder resin for the layer, or to use a silicon atom and / or a fluorine atom. There is a method of using a small amount of a block copolymer containing a polymer segment composed of a fluorine atom-containing polymer component (hereinafter referred to as a surface unevenly distributed copolymer) together with another binder resin. Further, such a resin containing silicon and / or fluorine atoms may be used in the form of particles.

In particular, when the overcoat layer is provided, the adhesion between the photoconductor layer and the overcoat layer can be sufficiently maintained, and therefore, the surface unevenly distributed block copolymer is used in combination. Is preferred. The above-mentioned surface unevenly distributed copolymer is usually used in an amount of 0.1 parts by weight per 100 parts by weight of the total composition of the overcoat layer.
It can be used in combination with another binder resin in a ratio of 1 to 20 parts by weight.

Specifically, in a PPC photosensitive member using a dry toner, a surface layer is formed on the photosensitive member, which is known as one means for maintaining durability of the photosensitive member surface against repeated use of the photosensitive member. A method similar to the content of the protective layer in the method of providing and protecting can be used. For example, known examples of protective layers using silicone block copolymers include JP-A-61-95358, JP-A-55-83049, JP-A-62-89771,
JP-A-61-189559 and JP-A-62-75461
JP-A-62-75461, JP-A-61-1395.
56, JP-A-62-139557, JP-A-62-2
Each publication such as 08055 is cited. Further, as a protective layer using a fluorine-based block copolymer, Japanese Patent Laid-Open No.
1-116362, JP-A 61-117563, JP-A 61-270768, JP-A 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, there are disclosed in JP-A-63-249152 and JP-A-63-22.
Each publication of No. 1355 is mentioned.

Further, the method of modifying the surface of the uppermost photoconductive layer to a state in which peelability is exhibited is a method of using a so-called dispersion type photoconductor in which at least a photoconductor and a binder resin are used. Effectively applied. That is, in the layer constituting the uppermost layer of the photoconductive layer, a resin of a block copolymer containing 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
Alternatively, by allowing at least one of the resin particles containing the polymer component containing a silicon atom to coexist, these materials are concentrated / migrated to the surface and unevenly distributed, so that the surface can be modified to a peelable surface. As for the copolymer and the resin particles, the same as those described in Japanese Patent Application No. 3-249819 can be mentioned.

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 heat and / or photocuring 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. Regarding the polymer segment containing the heat and / or photocurable group-containing component, Japanese Patent Application Nos. 3-259430 and 3-2.
The same as those described in No. 89649 and No. 3-289648 can be mentioned. Alternatively, 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, in addition to the electrophotographic photosensitive member mainly containing amorphous silicon, the fluorine atom and / or the silicon atom of the present invention effective for modifying the surface of the photosensitive member is obtained by the above-mentioned method. The polymer containing the polymer component contained therein is composed of resin (hereinafter referred to as resin [P]) or resin particles (hereinafter referred to as resin particle [L]).

When the polymer is a random copolymer, the content of the polymer component containing a fluorine atom and / or a silicon atom is preferably at least 60% by weight based on the total polymer component, It is preferably 80% by weight or more. More preferably, the polymer contains a polymer segment (A) containing 50% by weight or more of a polymer component containing a fluorine atom and / or a silicon atom and 0 to 20% of the polymer component containing a fluorine and / or silicon atom. It is a block copolymer in which the polymer segments (B) contained in the amount of wt% are linked by blocks. More preferably, the block copolymer is characterized by containing at least one polymer component containing at least one photo- and / or thermosetting functional group in the segment (B) in the block copolymer. is there.

In these block copolymers, it is preferable that the segment (B) contains no fluorine atom and / or silicon atom-containing polymer component. In the polymer of the present invention, as compared with a random copolymer, by using a block copolymer containing the polymer segments (A) and (B) (surface uneven distribution type copolymer), the surface peelability itself Is maintained, and further, the peelability is maintained.

That is, when a coating film is formed by coexisting a small amount of the resin and / or resin particles containing a fluorine atom and / or a silicon atom of the present invention, the present invention can be easily obtained before the drying step after coating. Resin [P] and resin particles [L] of
It is transferred to and concentrated on the surface of the film, and the surface of the film is modified so that it can exhibit peelability. As described above, when the polymer segment containing a fluorine atom and / or a silicon atom is blocked in the resin [P], the other polymer segment (a polymer containing a fluorine atom and / or a silicon atom). However, even when the transfer layer coating film is formed, these resins do not interact with each other even when the transfer layer coating film is formed. The further transition to is suppressed or eliminated, and the transfer layer can clearly form and maintain the interface of the photoconductive layer (that is, the anchor effect).

Further, the segment (B) of the block copolymer
By using a polymer containing a curable group therein, and cross-linking between the polymers at the time of film formation, the effect of further maintaining the peeling property at the interface between the photoreceptor and the transfer layer is exerted. . The polymer may be used as resin particles as described above.
Preferred resin particles [L] are resin particles dispersed in a non-aqueous solvent. Such resin particles contain a polymer component containing a fluorine atom and / or a silicon atom, a polymer segment insoluble in the non-aqueous solvent, and a polymer component containing a fluorine atom and / or a silicon atom. Also 20%
The following may be mentioned, in which a polymer segment soluble in the non-aqueous solvent is bonded.

In the case of the resin particles according to the present invention, the action of the insolubilized polymer portion causes migration and concentration on the surface, and further the polymer portion soluble in the non-aqueous solvent bound to the particles is formed. As in the case of the above-mentioned resin, it interacts with the binder resin and acts as an anchor effect. Furthermore, by containing a curable group in the polymer or in the binder resin, transfer to the transfer layer is eliminated.

The polymer component containing a substituent containing a fluorine atom and / or a silicon atom of the present invention is a polymer component incorporated in the polymer main chain of the polymer or a substitution of a side chain of the polymer as the substituent. Both of those contained as a group are included. Specific examples thereof include those having the same content as the polymer component (s) that can be contained in the resin [AH] or [AL].

The case where the resin [P] and the resin particles [L] of the present invention are so-called surface unevenly distributed copolymers will be described. In the block (A) containing the silicon atom and / or the silicon atom-containing polymer component, the polymer component is at least 50 in the total amount of the entire block (A).
%, Preferably 70% by weight or more, more preferably 80% by weight or more.

In the other block (B) formed by combining with the block (A), the content of the fluorine atom- and / or silicon atom-containing polymer component is 20% by weight or less of the total amount of the block (B). Yes, and preferably 0% by weight.
The weight ratio of the block (A) to the other block (B) is 1 to
The ratio is 95: 5 to 99 (weight ratio), preferably 5 to 90:10 to 95 (weight ratio). Outside this range, both the resin [P] and the resin particles [L] of the present invention have a reduced concentration effect and anchor effect on the surface of the uppermost layer of the photoconductive layer, and as a result, the releasability of the transfer layer is reduced. Will fall.

The weight average molecular weight of the resin [P] is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 1 ×.
It is 10 ^{4 to} 5 × 10 ⁵ . On the other hand, the weight average molecular weight of the block [A] part in the resin [P] is at least 1 ×.
It is preferably 10 ³ or more. On the other hand, resin particles [L]
Has an average particle size of preferably 0.001 to 1 μm, more preferably 0.05 to 0.5 μm.

Preferred embodiments of the so-called surface unevenly distributed copolymer in the resin [P] of the present invention will be described below. That is, any resin may be used as long as the polymer component containing a fluorine atom and / or a silicon atom is constituted by a block in the resin [P]. Here, being composed of blocks means that the polymer has a polymer segment containing 50% by weight or more of a fluorine atom and / or a silicon atom, and for example, as in the case of the resin [A] described above. , A
-B type block, ABA type block, BAB type block, graft type block, star type block and the like.

These various block copolymers [P] are
It can be synthesized according to a conventionally known polymerization method, and specifically, the same methods as those cited for the resin [A] containing the polymer component (s) in a block can be mentioned. Next, a preferred embodiment of the resin particles [L] of the present invention will be described. As described above, the resin particles [L] are preferably a fluorine atom and / or silicon atom-containing polymer portion (A) insoluble in a non-aqueous solvent and a fluorine atom and / or silicon soluble in the solvent. It is composed of a polymer portion (B) containing few atoms, and is a fine particle having an average particle diameter of 1 μm or less. Furthermore, the polymer component (A) part constituting the insoluble part of the resin particles may form a crosslinked structure.

As a preferred method for specifically synthesizing the above-mentioned particles [L], there may be mentioned the non-aqueous dispersion polymerization method described for the above-mentioned non-aqueous thermoplastic dispersed particles. The same thing as the content that was done is mentioned. The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or in combination of two or more.

Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, benzyl alcohol, acetone,
Ketones such as methyl ethyl ketone, cyclohexanone, diethyl ketone, ethers such as diethyl ether, tetrahydrofuran, dioxane, carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, hexane, octane, decane, dodecane, tridecane , Aliphatic hydrocarbons having 6 to 14 carbon atoms such as cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane,
Examples include halogenated hydrocarbons such as 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. Can be Further, specifically, a monomer (a) corresponding to the polymer component forming the block (A) and a monomer (b) corresponding to the polymer component forming the block (B) The non-aqueous solvent which dissolves the monomer (a) but becomes insoluble when polymerized is used to prepare a peroxide (eg, benzoyl peroxide, lauroyl peroxide, etc.), an azobis compound (eg, azobisisobutyronitrile, azobisisonitrile). The polymerization may be carried out by heating in the presence of a polymerization initiator such as valeronitrile) or an organometallic compound (eg butyllithium). Alternatively, the above-mentioned monomer (a) and the polymer [PB] composed of the block (B) may be polymerized in the same manner as above.

Furthermore, the inside of the insolubilized polymer particles of the resin particles [L] of the present invention 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 the polymer component (A) with various crosslinking agents or curing agents, and a polymerization reaction in which at least a monomer (a) corresponding to the polymer component (A) is contained. In the case of carrying out, a method of forming a network structure between molecules by allowing a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups to coexist, and the polymer component (A) And a polymer containing a component containing a reactive group are crosslinked by a polymerization reaction or a polymer reaction.

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 Society of Japan, "Polymer Data Handbook, Basic Edition", Baifukan (1986) and the like can be used. For example, an organic silane-based compound (for example, vinyltrimethoxysilane,
Silane coupling agents such as vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-aminopropyltriethoxysilane), polyisocyanate compounds (for example, toluylene diisocyanate) Nato, o-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.), polyol compound (For example, 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,
1-trimethylolpropane, etc.), polyamine compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds and Epoxy resin (for example, "New epoxy resin" edited by Hiroshi Kakiuchi, Shokoido (1985), "Epoxy resin" edited by Kuniyuki Hashimoto)
Compounds described in Nikkan Kogyo Shimbun (Published in 1969), etc.), melamine resins (for example, compounds described in “Yuria Melamine Resin” edited by Ichiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbun (1969)) , Poly (meth) acrylate compounds (eg, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura, “Oligomer” Kodansha (Published in 1976), Eizo Omori “Functional Acrylic Resin” Techno System (published in 1985), etc. Compounds.

Further, a polyfunctional monomer containing two or more polymerizable functional groups coexisting by the above method [also referred to as polyfunctional monomer (d)] or a polyfunctional oligomer polymerizable functional group. Specifically, CH ₂ ═CHCH
_{2 -, CH 2 = CHCOO-,} CH 2 = CH-, CH 2
_{= C (CH 3) -COO-,} CH (CH 3) = CHCO
_{O-, CH 2 = CHCONH-, CH} 2 = C (CH 3)
_{-CONH-, CH (CH 3) =} CHCONH-, CH
_{2 = CHOCO-, CH 2 = C} (CH 3) -OCO-,
_{CH 2 = CHCH 2 OCO-, CH} 2 = CHNHCO
_{-, CH 2 = CHCH 2 NHCO-} , CH 2 = CHSO
_{2 -, CH 2 = CHCO-,} CH 2 = CHO-, CH 2
= CHS- and the like can be mentioned. 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, a monomer or oligomer having the same polymerizable functional group, a styrene derivative such as divinylbenzene or trivinylbenzene: a polyhydric alcohol. (For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 20
0, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or polyhydroxyphenols (eg hydroquinone, resorcin, catechol) And their derivatives)
Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (eg malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) Vinyl esters, allyl esters, vinyl amides or allyl amides: polyamines (eg ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and carboxylic acids containing vinyl groups (eg methacrylic acid, acryl) 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 (for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, and arylloyl). Propionic acid, itaconiloylacetic acid, itaconiloylpropionic acid, carboxylic acid anhydride, etc.) and alcohol or amine reactants (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropione) Acid or the like) -containing ester derivative or amide derivative (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate,
Allyl methacrylate, allyl acrylate, itaconic acid allyl, 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 based on the total amount of the monomer (a) and other monomers coexisting with the monomer (a). Polymerization is carried out using 10 mol% or less, preferably 5 mol% or less, to form a resin.

Further, in the case of forming a chemical bond by the reaction of reactive groups between polymers and bridging between 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 dispersion polymerization, since monodisperse particles having a uniform particle size are obtained and fine particles of 0.5 μm or less are easily obtained, a polyfunctional monomer is used as a method for forming a network structure. The method used is preferred. That is, the above-mentioned monomer (a), monomer (b) and /
Alternatively, the compound [PB] can be synthesized by further allowing the polyfunctional monomer (d) to coexist and performing a polymerization granulation reaction. Furthermore, when the polymer [PB] composed of the block (B) is used, a monomer (a) is added to a side chain in the polymer main chain of the polymer [PB] or one end of the main chain. ), A polymer having a polymerizable double bond group [P
B '] is preferred.

The polymerizable double bond group may be any as long as it has a copolymerization 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 C
_{OOH) -COO-, CH 2 = C} (p) -CONH-,
_{CH 2 = C (p) -CONHCOO-} , CH 2 = C
(P) -CONHCONH-, C (CH 3) H = CHC
_{ONH-, CH 2 = CHCO-, CH} 2 = CH (C
H ₂ ) _n -OCO- (n is 0 or an integer of 1 to 3), CH
_{2 = CHO-, CH 2 = CHC} 6 H 4 - ( represent where p is -H or -CH ₃₎ the like.

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, and Japanese Patent Application No. 2-177.
It can be carried out in the same manner as the method described in the specification such as No. 449.

The total amount of the polymerizable compound is about 5 to 8 parts by weight, preferably 10 to 100 parts by weight of the non-aqueous solvent.
It is 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 30
It is about 180 ° C, preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours.

Next, a light and / or thermosetting group is contained in the binder resin [P] of the present invention as a polymer component or in combination with the resin [P] as the curable group-containing resin. A case will be described. Examples of the polymer component containing at least one photo- and / or thermosetting group that can be contained in the binder resin [P] include those described in the above-mentioned known documents. Specific examples thereof include the same as those described as the polymerizable functional group.

The polymer component containing at least one light and / or curable group contained in these polymers is the polymer segment [B] 100 of the block copolymer.
0.1 to 40 parts by weight, preferably 1 to 3 parts by weight.
0 parts by weight. 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 film interface with the surface portion of the photoconductive layer during the coating of the transfer layer is insufficiently retained, resulting in the peeling of the transfer layer. Affect sexuality. 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 light and / or thermosetting group-containing block copolymer [P] is used in an amount of 40 parts by weight based on 100 parts by weight of the total binder resin.
It is preferable to use more than weight%. The resin [P] is 40
If it is less than wt%, the electrophotographic characteristics will deteriorate. Further, in the present invention, a photo- and / or thermosetting resin [D] together with the above-mentioned fluorine atom and / or silicon atom-containing resin.
You may use together. The light and / or thermosetting group contained in the resin [D] may be any one, but specific examples thereof include those having the same content as the curable group contained in the block copolymer.

The light and / or thermosetting resin [D] may be any conventionally known curable resin, for example,
An example thereof is a resin containing a functional group similar to the curable group described for the block copolymer [P] of the present invention. These conventionally known binder resins for electrophotographic photosensitive layers are, for example, Ryuji Shibata, Jiro Ishiwata, Kogaku, Vol. 17, Vol. 278.
Page (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No.8), Koichi Nakamura, "Practical Technology of Binder for Recording Material", Chapter 10, C.I. M. C. Publishing (1
1985), Electrophotographic Society ed., "Present Symposium on Organic Photoreceptors for Electrophotography" Proceedings (1985), Hiroshi Komon, "Recent Developments and Practical Applications of Photoconductive Materials and Photoreceptors", Japan Science Information Co., Ltd. ) (1986), edited by The Institute of Electrophotography "Basics and Applications of Electrophotographic Technology" Chapter 5, Corona Publishing Co., Ltd. (1988)
Year), D. Tatt, S.H. C. Heidecker, Tappi, 49
(No. 10), 439 (1966), E.I. S. Balta
zzi, R .; G. Blanclotte et al, Phot. Sci. E
ng. 16 (No. 5), 354 (1972), Nguyen
Jang Kae, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography 18
(No. 2), 22 (1980) and the like, and the compounds described in the reviews.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Derivatives, polymers and copolymers, 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 specifically, Takeshi Endo, "Refinement of Thermosetting Polymers" (CMC, 1986), Yuji Harazaki, "Handbook of Latest Binder Technology," Chapter II-1 ( General Technology Center, 1985), Takayuki Otsu "Synthesis and design of acrylic resin and new application development" (Chubu Business Development Center Publishing Department 1985), Eizo Omori "Functional acrylic resin" (Technosystem 1985), etc. Conventionally known resins cited in the above review are used.

As described above, in the present invention, the overcoat layer or the photoconductive layer contains at least one binder resin [B] and at least one block copolymer [P] for the surface interface. It is preferable that a small amount of a light and / or thermosetting resin [D] and / or a cross-linking agent coexist in order to improve the curing of the film. The amount used is preferably 0.01 to 20% by weight, and more preferably 0.1 to 15% by weight, based on the total amount of the binder resin [B] and the block copolymer [P]. If the amount used is 0.01% by weight or less, 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.

Further, it is preferable to use a crosslinking agent in combination,
As the cross-linking agent, a compound usually used as a cross-linking agent can be used. Specifically, "Crosslinking Agent Handbook" edited by Fuzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981),
The compounds described in, for example, "Polymer Data Handbook Basic Edition", Baifukan (1986), edited by The Photobranch Society can be used.

For example, an organic silane compound (eg, vinyltrimethoxysilane, vinyltributoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropylethoxysilane, and other silane coupling agents), polyisocyanate compounds (eg, toluylene diisocyanate, o-toluylene disilane) Isocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high molecular polyisocyanate, etc.), polyol compound (for example, 1, 4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine compounds (for example, ethylenediamine, γ-hydroxypropene). Ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), titanate coupling compounds (eg tetrabutoxy titanate, tetrachloropoxy titanate, isopropyl tristearoyl titanate, etc.) aluminum coupling Based compounds (e.g. aluminum-butyrate,
Aluminum acetyl acetate, aluminum oxide octoate, aluminum tris (acetyl acetate), etc., polyepoxy group-containing compounds and epoxy resins (for example, "Epoxy Resin", edited by Hiroshi Kakiuchi, Shokoido (1985).
Compound published in "Epoxy Resin" edited by Kuniyuki Hashimoto (Nikkan Kogyo Shimbun) (published in 1969), melamine resin (for example, "Yuria Melamine Resin" edited by Ichiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbun (1969). (Compounds listed in annual publications), poly (meth) acrylate compounds (for example, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura "Oligomer" Kodansha (1976), Eizo Omori "Functional acrylic resin" Examples thereof include compounds described in Techno System (published in 1985), etc. Further, monomers having a polyfunctional polymerizable group (for example, vinyl methacrylate, acryl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinic acid). Ester, divinyl adipate, diacrylic succinate, 2- Chill vinyl methacrylate, trimethylolpropane trimethacrylate, divinylbenzene, pentaerythritol polyacrylate) and the like.

As described above, the uppermost layer (layer adjacent to the transfer peeling layer) of the photoconductive layer of the present invention is preferably cured after the film formation. The binder resin [B], the block copolymer [P], the curing 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, a well-known method can be mentioned as a polymer reaction by a combination of functional groups, and examples thereof include a combination of a functional group of group A and a functional group of group B as shown in the following table. However, it is not limited to this.

[0107]

[Table 1]

In the present invention, a reaction accelerator may be added to the binder resin, if necessary, in order to accelerate the crosslinking reaction in the photosensitive layer 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, dibutoxytin dilaurate, etc.), dithiocarbamic acid compound (diethyldithiocarbamate, etc.),
Tinoulam disulfide compounds (tetramethyltinouram disulfide, etc.), carboxylic acid anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butylsuccinic anhydride, 3,3 ′, 4,4′-tetracarboxylic acid benzophenonedione Anhydride, trimellitic anhydride, etc.) and the like. When the crosslinking reaction is in a polymerizable reaction mode, a polymerization initiator (peroxide, azobis compound, etc. may be mentioned.

The binder resin that can be used in the photoreceptor of the present invention may be any of the resins used in conventionally known electrophotographic photoreceptors, and the weight average molecular weight is preferably 5 × 10 5.
³ to 1 × 10 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10
^{It's five} . The glass transition point of the binder resin is preferably −40 ° C. to 200 ° C., more preferably −10 ° C.
It is 140 ° C. For example, Ryuji Shibata, Jiro Ishiwatari, Kogaku, Vol. 17, p. 278 (1968) Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No.8), Koichi Nakamura, "Practical Technology of Binders for Recording Materials", No. 1 Chapter 10, C.I.
H. C. Published (1985) edited by The Electrophotographic Society of Japan, "Presentation Symposium on Organic Photoreceptors for Electrophotography" (1985)
1) Hiroshi Kodomo, "Recent Development and Practical Use of Photoconductive Materials and Photoconductors", Japan Science Information Co., Ltd. (1986), The Electrophotographic Society, "Basics and Applications of Electrophotographic Technology," Chapter 5, Corona Publishing Co., Ltd. (stock)
(1988), D.I. Tatt, S.H. C. Heidecker, T
appi, 49 (No. 10), 439 (1966), E.I.
S. Baltazzi, R.A. G. Blanclotte et al, Phot
． Sci. Eng. 16 (No. 5), 354 (197)
2), Nguyen Chan Kay, Isamu Shimizu, Eiichi Inoue, Electrophotographic Society Journal 18 (No. 2), 22 (1980) and the like.

Specifically, olefin polymers and non-polymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Derivatives, polymers and copolymers, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers Polymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, itaconic acid diester polymers and copolymers , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymer, hydroxyl group modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl group and carboxyl group modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, 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.

In particular, as a binder resin for the photoconductor, a relatively low molecular weight (about 10 ³ to 10 ⁴ ) containing an acidic group such as a carboxyl group, a sulfo group or a phosphono group is used. By using the resin of 2) together, the electrostatic characteristics can be improved. 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,
-70761, a resin obtained by bonding an acidic group to one end of a polymer main chain, JP-A-2-67563, and JP-A-2-6753.
No. 36561, No. 2-238458, No. 2-2365
No. 62 and No. 2-247656, etc., and a resin containing an acidic group bonded to the end of the main chain of the graft copolymer, or a resin containing an acidic group in the graft portion of the graft copolymer, 3 An AB type block copolymer containing an acidic group in a block as described in JP-A-181948. Furthermore,
In order to make the mechanical strength of the photoconductive layer insufficient by using only these low molecular weight resins, it is preferable to use another medium to high molecular weight resin in combination. For example, Japanese Patent Laid-Open No. 2-6
Thermosetting resin forming a cross-linking structure between polymers described in JP-A-8561, resin partially having a cross-linking structure described in JP-A-2-68562, and graft type acidic group described in JP-A-2-69759. Examples thereof include resins that are bonded to the ends of the main chain of the copolymer. Further, by using a specific medium to high molecular weight resin, stable performance can be maintained even when the environment is significantly changed.
No. 954, No. 3-77954, No. 3-92861, and No. 3-53257, and a resin for binding an acidic group to the end of the graft portion of the graft copolymer or an acidic group of the graft copolymer. Resin contained in the graft part, the same 3
Examples thereof include graft-type copolymers containing an AB block-type copolymer composed of an acidic group-containing A block and an acidic group-free B block described in Nos. 206464 and 3-223762 in a graft portion. By using these 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 binder resin of the present invention is 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 may be high temperature and / or
Or it is a long time. Alternatively, it is preferable to further heat-treat after drying the coating solvent. For example, the treatment is performed at 60 ° C. to 150 ° 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 for curing a 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 "chemically 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. It is more preferable to emit light in the wavelength range of 310 nm to 500 nm, and a low-pressure, high-pressure or ultra-high-pressure mercury lamp, halogen lamp or the like is generally used. The light irradiation is usually performed for 10 seconds to 1 from a distance of 5 cm to 50 cm.
Irradiation for 0 minutes is sufficient.

The constitution and materials of the electrophotographic photosensitive member to be used in the present invention may be any conventionally known ones and are not limited. As the photoconductor, for example, "Basics and Applications of Electrophotographic Technology" edited by The Electrophotographic Society (Corona Publishing (1988)), Hiroshi Komon, "Recent Development of Photoconductive Materials and Photoconductors"
Practical use ”(published by Japan Scientific Information Co., Ltd., published in 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. But either is fine.
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 conventionally known inorganic photoconductive compounds such as zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, selenium, selenium-tellurium and lead silicon sulfide. Can be mentioned. When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used as the photoconductive compound, the binder resin is contained in an amount of 10 to 100 parts by weight, preferably 15 parts by weight, based on 100 parts by weight of the inorganic photoconductive compound. Used in a proportion of -40 parts by weight.

On the other hand, the organic compound may be any of the conventionally known compounds.
162, 62-51462, JP-A-52-243.
7, 54-19803, 56-107246,
No. 57-161863, etc., it has a photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye, and a binding resin, and the second one is JP-A-56-14.
6145, 60-17775, 60-1775
No. 2, No. 60-17760, No. 60-254142
No. 62-54266, those having a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent, and a binding resin, and JP-A-60-230147 and 6).
There is also known a two-layered photoconductive layer containing a charge generating agent and a charge transporting agent in separate layers, as described in, for example, 0-230148 and 60-238853.

The electrophotographic photoreceptor of the present invention may take any form of the above-mentioned photoconductive layer. In the case of the second example, the organic photoconductive compound referred to in the present invention functions as a charge transport agent. Examples of the organic photoconductive compound in the present invention include (a) a triazole derivative described in US Pat. No. 3,121,197, etc., and (b) US Pat. No. 318.
Oxadiazole derivatives described in Japanese Patent No. 9447,
(C) Imidazole derivative described in JP-B-37-16096, (d) US Pat. Nos. 3,615,402 and 3
No. 820989, No. 3542544, each Japanese Patent Publication No. 45-555, No. 51-10983, JP-A Nos. 51-93224, 55-108667, 55.
No. 156953, No. 56-36656, and the like, polyarylalkane derivatives described in (e) US Pat.
No. 180729, No. 4278746, JP-A Nos. 55-88064, 55-88065, and 49-.
No. 105537, No. 55-51086, No. 56-80
No. 051, No. 56-88141, No. 57-45545.
Nos. 54-112637, 55-74546 and the like, and the like, pyrazoline derivatives and pyrazolone derivatives, (f) U.S. Pat. No. 3,615,404, Japanese Patent Publication Nos. 51-10105, 46-3712, 47-2
No. 8336, JP-A Nos. 54-83435 and 54
Phenylene diamine derivatives described in JP-A-110836 and JP-A-54-1199925;

(G) US Pat. Nos. 3,567,450 and 3
No. 180703, No. 340597, No. 365585
No. 0, No. 4232103, No. 4175961, No. 4
No. 012376, Japanese Patent Publication No. Sho 49-35702, West German Patent (DAS) No. 1110518,
JP-B-39-27577, JP-A-55-144250
No. 56-119132, No. 56-22437, etc., arylamine derivatives,
(H) Amino-substituted chalcone derivatives described in US Pat. No. 3,526,501, etc., (i) US Pat. No. 35425
46, etc., N, N-bicarbazyl derivatives, (i) oxazole derivatives described in US Pat. No. 3,257,203, etc., (k) JP-A-56-4623.
4, a styrylanthracene derivative,
(L) Fluorenone derivatives described in JP-A-54-110837, (m) US Pat. No. 3,717,462, JP-A-54-59143 (US Pat. No. 415
(Corresponding to the specification of 0987), JP-A-55-52063.
No. 55, No. 55-52064, No. 55-46760, No. 55-85495, No. 57-11350, No. 57-.
148749, 57-104144, and other hydrazone derivatives described in

(N) US Pat. Nos. 4,047,948 and 4,
047949, 4265990 and 427384.
Nos. 6,4299,897 and 4,306,008, etc., benzidine derivatives, and (o) JP-A-58-
190953, 59-95540, 59-97
148, 59-195658 and 62-3667.
No. 4, stilbene derivatives described in each publication, etc.,
(P) Polyvinylcarbazole and its derivatives described in JP-B-34-10966, (q) JP-B-43-18
Nos. 674 and 43-19192, polyvinylpyrene, polyvinylanthracene, poly-2-vinyl-4- (4'-dimethylaminophenyl) -5-phenyl-oxazole, poly-3-vinyl-N-ethylcarbazole. Vinyl polymers such as (r) JP-B-43-1919
Polymers such as polyacenaphthylene, polyindene, and a copolymer of acenaphthylene and styrene described in JP-A-3, (s)
Condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin described in JP-B-56-13940 and the like, (t) JP-A-56-90833 and 56-
There are various triphenylmethane polymers described in JP-A-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 of the first example, conventionally known sensitizing dyes used for electrophotographic photoreceptors can be used. These are "electrophotographic" 12 9 (1973), "Synthetic Organic Chemistry" 24 (11), have been described in 1010 (1966) and the like. For example, U.S. Pat. Nos. 3,141,770 and 42,
No. 83475, JP-A-48-25658, JP-A-62-71965, and other pyrylium dyes, Applied Optics Suppl.
ement 3 50 (1969), JP-A-50-395
48, etc., cyanyl dyes described in U.S. Pat. No. 3,597,196, JP-A Nos. 60-163047, 59-16458.
The styryl dyes described in JP-A No. 8 and 60-252517, etc. are advantageously used.

As the charge generating agent contained in the photoconductive layer of the second example, 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) US Pat. Nos. 4,436,800 and 4
No. 439506, 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 and 4,666,802, JP-A Nos. 51-90827 and 52-55643. Phthalocyanine pigments such as metal-free or metal phthalocyanines described in JP-A Nos. 3 to 4300, (3) US Pat. No. 3,371,884, perylene pigments described in JP-A 47-30330, and (4) British Patent No. 2237680. Indigo and thioindigo derivatives described in JP-A No. 47-30331, (5) British Patent No. 2237679, JP-A No. 47-30332, and the like, quinacridone-based pigments (6 ) British Patent No. 2237678, Japanese Patent Laid-Open Nos. 59-184348 and 62-28738.
No. 47-18544, polycyclic quinone pigments described in JP-A Nos. 47-30331 and 47-1.
Bisbenzimidazole pigments described in JP-A-8543, (8) U.S. Pat. Nos. 4,396,610 and 4,644.
No. 082 Squarium salt-based pigments described in each specification,
(9) JP-A-59-53850 and JP-A-61-212254.
And the azurenium salt-based pigments described in Japanese Patent No. 2 and the like. These may be used alone or in combination of two or more.

Further, regarding the mixing ratio of the organic photoconductive compound and the binding resin, the upper limit of the content rate of the organic photoconductive compound is determined by the compatibility between the organic photoconductive compound and the binding resin, and an amount exceeding this is added. Then, crystallization of the organic photoconductive compound occurs, which is not preferable. Since the electrophotographic sensitivity decreases as the content of the organic photoconductive compound decreases, it is preferable to include as many organic photoconductive compounds as possible within the range where crystallization of the organic photoconductive compound does not occur. The content of the organic photoconductive compound is 5 to 120 parts by weight, preferably 10 to 100 parts by weight of the organic photoconductive compound, relative to 100 parts by weight of the binding resin. The organic photoconductive compounds may be used alone or in combination of two or more.

The thickness of the photoconductive layer is 1 to 100 μm, particularly 1
0 to 50 μ 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 0.01 to 5 μm, and particularly,
0.05 to 2 μ is preferable. In the present invention, various dyes can be used together as a spectral sensitizer depending on the type of light source such as visible light exposure or semiconductor laser light exposure. For example, Harumiya Miyamoto, Hidehiko Takei; Imaging
1973 (No. 8) page 12, C.I. J. Young, etc .: R
CA Review 15 , 469 (1954), Kouhei Kiyota et al . : Transactions of the Institute of Electrical Communication, J63-C (No. 2),
97 pages (1980), Yuji Harasaki et al., Journal of Industrial Chemistry, 6
6 , 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan, 35 , 208 (1972), and other general reference carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes. , Polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (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.
And those described in JP-A-57-16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Harmmer "The Cyanine Dyes and
The dyes described in "Related Compounds" and the like can be used, and more specifically, U.S. Pat. No. 3,047,384,
3110591, 3121008, 3125
No. 447, No. 3128179, No. 3132942,
No. 3,622,317, British Patent No. 122689
No. 2, No. 1309274, No. 1405898, and Japanese Patent Publication Nos. 48-7814 and 55-18892.

Furthermore, the near-infrared light with a long wavelength of 700 nm or more
As polymethine dyes for spectrally sensitizing infrared light region, JP-A-47-840, JP-A-47-44180 and JP-B-51-
41061, 49-5034, 49-4512
No. 2, No. 57-46245, No. 56-35141,
57-157254, 61-26044, 6
No. 1-275551, U.S. Pat. No. 3619154
No. 4175956, each specification, "Research Discl
oseure ”, 1982, 216, pages 117 to 118, and the like.

The photoconductor of the present invention is also excellent in that its performance does not easily change depending on the sensitizing dye even when various sensitizing dyes are used in combination. 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, promannyl,
Dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, phthalic anhydride, maleic anhydride, N-hydroxymaleinimide, N-hydroxyphthalimide, 2,
Electron-withdrawing compounds such as 3-dichloro-5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone, tetracyanoethylene, nitrobenzoic acid and dinitrobenzoic acid, Hiroshi Komon et al. "Recent photoconductive materials and photoconductors Development / Practical use ”Chapters 4 to 6: Japan Science Information Co., Ltd.
Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds and the like, which are cited as references in the publication section (1986), are mentioned. In addition, JP-A-58-
65439, 58-102239, 58-12.
The compound etc. which are described in 9439, 62-71965, etc. can also be mentioned.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methylphthalyl glycolate, dimethyl glycol. Phthalates and the like can be added to improve the flexibility of the photoconductive 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 according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, 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. Conductive treated by, for example, the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) to have conductivity, and at least one layer coated for the purpose of preventing curling, the support 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),
2-11 pages (published in 1975), Hiroyuki Moriga "Introduction to Special Paper Chemistry" Polymer Publishing (1975), M.S. F. Hoove
r, J. Macromol. Sci. Chem. A-4 (6), 1
Those described in pages 327 to 1417 (published in 1970) and the like are used.

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, Koichi Nakamura, "Development and Practical Use of Toner Materials," Chapter 3 (published by Nihon Kagaku Information Co., Ltd., 1985), Hajime Machida, "Recording Materials" And photosensitive resin ", pp. 107-127 (published in 1983),
Academic Publishing Center, Electrophotographic Society "Imaging No.
2-5 Development, fixing, charging, transfer of electrophotography "and the like.

As the dry developer, one-component magnetic toner,
Two-component toner, one-component non-magnetic toner, capsule toner, and the like are in practical use, and any of these can be used. More preferably, a combination of a scanning exposure method using laser light that is exposed based on digital information and a development method using a liquid developer is an effective process because a high-definition image can be formed.

Further, as a 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 (Made by Shell), IP-solvent 1620 (made by Idemitsu Petrochemical, 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. And a resin for imparting dispersion stability / fixability and chargeability, and if desired, various additives are added to enhance charge characteristics or improve image characteristics.

Known dyes and pigments may be arbitrarily selected as the colorant, and examples thereof include benzidine type, azo type and
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, for example, those specifically described in Yuji Harazaki "Electrophotography" Vol. 16, No. 2, p. 44 are used. For example,
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), a copolymer containing a semi-maleic acid amide component, Examples include malon indene resin, higher alcohols, polyethers, polysiloxanes, waxes and the like. 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 developer. That is, if the electric resistance of the liquid developer with the toner particles removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a good quality continuous tone image. Therefore, the amount of each additive added is controlled within this limit. ing.

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 which obtains fine particles having good monodispersity, and coloring the resin particles is used. Can be mentioned. As one of the coloring methods,
As described in JP-A-57-48738,
There is a method of dyeing the dispersed resin with a preferable dye. Also,
As another method, as disclosed in JP-A-53-54029, a method of chemically bonding a disperse resin and a dye, or as described in JP-B-44-22955, polymerization granulation In the production by the method, there is a method of using a dye-containing monomer in advance to prepare a dye-containing copolymer.

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

As a method of forming a color image of the present invention, first, a copied image is formed on a photosensitive material having the transfer layer through an ordinary electrophotographic process. That is, charging
Each process of exposure-developing-fixing is performed by a conventionally known method. The developer used in the development process may be any conventionally known developer, and examples thereof include a dry developer and a liquid developer.

More preferably, a combination of a scanning exposure method using a laser beam for exposing on the basis of digital information and a developing method using a liquid developer is an effective process since a high-definition image can be formed. An example is shown below. First, the photosensitive material is positioned on the flat bed by the register pin method, and then sucked and fixed by air suction from the back surface. Then, the photosensitive material is charged by, for example, a charging device described in "Basics and Applications of Electrophotographic Technology" (edited by the Electrophotographic Society, published by Corona, June 15, 1988), page 212 and thereafter. The corotron or scotron system is common. At this time, it is also preferable to control the charging condition by giving feedback so that the surface potential is always within a predetermined range based on the information from the charging potential detection means of the photosensitive material.

After that, for example, the same as the above cited document 254.
Scanning exposure with a laser light source is performed using the method described on the following pages. First, an image corresponding to a yellow plate, which is obtained by separating a color image into four colors, is converted into a dot pattern and exposed. Then, a toner image is formed using the liquid developer. The light-sensitive material charged and exposed on a flat bed can be removed from the light-sensitive material and the direct wet development method shown on page 275 and subsequent pages of the above cited document can be used. The exposure mode at this time is performed corresponding to the toner image development mode,
For example, in the case of reversal development, a negative image, that is, an image portion is irradiated with laser light and toner having the same charge polarity as that when the photosensitive material is charged is used. To be electrodeposited. The details of the principle are described on page 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.

Next, the toner image on the photosensitive material is thermally transferred together with the transfer layer to the transfer material. Known methods and apparatuses can be used for this thermal transfer. FIG. 2 shows an example of an apparatus for thermally transferring the transfer layer onto the transfer material. This is heating means 5
It drives while applying a predetermined nip pressure between a pair of built-in rubber-coated metal rollers 4. The surface temperature of the roller 4 at this time is preferably 50 to 150 ° C, more preferably 80 to 120 ° C, and the nip pressure between the rollers is preferably 0.2 to 20 kgf / cm ² , more preferably 0.5 to 10 kgf /. cm ² , transport speed is preferably 0.1 to 100 mm / sec, more preferably 1 to 30 m
The range is m / sec. It is natural that these condition settings are optimized depending on the physical properties of the photosensitive material used, that is, the material of the peeling layer, the photosensitive layer and the support.

The roller surface temperature is preferably kept within a predetermined range by the known surface temperature detecting means 6 and temperature controller 7. Further, a preheating means for the photosensitive material may be provided in front of the heating roller portion, and a cooling means may be provided afterwards. Figure 2
Although not shown in the figure, an air cylinder that uses springs or compressed air at both ends of the shaft of at least one roller can be used as the inter-roller pressing means.

In the present invention, as described in claim 5,
In an apparatus for carrying out an electrophotographic process, the thermoplastic resin containing the resins [AH] and [AL] of the present invention as main components,
It is preferably formed as a transfer layer on an electrophotographic photosensitive member having a surface having an adhesive force of 200 gf or less. As a result, the electrophotographic photosensitive member can be repeatedly used in the apparatus, and the electrophotographic process can be continuously performed without disposing the photosensitive member. As a result, there is an advantage that the cost of the printing plate produced can be significantly reduced.

In order to form the transfer layer on the surface of the photoconductor in the apparatus for carrying out the electrophotographic process, the "hot melt" method, the "release paper transfer" method or the "electrodeposition" method is effective. The "hot melt" method is a method in which a transfer layer composition is hot melt coated by a known method, and is a solventless coating machine, for example, 197 to 2 of the above-mentioned document "Actual of hot melt adhesion".
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 thickness of the peel transfer layer is preferably 0.1 to 20 μm, more 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. The melting temperature of the thermoplastic resin at the time of application is optimized depending on the component composition of the thermoplastic resin used, but it is usually 50 to 1
It is in the range of 80 ° 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 system, the coating amount, etc., but it is from 1 to 10
mm / sec is suitable, and more preferably 5-40 mm /
It is in the range of seconds. FIG. 3 is a schematic view of a color image forming apparatus using a method of forming a transfer layer on a photoconductor by a melt coating (hot melt) method in the apparatus.

The thermoplastic resin 12a is applied by the hot melt coater 13 to, for example, the surface of the photosensitive member 11 on the drum peripheral surface, and is cooled to a predetermined temperature by passing under the intake / exhaust unit 15. Hot melt coater 13
After moving to the standby position 13a, the liquid developing unit 14 is moved to that position. This unit 14 is composed of a developing device containing liquid developers of yellow, magenta, cyan and black, respectively. 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. A wet developer carrier liquid is usually used as the pre-bath and rinse liquid.

The photoconductor 11 on which the transfer layer 12 made of a thermoplastic resin is formed then enters the electrophotographic process. The photoconductor 11 is uniformly charged positively, for example, by the corona charging device 18, and then the exposure device (for example, semiconductor laser) 1
First, when image exposure is performed based on yellow image information in 9, the potential of the exposed portion is reduced, and a potential contrast is obtained with the unexposed portion. Only the yellow liquid developing unit 14y containing the liquid developer in which the yellow pigment having the positive electrostatic charge is dispersed in the electrically insulating dispersion medium is brought close to the surface of the photoreceptor 11 from the developing unit set 14 and the gap is set to 1 mm. Fix it.

First, the photoconductor 11 is pre-bused by a pre-bus means provided in the developing section, and then wet type while applying a development bias voltage between the photo conductor and the development electrode by a bias power source and electric connection not shown in the figure. A developer is supplied to the surface of the photoconductor. 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 adhering to the surface of the photoconductor is washed off by the rinsing means built in the developing unit 14, and then the rinsing solution adhering to the surface of the photoconductor is removed by the squeeze means. Dry by passing. The above process is repeated for magenta, cyan, and black. During this time, the thermal transfer means 17
Is placed away from the surface of the photoconductor.

After forming a four-color image on the transfer layer, a predetermined preheating is performed by the heating means 17a for thermal transfer, and then a rubber containing a heating element having a temperature control means via the material 16 to be transferred. The roller 17b is pressed and further passed under the cooling roller 17c to be cooled, and the toner on the surface of the photoconductor is thermally transferred together with the transfer layer 12 to the transfer material 16, and the series of steps is completed.

The transfer means 17 for thermally transferring the peeling layer (transfer layer) 12 to the transfer paper 16 is composed of a heating means 17a, a metal heating roller 17b covered with rubber containing a heating element, and a cooling roller 17c. The heating means 17a is a non-contact type infrared line heater or flash heater, and is preheated within a range not exceeding the surface temperature of the photosensitive layer obtained by the heating roller 17b. The surface temperature of the photosensitive layer heated by the heating roller 17b is preferably 50-
150 degreeC, More preferably, it is 80-120 degreeC.

As the material of the cooling roller 17c, it is desirable that a heat conductive metal such as aluminum or copper is coated with silicone rubber, and heat is radiated to the inside of the roller or the outer peripheral portion not in contact with the transfer paper by using a cooling means. The cooling means uses a cooling fan, a refrigerant circulation or an electronic cooling element,
It is preferable to maintain a predetermined temperature range in combination with a temperature controller.

The nip pressure of these rollers is 0.2 to
20 kgf / cm ² , more preferably 0.5 to 15 kg
Although not shown in the figure, a spring or an air cylinder using compressed air at both ends of the roller shaft can be used as the roller pressing means although it is f / cm ² .
The transport speed is in the range of 0.1 to 100 mm / sec, more preferably 1 to 30 mm / sec, and may be different in the electrophotographic process and the thermal transfer process.

Further, by stopping the apparatus with the transfer layer formed, the electrophotographic process can be started immediately when the next apparatus is in operation, and the surface of the photosensitive layer is protected to prevent the characteristic deterioration due to the influence of the external environment. be able to. Naturally, the above condition setting should be optimized depending on the photoconductor used, that is, the transfer layer, the photoconductive layer and the support, and the physical properties of the material of the transfer paper. Especially in the heat transfer step, the preheating, roller heating, and cooling conditions are the glass transition point of the transfer layer,
It is necessary to take into consideration factors such as softening temperature, fluidity, tackiness, film formability and 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 transfer paper. Then, after passing under the cooling roller, conditions should be set so that the temperature decreases, the fluidity and adhesiveness decrease, and the film remains as a film and is peeled off from the photosensitive layer surface while being adhered to the transfer layer together with the toner. Is.

Next, the "release paper transfer" system, which is another mode of the electrophotographic plate-making printing plate making apparatus that can be used in the present invention, will be described. According to the "release paper transfer" method, a transfer layer is formed on the release paper in advance by hot melt coating, solvent coating, latex electrodeposition, etc., and then the transfer layer is thermally transferred onto the surface of the photosensitive material, and an electrophotographic toner image is formed thereon. Then, the entire transfer layer is thermally transferred to the transfer target material to form a color copy.

The release paper on which the release layer is formed is roll-shaped,
In sheet form, it can be easily supplied to an electrophotographic plate making printing plate making apparatus. As the release paper used in this method, any conventionally known release paper can be used. For example, a new technology of adhesion (adhesive) and its use / development materials for various applied products (issued by: Management Development Center Publishing Department, May 20, 1978), published by All Paper Guide Paper Product Encyclopedia, Volume 1, Culture Industry Edition; Paper Industry Times Co., Ltd., December 1, 1983) Can be mentioned. Specifically, as release paper, a release agent mainly composed of silicone was applied to unbleached Clupak paper laminated with polyethylene resin, high-grade paper precoated with solvent-resistant resin, kraft paper, and undercoat. It is applied on PET base or glassine paper directly.

As the silicone, a solvent type is generally used, which is applied and dried at a concentration of 3 to 7% by a gravure roll or wire bar method, and then heat-treated at 150 ° C. or higher to be cured. The coating amount is about 1 g / m ² . Commercially available tapes, labels, forming industry and cast coat industry can be used. For example, separate paper (Oji Paper), Kingleys (Shikoku Paper), Sun Release (Sanyo Kokusaku Pulp), NK
Examples include high release (Nippon Kogyo Paper).

As an apparatus for easily forming a transfer layer using a release paper on a photosensitive member, for example, the apparatus shown in the schematic view of FIG. 4 can be mentioned. That is, the release paper 10 provided with the transfer layer 12 containing the resins [AH] and [AL] is thermocompression-bonded by the heating roller 17b to transfer the transfer layer 12 to the surface of the photoconductor 11. The release paper 10 is cooled by the cooling roller 17c and collected. Further, if necessary, the photoconductor 11
The transfer layer 12 may be heated by the preheating means 17a to improve transferability of the transfer layer 12 by thermocompression bonding.

FIG. 5 is a conceptual diagram showing an example of a concrete mode in which the apparatus for transferring from the release paper is incorporated in the apparatus for performing the electrophotographic process and the thermal transfer to the material to be transferred. The apparatus of FIG. 5 has basically the same configuration as the apparatus of the hot melt system (FIG. 3) described above, except for a portion 117 for forming the transfer layer 12 on the photoconductor 11.

In the 117 part of FIG. 5, the transfer layer 12 is transferred onto the photoreceptor 11 by the release paper 10 and then a toner image is formed by an electrophotographic process, and then the part 117 is transferred to the part having the transfer material 16. Instead of 17, the transfer method may be used in the same manner as in the hot melt method, or the transfer layer 12 may be transferred onto the photoreceptor 11 by the release paper 10 and the transfer layer 12 on which the toner image is formed. It is also possible to incorporate both of the portion for transferring the material to the transfer material 16 into the apparatus.

The transfer layer 12 is formed on the photoreceptor 11 by the release paper 10.
The transfer conditions when transferring to the surface are preferably as follows. Roller nip pressure is 0.1-10kgf
/ Cm ² , more preferably 0.2 to 8 kgf / cm ² , and the temperature at the time of transfer is 25 to 100 ° C, more preferably 40 to 80 ° C. Transport speed is 0.5-100m
m / sec, more preferably 3 to 50 mm / sec, and may be different in each of the transfer layer forming step, the electrophotographic step, and the thermal transfer step to the material to be transferred.

Next, the "electrodeposition" method that can be used in the present invention will be described. In the present invention, the thermoplastic resin as described above is electrodeposited in the form of resin particles on the surface of the photoconductor, and a uniform thin film is formed by, for example, 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 size of 0.01 μm to
15 μm range, preferably 0.05 μm to 5 μm
m, more preferably 0.1 μm to 1 μm. . The particles may be in the form of particle powder (dry type) or non-aqueous resin particles (wet type). Preferred are non-aqueous dispersed resin particles, which can easily adjust the film thickness of the peeling transfer layer to a thin film with a uniform thickness.

The fine resin particles of the present invention can be produced by a conventionally known mechanical grinding method or polymerization granulation method. In these production methods, particles of either dry electrodeposition or wet electrodeposition can be used. In the case of producing fine particles used in the dry electrodeposition method, as a mechanical pulverization method, directly pulverized by a conventionally known pulverizer,
Examples of the method of forming fine particles (for example, a method using a ball mill, a paint shaker, a jet mill, etc.),
If necessary, the materials to be resin particles are mixed, pulverized through melting and kneading, or classification may be performed to make the particle diameter uniform after pulverization, or post-treatment for treating the surface of the particles may be appropriately combined. it can. A spray dry method is also known.

Specifically, "Granulation Handbook", Part II, edited by Japan Powder Industry Technical Association (published by Ohmsha, 1991)
Year), Kanagawa Management Development Center "Practice of the latest granulation technology"
(Kanagawa Business Development Center Publishing Department, 1984), Masafumi Arakawa et al. "Latest powder design technology" Techno System Co., Ltd., 1988), etc. Can be manufactured.

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, "Polymer Latex Chemistry," Polymer Publishing Society (1970), Tadashi Okuda, Hiroshi Inagaki, "Synthetic Resin Emulsion" Polymer Publishing Society (1978)
Souichi Muroi "Introduction to Polymer Latex" Kobunsha (19)
1983), I. Pirma, P .; C. Wang "Emuls
ion Polmerization "I. Piirma & J. L. Gavdo
n, ACS symp. Sev. 24, p. 34 (1974
Fumio Kitahara et al., "Chemistry of Dispersed Emulsion Systems" Engineering Book (19
1979), Souichi Muroi, "State-of-the-art technology of ultrafine polymer" C.I. M. C. (1991) and the like, and then granulated by the method described in the textbook of the above-mentioned mechanical method, and then collected and pulverized by various methods as described in the textbook related to the above-mentioned mechanical method. .

As a method of dry electrodeposition of the obtained fine particle powder, a conventionally known coating method of electrostatic powder or a developing method of a dry electrostatic photograph developer can be used. Specifically, J. F. By Hughes (Translated by Hideo Nagasaka and Machiko Midorikawa)
As described in "Electrostatic powder coating", etc., a method of electrodepositing fine particles charged by a method such as corona charging, friction charging, induction charging, ion wind charging, and reverse ionization phenomenon, edited by Koichi Nakamura, "Recent Electronics Development and Practical Use of Photographic Development System and Toner Material "Chapter 1 (Japan Science Information Co., Ltd., 1985)
Yearly) etc., it can be appropriately performed by using a developing method such as a cascade method, a magnetic brush method, a fur brush method, an electrostatic method, an induction method, a touchdown method, and a powder cloud method. it can.

When the non-aqueous latex used in the wet electrodeposition method is produced, it can be produced by either the mechanical method or the polymerization granulation method as described above. For example, a method in which a dispersion polymer is used in combination and further dispersed by a wet disperser (for example, a ball mill / paint shaker, Keddy mill, Taino mill, etc.), a material serving as a resin particle component and a dispersion assisting polymer (or coating polymer) are kneaded in advance. And the like, and then pulverized, and then a dispersing polymer is coexisted and dispersed. Specifically, a method for producing a paint or a developer for electrostatic photography can be used. For example, “Flow of Paint and Dispersion of Paint” by Kenji Ueki, Kyoritsu Shuppan (197).
1 year), "Solomon, Science of Paint", "Paint and S"
urface Coating Theory and Practice ", Yuji Harazaki" Coating Engineering "Asakura Shoten (1971), Yuji Harasaki" Basic Science of Coating "Bookstore (1977)
Etc. are described in the book.

As the polymerization granulation method, a conventionally known non-aqueous dispersion polymerization method can be used. Specifically,
"Latest Technology of Ultrafine Polymer", Chapter 2, "Recent Electrophotographic Development System and Development and Practical Use of Toner Materials"
Chapter 3, K. E. J. Barvett "Dispersion Polymer
ization in Organic Media ”John Wiley (197
5 years) and the like.

In the polymerization granulation method, in order to introduce the polymer component (s) for improving the peeling property into the resin [A], it is soluble in the organic solvent to be a thermoplastic resin and polymerizes. Thus, a monomer corresponding to the polymer component (s) is allowed to coexist with the insolubilized monomer to carry out a polymerization reaction, whereby the resin is copolymerized in the resin [A] and the resin particles of the random copolymer [AP ] Is easily obtained.

Further, in order to introduce the polymer component (s) in the form of a polymer block, at least a block copolymer containing the polymer component (s) in a block is used in the dispersion stabilizing resin used. , Or a weight average molecular weight of 1 × 10 6 having the polymer component (s) as a main repeating unit.
^{3 to} 2 × 10 ⁴ (preferably 3 × 10 ^{3 to} 1.5 × 10
⁴ ) The resin [A] can be easily made into a block copolymer by coexisting the monofunctional macromonomer and copolymerizing with the monomers. As another method, a polymer initiator containing the polymer component (s) as a main repeating unit (azobis polymer initiator or peroxide polymer initiator) is also used, and the block copolymerization is similarly performed. Coalescent resin particles [AP] can be obtained.

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

By synthesizing dispersed resin particles in these non-aqueous solvent systems by 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. Can be Since these non-aqueous dispersion resin particles are subjected to a wet electrostatic development method or a method in which they are electrophoresed in a pressure field of an electric field, they are used as a dispersion medium at the time of electrodeposition.
It is adjusted to a nonaqueous solvent system having a dielectric constant of 3.5 or less and ⁸ Ωcm or more.

Specifically, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, and halogen-substituted products thereof can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L (Isoper; product of Exxon Corporation Name), Shersol 70, Shersol 71
(Shell sol; trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits Co., Ltd.) and the like can be used alone or in combination.

Therefore, as the solvent used in the polymerization granulation,
It is preferable to use the insulating organic solvent from the beginning, but it is also possible to adjust by adjusting the dispersion medium after granulating with a solvent other than these solvents. As another method for synthesizing the non-aqueous latex, the above-mentioned electric resistance of 10 ⁸ Ωc is used.
By wet-dispersing a block copolymer composed of a polymer component which is soluble in a non-aqueous solvent having a dielectric constant of 3.5 or more and 3.5 or less and a polymer component which is insoluble in the solvent in the solvent. It can also be provided as fine resin particles. That is, a block copolymer consisting of a soluble polymer component and an insoluble polymer component was made into a polymer in the organic solvent in which the block copolymer was previously dissolved, by using the block polymer synthesis method described above. After that, it is a method of dispersing in a non-aqueous solvent for electrodeposition.

As described above, in order to electrodeposit dispersed particles in a dispersion medium by electrophoresis, the particles are positively-charged or negatively-charged electro-detectable particles, and a technique for imparting electro-detection property to the particles. Is
This can be achieved by appropriately using the technique of the developer for wet electrostatic photography. Specifically, the above-mentioned "Recent Electrophotographic Development System and Development and Practical Use of Toner Materials" 139-148
Page, "Basics and Applications of Electrophotographic Technology", edited by The Institute of Electrophotography 49
7-505 (Corona Publishing, 1988), Yuji Harazaki "Electronic Photography" 16 (No. 2), 44 (1977).
It is carried out by using the electrophotographic material and other additives described in the above.

For example, British Patent Nos. 893429 and 9
34038, U.S. Pat. Nos. 1,122,397 and 390.
0412, 46096989, JP-A-60-179.
751, 60-185963, JP-A-2-139.
No. 65, etc. The composition of the non-aqueous latex used for electrodeposition is usually at least 0.1 to 20 g of particles mainly containing a thermoplastic resin in at least 1 liter of an electrically insulating dispersion medium, and 0.01 to 100 g of a dispersion stabilizing resin. 5
0 g, the charge control agent added as necessary is 0.0001
It is in the range of 10 g.

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

The thermoplastic resin particles which have been microparticulated and imparted with an electric charge and dispersed in the electrically insulating liquid in this manner behave like an electrophotographic wet developer. Therefore, for example, it is possible to perform electrophoresis on the surface of the photoconductor by using the developing device, for example, the slit developing electrode device described in "Basics and Applications of Electrophotographic Technology" on pages 275 to 285. 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 developing electrode of the developing device so that the photoconductor side has a negative potential. Then, the particles are electrostatically electrodeposited on the surface of the photoreceptor. It is also possible to perform electrodeposition by wet toner development by a usual electrophotographic process. That is, as shown in 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 exposed only to unnecessary areas. Perform normal wet toner development.

The adhered amount of the thermoplastic resin particles in the form of a photosensitive member can be arbitrarily adjusted by the applied voltage of the external bias, the charging potential of the photosensitive member, the developing time and the like. After electrodeposition, the developer is wiped off by a squeeze using a known rubber roller, gap roller, reverse roller or the like. Methods such as corona quiz and air squeeze are also known. In addition, cold or warm air,
Alternatively, it is dried by an infrared lamp or the like, and preferably thermoplastic resin particles are formed into a film to form a transfer layer.

The thickness of the transfer layer at this time is preferably 0.
In the range of 1 to 10 g / m ² , more preferably 0.5 to 5
It is g / m ² . 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 and sufficient image density cannot be obtained, or image quality is likely to deteriorate. The method of forming the transfer layer by the electrodeposition method will be described in detail below with reference to the accompanying drawings. FIG. 6 is a schematic view of an electrophotographic transfer device incorporating a device for forming a transfer layer by an electrodeposition method. The apparatus shown in FIG. 6 has basically the same configuration as the apparatus of the hot melt method (FIG. 3) described above, except for the portion where the transfer layer 12 is formed on the photoreceptor 11.

The dispersion liquid 12b of the thermoplastic resin particles is contained in the movable wet development unit set 14 and is in the electrodeposition unit 1.
It is supplied within 4T. First, the electrodeposition unit 14T is brought close to the photoreceptor surface 11 and fixed so that the distance between the electrodeposition unit 14T and the developing electrode is 1 mm. The particle dispersion 12b is supplied between the gaps and is rotated while applying a voltage from an external power source (not shown) so that the particles are electrodeposited on the entire surface of the image forming area on the surface 11 of the photoreceptor.

The particle dispersion liquid 12 adhering to the surface 11 of the photoconductor by the squeeze device built in the electrodeposition unit 14T.
After removing b, it is then passed under the air intake / exhaust unit 15 to be dried, and the thermoplastic resin particles are heat-melted by the heating means 17a to obtain a film of the thermoplastic resin transfer layer 12. Thereafter, if necessary, a cooling device similar to the intake / exhaust unit 15 (not shown) is used to cool to a predetermined temperature from the outside of the photoconductor or the inside of the photoconductor drum. Electro-deposition unit 1
After lowering 4T, the wet developing unit set 14 is moved.

[0189]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. [Synthesis Example of Thermoplastic Resin Particles [AR]] Synthesis Example 1: Thermoplastic Resin Particles [ARH] [ARH-
1] A mixed solution of 10 g of a dispersion stabilizing resin [Q-1] having the following structure, 100 g of vinyl acetate and 384 g of Isopar H was heated to 70 ° C. while stirring under a nitrogen stream. 0.8 g of 2,2'-azobis (isovaleronitrile) (abbreviation AIVN) was added as a polymerization initiator, and the reaction was carried out 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, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having a polymerization rate of 90% and an average particle size of 0.23 μm and good monodispersity. The particle size was measured by CAPA-500 (manufactured by Horiba, Ltd.).

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 particles, and the resin particles When the weight average molecular weight (Mw) and the glass transition point (Tg) of the powder were measured, Mw was 2 × 10 ⁵ (polystyrene equivalent G
The PC value) and Tg were 38 ° C.

[0191]

[Chemical 12]

Synthesis Example 2 of thermoplastic resin particles [ARH]:
[ARH-2] 15 g of a dispersion stabilizing resin [Q-2] having the following structure, 75 g of benzyl methacrylate, 25 g of methyl acrylate, 3
-A mixed solution of 1.3 g of methyl mercaptopropionate and 552 g of Isopar H was heated to a temperature of 50 ° C with stirring under a nitrogen stream. As a polymerization initiator, 1 g of 2,2'-azobis (2-cyclopropylpropionitrile) (abbreviation ACPP) was added and reacted for 2 hours. Furthermore, A. C. P. P. 0.8 g was added and reacted for 2 hours, and then the initiator A. I. V. N. After adding 0.8 g, the reaction temperature was adjusted to 75
The temperature was set to 0 ° C. and the reaction was performed for 3 hours. Then, the mixture was heated to a temperature of 90 ° C., the unreacted monomers were distilled off under a reduced pressure of 20 to 30 mmHg, and then cooled. The white dispersion obtained through a 200-mesh nylon cloth had an average polymerization rate of 98%. Particle size 0.2
The latex was 0 μm with good monodispersity. The Mw of the resin particles was 2.8 × 10 ⁴ , and the Tg was 55 ° C.

[0193]

[Chemical 13]

Synthesis Example 3 of thermoplastic resin particles [ARH]:
[ARH-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 heated to 50 ° C while stirring under a nitrogen stream. Benzyl methacrylate 8
0 g, vinyltoluene 20 g and A. C. P. P. 0.
8 g of the mixture was added dropwise at a dropping time of 1 hour, and the reaction was continued for another 1 hour. Furthermore, A. C. P. P. Of 0.8 g of the initiator A. I. V. N. 0.8 g was added and the mixture was heated to a temperature of 80 ° C. for 2 hours. I. V.
N. 0.5g was added and reaction was performed for 2 hours. Then, the mixture was heated to a temperature of 100 ° C., unreacted monomers were distilled off under a reduced pressure of 10 to 20 mmHg, and then cooled. The white dispersion obtained through a 200-mesh nylon cloth had an average polymerization rate of 90%. The latex had a particle size of 0.17 μm and good monodispersity. In addition, the resin particles have Mw of 1 × 10 ⁵ and Tg of 5
It was 5 ° C.

[0195]

[Chemical 14]

Synthesis Example 4 of thermoplastic resin particles [ARH]:
[ARH-4] 14 g of a resin [Q-4] for stabilizing dispersion having the following structure, monofunctional macromonomer (M-1): Praxel FM-0725
A mixed solution of 10 g (manufactured by Chisso Corporation) and Isopar H553 g was heated to a temperature of 50 ° C. with stirring under a nitrogen stream. 70 g of methyl methacrylate, 20 g of ethyl acrylate, methyl 3-mercaptopropionate 1.
3 g and A. C. P. P. 1.0 g of the mixture was added dropwise for 30 minutes, and the reaction was continued for another 1.5 hours. Furthermore, A. C. P. P. Of 0.8 g of the initiator A. I. V. N. 0.8 g was added and the temperature was set to 80 ° C. for 2 hours. C. P. P. 0.5g was added and reaction was performed for 2 hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having a polymerization rate of 99% and an average particle size of 0.15 μm and good monodispersity. Also, the Mw of the resin particles is 3 × 10 ⁴ , and the Tg is 50.
It was ℃.

[0197]

[Chemical 15]

Synthesis Examples 5 of Thermoplastic Resin Particles [ARH]
9: [ARH-5] to [ARH-9] In Synthesis Example 4 of the thermoplastic resin particles [ARH],
Instead of 10 g of macromonomer (M-1), the following table-B
Except that each macromonomer described in 1) is used,
Operate in the same manner as in [ARH-5]-[ARH-5]
-9] was manufactured. The polymerization rate of the obtained particles is 98 to 9
At 9%, the average particle size was within the range of 0.15 to 0.25 μm, the particle size distribution of the particles was narrow, and the monodispersibility was good.
The Mw of the resin particles was 2.5 × 10 ⁴ to 4 × 10 ⁴ , and the glass transition point was in the range of 40 ° C. to 70 ° C.

[0199]

[Table 2]

Synthesis Example 1 of thermoplastic resin particles [ARH]
0: [ARH-10] Styrene having a softening point of 45 ° C. as the thermoplastic resin [A]
Butadiene copolymer [(48/52) weight ratio] (Sorprene 303: manufactured by Asahi Kasei Co., Ltd.) 5 g of a pulverized product obtained by coarsely pulverizing the solid content with a pulverizer trio blender, dispersion stabilizing resin:
4 g of Sorprene 1205 (manufactured by Asahi Kasei Co., Ltd.) and 51 g of Isopar H were charged into a paint shaker (manufactured by Toyo Seiki Co., Ltd.) having glass beads with a diameter of about 4 mm as a media and preliminarily dispersed for 20 minutes. This predispersion was treated with a diameter of 0.
Using a Dynomill KDL type (manufactured by Shinmaru Enterprises Co., Ltd.) having glass beads of 75 to 1 mm as a media, 4500 r. p. m. Wet-dispersed for 6 hours. 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.

Synthesis Example 11 of thermoplastic resin particles [ARH]
-16: [ARH-11] to [ARH-16] In Synthesis Example 10 of thermoplastic resin particles [ARH], each compound of the following Table-C was used instead of the thermoplastic resin [A]: Sorprene 303. A dispersion was prepared by the same wet dispersion method as in Synthesis Example 10. The white dispersion had an average particle size of 0.3 to 0.6 μm, and the softening point of the obtained resin particles was 40 ° C. to 100 ° C.

[0202]

[Table 3]

Synthesis Example 1 of thermoplastic resin particles [ARL]:
[ARL-1] 12 g of 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, A. I. B. N. 1.5 g was added and reacted for 2 hours. I. B. N. The reaction was carried out by adding 0.8 g twice every 2 hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth had a polymerization rate of 93%.
It was a latex having an average particle size of 0.18 μm and good monodispersity. The resin particles had Mw of 8 × 10 ⁴ and Tg of 18 ° C.

Synthesis Example 2 of thermoplastic resin particles [ARL]:
[ARL-2] 18 g of dispersion stabilizing resin [Q-3] and Isopar H54
9 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, 2.6 g of methyl 3-mercaptopropionate and A. I. V. N. 1.0 g of the mixture was added dropwise at a dropping time of 1 hour, and the reaction was continued for another 1 hour. A. I. V. N. After the addition of 0.8 g, the temperature was set to 75 ° C. for 2 hours, and then A. I. V. N. 0.8 g was added and the reaction was carried out for 3 hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having a polymerization rate of 98% and an average particle size of 0.18 μm and good monodispersity. Further, the resin particles have Mw of 3 × 10 ⁴ and Tg of 18 ° C.
Met.

Synthesis Example 3 of thermoplastic resin particles [ARL]
12: [ARL-3] to [ARL-12] In Synthesis Example 2 of thermoplastic resin particles [ARL], 70 g of benzyl methacrylate and 30 of methyl acrylate were used.
Each resin particle [AR] was operated in the same manner as in Synthesis Example 2 except that each monomer shown in Table D below was used instead of g.
L] was produced. The polymerization rate of each obtained white dispersion was 90.
% To 99%, the average particle size was 0.13 to 0.20 μm, and the latex had good monodispersity. The Tg of each resin particle was in the range of 10 ° C to 25 ° C.

[0206]

[Table 4]

[Synthesis Example of Resin [P]] Synthesis Example 1: Resin [P] 1: [P-1] 80 g of methyl methacrylate, dimethylsiloxane macromonomer (FM0725) (manufactured by Chisso Corporation, Mw)
A mixed solution of 20 g of 1 × 10 ⁴ ) and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. Azobisisobutyronitrile (abbreviation: AIBN) 1.0
g, and reacted for 4 hours. I. B. N. 0.7 g
Was added and reacted for 4 hours. The Mw of the obtained copolymer was 5.8 × 10 ⁴ (measured by GPC method).

[0208]

[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 (FM-0725), each monomer corresponding to the polymer component shown in Table E below was used. In the same manner as in Synthesis Example 1, each polymer was synthesized.
The Mw of each polymer obtained was 4.5 × 10 ^{4 to} 6 × 10 ^4.
It was in the range of ⁴ .

[0210]

[Table 5]

[0211]

[Table 6]

Synthesis Example 10 of Resin [P]: [P-10] 60 g of 2,2,3,4,4-hexafluorobutyl methacrylate, macromonomer of methyl methacrylate (AA-6) (Toa Gosei Kagaku KK) Made, Mw1 x 1
A mixed solution of 40 g of O ⁴ ) and 200 g of benzotrifluoride was heated to a temperature of 75 ° C. under a nitrogen stream. A.
I. B. N. 1.0 g was added and reacted for 4 hours.
I. B. N. 0.5 g was added and reacted for 4 hours. The Mw of the obtained copolymer was 6.5 × 10 ⁴ .

[0213]

[Chemical 17]

Synthesis Examples 11 to 15 of Resin [P]: [P-1
1] 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 1F below. Each copolymer was synthesized in the same manner as in Synthesis Example 10 except that was used.
Mw of the obtained copolymer was 4.5 × 10 ^{4 to} 6.5 × 1.
It was in the range of 0 ⁴ .

[0215]

[Table 7]

[0216]

[Table 8]

[0217]

[Table 9]

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

[0219]

[Chemical 18]

Synthesis Example 17 of Resin [P]: [P-17] 70 g of methyl methacrylate and tetrahydrofuran 2
Thoroughly degas the mixed solution of 00g under a nitrogen stream, and
Cooled to ° C. 1,1-diphenylbutyllithium 0.
8 g was added and reacted for 12 hours. Furthermore, in this mixed solution,
30 g of the following monomer (m-1) and 6
0 g of the mixed solution was thoroughly degassed under a nitrogen stream and then added, and the mixture was further reacted for 8 hours.

After the mixture was brought to 0 ° C., methanol 1
Polymerization was stopped by adding 0 ml and reacting for 30 minutes. The temperature of the obtained polymer solution was raised to 30 ° C. with stirring, and
3 ml of 0% hydrogen chloride ethanol solution was added and 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 precipitate was collected and dried under reduced pressure to obtain a polymer having an Mw of 6.8 × 10 ⁴ and a yield of 76 g.

[0222]

[Chemical 19]

Synthesis Example 18 of Resin [P]: [P-18] A mixed solution of 52.5 g of methyl methacrylate, 22.5 g of methyl acrylate, 0.5 g of (tetraphenylporphinato) aluminum methyl and 200 g of methylene chloride was used as a nitrogen stream. The temperature was set to 30 ° C. below. 300 for this
25 W-xenon lamp light is passed through the glass filter
It was irradiated with light from a distance of cm and reacted for 20 hours. 25 g of the following monomer (m-2) was further added to the mixture, and the mixture was irradiated with light for 12 hours in the same manner.
g was added 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 is 78 g.
And the Mw was 9 × 10 ⁴ .

[0224]

[Chemical 20]

Synthesis Example 19 of Resin [P]: [P-19] A mixture of 50 g of ethyl methacrylate, 10 g of glycidyl methacrylate and 4.8 g of benzyl N, N-diethyldithiocarbamate was sealed in a container under a nitrogen stream,
The temperature was raised to 50 g. This was irradiated with light from a high-pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 6 hours for photopolymerization. Tetrahydrofuran 10
After dissolving in 0 g, 40 g of the following monomer (m-3) was added, the atmosphere was replaced with nitrogen, and irradiation with light was carried out again for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, collected, and dried. The polymer obtained had a yield of 73 g and a Mw of 4.8 × 10.
^{Was 4} .

[0226]

[Chemical 21]

Synthesis Example 20 of Resin [P]: [P-20] Methyl Methacrylate 50 g, Ethyl Methacrylate 2
A mixture of 5 g and 1.0 g of benzylisopulsanate 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 from a distance of 10 cm through a glass filter for 6 hours for photopolymerization.
The monomer (m-1) (25 g) was added thereto, and the atmosphere was replaced with nitrogen, and light irradiation was carried out again for 10 hours. The resulting 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 ⁴ .

[0228]

[Chemical formula 22]

Synthesis Examples 21 to 27 of Resin [P]: [P-2
1] to [P-27] In the same manner as in Synthesis Example 19 of Resin [P], each copolymer shown in Table G below was synthesized. Mw of the obtained polymer is 3.5 ×
It was in the range of 10 ^{4 to} 6 × 10 ⁴ .

[0230]

[Table 10]

[0231]

[Table 11]

Synthesis Example 28 of Resin [P]: [P-28] In Synthesis Example 19 of Resin [P], benzyl N, N-
A copolymer having Mw of 4.5 × 10 ⁴ was obtained in the same manner as in Synthesis Example 19 except that 18 g of an initiator [I-11] having the following structure was used instead of diethyldithiocarbamate.

[0233]

[Chemical formula 23]

Synthesis Example 29 of Resin [P]: [P-29] In Synthesis Example 20 of Resin [P], an initiator [I-12] 0.
Mw was reacted in the same manner as in Synthesis Example 20 except that 8 g was used.
2.5 × 10 ⁴ copolymer was obtained.

[0235]

[Chemical formula 24]

Synthesis Example 30 of Resin [P]: [P-30] Methyl methacrylate 68 g, methyl acrylate 22
g, 10 g of glycidyl methacrylate, 17.5 g of an initiator [I-13] having the following structure, and tetrahydrofuran 1
50 g of the mixed solution was heated to a temperature of 50 ° C. under a nitrogen stream. This solution was irradiated with light from a high pressure mercury lamp of 400 W at a distance of 10 cm through a glass filter for 10 hours to perform photopolymerization. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to give a yield of 72 g and a Mw of 4.0.
A polymer of × 10 ⁴ was obtained.

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

[0238]

[Chemical 25]

Synthesis Examples 31 to 38 of Resin [P]: [P-3
1] to [P-38] In the synthesis example 30 of the resin [P], the initiator [I-13]
Instead of 17.5 g, the initiator [I] 0.
It operated on the same conditions as the synthesis example 30 except having used 031 mol. The yield of each polymer obtained was 70 to 80 g and Mw.
It was 4 × 10 ^{4 to} 6 × 10 ⁴ .

[0240]

[Table 12]

[0241]

[Table 13]

[0242]

[Table 14]

[Synthesis Example of Resin Particles [L]] Synthesis Example 1: Resin Particles [L] 1: [L-1] 40 g of the monomer (LM-1) having the following structure, 2 g of ethylene glycol dimethacrylate, and the following structure Dispersion stabilizing resin [LP-1] 4.0 g and methyl ethyl ketone 180 g
The mixed solution of 1 was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. 0.3 g of 2,2'-azobis (isovaleronitrile) (abbreviation AIVN) was added and reacted for 3 hours.
In addition, A. I. V. N. 0.1 g was added and reacted for 4 hours. After cooling, a white dispersion was obtained through a 20-mesh nylon cloth, which was a latex having an average particle size of 0.25 μm (particle size: CAPA-500 (manufactured by Horiba, Ltd.)).
Measured by).

[0244]

[Chemical formula 26]

Synthesis Example 2 of Resin Particles [L]: [L-2] [AB-6] as a dispersion stabilizing resin (Toa Gosei Co., Ltd.)
A mixed solution of 5 g of monofunctional macromonomer (manufactured by butyl acrylate unit) and 140 g of methyl ethyl ketone was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. To this, 40 g of the monomer (LM-2) having the following structure, 1.5 g of ethylene glycol diacrylate, A. I.
V. N. A mixed solution of 0.2 g and 40 g of methyl ethyl ketone was added dropwise over 1 hour. After reacting for 2 hours as it is, A. I. V. N. 0.1 g was added and reacted for 3 hours to obtain a white dispersion. After cooling, the average particle size of the dispersion obtained through a 200-mesh nylon cloth was 0.35 μm.

[0246]

[Chemical 27]

Synthesis Examples 3 to 11 of Resin Particles [L]: [L-
3] to [L-11] In Synthesis Example 1 of resin particles [L], 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 I below. The average particle diameter of the obtained resin particles is 0.15 to 0.30 μm.
Was in the range.

[0248]

[Table 15]

[0249]

[Table 16]

Synthesis Examples 12 to 17 of Resin Particles [L]: [L
-12] to [L-17] In Synthesis Example 2 of resin particles [L], 5 g of the dispersion stabilizing resin [AB-6] is used instead of the resin [LP] shown in Table J 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 is 0.10 to 0.25.
It was in the range of μm.

[0251]

[Table 17]

[0252]

[Table 18]

Synthesis Examples 18 to 23 of Resin Particles [L]: [L
-18] to [L-23] In Synthesis Example 2 of resin particles [L], the monomer (LM-
2) Synthesis Example 2 except that 6 g of a resin [LP-8] having the following structure was used in place of 5 g of the resin [AB-6] for dispersion stabilization instead of 40 g of the monomers shown in Table K below. Each resin particle was synthesized in the same manner as. The average particle size of the obtained particles was in the range of 0.05 to 0.20 μm.

[0254]

[Chemical 28]

[0255]

[Table 19]

[0256]

[Table 20]

Example 1 and Comparative Examples 1 and 2 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, 0.15 g of a compound [A] having the following structure, and 80 g of tetrahydrofuran.
The mixture was put in a 500 ml glass container together with glass beads, dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.) for 60 minutes, and 0.2 g of resin [P-1] was added to the mixture and dispersed for 2 minutes. The beads were filtered to obtain a photosensitive layer dispersion liquid.

[0258]

[Chemical 29]

Then, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate with a wire bar, dried by touch with a finger, and then dried in a circulating oven at 110 ° C. for 20 minutes. Heated for seconds. The film thickness of the obtained photosensitive layer was 8 μm. The adhesive force on the surface of the photoconductor was 5 gf. On the other hand, the adhesive force of the surface of the photosensitive member made of a photosensitive layer prepared in exactly the same manner except that 0.2 g of the resin [P-2] used in the present invention was removed from the photosensitive layer was 450 gf.
No peelability was exhibited.

The above photoconductor was mounted as an electrophotographic photoconductor in the apparatus shown in FIG. The peripheral speed of the photosensitive drum is 1
The resin particles were rotated at 0 mm / sec and a slit electrodeposition device was used on the surface of the photoconductor to produce 4.2 g (as solid content) of thermoplastic resin particles [ARH-3], thermoplastic resin particles [ARL-1] 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
While supplying a positively charged resin particle dispersion liquid prepared by adding 1 g of Isopar H (manufactured by Esso Co., Ltd.), the photoconductor side is grounded and -180 V is applied to the electrode side of the slit electrodeposition apparatus.
Was applied to electrodeposit the resin particles. Then remove the dispersion with an air squeeze and melt with an infrared line heater,
A film was formed to form a thermoplastic resin transfer layer. The film thickness at this time was 4 μm. (Comparative Example 1) In Example 1, only 6 g of resin particles [ARH-3] were used instead of 4.2 g of transfer layer-forming resin particles [ARH-3] and 1.8 g of [ARL-1]. In the same manner as in Example 1, a transfer layer-forming electrophotographic photosensitive member was prepared. (Comparative Example 2) In Example 1, only 6 g of resin particles [ARL-1] were used instead of 4.2 g of transfer layer forming resin particles [ARH-3] and 1.8 g of [ARL-1]. In the same manner as in Example 1, a transfer layer-forming electrophotographic photosensitive member was prepared.

Toner images were formed on these photoconductors by the following operations. After corona charging the photosensitive member to +450 V in a dark place, the original document is read by a color scanner in advance, color separation is performed, and some corrections relating to color reproduction unique to the system are added, and then digital image data in the system is recorded. 5mW in negative mirror image mode based on the information about yellow among the colors of yellow, magenta, cyan and black stored in the hard disk
An output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength of 780 nm) is used, and 30e is applied on the surface of the photosensitive material.
Exposure was performed at a pitch of 25 μm and a scan speed of 300 cm / sec under an irradiation amount of rg / cm ² . continue,
A yellow liquid developer for Signature System (Eastman Kodak), diluted 75 times (weight ratio) with Isopar H (Esso Standard Petroleum), is used, and a developing device having a pair of flat plate developing electrodes is used as a photosensitive material. + For surface electrode
A bias voltage of 400 V was applied to carry out reversal development in which the toner was electrodeposited on the exposed portion.
Rinsing was performed in a single bath to remove stains on the non-image area.

The above processing was repeated for each color of magenta, cyan and black. An image was fixed on the photosensitive material after plate making obtained as described above by a fixing method using a heat roll. The image (fogging, fog, etc.)
The image quality) was visually evaluated. Next, the coated paper, which is the material to be transferred, and the light-sensitive material after four-color development are overlaid, and 8 kgf / c
It was passed at a speed of 12 mm / sec between a pair of rubber rollers whose surface temperature was controlled at 80 ° C. at a pressure of m ² in contact with each other.

After that, the coated paper and the photosensitive material were peeled off after being cooled to room temperature while being piled up, and the image (fog, image quality of the image) formed on the obtained coated paper was visually evaluated. Next, the obtained copy paper is put into a file made of a commercially available vinyl chloride sheet, and a load of 1 kg is applied (30 ° C. 80% RH).
The sample was left to stand for 1 week under the condition of 1. and the presence or absence of transfer of the transfer layer and the toner image to the sheet was visually evaluated. Table above
It is shown in L.

[0264]

[Table 21]

The copied image formed on the electrophotographic photosensitive member provided with the transfer layer was free from the fog in the non-image area in each of the present invention, Comparative Example 1 and Comparative Example 2, and the image quality of the toner image was clear. It was good. This indicates that the resin [P] of the present invention used in the photoconductive layer and the transfer layer formed on the photoconductive layer do not adversely affect the electrophotographic characteristics in practical use.

Next, the characteristic of the color image forming system of the present invention, the image reproducibility on the coated paper when the toner image portion together with the transfer layer is peeled off from the photoconductor and transferred to the coated paper which is the material to be transferred. As a result of examination, only the present invention completely transferred the toner image onto the coated paper without transfer residue on the photoreceptor. Furthermore, when visually observing the toner image area on the coated paper with a 200x optical microscope, no defects such as fine lines / fine characters, high-definition image areas such as halftone dots or crushing were observed, and the reproducibility of the copied image to the original Was good.

On the other hand, in Comparative Examples 1 and 2, the transfer layer had a large amount of transfer unevenness, and the color image on the coated paper was not suitable for practical use. The occurrence of transfer unevenness in Comparative Example 1 is mainly due to insufficient release of the transfer layer from the photosensitive layer due to insufficient thermoplasticization of the transfer film under the transfer conditions of this example. Conceivable. In addition, the transfer unevenness of Comparative Example 2 is
It is considered that since the thermoplastic layer temperature of the transfer layer film was too low, the cohesive force of the transfer layer resin itself became weaker than the adhesion force of the transfer layer with the coated paper, and the transfer layer itself was indiscriminately peeled off.

As described above, the transfer layer used in the present invention has good releasability from the surface of the photoreceptor and adhesion to the material to be transferred, and does not peel due to cohesive failure of the transfer layer itself. I am satisfied. Further, the obtained color copying paper is subjected to filing on various poly sheets and the like, but it is practically important that the image side does not peel off at this time, and the present invention has no problem. Furthermore, even if the copy paper was added or stamped, it could be performed in the same manner as the case of the plain paper.

From the above, it was found that the full-color copying paper obtained by the color image forming method of the present invention has excellent image reproducibility and image storability.

Example 2 and Comparative Examples 3 and 4 In the apparatus shown in FIG. 6, an amorphous silicon photoconductor was used as the electrophotographic photoconductor (the adhesive force on the photoconductor surface was 170 gf). The surface temperature of the photoconductor is 60 ° C.
In addition, 6 g (as solid content) of the thermoplastic resin particles [AH-4], the charge control agent (CD- 1) 0.03g and silicone oil (KF
-96; manufactured by Shin-Etsu Silicone Co., Ltd.) (10 g) was added to 1 liter of Isopar G to supply the first positively charged resin particle dispersion liquid, and the photoreceptor side was grounded, and -200 V was applied to the electrode side of the slit electrodeposition apparatus. Voltage was applied to electrodeposit and fix the resin particles.

Next, on the surface of the photosensitive member provided with the first transfer layer, the thermoplastic resin particles [ARL-
7] 6 g (as solid content) and charge control agent (CD-
1) A second transfer layer was provided using the second positively charged resin particle dispersion liquid prepared by adding 0.03 g to 1 liter of Isopar G. By operating as described above, a transfer layer having a film thickness of the first transfer layer of 2 μm and a film thickness of the second transfer layer of 2 μm was provided on the amorphous silicon photoconductor.

(Comparative Example 3) A transfer layer forming electron was prepared in the same manner as in Example 2 except that only the first positively charged resin particle dispersion liquid was used and the applied voltage condition was -150V. A photographic photoreceptor was created. The thickness of the formed transfer layer was 4 μm. (Comparative Example 4) A transfer layer-forming electrophotographic photosensitive member was prepared in the same manner as in Example 2 except that only the second positively charged resin particle dispersion liquid was used and the applied voltage condition was -150V. It was created. The thickness of the formed transfer layer was 4 μm.

Toner images were formed on these photoconductors by the following operations. After each photoreceptor was corona-charged to +700 V, the same digital image data as in Example 1 was used. First, based on the information about yellow, this time in positive bust mode, a semiconductor laser was used to emit light at 780 nm. The exposure was performed so that the 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 photosensitive material side electrode. A bias voltage of +300 V was applied to the exposed area to perform reversal development so that the toner was electrodeposited on the exposed area, and then rinsed in a bath of Isopar H alone to remove stains on the non-image area.

The above processing was repeated for each color of magenta, cyan and black. Next, the coated paper, which is the material to be transferred, and the light-sensitive material after the four-color development are superposed, and the surface temperature which is in contact with at a pressure of 10 kgf / cm ² is kept between 70 ° C. between a pair of rubber rollers. It was passed at a speed of 8 mm / sec. After that, the coated paper and the light-sensitive material were peeled off by cooling to room temperature while being piled up to obtain a color image copying paper.

In the same manner as in Example 1, the image pickup property, image reproducibility and filing suitability were examined. All of the present inventions were good. On the other hand, in Comparative Examples 3 and 4, due to uneven transfer, the color image reproducibility on the coated paper lacked the image portion. Regarding the filing suitability, in Comparative Example 4, peeling to the sheet occurred. From the above, only the one of the present invention showed good performance. Example 3 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 2
g, 10 g of a binder resin [B-2] having the following structure, 0.18 g of a compound [B] having the following structure, and 80 g of tetrahydrofuran.
The mixture was placed in a 500 ml glass container together with glass beads and dispersed with a bainto shaker (manufactured by Toyo Seiki Seisakusho) for 60 minutes, and further resin [P-2] 0.3
g, 0.03 g of phthalic anhydride and 0.001 g of O-chlorophenol were added and dispersed for 2 minutes, and then the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0276]

[Chemical 30]

[0277]

[Chemical 31]

Then, this dispersion was applied onto a 0.2 mm thick aluminum plate that had been subjected to conductivity treatment and solvent resistance treatment with a wire bar, and was dried by touch with a finger, and then heated in a circulating oven at 110 ° C. for 30 minutes. Crosslinked The film layer was 8 μm. The peeling property of the surface of the photoconductor was measured by the above-mentioned “adhesive tape / adhesive sheet test method”, and the adhesive force was 5 g · f.
Met.

In the above photoreceptor, the resin of the present invention [P
-2] The adhesive strength of the surface of the photoconductor prepared except for 0.3 g was 450 g · f or more and showed no peeling property. The photoconductor was attached to the apparatus shown in FIG. In the transfer layer, as a thermoplastic resin, an ethylene-vinyl acetate copolymer (vinyl acetate content 20% by weight, Tg 40 ° C.) and a (vinyl acetate / vinyl butyrate (80/30) weight ratio) copolymer (Tg18
C.) at a (6/4) weight ratio, and is coated on the surface of the photosensitive layer at a speed of 20 mm / sec by a hot melt coater set at 120.degree. C., and then cooled by blowing cooling air from an intake / exhaust unit on the surface of the photosensitive member. The temperature was kept at 30 ° C. The thickness of the transfer layer at this time was 3 μm.

Next, this photosensitive material (hereinafter also referred to as a light-sensitive material) 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 obtain a system-specific number. Of the colors yellow, magenta, cyan, and black, which were stored in the hard disk of the system as digital image data after correction related to color reproduction, the semiconductor laser was first based on information about yellow. Was used to expose with 780 nm light. The potential of the exposed part is + 220V
The unexposed portion was + 600V.

Then, after pre-basing with Isopar H (manufactured by Esso Standard Petroleum) using a pre-bath device incorporated in the developing unit, Versatec 3000
A wet developer prepared by diluting positively charged yellow toner for (Xerox color electrostatic blotter) with 50 times Isopar H was supplied from the developing unit to the surface of the photoreceptor. At this time, a developing bias voltage of +500 V was applied to the developing unit side to carry out reversal development so that the toner was electrodeposited on the yellow unexposed portion. Then, rinsed in a bath of Isopar H alone to remove stains on the non-image area, and dried in an intake / exhaust unit.

The above processing was repeated for each color of magenta, cyan and black. Next, turn on the infrared line heater and let it pass underneath, measure the surface temperature with a radiation thermometer to approximately 80 ° C, and then stack the coated paper and contact it with a pressure of 10 kgf / cm ² Is 12
It was passed under a heated rubber roller which was constantly controlled at 0 ° C. at a speed of 15 mm / sec.

Then, when the coated paper was peeled off after passing through a cooling roller to cool it, the toner on the photosensitive material was thermally transferred to the coated paper side together with the transfer layer. Further, since the toner was completely covered with the thermoplastic resin as the transfer layer on the coated paper, it did not rub off. Example 4 Amorphous silicon for an electrophotographic photosensitive member was surface-treated with a silane coupling agent of tridecylhexyltrimethoxysilane to modify the surface of the amorphous silicon and adjust the releasability of the surface.

By the above treatment, the adhesive strength, which was 180 g · f, was lowered to 50 g · f. The photoconductor was mounted on the apparatus shown in FIG. 4, and the transfer layer was transferred from the release paper shown in FIG. That is, a separate paper (manufactured by Oji Paper Co., Ltd.) was used as a release paper, and a resin [AL] [vinyl acetate / vinyl propionate (75/25) weight ratio] was added on top of this.
Copolymer (Tg22 ° C.) and resin [AH] [methyl methacrylate / methyl acrylate (6/4) weight ratio] Copolymer (Tg40 ° C.) in a (50/50) weight ratio with a film thickness of 3 μm. The paper on which the coating film was formed was pressed against the photoreceptor to transfer the transfer layer onto the surface of the photoreceptor. Then, the photosensitive material is subjected to color image formation and image transfer operation for each transfer layer onto coated paper in the same manner as in Example 2,
A color image was created.

The color image of the obtained coated paper was a good image without fog, and the image strength was sufficient, as in Example 2. Examples 5 to 16 In Example 1, the resin [P-1] used in the photosensitive layer was 0.1.
2 g and resin particles for transfer layer [ARH-3] and [ARL
-1] instead of each resin [P] and / or resin particle [L] and each resin particle [ARH] 4 g / [A] in Table-M.
A color image was formed in the same manner as in Example 1 except that 4 g of RL] was used.

[0286]

[Table 22]

The color image on the coated paper obtained by operating under these conditions had no problem at all. In addition, no transfer layer remained on the surface of the photoreceptor after transfer when transferred under these conditions. The above shows that the transferability of the transfer layer becomes easier because the transfer layer is composed of the resin [A] having a low Tg and the resin [A] having a high Tg. Examples 17 to 26 In Example 2, as transfer layer resin particles, 6 g of resin particles [AGH-4] of the first layer and resin particles of the second layer [A
RL-7] Instead of 6 g, each resin particle 6 in Table N below.
Using the dispersion liquid in which g was dispersed, the transfer layer was adjusted to 4 μm, and the distribution ratio of [ARH] and [ARL] was adjusted to the values shown in Table-N. Then, a color image was created on the coated paper.

[0288]

[Table 23]

The color copy paper obtained had a good copy image as in Example 2. The image storability was also very good. Examples 27 to 32 Resin [P-12] 1.0 g, binder resin [B-
3] 15 g, phthalic anhydride 0.03 g and toluene 10
A coating film having a thickness of 1.5 μm was formed on an amorphous silicon photoconductor using 0 g of the mixed solution, dried by touch with a finger, and further heated at 130 ° C. for 1 hour to cure the film.
The adhesive force on the surface of the amorphous silicon photoconductor provided with the transfer layer was 3 gf.

[0290]

[Chemical 32]

In Example 3, the above photoconductor was used instead of the X-type phthalocyanine photoconductor, and each resin [AH] and resin [AH] of the following Table-O was used as the resin [A] for the transfer layer.
L] was used to form a transfer layer. Subsequent operations were performed in the same manner as in Example 2 to form a color image and transfer it to coated paper to form a color image. However, in Table-O below, the Tg of the resin [AH] is in the range of 40 ° C to 90 ° C, and the Tg of each resin [AL] is -20 ° C to 25 ° C.
It was in the range of ° C.

[0292]

[Table 24]

[0293]

[Table 25]

Examples 33 to 42 A color image was formed on coated paper in the same manner as in Example 4 except that the method for forming the transfer layer was changed to the following contents. [Method of forming transfer layer] As a release paper, a paper of each resin [A] of the following Table-P having a film thickness of 4 μm was mounted on Sunrelease (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) on 117 of FIG. A transfer layer was transferred and formed on the surface of the photoconductor under the conditions of a roller pressure of 3 kgf / cm ² , a surface temperature of 80 ° C., and a passing speed of 10 mm / sec.

[0295]

[Table 26]

[0296]

[Table 27]

[0297]

[Table 28]

The color image obtained was a clear image without background fog, and almost no deterioration in image quality was observed as compared with the original. This means that the transfer layer at each transfer is evenly and completely transferred by the method of forming the transfer layer on the photoconductor using a release paper, and then transferring the toner image to the coated paper. It shows that the adverse effect of deterioration does not occur. Examples 43 to 55 In Example 3, 10 g of resin [B-2] and resin [P-
2] In place of 0.3 g and the compound for crosslinking (phthalic anhydride, o-chlorophenol), each resin (resin [B] 10 g, resin [P] 0.3 g) described in the following Table-Q was used.
Further, an electrophotographic photosensitive member and a color copying paper were prepared in the same manner as in Example 3 except that each compound shown in Table-Q below was used as a crosslinking compound.

When various materials were evaluated in the same manner as in Example 3, the same results as in Example 1 were obtained in all cases. That is, a coated paper on which a clear color image having no background stain was formed was obtained. Also, filing property,
The writing and stamping properties were also good.

[0300]

[Table 29]

[0301]

[Table 30]

[0302]

[Table 31]

[0303]

[Table 32]

Example 56 As an organic photoconductive substance, 5 g of 4,4'-bis (diethylamino) -2,2'-dimethyltriphenylmethane,
Polyester resin; Byron 200 (Toyobo Co., Ltd.)
5 g), 40 mg of the dye [D-1] having the following structural formula, and 0.2 anilide compound (B) having the following structural formula as a chemical sensitizer.
g was dissolved in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride to prepare a photosensitive solution.

[0305]

[Chemical 33]

This photosensitive solution was applied onto a conductive transparent support (100 μm polyethylene terephthalate support with a vapor-deposited film of indium oxide; surface resistance 10 ³ Ω) using a wire round rod, and applied to about 4 μm. An organic thin film having a photosensitive layer of was obtained. Then, on this photoreceptor,
The following solutions were prepared in order to form an overcoat layer for imparting releasability.

[Methyl methacrylate / 3- (trimethoxysilyl) propyl methacrylate] (70/30) copolymer (Mw4 × 10 ⁴ ) 3 g Resin [P-11] 0.15 g Crosslinking compound having the following structure 0.01 g Dibutyl Dilauryl tin 0.002 g Toluene 100 g

[0308]

[Chemical 34]

This solution was applied with a wire bar to a thickness of 2.0 μm, oven-dried at 100 ° C. for 20 seconds, and further heated at 120 ° C. for 1 hour. Then, the electrophotographic photosensitive member was prepared by leaving it in the dark at 20 ° C. and 65% RH for 24 hours. The adhesive strength of the surface of the photoconductor was 0 gf. On the surface of this photoreceptor, in the same manner as in Example 1, instead of 4.8 g of resin particles [AH-3] and 1.8 g of resin particles [AL-1], 3 g of resin particles [AH-2] and resin particles [AL-4] A film thickness of 4 μm was obtained in the same manner as in Example 1 except that 3 g (each as a solid content) was used.
To form a transfer layer.

The surface potential of this photosensitive material was +500 in the dark.
After charging to V, 633 using He-Ne laser
After exposing the plate to an exposure amount of 30 erg / cm ² with a light of nm, the same operation as in Example 1 was carried out to prepare a color copying paper. The color image on the obtained coated paper was a clear image quality without background stain. In addition, there was no problem in the filing property, the writing property and the marking property. Example 57 5 g of a bisazo pigment having the following structure, tetrahydrofuran 95
g, a polyester resin (Vylon 200) 5 g, and a tetrahydrofuran solution 30 g were thoroughly ground in a ball mill. Then, 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 1 using a wire round rod to form a charge generation layer having a thickness of about 0.7 μm. Next, a hydrazone compound 20 having the following structural formula
g, 20 g of polycarbonate resin (trade name: Lexan 121, manufactured by GE) and 160 g of tetrahydrofuran are applied on the charge generation layer using a wire round rod, dried at 60 ° C. for 30 seconds, and dried at a temperature of 100.
The film was heated at 0 ° C. for 20 seconds to form a charge transport layer having a thickness of about 18 μm, and an electrophotographic photosensitive member having a two-layer photosensitive layer was obtained.

[0311]

[Chemical 35]

[0312]

[Chemical 36]

Further, in order to form a surface layer for imparting releasability on this photosensitive layer, a resin of the following structural formula [P
-39] A mixed solution of 13 g, phthalic anhydride 0.2 g, o-chlorophenol 0.002 g and toluene 100 g was applied to a coating film of 1 μm using a wire round rod, dried at the touch and further 120 ° C. Heated for 1 hour. The adhesive force on the surface of the obtained photoreceptor was 3 gf.

[0314]

[Chemical 37]

Further, in order to form a transfer peeling layer on this photosensitive layer, 4.5 g of resin particles [ARH-9] and 2 g of resin particles [ARL-9] were used in the same manner as in Example 1 to obtain a film thickness. A 4.5 μm transfer layer was formed. In the same manner as in Example 1, a full-color image was formed on the coated paper. The copy paper obtained showed good performance as in Example 1. Example 58 100 g of photoconductive zinc oxide, a binder resin [B-
17] 20 g, the resin [P-35] 3 g, uranine 0.01 g, rose bengal 0.02 g, bromphenol blue 0.01 g, maleic anhydride 0.15 g, and toluene 150 g are homogenized (Nippon Seiki Co., Ltd.). Manufactured), and the rotation speed is 9 × 10 ³ r. p. m. In 1
Dispersed for 0 minutes.

[0316]

[Chemical 38]

To this dispersion, 0.02 g of phthalic anhydride and 0.001 g of o-chlorophenol were added and further dispersed at a rotation speed of 1 × 10 ³ for 1 minute. Next, this dispersion was coated on a 0.2 mm thick base paper for a master for a printing plate with a conductive treatment and a solvent resistance treatment with a wire bar so as to have a coating amount of 25 g / m ^2, and was dried by touch with a finger. Heated in a circulating oven for 1 hour.

The adhesive force of the photoreceptor thus obtained was 10 gf. On the other hand, as a comparison, in the above photoreceptor, the adhesive force of the surface of the electrophotographic photoreceptor prepared in the same manner except that 3 g of the resin [P-35] was not used, was 380 g.
It was f and did not show peelability. Further, a transfer layer having a two-layer structure was formed on the photosensitive layer by the following method.

A film was prepared in the same manner as in Example 1 except that 6 g of resin particles [ARH-2] and 0.03 g of zirconium naphthenate as a charge control agent were added to 1 liter of Isopar H to prepare a dispersion. A transfer layer having a thickness of 2.5 μm was formed. Next, thermoplastic resin particles [ARL-10]
6 g and (CD-1) 0.02 g were added to 1 liter of Isopar H to prepare a positively charged particle dispersion liquid, and in the same manner as above, on the surface of the first transfer layer forming photoconductor, A transfer layer having a film thickness of 2.5 μm was formed.

This photoreceptor was corona-charged to -550V,
After image exposure by flash exposure with a halogen lamp having an output of 1.6 kW, the bias voltage of the developing section was set to 100 V, and positive development was performed using the color toner for Versatec 3000 used in Example 2 as the liquid toner. Then, a color image was formed. The copy image formed on the obtained transfer layer is clear and good even in high-definition image areas such as continuous gradation areas consisting of character thin lines and halftone dots, and scumming in non-image areas is also recognized. There wasn't.

Next, the photoreceptor on which an image was formed as described above was passed between a pair of heating rollers in which an infrared lamp heater was incorporated inside a hollow metal roller coated with silicone rubber so as to overlap the coated paper. It was At this time, the roller surface temperature was 70 ° C. both above and below, the nip pressure between the rollers was 8 kgf / cm ² , and the transport speed was 12 mm /
Set to seconds. After passing, the coated paper was cooled to room temperature while being overlapped with the coated paper, and then the photoreceptor was separated from the coated paper.

The toner image area and the transfer layer were completely transferred to the coated paper side, and the color image on the coated paper was a clear image with clear image quality without background fog. Furthermore, the filing suitability, the writing property, and the imprintability were good without any practical problems. Example 59 100 g of photoconductive zinc oxide, a binder resin [B-
18] 2 g and [B-19] 18 g, resin [P-12]
2 g, dye [D-2] of the following structure 0.02 g, N-hydroxysuccinimide 0.02 g and toluene 150 g
Was put into a homogenizer (manufactured by Nippon Seiki Co., Ltd.), and the rotation speed was 1 × 10 ⁴ r. p. m. Dispersed for 5 minutes.

[0323]

[Chemical Formula 39]

Next, this dispersion was coated on a 0.2 mm thick base paper for a master for a printing plate with a wire bar, dried by touch with a finger, and then dried in a circulating oven at 110 ° C. for 15 minutes. Heated for seconds. The film thickness was 12 μm. In order to confirm the uneven distribution of the block copolymer of the present invention on the surface of the photosensitive layer, the adhesive force was measured with an adhesive tape, and the adhesive force of the sample in which the block copolymer [P-12] was not added was measured. It has been reduced to 1/100 and 5
It was gf.

Further, a transfer layer having a two-layer structure was formed on this photosensitive layer by the same operation as in Example 58. However, Example 5
8, 6 g of resin particles [ARH-5] were used instead of 6 g of resin particles [ARH-2].
6 g of resin particles [ARL-8] were used instead of 6 g of 0]. Next, after charging this photosensitive material at −6 kV, the original was read by a color scanner in advance, and in the positive mirror image mode based on the information stored in the hard disk in the system as digital image data, 5
Using a gallium-aluminum-arsenic semiconductor laser with an mW output (oscillation wavelength 780 nm), exposure was performed on the surface of the photosensitive material at an irradiation dose of 30 erg / cm ² at a pitch of 25 μm and a scan speed of 300 cm / sec. After the developing operation, the color image was formed on the coated paper in the same manner as in Example 1.

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 being observed, and the transfer of each transfer layer to the coated paper causes uneven transfer. It was completely transcribed without occurring. This embodiment shows that a high-definition image can be reproduced even by the scanning exposure method using a low-output semiconductor laser light in contrast to the flash exposure with high-output visible light as in the above-mentioned Embodiment 58. This is due to the effect of using a low molecular weight copolymer composed of a specific methacrylate component and a specific polar group-containing polymer component as a binder resin for the photoconductor.

In the photoconductive layer, instead of the binder resin [B-18] 2 g and [B-19] 18 g,
In the transfer layer forming photoreceptor prepared in the same manner as described above except that only 20 g of the resin [B-19] was used, the image transferred to the material to be transferred is a sub-line image of a character line drawing at a level at which there is no practical problem. However, the image composed of continuous halftone dots had unevenness especially in the halftone part. Furthermore, when the environmental conditions fluctuate, the image part of the character / drawing is deteriorated.

Therefore, unlike the case where the electrophotographic photosensitive member is exposed by the whole surface simultaneous exposure system using a high output visible light source, the electrophotographic characteristics can be obtained by the combined photoconductive layer even in the scanning exposure system using the low output semiconductor laser beam. The color image forming system can be further improved in performance by using it together with a technique for improving (especially the charge retention ratio in the dark and photosensitivity). Examples 60 to 65 In Example 59, the resin [B-18] 2 g, the dye [D
-2] A full-color copying paper was prepared in the same manner as in Example 59 except that each material shown in Table-R below was used instead of 0.02 g of the resin [P-12] 2 g.
In each case, a copy paper having the same performance as that of Example 59 was obtained.

[0329]

[Table 33]

[0330]

[Table 34]

[0331]

INDUSTRIAL APPLICABILITY The present invention provides a releasable photoreceptor surface with
By forming a transfer layer containing a thermoplastic resin having a high glass transition point and a thermoplastic resin having a low glass transition point, and performing wet toner development, by transferring the transfer layer together with the transfer target material, high definition, It is possible to easily obtain a high quality glass image. Further, the obtained color copy has excellent storage stability. Further, by performing the step of forming the transfer layer on the surface of the photoconductor in the apparatus that performs the electrophotographic process step and the thermal transfer step to the material to be transferred, the photoconductor can be repeatedly used without being discarded. Yes, low cost can be achieved.

[Brief description of drawings]

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

FIG. 2 is a diagram showing an example of an apparatus for thermally transferring a transfer layer onto a transfer material.

FIG. 3 is a diagram showing an example of a transfer device to which a transfer layer forming method by melt coating is applied.

FIG. 4 is a diagram showing an example of an apparatus for forming a transfer layer on a photoconductor by using a release paper.

FIG. 5 is a diagram showing an example of a transfer device to which a transfer layer forming method using release paper is applied.

FIG. 6 is a diagram showing an example of a transfer device to which a transfer layer forming method utilizing an electrodeposition method is applied.

[Explanation of symbols]

1 Support for photoconductor 2 Photosensitive layer 3 Toner image 4 rubber covered roller 5 Built-in heater 6 Surface temperature detection means 7 Temperature controller 10 Release paper 11 photoconductor 12 Transfer layer 12a thermoplastic resin 12b Dispersion of thermoplastic resin particles 13 Hot melt coater 13a Hot melt coater standby position 14 Liquid development unit set 14T electrodeposition unit 14y Yellow liquid developing unit 14m magenta liquid development unit 14c Cyan liquid developing unit 14b Black liquid developing unit 15 Intake and exhaust unit 15a intake part 15b Exhaust part 16 Transfer material 17 Thermal transfer means 17a Preheating means 17b heating roller 17c Cooling roller 18 Corona charging device 19 Exposure equipment 117 thermal transfer means 117b heating roller 117c Cooling roller

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-5-197169 (JP, A) JP-A-1-281464 (JP, A) JP-A-1-112264 (JP, A) JP-A-61- 174557 (JP, A) JP 2-244146 (JP, A) JP 64-52135 (JP, A) JP 3-180858 (JP, A) JP 50-31824 (JP, A) JP-A-3-11347 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 5/00-5/16 G03G 13/16 G03G 15/01

Claims (6)

(57) [Claims] 1. A color image forming method in which a toner image of one or more colors is formed on a transfer layer provided on the surface of an electrophotographic photosensitive member by an electrophotographic process, and the toner image together with the transfer layer is thermally transferred to a transfer material. JIS of the surface of the photoconductor
Z0237-1980 “Adhesive tape / adhesive sheet test method” has an adhesive force of 200 gram · force (g
f) or less, and the transfer layer has a glass transition point of 30 ° C.
-140 ° C thermoplastic resin [AH] and glass transition point -2
It mainly contains a thermoplastic resin [AL] at 0 ° C to 40 ° C, and has a glass transition between the resin [AH] and the resin [AL].
A color image forming method characterized in that the difference between the points is 2 ° C. or more. 2. The transfer layer, wherein a layer mainly containing a thermoplastic resin [AH] is provided on a photoreceptor having an adhesive force of 200 gf or less, and a layer mainly containing a thermoplastic resin [AL] is further provided thereon. 2. The color image forming method according to claim 1, wherein the color image forming method has a laminated structure. 3. A polymer component (s) in which at least one of the thermoplastic resins [AH] and [AL] contains at least one of a fluorine atom and a silicon atom.
3. The method for forming a color image according to claim 1, further comprising: as a copolymer component. 4. The electrophotographic photosensitive member is a photosensitive member containing amorphous silicon as a main component, or contains a polymerization component containing at least one of a fluorine atom and a silicon atom in a layer adjacent to the transfer layer. The color image forming method according to claim 1, which is a photoreceptor containing a polymer. 5. The adhesive strength according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method” is 200 g.
A transfer layer containing a thermoplastic resin [AH] and a thermoplastic resin [AL] is formed on the surface of the electrophotographic photosensitive member having a thickness of f or less, and one or more toner images are formed on the transfer layer by an electrophotographic process. 2. The method for forming a color image according to claim 1, wherein the toner image is transferred together with the transfer layer to the transfer material by thermal transfer. 6. A peelable transfer layer containing, as a main component, a thermoplastic resin [A] containing the resin [AH] and the resin [AL] according to any one of claims 1 to 3 as a top layer. And JIS Z on the surface of the photoconductor adjacent to the transfer layer.
An electrophotographic color image-forming photoreceptor having an adhesive strength of 200 gf or less according to “Test method for adhesive tape / adhesive sheet” of 0237-1980.