JPH0850380A - Production of electrophotographic printing plate and producing device for printing original plate - Google Patents

Abstract

PURPOSE:To obtain a printing plate having an image of high precision and high picture quality in which transferability and desensitizing property of a transfer layer is improved. CONSTITUTION:A toner image 5 is formed on an electrophotographic photoreceptor 11 by an electrophotographic process, on which a peelable transfer layer 12 containing a resin (A) which can be removed by chemical reaction treatment is formed. Then the toner image 5 and the transfer layer 12 are transferred altogether onto a primary receptor 20. Further, the toner image 5 on the primary receptor 20 is transferred to a material 30 as a hydrophilic surface on which planographic printing is enabled in a printing process together with the transfer layer 12. The transfer layer 12 of the transferred material 30 is removed by chemical reaction treatment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of preparing a lithographic printing plate using an electrophotographic photoreceptor and a transfer layer. The present invention relates to a method for making an electrophotographic plate-making printing plate and a printing original plate making apparatus used therefor.

[0002]

2. Description of the Related Art A lithographic printing plate, especially an electronic editing system which can be operated by a computer consistently from manuscript input, correction, editing, layout to page setting and can be immediately output to a terminal plotter at a remote place by a high speed communication network or sanitary communication. An electrophotographic photosensitive member is used as a photosensitive member having a high photosensitivity, which can provide a direct type printing plate for directly producing a lithographic printing plate from the output of an end plotter. As a method for creating a lithographic printing plate using an electrophotographic photosensitive member, after forming a toner image by an electrophotographic process, a method of desensitizing (hydrophilizing) the non-image area with a desensitizing treatment liquid, and using it as a printing plate, A method is known in which after the toner image is formed, the photoconductive layer in the non-image area is removed to form a printing plate. However, in the method of hydrophilizing the photosensitive layer to modify the surface of the electrophotographic photosensitive member itself to form a hydrophilic non-image area or the method of eluting and removing the photosensitive layer to expose the hydrophilic support surface, There are various restrictions on the body, especially on the photoconductive compound and the binder resin used in the photoconductive layer, and there have been many problems in terms of the image quality and printing durability of the obtained printing plate.

In order to solve such a conventional problem, a transfer layer made of a thermoplastic resin which can be removed by a chemical reaction treatment is provided on the surface of an electrophotographic photoreceptor, and a usual electrophotographic process is performed on the transfer layer. A toner image is formed using the toner image, and the toner image is transferred together with the transfer layer onto a transfer material that forms a hydrophilic surface as a lithographic printing plate, and then the transfer layer is removed to leave the toner image on the transfer material. The method of preparing a lithographic printing plate is described in International Publication WO93 / 16418.

[0004]

The method of making a printing plate using this transfer layer does not involve modifying the surface of the photoconductor to form a hydrophilic non-image area, but rather a transfer layer separate from the photoconductor. After the toner image is formed on the other support having a hydrophilic surface and the toner image is transferred together with the transfer layer, the transfer layer is removed by a chemical reaction treatment. A printing plate with good image quality can be obtained without being subject to various required restrictions.

However, according to this method, the transferability at the time of heat-pressure transfer of the transfer layer is not always sufficient, and a fine image portion may be missing, or the toner image and the transfer layer may remain on the surface of the photoreceptor. Was recognized. In particular, in order to satisfy the transferability of the transfer layer, there are restrictions on the material to be transferred.
It has been found that in the case of a transfer material having a relatively rough surface made of a paper support, the adhesion of the transfer layer is lowered, and as a result, the transfer property is not sufficient. In addition, in this method, a toner image is formed on a photoconductor having a transfer layer by a normal electrophotographic process. It was also necessary to satisfy the Ep characteristic).

[0006] Transferability, elution and Ep in one transfer layer
It is not easy to satisfy all of the characteristics, and various restrictions occur on the primary structure of the polymer such as the polymerization component and molecular weight of the resin used. In particular, the quality of Ep characteristics is
The effect of resin chargeability and dark decay (DQR) is large,
When the film thickness of the transfer layer exceeds 5 μm, the effect becomes more remarkable. As a result, inconvenience is likely to occur in the image reproducibility such as a decrease in the density of the copied image and a loss of fine lines and characters. On the other hand, if the transfer layer is made thin, the transferability tends to deteriorate, and it is very difficult to satisfy both the electrophotographic characteristics and the transferability.

The present invention, in the method of preparing a lithographic printing plate using such a transfer layer, can achieve excellent transferability and obtain a good image without considering the electrophotographic characteristics of the transfer layer. The object is to provide a method for producing a lithographic printing plate that can be used. Another object of the present invention is to provide a method for producing a lithographic printing plate using a transfer layer, which can completely transfer the transfer layer and the toner image portion regardless of the type of the material to be transferred. Another object of the present invention is to provide a method for producing a lithographic printing plate using a transfer layer, which has good transferability even if the transfer layer is made thin. Further, it is an object of the present invention to provide a method for preparing a lithographic printing plate using a transfer layer, which is capable of expanding the transfer latitude and relaxing the conditions for desensitizing treatment.

[0008]

The above object of the present invention is to form a toner image on an electrophotographic photosensitive member by an electrophotographic process, and then remove the resin (A) by a chemical reaction treatment.
Is formed on the toner image, the toner image and the transfer layer are collectively transferred onto a primary receptor, and the toner image on the primary receptor is transferred together with the transfer layer. Of an electrophotographic plate-making printing plate characterized by transferring to a transfer material which becomes a hydrophilic surface capable of lithographic printing at the time of printing, and then removing the transfer layer of the transferred transfer material by a chemical reaction treatment. It was found that this was achieved by the method of preparation.

As shown in FIG. 1, the process for producing the electrophotographic plate-making printing plate of the present invention comprises a conventional electrophotographic photosensitive member 11 comprising at least a support 1 and a photosensitive layer 2. Toner image 5 is formed by photographic process,
The transfer layer 12 is formed on the photoconductor 11 provided with the toner image 5. Then, the toner image 5 and the transfer layer 12 are collectively transferred onto the primary receptor 20, and further, the toner image is transferred onto the transfer material 30 which is a support similar to the support used for the offset printing plate by thermal transfer. 5 is transferred together with the transfer layer 12 to obtain a printing original plate. The transfer layer 12 transferred to the transfer material 30 is removed by a chemical reaction process to form a lithographic printing plate.

The first feature of the present invention is to form a transfer layer after forming a toner image on a photoreceptor by a usual electrophotographic process. Since the transfer layer used in the method for preparing a lithographic printing plate using a known transfer layer forms the transfer layer before forming a toner image by an electrophotographic process, the transfer layer has electrophotographic properties (chargeability, dark charge). Retention rate,
It was necessary to form a good copy image without deteriorating the photosensitivity). According to the present invention, the transfer layer may be designed so as to satisfy the transfer property and the elution property, and the electrical insulating property of the resin used can be ignored. As a result, it is possible to increase the latitude of transferability (reduce transfer pressure and transfer temperature, improve transfer speed) and reduce desensitization processing conditions.

A second feature of the present invention is that after the transfer layer is formed, the transfer layer is once transferred onto the primary receptor (intermediate medium) and then transferred onto the final transfer target material. Since it passes through the intermediate medium, the function of the intermediate medium as an elastic body (cushion effect) improves the transferability of the transfer layer and the toner image. That is, the transferability is improved because the primary receptor takes charge of the cushioning effect due to the thickness of the transfer layer itself. This makes it possible to find conditions for 100% complete transfer even when the final transfer materials differ, and it is possible to make the transfer layer thinner. Therefore, according to the present invention, the toner image formed on the photoconductor can be transferred to the final transfer material while reducing or eliminating the image deterioration, and a high-definition and high-quality image can be obtained. Further, the transfer condition and the desensitizing condition can be relaxed.

The present invention also provides a means for forming a toner image on an electrophotographic photosensitive member by an electrophotographic process suitable for carrying out the above method, and a peelable transfer layer on the photosensitive member on which the toner image is formed. Provided is an electrophotographic plate-making printing plate making apparatus having at least a means for providing, a means for transferring the toner image together with a transfer layer onto a primary receptor, and a means for transferring the toner image together with the transfer layer from the primary receptor onto a transfer material. .

The present invention will be described in more detail below. The electrophotographic photoreceptor used in the present invention will be described. As the electrophotographic photoreceptor, any conventionally known one can be used. What is important is that the surface of the photoreceptor has releasability when the toner image is formed so that the toner image formed on the photoreceptor can be easily peeled together with the transfer layer later. Particularly in the present invention, it is preferable that the surface of the photoreceptor at the time of forming a toner image has an adhesive force of 100 g · f or less according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method”. By adjusting the adhesive force in this manner, the toner image and the transfer layer formed on the photoconductor can be easily and completely transferred onto the primary receptor all at once.

Adhesive strength is measured according to JIS Z 0237-1980 "Adhesive tape / adhesive sheet test method" described in 18 of 8.3.1.
Follow the 0-degree peeling method with the following modifications. An electrophotographic photoreceptor on which a toner image and a transfer layer are to be formed is used as a "test plate". As the “test piece”, an adhesive tape having a width of 6 mm and manufactured according to JIS C 2338-1984 is used. Peel at a speed of 120 mm / min using a constant speed tension type tensile tester. That is, with the adhesive surface of the test piece facing down, the roller is reciprocated once over the test piece at a speed of about 300 mm / min to the test plate. During 20 to 40 minutes after crimping, using a constant speed tension type tensile tester, after peeling off about 25 mm, 120
Peel off at a speed of mm / min. The force is read every time it is peeled off by 20 mm, and a total of 4 times is read. The test is performed on three test pieces, and an average value of twelve pieces measured from the three test pieces is obtained, and the average value is proportionally converted per 10 mm width.

The adhesion of the primary receptor and the material to be transferred can be measured in the same manner by using these as test plates. The adhesive force on the surface of the electrophotographic photosensitive member is more preferably 50 g · f or less, particularly preferably 30 g · f.
It is the following.

In the present invention, an electrophotographic photosensitive member having a surface releasability may be used in advance, but before the toner image is formed, the surface of the photosensitive member contains at least a fluorine atom and / or a silicon atom. A desired releasability may be imparted to the surface of the photoreceptor by applying the compound (S). As a result, a normal electrophotographic photosensitive member can be used without considering the releasability of the surface of the electrophotographic photosensitive member. Further, the compound (S) may be applied when the releasability of the surface of the photoreceptor is lowered when the electrophotographic photoreceptor having the surface releasability is repeatedly used in the present invention. Thereby, the releasability of the surface of the photoconductor can be easily maintained. It is preferable that the release property is imparted to the electrophotographic photosensitive member in the above apparatus. This is performed by further installing a means for applying the compound (S) on the surface of the electrophotographic photosensitive member in the electrophotographic plate-making printing plate making apparatus.

In order to obtain a photoreceptor having a releasable surface, specifically, a method of using a photoreceptor having a releasable surface in advance, and a releasing compound (S ) Is used to impart releasability to the photoreceptor surface.

An example of a photoreceptor having a releasable surface that can be used in the former method is one using a photoconductor in which the surface of amorphous silicon is modified to be releasable. As a method of modifying the surface of the electrophotographic photosensitive member mainly containing amorphous silicon to be peelable,
There is a method of treating the surface of the amorphous silicon layer with a coupling agent (silane coupling agent, titanium coupling agent, etc.) containing a fluorine atom and / or a silicon atom, and the method is disclosed in JP-A-55-89844 and JP-A-4-89844. 2313
18, JP-A-60-170860, 59-102.
No. 244, No. 60-17750 and the like.
Further, as another method, a compound (S) described later, particularly a compound containing a component containing a fluorine atom and / or a silicon atom as a substituent in a block (for example, polyether, carboxylic acid, amino group, carbinol, etc.) A method of adsorbing and fixing modified polydialkyl silicons and the like can be mentioned.

Further, as another example of the photoconductor having a releasable surface, the electrophotographic photoconductor contains at least one of a silicon atom and a fluorine atom near the surface thereof (containing a silicon atom and / or a fluorine atom). The thing containing the polymer containing a polymer component is mentioned. Here, the vicinity of the surface of the electrophotographic photosensitive member means the uppermost layer of the photosensitive member, and includes the cover coat layer provided on the photoconductive layer and the uppermost photoconductive layer. That is, an overcoat layer is provided as the uppermost layer of the photoconductor having a photoconductive layer, and the polymer is added to the overcoat layer to impart releasability, or a photoconductive layer (single photoconductive layer and laminated light The above-mentioned polymer may be contained in the uppermost layer of any of the conductive layers), and the surface thereof may be modified so as to exhibit releasability. Since the surface of such a photoreceptor has a good releasability, the toner image and the transfer layer can be easily and completely transferred onto the transfer material together.

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

As such an overcoat layer, specifically, in a PPC photoreceptor using a dry toner,
A protective layer used for providing a surface layer on the photoconductor to protect the photoconductor is known as one means for maintaining durability of the photoconductor surface against repeated use of the photoconductor. For example, as a technique relating to a protective layer using a silicone block copolymer, JP-A-61-95358 is known.
No. 55, No. 55-83049, No. 62-89771, No. 61-189559, No. 62-75461, No. 61.
-139556, 62-139557, 62-
Examples thereof include those described in No. 208055. Further, examples of the protective layer using a fluorine-based block copolymer include those described in JP-A Nos. 61-116362, 61-117563, 61-270768, and 62-14657. Furthermore, as a protective layer that uses a resin containing a fluorine atom-containing polymer component in combination in the form of particles,
JP-A-63-249152 and 63-221355.
The items described in No.

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

In order to further strengthen the uneven distribution of the surface,
As a binder resin for the overcoat layer or the photoconductive layer, a polymer segment containing a silicon atom and / or a fluorine atom,
It is possible to use a block copolymer obtained by binding at least one kind of polymer segment containing a heat and / or photocurable group-containing component in a block. Examples of the polymer segment containing such a heat and / or photocurable group-containing component include those described in JP-A-5-197169. Alternatively, a light and / or thermosetting resin may be used together with a resin containing a fluorine atom and / or a silicon atom.

A polymer containing a polymer component containing a silicon atom and / or a fluorine atom of the present invention which is effective for modifying the surface of a photoreceptor is a resin {hereinafter referred to as a resin (P)}.
Alternatively, it is used in the form of resin particles {hereinafter referred to as resin particles (PL)}.

When the polymer is a random copolymer, the content of the polymer component containing silicon atoms and / or fluorine atoms is preferably 60% by weight or more, more preferably 80% by weight based on the total polymer components. It is more than weight%. More preferably, a polymer segment (α) containing 50% by weight or more of a polymer component containing a silicon atom and / or a fluorine atom and a polymer segment (α) containing 0 to 20% by weight of a polymer component containing a silicon and / or a fluorine atom. It is a block copolymer in which united segments (β) are linked by blocks. More preferably, it is a block copolymer containing at least one polymer component containing a photo- and / or thermosetting functional group in the above-mentioned segment (β) in the block copolymer. In these block copolymers, the segment (β) preferably contains no fluorine atom and / or silicon atom-containing polymer component.

When the block copolymer containing the polymer segments (α) and (β) (surface uneven distribution type copolymer) is used, the peelability of the surface itself is improved as compared with the random copolymer, and further the peeling is achieved. Sex is retained. That is, when a small amount of a block copolymer containing a fluorine atom and / or a silicon atom is made to coexist to form a coating film, these are easily transferred to and concentrated on the surface portion of the film by the end of the drying step after coating. , The surface of the film is modified so that peelability can be exhibited.

As described above, in the resin (P), when the fluorine atom and / or silicon atom-containing polymer segment (α) is blocked, the other fluorine atom and / or silicon atom-containing polymer segment (α) is used. The small amount of the polymer segment (β) even if it contains the polymer component has a good compatibility with the binder resin for film formation, and therefore, it interacts sufficiently with this to form a toner image or a transfer layer. Even in these cases, these resins can suppress or eliminate the transfer to the toner image and the transfer layer, and can clearly form and maintain the interface between the toner image and the transfer layer and the electrophotographic photoreceptor (that is, the anchor effect). ). By using a polymer containing a curable group in the segment (β) of the block copolymer and cross-linking between the polymers during film formation, the effect of further clearly maintaining the interface with the photoreceptor is exhibited. .

As described above, the polymer is a resin particle (PL).
May be used as. Preferred resin particles (PL)
Are resin particles dispersed in a non-aqueous solvent. Such resin particles include a polymer component containing a fluorine atom and / or a silicon atom-containing polymer component, which is insoluble in a non-aqueous solvent, and a polymer component containing a fluorine atom and / or a silicon atom. Even if it is 20% or less, a polymer segment (β) soluble in a non-aqueous solvent is preferably bonded. In the case of resin particles (PL), the insolubilized polymer segment (α) causes migration and concentration on the surface, and further, a polymer segment soluble in the non-aqueous solvent bound to the particles ( β) interacts with the binder resin to perform an anchor effect, as in the case of the resin. Further, by containing a curable group in the polymer or the binder resin, transfer to a toner image is eliminated.

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

[0030]

Embedded image

[0031]

Embedded image

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

[0033]

[Chemical 3]

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

Further, the organic residue containing a fluorine atom and / or a silicon atom may be constituted in combination, in which case it may be directly bonded or further combined via another connecting group. May be done. Specific examples of the linking group include a divalent organic residue, and -O-, -S-, -N
^{(D 1) -, - CO} -, - SO -, - SO 2 -, - COO
-, -OCO-, -CONHCO-, -NHCONH
^{-, - CON (d 1)} -, - SO 2 N (d 1) - may be interposed selected linking groups from such a divalent aliphatic group or a divalent aromatic group, or these It represents an organic residue composed of a combination of divalent residues. Here, d ¹ represents the same content as R ³¹ .

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

[0037]

[Chemical 4]

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

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

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

[0041]

Embedded image

However, in the above (1) to (11), R _f 'represents the groups represented by the above (1) to (8), n is an integer of 1 to 18, and m is 1 to 18. It shows an integer, and p shows an integer of 1 to 5.

[0043]

[Chemical 6]

[0044]

[Chemical 7]

[0045]

Embedded image

[0046]

[Chemical 9]

[0047]

[Chemical 10]

In the resin (P) and the resin particles (PL), in the case of a so-called surface uneven distribution type copolymer, in the segment (α) containing a polymer component containing a silicon atom and / or a fluorine atom, the polymer is The component comprises at least 50% by weight of the total amount of the entire segment (α),
Preferably 70% by weight or more, more preferably 80% by weight
That is all. In the segment (β), the content of the polymer component containing a fluorine atom and / or a silicon atom is 20% by weight or less, preferably 0% by weight, of the total amount of the segment (β). The weight ratio of the segment (α) to the segment (β) is 1 to 95: 5 to 99 (weight ratio),
It is preferably 5 to 90 to 10 to 95 (weight ratio).
Within this range, both the resin (P) and the resin particles (PL) can exhibit good concentration effect and anchor effect on the uppermost surface of the photoconductive layer.

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

Preferred embodiments of the so-called surface unevenly distributed copolymer in the resin (P) will be described below. The resin (P) may be in any form as long as the polymer component containing a fluorine atom and / or a silicon atom is composed of a block. Here, being composed of a block means that the polymer has a polymer segment (α) containing 50% by weight or more of a fluorine atom and / or a silicon atom, for example, A-B as shown below. Examples of the block include a mold block, an ABA type block, a BAB type block, a graft type block, and a star type block.

[0051]

[Chemical 11]

These various block copolymers can be synthesized by a conventionally known polymerization method. For example,
WJ Burlant, AS Hoffman `` Block and Graft Poly
mers ”(1986, Reuhold), RJ Cevesa“ Block and
Graft Copolymers "(1962, Butterworths), DC
Allport, WH James "Block Copolymers" (1972,
Applied Sci), A. Noshay, JE McGrath `` Block Copo
lymers '' (1977, Academicis Press.), G. Huvterg, D.
J. Wilson, G. Riess, NATO ASIser. SerE. 1985, 14
9, V. Perces, Applied. Polymer Sci. 285, 95 (1985)
It is described in the book and review articles.

For example, regarding an ionic polymerization reaction using an organic metal compound (eg, alkyllithium, lithium diisopropylamide, alkali metal alcoholates, alkylmagnesium halides, alkylaluminum halides) as a polymerization initiator, TE Hogeu- Esc
h, J. Smid `` Recent Advances in Anion Polymerizatio
n '' (1987, Elsevier New York), Okamoto Yoshio, Polymer, 38 , 912 (1989), Sawamoto Mitsuo, Polymer, 38 , 1018 (198)
9), Tadashi Narita, Polymer, 37 , 252 (1988), BC Anderson
et al., Macromolecules 14 , 1601 (1981), S. Aoshim
a, T. Higashimura, Macromolecules 22, 1009 (1989) and the like. Regarding the ionic polymerization reaction with hydrogen iodide / iodine system, etc., see T. Higashimura.
at al., Macromol. Chem. , Macromol. Symp., 13/14,
457 (1988), Toshinobu Higashimura, Mitsuo Sawamoto, Transactions on Polymers 46 , 189
(1989) etc.

For the group transfer polymerization reaction, DY
Sogah et al., Macromolecules, 20 , 1473 (1987), O.
W. Webster, DY Sogah, Polymer, 36 , 808 (1987), M.
T. Reetg et al., Angew. Chem. Int. Ed. Engl. 25 ,
9108 (1986), JP-A-63-97609 and the like. For the living polymerization reaction using metalloporphyrin complex, see T. Yasuda, T. Aida, S. Inoue, Macromole.
cules, 17 , 2217 (1984), M. Kuroki, T. Aida, S. Inou
e, J. Am. Chem. Soc. 109, 4737 (1987), M. Kuroki et
al., Macromolecules, 21 , 3115 (1988), M. Kuroki,
I. Inoue, Synthetic Organic Chemistry, 47 , 1017 (1989).

Further, regarding the ring-opening polymerization reaction of a cyclic compound, S. Kobayashi, T. Saegusa "Ring Opening Polym"
erization '' (1984, Applied Scence Publishers Lt.
d.), W. Seeliger et al., Angew. Chem. Int. Ed. Eng
l. 5, 875 (1966), S. Kobayashi et al., Poly. Bull. 1
3 , 447 (1985), Y. Chujo et al., Macromolecules, 22 , 1
074 (1989) and the like. Furthermore, regarding the living photopolymerization reaction using a dithiocarbamate compound or a xanthate compound as an initiator, Takayuki Otsu, Kogaku, 37 , 248 (1988), Shunichi Hinomori, Ryuichi Otsu, Polym. Rep.
Jap. 37 , 3508 (1988), JP-A 64-111, JP-A 64-26619, M. Niwa, Macromolecules, 189, 2
187 (1988) and the like.

[0056] On the other hand, a method of synthesizing a block copolymer by radical polymerization reaction to polymeric initiator containing an azo group or a peroxide group, Ueda Akirato, polymeric Ronbunshu 33,
931 (1976), Akira Ueda, Osaka City Research Institute Report, 84 (198)
9), O. Nuyken et al., Macromol. Chem., Rapid. Comm.
un. 9, 671 (1988), Yasuo Moriya et al. "Reinforced plastic" 2
9 , 907 (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), Polymer Society, edited by “Polymer”・ Alloy ”(1981, Tokyo Kagaku Dojin). 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. Shiota et al., J. Appl. Polym. S.
ci. 13 , 2447 (1969), WH Buck, Rubber Chemistry a
nd Technology, 50 , 109 (1976), Takeshi Endo, Tsutomu Uezawa, Japan Adhesive Society Magazine 24 , 323 (1988), Takeshi Endo, ibid. 25 , 409 (198)
9) etc. Further, as a method of polymerizing and grafting using a macromonomer, specifically,
P. Dreyfuss & RP Quirk, Encycl. Polym. Sci. En
g., 7, 551 (1987), PF Rempp, E. Franta, Adv. Pol
ym.Sci., 58 , 1 (1984), V. Percec, Appl. Poly. Sc
i., 285, 95 (1984), R. Asami, M. Takari, Macromol. C
hem. Suppl., 12 , 163 (1985), P. Rempp et al., Macrom
ol. Chem. Suppl., 8, 3 (1985), Yusuke Kawakami, Chemical Industry, 3
8 , 56 (1987), Yuya Yamashita, Polymer, 31 , 988 (1982), Shiro Kobayashi, Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of Japan Adhesion Society, 18 , 536 (1982), Ito Koichi, Polymer Processing, 35 , 262
(1986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No.10,
5. Yuya Yamashita, "Chemistry and Industry of Macromonomers" (1989
YPC, ed., Takeshi Endo, "Molecular Design of New Functional Polymers", Chapter 4 (1991, CMC Co., Ltd.), Y.
Yamashita et al., Polym. Bull. 5, 361 (1981) and the like.

The synthesis method of the star type block copolymer is as follows:
For example MT Reetz, Angew. Chem. Int. Ed. Engl., 2
7 , 1373 (1988), M. Sgwarc `` Carbanions, Living Polym
ers and Electron Transfer Processes '' (1968, Wille
y. New York), B. Gordon et al., Polym. Bull. 11 , 349
(1984), RB Bates et al., J. Org. Chem. 44 , 3800.
(1979), Y. Sogah, ACS Polym. Rapr. 1988 , No.
2, 3, JW Mays, Polym. Bull. 23 , 247 (1990), IM
Khan et al., Macromolecules, 21 , 2684 (1988), A. Mo
rikawa, Macromolecules, 24 , 3469 (1991), Akira Ueda, Toru Nagai, Polymer 39 , 202 (1990), T. Otsu, Polym. Bull. 1
1 , 135 (1984) etc. However, the method of synthesizing the block copolymer is not limited to these methods.

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

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

By synthesizing 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 Specifically, the monomer (a) corresponding to the polymer component forming the segment (α) and the monomer (b) corresponding to the polymer component forming the segment (β) (A) is a non-aqueous solvent that dissolves but becomes insoluble when polymerized, using a peroxide (eg, benzoyl peroxide, lauroyl peroxide, etc.), an azobis compound (eg, azobisisobutyronitrile, azobisisovaleronitrile). Etc.), an organic metal compound (eg, butyl lithium, etc.) and the like in the presence of a polymerization initiator. Alternatively, the monomer (a) and the polymer (Pβ) composed of the segment (β) may be polymerized in the same manner as above.

Furthermore, the inside of the polymer particles in which the resin particles (PL) are insolubilized may have a crosslinked structure. Any conventionally known method can be used to form these crosslinked structures. That is, a method of crosslinking a polymer containing a polymer segment (α) with various crosslinking agents or curing agents, and a polymerization reaction is carried out by containing at least a monomer (a) corresponding to the polymer segment (α). At this time, 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 reactivity with the polymer segment (α) It can be carried out by a method of crosslinking with a polymer containing a group-containing component 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 Data Handbook, Basic Edition" edited by The Polymer Society of Japan, Baifukan (1986), etc. can be used.

For example, organic silane compounds (for example, vinyltrimethoxysilane, vinyltributoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane and other silane coupling agents), polyisocyanate compounds (eg, toluylene diisocyanate, diphenylmethane diisocyanate) Nato, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high molecular polyisocyanate, etc.), a polyol compound (for example,
1,4-butanediol, polyoxypropylene glycol, polyoxyethylene glycol, 1,1,1-trimethylolpropane, etc., polyamine compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine). , N-aminoethylpiperazine, modified aliphatic polyamines, etc.), titanate coupling compounds (eg, tetrabutoxy titanate, tetrapropoxy titanate, isopropyl tristearoyl titanate, etc.),
Aluminum coupling compounds (for example, aluminum butyrate, aluminum acetyl acetate, aluminum oxide octate, aluminum tris (acetyl acetate), etc.), polyepoxy group-containing compounds and epoxy resins (for example, "New Epoxy Resin" by Hiroshi Kakiuchi) Do (1985), Kuniyuki Hashimoto, "Epoxy Resin," compounds listed in Nikkan Kogyo Shimbun (1969), melamine resin (for example, Ichiro Miwa, Hideo Matsunaga, "Uria Melamine Resin," Nikkan Kogyo Shimbun Company (1969)
Etc.), poly (meth) acrylate compounds (for example, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura "Oligomer" Kodansha (1976), Eizo Omori "Functional Acrylic Resin" Techno System (Compounds described in (1985)) and the like.

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) = CHCOO-, 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 NHC
_{O-, CH 2 = CHSO 2 -} , CH 2 = CHCO-, CH 2
= CHO-, can be mentioned CH ₂ = CHS-like. Any monomer or oligomer having two or more of these same or different polymerizable functional groups may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, a monomer or oligomer having the same polymerizable functional group, a styrene derivative such as divinylbenzene or trivinylbenzene: a polyhydric alcohol. (For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 20
0, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or 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 (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, and arylloyl). Propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic acid anhydride, etc.) and ester or amide derivatives containing vinyl groups such as alcohol or amine reactants (eg vinyl methacrylate, vinyl acrylate, vinyl itaconic acid) , Allyl methacrylate, allyl acrylate, allyl itaconate, methacryloyl vinyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyl oxycarbonyl methyl methacrylate, vinyl acrylate Luoxycarbonylmethyloxycarbonylethylene ester, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconic acid amide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (eg aminoethanol, 1-aminopropanol, 1-amino) Butanol,
1-aminohexanol, 2-aminobutanol, etc.) and a condensate of a carboxylic acid containing a vinyl group. The amount of the monomer or oligomer having two or more polymerizable functional groups used in the present invention is 10 with respect to the total amount of the monomer (a) and the other monomer coexisting with the monomer (a).
Polymerization is carried out using less than mol%, preferably less than 5 mol% to form a resin.

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

In dispersion polymerization, monodisperse particles having uniform particle diameters are obtained, and fine particles of 0.5 μm or less are easily obtained. The method using a monomer is preferable. In other words, the monomer (a), the monomer (b) and / or the polymer (Pβ) described above are further coexisted with the polyfunctional monomer (d) to carry out a polymerization granulation reaction to synthesize the compound. can do.
Further, when the polymer (Pβ) composed of the above-mentioned segment (β) is used, the monomer (a) is attached to a side chain in the polymer main chain of the polymer (Pβ) or one end of the main chain. A polymer having a polymerizable double bond group copolymerizable with (P
β ′) is preferred.

The polymerizable double bond group may be any as long as it has copolymerizability with the monomer (a) as described above, but a specific example thereof is CH ₂ ═C (p) COO. -, C (C
_{H 3) H = CHCOO-, CH} 2 = C (CH 2 COOH) C
_{OO-, CH 2 = C (p} ) CONH-, CH 2 = C (p)
_{CONHCOO-, CH 2 = C (p} ) CONHCONH
_{-, C (CH 3) H} = CHCONH-, CH 2 = CHCO
_{-, CH 2 = CH (CH} 2) n OCO- (n is 0 or 1-3
, CH ₂ ═CHO—, CH ₂ ═CHC ₆ H ₄ — and the like (where p represents —H or —CH ₃ ).

These polymerizable group double bond groups may be bonded directly 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 and JP-A 1-25.
7969, 2-74956, 1-282566
No. 2, No. 2-173667, No. 3-15862, No. 4
It is described in each publication such as -70669. The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the non-aqueous solvent.
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 about 30 to 180 ° C, preferably 40 to 120 ° C. Reaction time is 1
15 hours is preferred.

Next, in the case where a photo- and / or thermosetting group is contained in the binder resin (P) as a polymer component, or when the curable group-containing resin is used in combination with the resin (P). explain. 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 photo- and / or curable group contained in these polymers is the polymer segment (β) of the block copolymer (P).
1 to 95 parts by weight in 100 parts by weight, preferably 10
˜70 parts by weight. Furthermore, it is preferable to contain 5 to 40 parts by weight in 100 parts by weight of the total amount of the polymer components of the whole copolymer (P). When the photo- and / or curable group-containing polymer component is contained in an amount of 1 part by weight or more, the curing of the photoconductive layer after the film formation is sufficiently advanced, which effectively acts on the releasability of the toner image. Further, when the content is 95 parts by weight or less, good electrophotographic characteristics as a binder resin for the photoconductive layer can be obtained without lowering the original reproducibility of a copied image or causing background fog in the non-image area. It is preferable to use the light and / or thermosetting group-containing block copolymer (P) in an amount of 40 parts by weight or less based on 100 parts by weight of the total binder resin. Within this range, good electrophotographic characteristics can be obtained.

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

These conventionally known binder resins for the electrophotographic photosensitive layer are, for example, Ryuji Shibata, Jiro Ishiwatari, Kogaku, No. 17
Vol., Pp. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No.8), Koichi Nakamura, "Techniques of Binders for Recording Materials" Chapter 10, CMC Publishing (1985), Electronic Photographic Society, "Current Symposium on Organic Photoreceptors for Electrophotography"
Proceedings (1985), Hiroshi Komon, "Development and practical application of recent photoconductive materials and photoconductors", Japan Science Information Co., Ltd. (1986), Electrophotographic Society, "Basics and applications of electrophotographic technology" Chapter 5, Corona Corp. (1988), D. Tatt, SC Heidecker, Tapp
i, 49 (No.10), 439 (1966), ES Baltazzi, RG Blan
clotte et al, Phot. Sci. Eng. 16 (No.5), 354 (197
2), Nguyen Chan Kaye, Isamu Shimizu, Eiichi Inoue, Electrophotographic Society of Japan, 18 (No.2), 22 (1980) and the like.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and 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 concretely, Takeshi Endo "Refinement of thermosetting polymers" (CMC Co., Ltd., published in 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. The conventionally known resin cited in 1. is used.

As described above, in order to prepare a photoreceptor having a releasability in advance, the uppermost layer, for example, the overcoat layer or the photoconductive layer, contains at least one binder resin and at least one resin (P) for surface modification. Or more, and preferably a light and / or thermosetting resin (D) and / or in order to improve the curing of the film.
Alternatively, a small amount of a crosslinking agent is allowed to coexist. 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 and the resin (P).
Within this range, the effect of improving the hardening of the film is exhibited without adversely affecting the electrophotographic characteristics.

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

The uppermost layer (layer adjacent to the transfer layer) of the photoreceptor is preferably cured after the film formation. The binder resin, the resin (P), the curable resin (D) and the cross-linking agent to be provided are preferably used in a combination of functional groups in which polymers are easily chemically bonded. For example, a well-known method is generally used 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 Table 1 below. However, it is not limited to this.

[0082]

[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.),
Thiuram disulfide compounds (tetramethyl thiuram disulfide, etc.), carboxylic acid anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butylsuccinic anhydride,
3,3 ′, 4,4′-tetracarboxylic acid benzophenone dianhydride, trimellitic acid anhydride, etc.) and the like.
When the crosslinking reaction is a polymerizable reaction mode, a polymerization initiator (peroxide, azobis compound, etc.) may be used.

The binder resin is prepared by applying the photosensitive layer-forming material,
It is preferably light and / or heat cured. In order to carry out heat curing, for example, the drying conditions are set to be more severe than the conventional drying conditions for producing a photoreceptor. For example, it is preferable to set the drying conditions to a high temperature and / or a long time, or to further heat-treat after drying the coating solvent. For example, 60 ℃ ~
Process at 150 ° C. for 5 to 120 minutes. When the above reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As a method for curing the specific functional group in the resin by irradiation with light, a step of irradiating light with a chemically active ray may be included. The chemically active light may be any of visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, γ-ray, α-ray, etc., but preferably ultraviolet light, more preferably light having a wavelength of 310 nm to 500 nm. . Generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp or the like is used. Light irradiation is usually 5 cm to 5
Irradiation from a distance of 0 cm for 10 seconds to 10 minutes is sufficient.

Next, in the latter method of obtaining a photoreceptor having a releasable surface, the releasable compound (S) is applied onto the surface of an ordinary electrophotographic photoreceptor before toner development, and the photoreceptor surface is applied. A method for making the film peelable will be described.

Examples of the peelable compound (S) include compounds containing at least a fluorine atom and / or a silicon atom, and the structure thereof is not particularly limited as long as it improves the peelability of the surface of the electrophotographic photosensitive member. It may be a low molecular weight compound, an oligomer or a polymer. In the case of an oligomer or a polymer, the substituent containing a fluorine atom and / or a silicon atom may be incorporated in the main chain of the polymer, or may be present as a substituent on the side chain of the polymer. Preferred examples of the oligomer or polymer include those in which the repeating unit containing the substituent is contained in a block, and these exhibit particularly excellent adsorbability and releasability on the surface of the electrophotographic photoreceptor.

These substituents containing a fluorine atom and / or a silicon atom are specifically the same as those described in connection with the resin (P). Specific examples of the compound (S) containing a fluorine atom and / or a silicon atom used in the present invention include “New Edition Surfactant Handbook” edited by Toshiyuki Yoshida et al., Engineering Book Co., Ltd. (1987), "Silicon Handbook" edited by Takao Karime, "Latest Surfactant Application Technology", CMC (1990), edited by Kunio Ito
Published by Nikkan Kogyo Shimbun (1990), supervised by Takao Karime "Special Function Surfactant" CMC Co., Ltd. (1986), AM Schwartz e
t al “Surface Active Agents and Detergents vol.II
And the like, such as fluorine-based and / or silicon-based organic compounds. Furthermore, Nobuo Ishikawa “Synthesis and Function of Fluorine Compounds” CMC Co., Ltd. (1987), Jiro Hirano et al. “Fluorine-Containing Organic Compounds-Synthesis and Application-” Technical Information Institute Co., Ltd. (1991), Ishikawa The compound (S) of the present invention can be synthesized by using the synthetic method described in the literature such as “Organosilicon Strategy Material” Chapter 3 Science Forum (1991) supervised by Mitsuo.

Specific examples of the polymer component containing a substituent containing a fluorine atom and / or a silicon atom as the oligomer or polymer include the polymer component (F) described in the above resin (P). Can be mentioned.

When the compound (S) is a so-called block copolymer, the polymer component containing a fluorine atom and / or a silicon atom may be composed of a block. Here, to be composed of blocks means that the polymer has a polymer segment containing 70% by weight or more of a component having a fluorine atom and / or a silicon atom, for example, as described in the resin (P). Similar AB type block, A-
Examples thereof include B-A type blocks, B-A-B type blocks, graft type blocks and star type blocks. These can be synthesized by the same method as described above.

By applying the compound (S) to the surface of the electrophotographic photosensitive member, the surface is modified so as to have a desired releasability. Compound (S) on the surface of electrophotographic photoreceptor
The application of means that the compound (S) is supplied to the surface of the electrophotographic photosensitive member to form a state in which the compound (S) is adsorbed or attached to the surface of the photosensitive member.

To apply the compound (S) to the surface of the electrophotographic photosensitive member, any conventionally known method may be applied. For example, Yuji Harazaki "Coating Engineering" Asakura Shoten Co., Ltd. (published in 1971), Yuji Harazaki "Coating Method" Maki Shoten (1979), Hiroshi Fukada "Practice of Hot Melt Adhesion"
Air doctor coater, blade coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure coater, etc.
Examples include various methods such as a kiss roll coater, a spray coater, a curtain coater, and a calendar coater.

Further, cloth, paper impregnated with the compound (S),
A method in which a felt or the like is brought into close contact with the photoconductor, a method in which a curable resin impregnated with the compound (S) is brought into pressure contact with the photoconductor, and the photoconductor is wetted with a non-aqueous solvent in which the compound (S) is dissolved, and then the solvent is dried. And a method in which a nonaqueous solvent in which the compound (S) is dispersed is electrophoresed and adhered to the photoconductor in the same manner as the electrodeposition coating method described below. Further, the non-aqueous solution of the compound (S) can be uniformly wetted on the surface of the photoreceptor by the ink jet method and then dried to be adsorbed or attached. The ink jet method can be achieved, for example, by the principle and means described in Shin Ohno, “Non-Impact Printing”, CMC (published in 1986). For example, continuous injection type Sweet method, Hertz
Methods, intermittent jet Winston method, ink-on-demand pulse jet method, bubble jet method, ink mist type mist method, etc.

In any case, the compound (S) is used directly or diluted with a solvent instead of the ink and filled in the ink tank and / or the ink head cartridge portion. Normal liquid viscosity is 1-10cP, surface tension is 30-60dyne / cm
Then, if necessary, a surfactant or the like may be added, or the liquid may be heated. Conventional ink jet printers
The orifice system of the head is 30-
It is about 100 μm, and the particle size of the flying ink is about the same, but in the present invention, it may be larger than this. In this case, the amount of ink discharged will increase, so
The time required for coating can be shortened. Further, the use of multiple nozzles is also extremely effective for shortening the coating time.

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

In the present invention, these methods are not particularly limited, and various methods are selected depending on the state of the compound (S) to be used (liquid, waxy substance, solid), and if necessary a heating medium is used in combination. Thus, the fluidity of the compound (S) used can be adjusted. The compound (S) is preferably applied in such a manner that it can be easily incorporated into the electrophotographic plate-making printing plate making apparatus.

The amount of the compound (S) applied to the surface of the photoconductor is not particularly limited, and the adverse effect on the electrophotographic characteristics of the photoconductor should not be a practical problem. Usually, a coating film thickness of 1 μm or less is sufficient, and the release property of the present invention is expressed by “Weakboundary Layer” (Bikerman “The Science of Ad
(as defined by “Hesive Joints” Academic Press (published in 1961)) is sufficient. In the present invention, the compound (S) is adsorbed or adhered on the electrophotographic photoreceptor to impart releasability to the surface, preferably The adhesive strength of the surface is 100 g
It may be f or less. In the plate-making printing plate making step of the present invention, it is not necessary to repeat this step all the time, and it may be appropriately performed according to the combination of the photoreceptor used and the ability to maintain the releasability by application of the compound (S) and the means thereof.

As the constitution and material of the electrophotographic photosensitive member provided in the present invention, any conventionally known constitution can be used,
It is not limited. For example, RM Schaffert, "
Electrophotography "Focal Press London (1980), S.
W. Ing, MD Tabak, WE Haas, "Electrophotograp
hy Fourth International Conference "SPSE (1983), Isao Shinohara, Hidetoshi Tsuchida, Hideaki Kusagawa" Recording Materials and Photosensitive Resins "
Published by Gakkai Shuppan Center Co., Ltd. (1979), Hiroshi Komon, Kagaku to Kogyo, 39 (3), 161 (1986), Comprehensive technical data collection "Recent development and practical application of photoconductive materials and photoconductors" Japan Science Information Publishing Co., Ltd. (1986), Electrophotographic Society, "Basics and Applications of Electrophotographic Technology", Corona Publishing Co., Ltd. (1986), Electrophotographic Society, "Current Status Symposium on Organic Photoreceptors for Electrophotography" The various photoconductors described in the literature and reviews, such as the Proceedings (1985), are listed. That is, a single layer composed of the photoconductive compound itself or a photoconductive layer in which the photoconductive compound is dispersed in a binder resin can be mentioned. The dispersed photoconductive layer may be a single layer type or a laminated type. .

The photoconductive compound used in the present invention may be either an inorganic compound or an organic compound. Examples of the inorganic compound used as the photoconductive compound of the present invention include zinc oxide, titanium oxide, zinc sulfide,
Examples of conventionally known inorganic photoconductive compounds such as cadmium sulfide, selenium, selenium-tellurium, amorphous silicon, and lead sulfide may be used to form a photoconductive layer together with a binder resin, or vapor deposition or The photoconductive layer may be formed solely by sputtering or the like. When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used, the binder resin is used in an amount of 10 to 100 parts by weight, preferably 15 to 40 parts by weight, based on 100 parts by weight of the inorganic photoconductive compound. ..

On the other hand, the photoconductive layer using an organic compound may be any of the conventionally known ones, specifically, Japanese Examined Patent Publication No.
7-17162, 62-51462, JP-A-52
-24437, 54-19803, 56-107.
No. 246, No. 57-161863, etc.,
A photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye, and a binder resin, JP-A-56-146145 and 60-17.
No. 751, No. 60-17752, No. 60-17760
No. 60-254142, No. 62-54266, etc., a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent and a binder resin, and JP-A-60-230147.
Examples thereof include a photoconductive layer having a two-layer structure containing a charge generating agent and a charge transporting agent in separate layers as described in JP-A-60-230148 and JP-A-60-238853.

The electrophotographic photosensitive member of the present invention may take any form of the above-mentioned photoconductive layer. Examples of the organic photoconductive compound used in the present invention include (a) US Pat.
2,197, etc., (b) oxadiazole derivatives described in US Pat. No. 3,189,447, (c) imidazole derivatives described in JP-B-37-16096, (d) US Patents 3,615,402, 3,820,989, 3,542,544, Japanese Patent Publication Nos. 45-555, 51-10983, and JP-A-51
-93224, 55-108667, 55-1
56953, 56-36656, and other polyarylalkane derivatives, (e) US Pat. No. 3,180,72
9, 4,278,746, JP-A-55-8806.
No. 4, No. 55-88065, No. 49-105537.
No. 55, No. 55-51086, No. 56-80051, No. 56-88141, No. 57-45545, No. 54-.
112637, 55-74546 and the like, pyrazoline derivatives and pyrazolone derivatives, (f) US Pat.
615, 404, Japanese Patent Publication No. 51-10105, 46
-3712, 47-28336, JP-A-54-8
No. 3435, No. 54-110836, No. 54-119
A phenylenediamine derivative described in No. 925,

(G) US Pat. Nos. 3,567,450, 3,180,703, 3,240,597, 3,658,520, 4,232,103 and 4, 175,961; 4,012,376; JP-B-49-35702; West German Patent (DAS) 1,11.
0,518, JP-B-39-27577, JP-A-55-144250, JP-A-56-119132, JP-A-56-22437, and the like, arylamine derivatives,
(h) Amino-substituted chalcone derivative described in U.S. Pat. No. 3,526,501, (i) N, N-bicarbazyl derivative described in U.S. Pat. No. 3,542,546, etc., (j) U.S. Pat. , 203 and the like, oxazole derivatives,
(k) Styrylanthracene derivatives described in JP-A-56-46234, (l) Fluorenone derivatives described in JP-A-54-110837, (m) US Pat. No. 3,717,4
62, JP-A-54-59143 (U.S. Pat.
0-987), JP-A-55-52063, JP-A-55-52064, JP-A-55-46760, and JP-A-55-520.
No. 85495, No. 57-11350, No. 57-148.
749, 57-104144 and the like, hydrazone derivatives,

(N) US Pat. Nos. 4,047,948, 4,047,949, 4,265,990, 4,273,846, 4,299,897, and 4, 306,008, etc., benzidine derivatives,
(o) JP-A-58-190953 and 59-95540
No. 59-97148, 59-195658,
Stilbene derivatives described in JP-A-62-36674,
(p) Polyvinylcarbazole and its derivatives described in JP-B-34-10966, (q) JP-B-43-18674
, Polyvinylpyrene described in No. 43-19192,
Polyvinyl anthracene, poly-2-vinyl-4-
Vinyl polymers such as (4'-dimethylaminophenyl) -5-phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole; (r) polyacenaphthylene, polyindene, acenaphthylene described in JP-B-43-19193. Polymers such as copolymers of styrene and styrene, (s) JP-B-56-
Condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin and ethylcarbazole-formaldehyde resin described in 13940 and the like, and (t) various triphenylmethanes described in JP-A-56-90833 and 56-161550. Polymers, etc. In the present invention, the organic photoconductive compound is not limited to the compounds listed in (a) to (t), and all known organic photoconductive compounds can be used. Two or more kinds of these organic photoconductive compounds can be used in combination depending on the case.

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

As the charge generating agent contained in the photoconductive layer, various organic and inorganic charge generating agents known in the prior art for electrophotographic photoreceptors can be used. For example, selenium, selenium-tellurium, cadmium sulfide, zinc oxide, and the following (1)
The organic pigments shown in to (9) can be used.

(1) U.S. Pat.
8-219263, 59-78356, 60-
179746, 61-148453, 61-2
No. 38063, Japanese Patent Publication No. 60-5941, No. 60-45
Azo pigments such as monoazo, bisazo and trisazo pigments described in US Pat. No. 664, (2) US Pat. No. 3,397,086
No. 4,666,802, JP-A-51-90827.
Phthalocyanine pigments such as metal-free or metal phthalocyanines described in JP-A No. 52-55643, (3) Perylene pigments described in US Pat. British Patent 2,237,68
No. 0, indigo described in JP-A-47-30331, etc.,
Thioindigo derivatives, (5) British patent 2,237,679
Quinacridone pigments described in JP-A-47-30332,

(6) British Patent 2,237,678, JP-A-59-184348, JP-A-62-28738, and JP-A-59-284348.
7-18544 and other polycyclic quinone pigments, (7) JP-A-47-30331, JP-A-47-18543 and other bisbenzimidazole pigments, (8) US Pat.
396,610, 4,644,082, and the like, squalium salt pigments, (9) JP-A-59-53850
And the azurenium salt-based pigments described in JP-A-61-212542 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, based on 100 parts by weight of the binder resin.

The binder resin that may be used in the photoconductor of the present invention (hereinafter sometimes referred to as the binder resin (B)) may be any of the resins used in conventionally known electrophotographic photoconductors. The molecular weight is preferably 5 × 10 ³ to 1 × 1
0 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10 ⁵ . The glass transition point of the binder resin is preferably -40.
C. to 200.degree. C., more preferably -10.degree. C. to 140.degree. For example, Ryuji Shibata and Jiro Ishiwata, Kobunshi, Vol. 17, Vol.
278 (1968) Harumi Miyamoto, Hidehiko Takei, Imaging, 1
973 (No.8), Koichi Nakamura, "Practical Technology of Binders for Recording Materials," Chapter 10, CHC Publishing (1985), The Institute of Electrophotography,
"Present Symposium on Organic Photoreceptors for Electrophotography" Proceedings (1985) edited by Hiroshi Komon, "Recent Development and Practical Use of Photoconductive Materials and Photoreceptors" Japan Science Information Co., Ltd. (1986) The Electrophotographic Society of Japan Volume "Basics and Applications of Electrophotographic Technology" Chapter 5 Corona Publishing Co., Ltd.
(1988), D. Tatt, SC Heidecker, Tappi, 49 (No.1
0), 439 (1966), ES Baltazzi, RG Blanclotte et
al, Phot. Sci. Eng. 16 (No.5), 354 (1972), Nguyen
Jang Kae, Isamu Shimizu, Eiichi Inoue, The Journal of The Institute of Electrophotography 18 (N
o.2), 22 (1980) and the like, compounds and the like described in reviews.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Polymers and copolymers of the derivatives, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers. Polymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, itaconic acid diester polymers and copolymers , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymer, hydroxyl 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 the binder resin (B) for the photoconductor,
The electrostatic characteristics can be improved by using a resin having a relatively low molecular weight (about 10 ³ to 10 ⁴ ) containing an acidic group such as a carboxyl group, a sulfo group, and a phosphono group together. For example, a resin in which the acidic group-containing polymerization component described in JP-A-63-217354 is randomly present in the polymer main chain, or an acidic group is added to one end of the polymer main chain described in JP-A-64-70761. Resin formed by bonding, JP-A-2-67563, 2
-2365651, 2-238458, 2-23
No. 6562 and No. 2-247656, etc., a resin obtained by bonding an acidic group to the end of the main chain of a graft type copolymer, or a resin containing an acidic group in the graft part of the graft type copolymer, Japanese Patent Laid-Open No. 3-2980. An AB type block copolymer containing an acidic group in a block as described in JP-A-181948.
Further, in order to improve the mechanical strength of the photoconductive layer, which is insufficient with only these low molecular weight resins, it is preferable to use another medium to high molecular weight resin in combination. For example, Japanese Unexamined Patent Publication
Thermosetting resin forming a cross-linking structure between polymers described in No. 68561, 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.

By using a specific medium to high molecular weight resin, stable performance can be maintained even when the environment changes significantly. For example, JP-A-3-29954
No. 3, No. 3-779954, No. 3-92861 and No. 3
-53257, a resin having an acidic group bonded to the end of the graft part of the graft copolymer, or a resin having an acidic group in the graft part of the graft copolymer, JP-A-3-2-3.
The graft type copolymers described in Nos. 064464 and 3-223762, which contain an AB block type copolymer composed of an A block containing an acidic group and a B block not containing an acidic group in a graft part, can be mentioned. By using these resins, it is possible to uniformly disperse the photoconductor and form a photoconductive layer with good smoothness, and in the case of using a scanning exposure method using environmental changes or semiconductor laser light. Also, excellent electrostatic characteristics can be maintained.

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

In the present invention, various dyes can be used together as a spectral sensitizer depending on the kind of light source such as visible light exposure or semiconductor laser light exposure. For example, Harumi Miyamoto, Hidehiko Takei; Imaging 1973 (No.8) No. 12
Page, CJ Young et al .: RCA Review 15 , 469 pages (1954
,) Kyohei Kiyota: Transactions of the Institute of Electrical Communication, J63-C (No.
2), p. 97 (1980), Yuji Harasaki et al., Journal of Industrial Chemistry, 66 ,
78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35 , 2
Carbon dioxide dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (e.g., oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes) as referred to in page 08 (1972) etc. Etc.), a phthalocyanine dye (which may contain a metal), and the like.

More specifically, the carbon-based dyes, the triphenylmethane-based dyes, the xanthene-based dyes, and the phthalein-based dyes are mainly used.
2, JP-A-50-90334 and JP-A-50-11422.
No. 7, No. 53-39130, No. 53-82353,
US Pat. Nos. 3,052,540 and 4,054,450
And JP-A-57-16456.

As polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes, FM Hamer “The Cyanine Dyes and Related Co
The dyes described in "mpounds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,11.
0,591, 3,121,008, 3,12
5,447, 3,128,179 and 3,13
2,942, 3,622,317, British Patent 1,
No. 226,892, No. 1,309,274, No. 1,4
05,898, Japanese Patent Publication No. 48-7814, 55-1
Examples thereof include dyes described in No. 8892.

Further, as a polymethine dye for spectrally sensitizing near-infrared to infrared light region having a long wavelength of 700 nm or more, there is disclosed in Japanese Patent Laid-Open No.
No. 7-840, No. 47-44180, and Japanese Patent Publication No. 51-4
1061, JP-A-49-5034, and JP-A-49-451.
No. 22, No. 57-46245, No. 56-35141.
No. 57-157254, No. 61-26044,
U.S. Pat. No. 6,127,551, U.S. Pat. No. 3,619,154.
No. 4,175,956, "Research Discloseur
e ”, those described in 1982, 216, pages 117 to 118, etc.

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

Examples of the chemical sensitizer include halogen, benzoquinone, chloranil, fluoranyl, bromanil,
Dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, phthalic anhydride, maleic anhydride, N-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 Publishing Department (1986), are mentioned. Also, JP-A-58-65
No. 439, No. 58-102239, No. 58-1294.
The compounds described in No. 39, No. 62-71965 and the like can also be mentioned.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl glycolate, dimethyl glycol phthalate. Can be added to improve the flexibility of the photoconductive layer. It is preferable that these plasticizers are contained in a range that does not deteriorate the electrostatic characteristics of the photoconductive layer. The addition amount of these various additives is not particularly limited, but is usually 0.1% with respect to 100 parts by weight of the photoconductor.
001 to 2.0 parts by weight.

The electrophotographic photosensitive member can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, a low resistance substance is added to a substrate such as metal, paper, or a plastic sheet in the same manner as in the past. Those which have been subjected to a conductive treatment such as impregnation, those which are coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and further preventing curling, A support provided with a water-resistant adhesive layer on the surface thereof, a support provided with at least one precoat layer on the surface layer thereof, a substrate made of aluminum or the like vapor-deposited conductive plastic laminated on paper Those that have been made can be used. Specifically, as an example of a conductive substrate or a conductive material, Yukio Sakamoto, Electrophotography, 14 (No.1), pp. 2-11 (1975
Annual), Hiroyuki Moriga "Introduction to Special Paper Chemistry" Polymer Publishing (1975), MF Hoover, J. Macromol. Sci. Che
m. A-4 (6), those described in pages 1327 to 1417 (published in 1970) and the like are used.

Next, a method for forming a toner image on the electrophotographic photosensitive member will be described. As described above, a toner image is formed on the electrophotographic photosensitive member having a peelable surface by a normal electrophotographic process. That is, each process of charging-exposure-developing-fixing is performed by a conventionally known method.
Further, when the surface releasability is insufficient, the compound (S) may be applied to the surface of the photoconductor before the ordinary electrophotographic process.
By applying, it is possible to obtain a photoreceptor having a peeling property.

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

Further, the basic constitution of a concrete liquid developer is an electrically insulating organic solvent {for example, isoparaffin aliphatic hydrocarbon: Ansoper H, Isopar G (manufactured by Esso Co.) Shellsol 70, Shellsol 71 (shell Company),
IP-solvent 1620 (manufactured by Idemitsu Petrochemical Co., Ltd.) is used as a dispersion medium, and an inorganic or organic pigment or dye as a colorant and an alkyd resin, an acrylic resin, a polyester resin,
Styrene-butadiene resin, rosin and other resins for imparting dispersion stability, fixability and chargeability are dispersed, and various additives are added as desired to enhance charge characteristics or improve image characteristics. It becomes.

Known dyes and pigments may be arbitrarily selected as the colorant, and examples thereof include benzidine type, azo type,
Examples thereof include azomethine type, xanthene type, anthraquinone type, phthalocyanine type (including metal), titanium white, nigrosine, aniline black, carbon black and the like. Further, as other additives, those specifically described in Yuji Harasaki, "Electrophotography", Vol. 16, No. 2, p. 44 are used. For example, di-2-ethylhexyl sulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, alkylbenzene sulfonic acid metal salt, alkyl phosphoric acid metal salt, lecithin, poly (vinylpyrrolidone), a co-containing half maleic acid amide component. Examples thereof include polymers, coumarone indene resin, higher alcohols, polyethers, polysiloxanes and waxes.

The amount of each main component of the liquid developer is usually as follows. The amount of the toner particles containing a resin (and a colorant optionally used) as a main component is preferably 0.5 to 50 parts by weight with respect to 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. The carrier liquid-soluble resin for stabilizing the dispersion described above is also used if necessary, and is 0.5 per 1000 parts by weight of the carrier liquid.
About 1 to 100 parts by weight can be added. The charge control agent 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 controlled by the electric resistance of the liquid agent. That is, the electric resistance of the liquid developer with toner particles removed is 10 ⁹ Ωcm.
If it becomes lower, it becomes difficult to obtain a continuous tone image of high quality, and therefore the amount of each additive added is controlled within this limit.

Specific examples of the method for producing a liquid developer include:
A method for producing colored particles by mechanically dispersing a colorant and a resin by using a disperser such as a sand mill, a ball mill, a jet mill and an attritor is disclosed in, for example, JP-B-35-55.
No. 11, No. 35-13424, No. 50-40017.
No. 49-98634, No. 58-129438,
It is described in JP-A-61-180248. As another method of producing colored particles, for example, a method of producing dispersed resin particles by a non-aqueous dispersion polymerization method which obtains fine resin particles having a fine particle size and good monodispersibility, and coloring the particles can be mentioned.

As one of the coloring methods, Japanese Patent Application Laid-Open No. 57-4
As described in No. 8738, there is a method of dyeing a dispersed resin with a preferable dye. In addition, JP-A-53-54
No. 029, a method of chemically bonding a disperse resin and a dye, and as described in Japanese Examined Patent Publication No. 44-22955, a dye is preliminarily incorporated in the production by the polymerization granulation method. There is a method of using a monomer to prepare a dye-containing copolymer.

A combination of the scanning exposure method using laser light which is exposed based on digital information and the developing method using a liquid developer is an effective process because a high-definition image can be formed. An example is shown below. First, the photosensitive 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 with a charging device described in, for example, "Basics and Applications of Electrophotographic Technology" (edited by The Electrophotographic Society, Corona Publishing Co., Ltd., 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. Thereafter, for example, scanning exposure is performed with a laser light source using the method described on page 254 of the above cited reference.

Next, 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 wet development method described on page 275 and after of the above-mentioned reference can be used. The exposure mode at this time corresponds to the toner image development mode. For example, in the case of reversal development, a negative image, that is, an image portion is irradiated with laser light to charge the photosensitive material with the same charge polarity. The toner having the toner is used and a developing bias voltage is applied so that the toner is electrodeposited on the exposed portion. The details of the principle are explained on pages 157 and after of the above cited material. After development, in order to remove the excess developer, squeeze as shown on page 283 of the same document is performed, and then dried. It is also preferable to rinse only with the carrier liquid of the developer before squeezing.

Next, a peelable transfer layer is provided on the toner image on the photosensitive material. First, the transfer layer used in the present invention will be described in detail.

The transfer layer of the present invention transfers a toner image from an electrophotographic photoreceptor through a primary receptor to a material to be transferred which becomes a support of a printing plate, and is removed by a chemical reaction treatment to form a printing plate. This layer has the function of Therefore, the transfer layer of the present invention transfers the toner image formed on the photoconductor onto the primary receptor efficiently and without causing image deterioration, and can be easily transferred in the next transfer process regardless of the type of material to be transferred. It is desirable that it has a thermoplastic property to be transferred to a transfer material, and that it is easily removed by being dissolved or swelled by a chemical reaction treatment so as to be a printing plate and desorbed. The transfer layer of the present invention is usually colorless and transparent, but may be colored or opaque if necessary.

The transfer layer of the present invention is transferred at a temperature of 180 ° C. or less and / or a pressure of 30 kgf / cm ² or less, more preferably 160 ° C. or less and / or a pressure of 20 kgf / cm ² or less. Preferably. When the value is not more than the above value, there is almost no need to upsize the transfer device to maintain the heat capacity and pressure of the transfer device in order to peel and transfer the transfer layer from the surface of the photoconductor, and the transfer can be sufficiently performed at an appropriate transfer speed. It can be done and there is no practical problem. The lower limit is not particularly limited, but is usually room temperature or higher or 100 gf / c
It is preferable that peeling is possible under a transfer condition of a pressure of m ² or more.

Therefore, the resin (A) forming the transfer layer of the present invention is a thermoplastic resin which can be removed by a chemical reaction treatment. In terms of thermal characteristics, the resin (A) preferably has a glass transition point of 140 ° C. or lower or a softening point of 180 ° C. or lower, more preferably a glass transition point of 100 ° C. or lower or a softening point of 15 or lower.
It is 0 ° C or lower.

The resin (A) which can be removed by the chemical reaction treatment is
Resins that are dissolved and / or swelled by chemical reaction treatment and removed, and resins that are hydrophilized by chemical reaction treatment and consequently dissolved and / or swelled are included.

Resin (A) removed by chemical reaction treatment
Is a resin that can be removed with an alkaline treatment liquid, and a particularly useful resin is a resin containing a hydrophilic group in the polymer component. Further, as another representative example, a resin containing a hydrophilic group protected by a protecting group and capable of expressing the hydrophilic group by a chemical reaction can be mentioned. The chemical reaction capable of converting a functional group into a hydrophilic group is a conventionally known hydrolysis reaction, hydrogenolysis reaction, oxygenolysis reaction, β-elimination reaction,
It may be either a hydrophilization reaction by a treatment liquid utilizing a nucleophilic substitution reaction or the like, or a hydrophilization reaction by a decomposition reaction upon irradiation with a chemically active ray.

In particular, the thermoplastic resin (A) for transfer layer contains a polymer component (a) containing a specific hydrophilic group described below and a polymer group containing a functional group capable of forming a specific hydrophilic group by a chemical reaction. It is preferable that the polymer contains at least one polymer component of the united component (b).

Polymer component (a): --CO ₂ H group, --CH
O group, -SO ₃ H group, -SO ₂ H group, -P (= O) (OH )
R ¹ {R ¹ represents -OH group, hydrocarbon group or -OR ² (R ² represents hydrocarbon group) group} group, phenolic OH
Polymer component containing at least one group of the groups, acid cyclic anhydride-containing group, -CONHCOR ³ that (R ³ represents a hydrocarbon group) group and -CONHSO ₂ R ³ group. Polymer component (b): -CO ₂ H group in chemical reactions, -CHO
Group, -SO ₃ H group, -SO ₂ H group, -P (= O) (OH ) R
¹ {R ¹ represents an —OH group, a hydrocarbon group or an —OR ² (R ² represents a hydrocarbon group) group} group and at least one functional group forming an —OH group. Seed-containing polymer component.

Here, -P (= O) (OH) R ¹ represents a group shown below.

[0140]

[Chemical 12]

The above-mentioned hydrocarbon groups represented by R ¹ , R ² and R ³ specifically have 1 to 1 carbon atoms which may be substituted.
8 aliphatic groups (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2-
Methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group,
Methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc.) or optionally substituted aryl group (phenyl group, tolyl group, ethylphenyl group, propyl-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group) , Cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.) and the like.

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and the cyclic acid anhydride to be contained is an aliphatic dicarboxylic acid anhydride or an aromatic dicarboxylic acid anhydride. Things can be mentioned. Examples of the aliphatic dicarboxylic acid anhydrides include succinic anhydride, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-
1,2-dicarboxylic acid anhydride ring, cyclohexane-1,
2-dicarboxylic acid anhydride ring, cyclohexene-1,2-
Dicarboxylic acid anhydride ring, 2,3-bicyclo [2.2.
2] Octanedicarboxylic acid anhydride ring and the like, and these rings are substituted with, for example, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group or a hexyl group. Good. Examples of the aromatic dicarboxylic acid anhydride include a phthalic acid anhydride ring, a naphthalene dicarboxylic acid anhydride ring, a pyridine dicarboxylic acid anhydride ring, a thiophene dicarboxylic acid anhydride ring, and the like. Substituted with halogen atom such as bromine atom, alkyl group such as methyl group, ethyl group, propyl group and butyl group, hydroxyl group, cyano group, nitro group, alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, etc.) It may have been done.

When the amount of the polymer components (a) and (b) present is too small, it becomes difficult to remove the transfer layer by a chemical reaction treatment, and when printed as a printing plate, the non-image area is stained. On the other hand, when the amount is too large, the glass transition point or softening point of the resin (A) becomes high no matter how the other copolymerization component of the resin (A) is adjusted, resulting in deterioration of transferability of the transfer layer. Cause

Therefore, the contents of the polymerization component (a) and the polymerization component (b) in the resin (A) are preferably as follows. When only the polymer component (a) containing a specific hydrophilic group is contained in the resin (A), it is preferably 3 to 50% by weight, more preferably 5% by weight based on the total polymer components of the resin (A).
-40% by weight. Further, in the case of containing only the polymer component (b) containing a functional group capable of generating a hydrophilic group in the chemical reaction treatment, it is preferably 3 to 100% by weight in the total polymer components of the resin (A), It is preferably 5 to 70% by weight. Furthermore, when the polymer component (a) and the polymer component (b) are contained, the polymer component (a) is preferably 0.5 to 30% by weight in the total polymer components of the resin (A). , More preferably 1 to 25% by weight, the polymer component (b) is preferably 3 to 99.5% by weight, more preferably 5 to 50% by weight.
% By weight.

Next, each polymer component that can be contained in the resin (A) will be described in detail. The polymer component (a) is not particularly limited as long as it is a copolymer component containing a specific hydrophilic group as described above. The hydrophilic groups may take the form of salts. Specific examples of the hydrophilic group-containing copolymer component include
Any vinyl compound containing such a hydrophilic group may be used, and it is described, for example, in "Polymer Data Handbook [Basic Edition]" edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) ethyl form, α-chloro form, α-bromo form, α -Fluoro compound, α-tributylsilyl compound, α-cyano compound, β-chloro compound, β-bromo compound, α
-Chloro-β-methoxy, α, β-dichloro, etc.),
Methacrylic acid, itaconic acid, itaconic acid half-esters,
Itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (eg 2-pentenoic acid, 2-methyl-2-
Hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid,
Maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acids, vinylbenzenesulfonic acids, vinylsulfonic acids, vinylphosphonic acids, half-ester derivatives of vinyl groups or allyl groups of dicarboxylic acids and their carvone or sulfonic acid Examples thereof include compounds having a hydrophilic group in the substituents of ester derivatives and amide derivatives.

Examples of the hydrophilic group-containing copolymer component (a) are shown below. Wherein, R ⁴ represents -H or -CH _3, R ⁵ is -H, indicates -CH ₃ or -CH ₂ COOCH _3, R ⁶ represents an alkyl group having 1 to 4 carbon atoms, R ⁷ is It shows an alkyl group having 1 to 6 carbon atoms, a benzyl group or a phenyl group, e is an integer of 1 or 2, f is an integer of 1 to 3, g is an integer of 2 to 11, and h is 1 Indicates an integer of 1 to 11, i indicates an integer of 2 to 4, and j indicates an integer of 2 to 10.

[0147]

[Chemical 13]

[0148]

Embedded image

[0149]

[Chemical 15]

[0150]

Embedded image

[0151]

[Chemical 17]

[0152]

Embedded image

[0153]

[Chemical 19]

Next, the polymer component (b) will be described. The polymer component (b) contains at least 1 by a chemical reaction.
It is a polymer component containing at least one kind of functional group that generates a hydrophilic group. The number of the hydrophilic groups generated from one functional group by a chemical reaction may be one or two or more.

First, a functional group which produces at least one carboxyl group by a chemical reaction will be described. According to one preferred embodiment of the present invention, the carboxyl group-forming functional group includes, for example, a functional group represented by the following general formula (I). General formula (I) -COO-L ¹ in formula (I), L ¹ is represents the following group.

[0156]

Embedded image

Here, R ¹¹ and R ^{12, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group,
X represents an aromatic group, Z is a hydrogen atom, a halogen atom,
Trihalomethyl group, alkyl group, -CN group, -NO
₂ groups, -SO ₂ Z ¹ (Z ¹ represents a hydrocarbon group) group, -CO
Represents an OZ ² (Z ² represents a hydrocarbon group) group, —OZ ³ (Z ³ represents a hydrocarbon group) or —COZ ⁴ (Z ⁴ represents a hydrocarbon group) group, and n and m each represent Represents 0, 1 or 2. However, when both n and m are 0, Z does not represent a hydrogen atom.

A ¹ and A ² may be the same or different and each represents an electron-withdrawing group having a positive Hammet substituent constant σ value. R ¹³ represents a hydrogen atom or a hydrocarbon group.
R ¹⁴ , R ¹⁵ and R ¹⁶ and R ²⁰ and R ²¹ may be the same or different from each other, and each is a hydrocarbon group or —OZ.
⁵ (Z ⁵ represents a hydrocarbon group). Y ¹ represents an oxygen atom or a sulfur atom, R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different and each is a hydrogen atom, a hydrocarbon group or a —OZ ⁷ (Z ⁷ represents a hydrocarbon group) group. And p is 3
Or represents an integer of 4. Y ² represents an organic residue forming a cyclic imide group.

This will be described in more detail below. R ¹¹ and R ¹² may be the same as or different from each other, preferably a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (eg, methyl group, ethyl group, propyl group). , Chloromethyl group, dichloromethyl group, trichloromethyl group, trifluoromethyl group, butyl group, hexyl group, octyl group, decyl group, hydroxyethyl group, 3-
A phenyl group or a naphthyl group (eg, a phenyl group, a methylphenyl group, a chlorophenyl group, a dimethylphenyl group, a chloromethylphenyl group, a naphthyl group, etc.) which may be substituted.
Z is preferably a hydrogen atom, a halogen atom (eg, chlorine atom, fluorine atom, etc.), a trihalomethyl group (eg, trichloromethyl group, trifluoromethyl group, etc.),
A linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (eg, methyl group, chloromethyl group, dichloromethyl group, ethyl group, propyl group, butyl group, hexyl group, tetrafluoroethyl group, Octyl group, cyanoethyl group, chloroethyl group, etc.), -CN group, -NO ₂ group,-
SO ₂ Z ¹ {Z ¹ is an aliphatic group (eg, an alkyl group having 1 to 12 carbon atoms which may be substituted, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a chloroethyl group, a pentyl group, an octyl group. Group, etc., optionally substituted aralkyl group having 7 to 12 carbon atoms, specifically, benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, chlorophenethyl group, methylphenethyl group, etc., or aromatic group (eg, Phenyl group or naphthyl group which may have a substituent, specifically, phenyl group, chlorophenyl group, dichlorophenyl group, methylphenyl group, methoxyphenyl group, acetylphenyl group, acetamidophenyl group, methoxycarbonylphenyl group, naphthyl group Etc.) group, —COOZ ² (Z ² is the same as the above Z ¹ ) group,
-OZ ³ (Z ³ has the same meaning as Z ¹ ) group or -COZ
⁴ (Z ⁴ has the same meaning as Z ¹ above). n and m each represent 0, 1 or 2. However, when both n and m are 0, Z does not represent a hydrogen atom.

R ¹⁴ , R ¹⁵ , R ¹⁶ and R ²⁰ , R ²¹ may be the same as or different from each other, and preferably have 1 to 10 carbon atoms.
18 optionally substituted aliphatic groups {The aliphatic group represents an alkyl group, an alkenyl group, an aralkyl group or an alicyclic group,
Examples of the substituent include a halogen atom, -CN group, -OZ
⁶ (Z ⁶ represents an alkyl group, an aralkyl group, an alicyclic group, an aryl group) or the like}, and an optionally substituted aromatic group having 6 to 18 carbon atoms (for example, a phenyl group, a tolyl group, Chlorophenyl group, methoxyphenyl group, acetamidophenyl group, naphthyl group, etc.) or -OZ ⁵ (Z ⁵ is an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alkenyl group having 2 to 12 carbon atoms) Represents an optionally substituted aralkyl group having 7 to 12 carbon atoms, an optionally substituted alicyclic group having 5 to 18 carbon atoms, and an optionally substituted aryl group having 6 to 18 carbon atoms) group. .

[0161] A ^1, A ² may be the same or different, are each at least one electron withdrawing group, A ^1,
The sum of Hammet's σ _p values of A ² may be 0.45 or more. Examples of the electron withdrawing group referred to here include, for example, an acyl group, an aroyl group, a formyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, an alkylsulfonyl group,
Examples thereof include aroylsulfonyl group, nitro group, cyano group, halogen atom, halogenated alkyl group, carbamoyl group and the like.

Hammett's σ _p value is usually used as an index for estimating the degree of electron withdrawing / donating a substituent,
A larger value on the + side is treated as a stronger electron-withdrawing group. Specific numerical values for each substituent are described in Naoki Inamoto's "Hammett's Rule-Structure and Reactivity" Maruzen (1984). Further, it is considered that the Hammett σ _p value in this system is additive, and it is not necessary that both A ¹ and A ² are electron withdrawing groups. Thus, whereas, for example, when A ¹ is an electron withdrawing group, the substituent is other A ^2, of A ^1, A ² sigma _p
Any value may be used as long as the sum of the values is 0.45 or more, and there is no particular limitation.

R ¹³ preferably represents an optionally substituted hydrocarbon group having 1 to 8 carbon atoms, for example, a methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, allyl group, benzyl group, phenethyl group, 2-hydroxyethyl group, 2-methoxyethyl group,
2-ethoxyethyl group, 3-methoxypropyl group, 2-
A chloroethyl group etc. are mentioned. Y ¹ represents an oxygen atom or a sulfur atom.

R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same as or different from each other, preferably a hydrogen atom, and an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms (for example, a methyl group). , Ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc., optionally substituted alicyclic group (eg cyclopentyl) Group, cyclohexyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group,
Phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.), optionally substituted aromatic group (eg phenyl group,
Naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.) or -OZ ⁷ (Z ⁷ represents a hydrocarbon group,
Specifically, the same substituents as the above-mentioned hydrocarbon groups of R ¹⁷ , R ¹⁸ and R ¹⁹ are shown). p represents an integer of 3 or 4.

Y ² represents an organic residue forming a cyclic imide group. Preferably, the general formula (A) or the general formula (B)
Represents an organic residue represented by.

[0166]

[Chemical 21]

In the formula (A), R ²² and R ²³ may be the same or different and each may be substituted with a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.) or a C 1-18 substituent. Good alkyl groups (eg methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2
-Chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2- (methanesulfonyl) ethyl group, 2- (ethoxyoxy) ethyl group, etc.), substituted with 7 to 12 carbon atoms Aralkyl group (eg, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, bromobenzyl group, etc.), which may be substituted with 3 to 18 carbon atoms Good alkenyl groups (eg allyl group, 3-methyl-2-propenyl group, 2
-Hexenyl group, 4-propyl-2-pentenyl group, 1
2-octadecenyl group, etc.), —SZ ⁸ {Z ⁸ is a substituent having the same meaning as the alkyl group, aralkyl group, or alkenyl group of R ²² or R ²³ , or an aryl group which may be substituted (for example, a phenyl group). , Tolyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, ethoxyphenyl group, ethoxycarbonylphenyl group, etc.) or --NHZ ⁹ (Z ⁹ represents the same as Z ⁸ ) . In addition, a residue forming a ring by R ²² and R ²³ may be represented (for example, a 5- or 6-membered monocyclic ring (for example, cyclobenzyl ring, cyclohexyl ring), or 5 or 6
A membered bicyclo ring (for example, a bicycloheptane ring, a bicycloheptane ring, a bicyclooctane ring, a bicyclooctene ring, etc.), and these rings may be substituted, and the substituents are the same as those described above for R ²² and R ²³ . Including the same as the contents}. q represents an integer of 2 or 3.

[0168]

[Chemical formula 22]

In the formula (B), R ²⁴ and R ²⁵ may be the same or different and have the same contents as the above R ²² and R ²³ . Furthermore, R ²⁴ and R ²⁵ may represent an organic residue which continuously forms an aromatic ring (eg, benzene ring, naphthalene ring, etc.).

Furthermore, another preferable embodiment of the present invention is an oxazolone ring represented by the following general formula (II).

[0171]

[Chemical formula 23]

In the general formula (II), R ²⁶ and R ^{27, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group, or R ²⁶ and R ²⁷ together form a ring. . Preferably, R ²⁶ and R ²⁷ may be the same or different from each other, and each is a hydrogen atom, or an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, butyl group, hexyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-
Methoxycarbonylethyl group, 3-hydroxypropyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, 4-chlorobenzyl group, 4
-Acetamidobenzyl group, phenethyl group, 4-methoxybenzyl group, etc.), optionally substituted carbon number 2 to 1
2 alkenyl groups (eg vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, etc.), optionally substituted 5- to 7-membered alicyclic groups (eg cyclopentyl group, cyclohexyl group, chlorocyclohexyl group) Groups, etc.), optionally substituted aromatic groups (eg phenyl groups,
Chlorophenyl group, methoxyphenyl group, acetamidophenyl group, methylphenyl group, dichlorophenyl group,
Nitrophenyl group, naphthyl group, butylphenyl group, dimethylphenyl group, etc.) or R ²⁶ and R ²⁷ together form a ring (eg, tetramethylene group, pentamethylene group, hexamethylene group, etc.) Good.

As the functional group which forms at least one sulfo group by a chemical reaction, for example, a functional group represented by the following general formula (III) or (IV) can be mentioned. General formula (III) in -SO ^₂ -O-L ₂ formula _{(IV) -SO 2 -S-L} 2 formula (III) or (IV), L ² represents a group shown below.

[0174]

[Chemical formula 24]

Here, R ¹¹ , R ¹² , X, Z, n, m and Y
² , R ²⁰ and R ²¹ have the same contents as described above. R ²⁶ ′ and R ²⁷ ′ each represent a hydrogen atom or a hydrocarbon group (the same content as the hydrocarbon group for R ²⁶ ).

Further, examples of the functional group which forms at least one sulfinic acid group by a chemical reaction include a functional group represented by the following general formula (V).

[0177]

[Chemical 25]

In the formula (V), A ¹ , A ² and R ¹³ have the same contents as described above.

Further, by chemical reaction, -P (= O) (OH)
Examples of the functional group that forms the R ¹ group include the following general formula (V
The functional group represented by Ia) or (VIb) may be mentioned.

[0180]

[Chemical formula 26]

In formula (VIa) or (VIb), L ³ and L ⁴ may be the same or different and each has the same meaning as L ¹ . R ¹ has the same meaning as described above.

Further, examples of the functional group which produces a —OH group by a chemical reaction include a functional group represented by the following general formula (VII). In the general formula (VII) -O-L ⁵ formula (VII), L ⁵ represents a group of the following.

[0183]

[Chemical 27]

Here, R ²⁸ represents a hydrocarbon group, and specifically has the same contents as R ¹¹ . R ¹⁴ ~R ^19, Y ¹ and p each represent the same contents.

Furthermore, according to another preferred embodiment of the functional group which produces a —OH group by a chemical reaction, the hydroxyl group-forming functional group has at least two hydroxyl groups sterically close to each other as one protecting group. It is a functional group which is simultaneously protected with. Examples of the functional group having at least two hydroxyl groups sterically close to each other in one protected form include, for example, the following general formula (VIII),
The functional groups represented by (IX) and (X) may be mentioned.

[0186]

[Chemical 28]

In formulas (VIII) to (X), R ²⁹ and R ³⁰ may be the same or different from each other and each is a hydrogen atom, a hydrocarbon group or —OZ ¹⁰ (Z ¹⁰ represents a hydrocarbon group). Represents a group, and U represents a carbon-carbon bond which may pass through a hetero atom (provided that the number of atoms between oxygen atoms is within 5).

Explaining the above functional group in more detail, R ²⁹ and R ³⁰ may be the same or different from each other, preferably a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms (eg methyl group). Group, ethyl group, propyl group, butyl group, hexyl group, 2-methoxyethyl group, octyl group, etc.), an aralkyl group having 7 to 9 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, methylbenzyl group, Methoxybenzyl group, chlorobenzyl group, etc.), an alicyclic group having 5 to 7 carbon atoms (eg, cyclopentyl group, cyclohexyl group, etc.) or an optionally substituted aryl group (eg, phenyl group, chlorophenyl group, methoxyphenyl group, methylphenyl group, cyanophenyl group) or -OZ ¹⁰ (Z ¹⁰ has the same meaning as the hydrocarbon group of R ^29, R ³⁰⁾ display the group It is. U represents a carbon-carbon bond which may pass through a hetero atom, and the number of atoms between oxygen atoms is 5 or less.

Specific examples (b-1) to (b-67) of the functional groups represented by the above general formulas (I) to (X) are shown below. However, the content of the present invention is not limited to these. In the following specific examples, each symbol is as shown below.

[0190]

[Chemical 29]

[0191]

Embedded image

[0192]

[Chemical 31]

[0193]

[Chemical 32]

[0194]

[Chemical 33]

[0195]

Embedded image

A chemical reaction which can be used in the present invention is --CO ₂ H group, --CHO group, --SO ₃ H group, --CO ₂ H group,
The polymer component (b) containing a functional group that forms at least one hydrophilic group of SO ₂ H group, —P (═O) (OH) R ¹ group and —OH group is particularly limited. Not a thing. Preferably, the polymer component in which the hydrophilic group of the polymer component (a) is protected can be mentioned as an example.

The above-mentioned --CO ₂ H group, --CHO group, --SO ₃ H group, --SO ₂ H which can be used in the present invention.
Group, a -P (= O) (OH) R ¹ group and / or a functional group which expresses an -OH group by a chemical reaction is a functional group obtained by protecting these hydrophilic groups. The introduction method by a chemical bond to the group can be easily performed by a conventionally known method. For example, JFW McOmie "Prote
ctive groups in Organic Chemistry '' (Plenum Press.1
973), TW Greene "Protective groups in Orga
nic Synthesis "(Wiley-Interscience 1981), Chemical Society of Japan," New Experimental Chemistry Course, Volume 14, Synthesis and Reactions of Organic Compounds "(Maruzen Co., Ltd. 1978), Yoshio Iwakura, Keisuke Kurita" Reactivity " Each unit reaction described in "Polymer" (Kodansha) or the like is used.

As a method for introducing these functional groups into the resin (A), --CO ₂ H group, --CHO group and --SO ₃ H group are used.
Group, -PO ₃ H ₂ group, -SO ₂ H group, a polymer containing at least one hydrophilic group selected from -OH group, the functional group protecting the respective hydrophilic groups by reaction The method of converting by a so-called polymer reaction, or after synthesizing one or more monomers containing one or more functional groups represented by the general formulas (I) to (X) described above, It can be obtained by a method of forming a polymer by a polymerization reaction with any other monomer copolymerizable with.

Functional groups required for the present invention can be optionally adjusted in the polymer, or impurities (in the case of polymer reaction,
The latter method (a method in which a desired monomer is obtained in advance and then a polymerization reaction is performed) is preferably used for the reason that the catalyst to be used, by-products, etc. are not mixed. For example, in the case of introducing a functional group that generates a carboxyl group, specifically, a carboxylic acid containing a polymerizable double bond or an acid halide thereof, for example, according to the method described in the above-mentioned known literature, the carboxyl group After conversion into the functional group represented by the general formula (I), a polymerization reaction can be carried out for production.

The resin containing an oxazolone ring represented by the general formula (II) as a functional group which produces a carboxyl group by a chemical reaction is a resin containing one or more monomers containing the oxazolone ring. Alternatively, it can be obtained by a method of polymerizing the monomer and another monomer copolymerizable therewith. The oxazolone ring-containing monomer can be produced by a dehydration ring-closing reaction of N-acylloyl-α-amino acids having a polymerizable unsaturated bond. Specifically, it can be produced by the method described in the literature cited in the review article of “Reactive Polymer” by Yoshio Iwakura and Keisuke Kurita, Chapter 3 (published by Kodansha).

The resin (A) preferably contains, in addition to the above-mentioned specific polymer component (a) and / or polymer component (b), another polymer component in order to maintain thermoplasticity. As the other polymer component, one having a glass transition point of 130 ° C. or lower of a homopolymer composed of the polymer component is preferable. Specifically, for example, a component of a repeating unit represented by the following general formula (U) can be mentioned.

[0202]

Embedded image

In the formula (U), V is --COO--, --O.
CO -, - O -, - CO -, - C 6 H 4 -, - (CH 2) n
COO- or - (CH ₂₎ represents an _n OCO-. However, n
Represents an integer of 1 to 4. R ⁶⁰ represents a hydrocarbon group having 1 to 22 carbon atoms. b ¹ and b ² may be the same or different and each is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a trifluoromethyl group, a hydrocarbon group having 1 to 7 carbon atoms (eg, methyl group, ethyl group). Group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, benzyl group) or -COOZ ¹¹ (Z ¹¹ represents a hydrocarbon group, specifically, a hydrocarbon group having 1 to 7 carbon atoms) The same as the concrete contents can be mentioned).

R ⁶⁰ is preferably an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Decyl group, dodecyl group, tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-
Hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-hydroxypropyl group, etc., alkenyl group having 2 to 18 carbon atoms and which may be substituted (for example, vinyl group, allyl group, isopropenyl group) , Butenyl group, hexenyl group, heptenyl group, octenyl group, etc., and aralkyl groups having 7 to 12 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group). , An ethoxybenzyl group, a methylbenzyl group, etc.), a cycloalkyl group having 5 to 8 carbon atoms which may be substituted (eg, a cyclopentyl group,
Cyclohexyl group, cycloheptyl group, etc.) or carbon number 6
To 12 optionally substituted aryl groups (eg, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, methylchlorophenyl group, difluorophenyl group, bromo group) Phenyl group, chlorophenyl group, dichlorophenyl group, methylcarbonylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group,
Methanesulfonylphenyl group, cyanophenyl group, etc.) and the like.

The polymer component represented by the above formula (U) is 1
Or two or more of them are used, but the content is the resin (A)
It is preferably 30 to 97% by weight.

Further, the resin (A), together with the polymer component (a), the polymer component (b) and / or the polymer component represented by the general formula (U), has a releasability of the resin (A) itself. You may contain the polymer component (f) containing the substituent which has a fluorine atom and / or a silicon atom which has the effect which improves. This improves the releasability from the primary receptor, resulting in better transferability. The fluorine atom / silicon atom-containing substituent may be incorporated in the polymer main chain of the polymer or may be contained as a side chain substituent of the polymer. Preferably, the fluorine / silicon-containing polymer component (f) is contained as a block in the thermoplastic resin (A).

The polymer component (f) is 1 to 1 in all polymer components.
It is preferable to contain about 20% by weight. Component (f) is 1
When it is contained in an amount of not less than 10% by weight, the effect of improving its releasability is exhibited, and when it is not more than 20% by weight, the transfer layer can be removed without lowering the wettability of the resin (A) with the desensitizing treatment liquid. Well done. Specific examples of the polymer component (f) include those having the same contents as the fluorine / silicon-containing polymer component that can be contained in the resin (P) used in the photosensitive layer. Further, the aspect of the polymerization pattern of the block copolymer when the polymer component (f) is contained in a block and the method for synthesizing the copolymer are also the same as those of the block copolymer containing the above-mentioned fluorine / silicon-containing polymer component. It is exactly the same as the case.

The resin (A) may further contain, in addition to the above-mentioned specific polymer component and / or the polymer component represented by the general formula (U), another polymer component copolymerizable therewith. . Examples of such other polymer components include, in addition to methacrylic acid esters, acrylic acid esters, and crotonic acid esters having a substituent other than those described in the general formula (U), α-olefins, carvone, etc. Acid vinyl or allyl ester (for example, as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (for example, dimethyl ester, Diethyl ester etc.), acrylamides, methacrylamides, styrenes (eg styrene, vinyltoluene, chlorostyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene etc.), vinyl sulfone Containing compound, a vinyl ketone-containing compounds, heterocyclic vinyl compounds (e.g., vinylpyrrolidone,
Vinyl pyridine, vinyl imidazole, vinyl thiophene, vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine, etc.), but are not limited thereto. These other copolymerization components are the resin (A)
Can be optionally used within a range that does not deviate from the transferability of the above, but specifically, it is preferably not more than 30% by weight in the resin (A).

The resin (A) may be used alone or in combination of two or more kinds. Particularly, it is preferable to use at least two kinds of resins having different glass transition points or softening points in combination. This further improves the transferability of the transfer layer. That is, the glass transition point 1
Resin having 0 ° C. to 140 ° C. or softening point of 35 ° C. to 180 ° C. (hereinafter sometimes referred to as resin (AH)) and resin having glass transition point of 45 ° C. or lower or softening point of 60 ° C. or lower (hereinafter resin (AH)
L)), and the difference in glass transition point or softening point between the resin (AH) and the resin (AL) is 2 ° C. or more.

Further, the resin (AH) preferably has a glass transition point of 30 ° C to 120 ° C or a softening point of 38 ° C to 160 ° C, more preferably a glass transition point of 35 ° C to 90 ° C or a softening point of 40 ° C to 120 ° C. C., and the resin (AL) preferably has a glass transition point of −50 ° C. to 40 ° C. or a softening point of −30.
℃ -45 ℃, more preferably a glass transition point -20
C. to + 33.degree. C. or softening point 0.degree. C. to 40.degree. The glass transition point or softening point of the resin (AL) is the same as that of the resin (AH).
It is preferable that the temperature is 5 ° C. or higher, and particularly 10 ° C. or higher. Here, the difference in the glass transition point or the softening point in the case where two or more kinds of the resin (AH) or the resin (AL) are contained, the difference between the glass transition point and the softening point in the resin (AH) is the lowest. It is the difference from the one having the highest glass transition point or softening point in (AL).

Resin (AH) and resin (A
The ratio of L) is preferably 5 to 90/95 to 10 (weight ratio), and more preferably 10 to 70/90 to 30 (weight ratio). If the abundance ratio of the resin (AH) / (AL) deviates from the above range, the effect of the combined use decreases.

If necessary, one or more other resins may be used in combination with the resin (A) in the transfer layer. However,
In order not to deteriorate the elution and removal performance of the transfer layer, it is preferable that the content of the above-mentioned polymer components (a) and / or (b) is 3 parts by weight or more based on 100 parts by weight of the total resin for forming the transfer layer.

Examples of other resins that can be used in combination include, for example, vinyl chloride resin, polyolefin resin, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers. , Styrene-methacrylic acid ester copolymer, itaconic acid diester polymer and copolymer, maleic anhydride copolymer, acrylamide copolymer, methacrylamide copolymer, hydroxyl group-modified silicone resin, polycarbonate resin, ketone resin, polyester Resin, silicone resin, amide resin, 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, heterocycle Copolymer (eg as heterocycle If, furan ring, tetrahydrofuran ring, a thiophene ring, dioxane ring, Jiokisofuran ring,
Lactone ring, benzofuran ring, benzothiophene ring,
1,3-dioxetane ring, etc.), cellulose resin, fatty acid-modified cellulose resin, epoxy resin and the like.

Specifically, for example, Vol. 1 to Volume 18 of "Plastic Material Course Series" published by Nikkan Kogyo Shimbun (1981)
), "Polyvinyl chloride" edited by the Kinki Chemical Society Vinyl Section, published by Nikkan Kogyo Shimbun (1988), Eizo Omori "Functional Acrylic Resin" Techno System Co., Ltd. (1985), Eiichiro Takiyama "Polyester Resin Handbook" Published by Nikkan Kogyosha (1988
Yuki Kazuo, "Saturated Polyester Resin Handbook", published by Nikkan Kogyo Shimbun (1989), Polymer Society of Japan, "Polymer Data Handbook (Application)", Chapter 1 Rofukan (1986
), "Latest Binder Technology Handbook" edited by Yuji Harazaki, Chapter 2 General Technology Center Co., Ltd. (1985), Taira Okuda "Polymer Processing Separate Volume 8 Volume 20 Special Issue" Adhesive "" Polymer Publishing Association (Published in 1976), Keiji Fukuzawa "Adhesive Technology" Polymer Publishing Association (19
1987), Mamoru Nishiguchi "Adhesion Handbook 14th Edition", Polymer Publishing Co., Ltd. (1985), Adhesion Handbook 2
The various resins listed in, for example, Nikkan Kogyo Shimbun (1980) are listed.

Further, other additives may be used in the transfer layer in order to improve various physical properties such as adhesiveness, film-forming property and film strength. For example, polybutene, DOP, DBP, low molecular weight styrene resin, low molecular weight as a plasticizer and a softening agent such as rosin, petroleum resin and silicone oil for adjusting the adhesiveness, which improve the wettability to the photoreceptor and lower the melt viscosity. Polyethylene wax, microcrystalline wax,
Paraffin wax and the like, and polymeric hindered polyphenols, triazine derivatives and the like can be added as antioxidants. For details, see "Practice of hot melt adhesion."
(Written by Hiroshi Fukada, published by Kobunshi Shuppankai, 1983).

In the present invention, the transfer layer may have a laminated structure of two or more layers. For example, the transfer layer of the present invention includes a first layer made of a resin (for example, resin (AH)) having a relatively high glass transition point (softening point) on a photoreceptor on which a toner image is formed, and a first layer formed thereon. Formed of a resin having a low glass transition point (softening point) (for example, a resin (AL)), and a glass transition point (softening point) of both resins.
It is preferable that the difference is 2 ° C. or more. As a result, the transferability to the primary receptor is further improved, the latitude of transfer conditions (heating temperature, pressure, transport speed, etc.) is further expanded, and transfer is easily performed regardless of the type of final transfer material. It becomes possible.

The thickness of the transfer layer is preferably 0.1 to 10 μm.
m, more preferably 0.5 to 7 μm. When the film thickness is 0.1 μm or more, transfer is sufficiently performed, and when the film thickness is too thick, the effect of the present invention is not particularly adversely affected, but 10 μm or less is preferable from the viewpoint of saving resin consumption. .

In the present invention, a transfer layer is provided on the photoconductor after the toner image is formed on the photoconductor and before the transfer to the primary receptor. The transfer layer is preferably formed on the photoconductor on which the toner image is formed in the apparatus for performing the electrophotographic process. In this way, by incorporating the transfer layer forming device into the electrophotographic device, it becomes possible to repeatedly use the photoconductor after peeling the toner image together with the transfer layer in the same device, and continuously perform the plate making process. Therefore, there is an advantage that the cost of the printing plate can be remarkably reduced.

In order to form the transfer layer on the photoreceptor on which the toner image is formed, a known layer forming method can be used. For example,
The solution or dispersion of the transfer layer composition may be applied by a known method. In particular, it is preferable to form the transfer layer on the photoreceptor by at least one of the hot melt coating method, the electrodeposition coating method and the transfer method. These methods are preferable in that the transfer layer can be easily formed on the surface of the photoconductor in the electrophotographic apparatus.

Each preferable transfer layer forming method will be described below. The hot-melt coating (hot-melt) method is a method in which a transfer layer composition is hot-melt coated by a known method, and is described in a solventless coating machine, for example, on pages 197 to 215 of the above-mentioned document "Actual Hot Melt Adhesion". The mechanism of the hot-melt adhesive coating device for hot-melt adhesives (hot-melt coater) described above can be diverted to the drum-coating specification of the photoreceptor. Examples include direct roll coater, offset gravure roll coater, lot coater, extrusion coater,
A slot orifice coater, a carten coater, etc. are mentioned.

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

Next, the electrodeposition coating method will be described. In the electrodeposition coating method, the thermoplastic resin (A) in the form of resin particles is electrodeposited or electrostatically adhered (hereinafter also simply referred to as electrodeposition) onto the surface of the photoconductor, and for example, is uniformly heated by heating or the like. A thin film is formed and used as a transfer layer. Therefore, it is necessary that the thermoplastic resin particles (hereinafter also referred to as resin particles (AR)) have either a positive charge or a negative charge, and the electroscopic property thereof is the photosensitive property to be combined. It is arbitrarily determined by the chargeability of the body.

At least two kinds of resins having different glass transition points or softening points by 2 ° C. or more (preferably at least two kinds of the resin having a high glass transition point (AH) and the resin having a low glass transition point (AL)). By using resin particles (hereinafter especially referred to as resin particles (ARW)) containing the same in the same particle, the transferability of the transfer layer is further improved. In this case, the resin may exist in the particles in a simple mixed state, or may form a laminate like a core / shell structure.

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

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

In the case of producing fine particles used in the dry electrodeposition method, the mechanical pulverization method is a method of directly pulverizing with a conventionally known pulverizer to obtain fine particles (for example, ball mill, paint shaker, jet mill). Method to be used, etc.), and if necessary, the materials to be resin particles are mixed, pulverized through melting and kneading, or post-treatment for classifying or treating the surface of the particles to make the particle diameter uniform after pulverization. Etc. can be appropriately combined and performed. A spray dry method is also known. For example, "Granulation Handbook" edited by Japan Powder Industry Technology Association, Part II (Ohm Publishing, 1991), Kanagawa Management Development Center "Actual State of the Latest Granulation Technology" (Kanagawa Management Development Center Publishing Department, 1984) Year),
It can be easily produced by appropriately using the method described in detail in the textbooks such as “Latest Powder Design Technology” edited by Masafumi Arakawa (Technosystem Co., Ltd., 1988).

As the polymerization granulation method, conventionally known emulsion polymerization reaction, seed polymerization reaction, suspension polymerization reaction, which is carried out in an aqueous system,
A method of producing by a dispersion polymerization reaction performed in a non-aqueous solvent system and the like are known. Specifically, Soichi Muroi "Chemistry of Polymer Latex" Polymer Publishing (1970), Taira Okuda, Hiroshi Inagaki "Synthetic Resin Emulsion" Polymer Publishing (1978), Soichi Muroi "Polymer Latex""Introduction" Kobunsha (1983), I. Pii
rma, PC Wang "Emulsion Polymerization", I. Piir
ma & JL Gardon, ACS symp. Sev. 24, p.34 (1974
Fumio Kitahara et al. "Chemistry of Dispersed Emulsion Systems" Engineering Book (1979)
), Soichi Muroi's supervision, "Cutting-edge technology of ultrafine polymer"
It can be produced by granulating by the method described in the textbook such as CMC (1991), then collecting and pulverizing by various methods as described in the textbook on the above mechanical method. .

As a method of dry electrodeposition of the obtained fine particle powder, a conventionally known coating method of electrostatic powder or a developing method of a dry electrostatic photograph developer can be used. Specifically, as described in "Electrostatic Powder Coating" by JF Hughes (Translated by Hideo Nagasaka and Machiko Midorikawa), corona charging, friction charging,
Electrodeposition of charged fine particles by methods such as induction charging, ionic wind charging, and reverse ionization phenomenon, edited by Koichi Nakamura "Recent development of electrophotographic development systems and toner materials.
Practical use ”, as described in the publications such as Chapter 1 (Japan Science Information Co., Ltd., 1985), cascade method, magnetic brush method, fur brush method, electrostatic method, induction method, touchdown method, It can be appropriately performed using a developing method such as a powder cloud method.

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

Further, it can be easily produced by using a seed polymerization method as a polymerization granulation method. Specifically, the above-mentioned "Latest Technologies for Ultrafine Particle Polymers", Chapter 2, "Recent Electrophotographic Development Systems and Toner Materials Development and Practical Use", Chapter 3
Chapter, KEJ Barvett “Dispersion Polymerization in
Organic Media "John Wiley (1975).

At least two different glass transition points as described above.
In the case of obtaining resin particles (ARW) containing the same kind of resin in the same particle, it can be easily produced by using, for example, a seed polymerization method. Specifically, fine particles are first synthesized by the above-mentioned conventionally known non-aqueous dispersion polymerization method, and then the fine particles are used as seeds, and in the same manner as above, seed particles and a resin corresponding to a resin (A) having a different glass transition point are used. It can be produced by a method of feeding and polymerizing the monomers.

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

Further, in order to introduce the polymer component (f) into the polymer in blocks, a method of using a block copolymer containing the polymer component (f) in blocks in the dispersion-stabilizing resin to be used, or A weight-average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ (preferably 3 × 10 ^{3 to} 1.5 × 10 ⁴ ) containing the united component (f) as a main repeating unit is allowed to coexist with a monofunctional macromonomer. By copolymerizing with the monomers, the resin particles of the block copolymer can be easily obtained.
Further, as another method, a polymer initiator containing the polymer component (f) as a main repeating unit (azobis polymer initiator or peroxide polymer initiator) is also used. Coalescent resin particles can be obtained.

The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or in combination of two or more. 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 a dispersion polymerization method, the average particle diameter of the resin particles easily becomes 1 μm or less, and the particle diameter distribution is very narrow and monodisperse particles are obtained. You can

Since these non-aqueous dispersion resin particles are subjected to a wet electrostatic development method or a method of electrophoresing in a pressure field of an electric field, they are electro-deposited. A resistance of 10 ⁸ Ω · cm or more and a dielectric constant of 3.
It is preferable to adjust to a non-aqueous solvent system of 5 or less. Specifically, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, and halogen-substituted products thereof can be used. For example, octane, isooctane, decane, 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), Shelsol 70, Shelsol 71 (Shellsol; trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco; American Mineral.
The trade name of Spirits Inc.) and the like can be used alone or in combination. Therefore, it is preferable to use the insulating organic solvent from the beginning as a solvent to be used in the polymerization granulation, 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 a non-aqueous latex, a polymer component soluble in a non-aqueous solvent having an electric resistance of 10 ⁸ Ωcm or more and a dielectric constant of 3.5 or less as described above, and insoluble in this solvent A block copolymer composed of a polymer component may be wet-dispersed in the solvent to be provided as fine resin particles. That is, a block copolymer consisting of a soluble polymer component and an insoluble polymer component, in an organic solvent that dissolves the block copolymer in advance,
This is a method in which a polymer is prepared using the above-mentioned block polymer synthesis method and then dispersed in a nonaqueous solvent for electrodeposition.

In order to electrodeposit the dispersed particles in the dispersion medium by electrophoresis, the resin particles are positively-charged or negatively-charged electro-detectable particles. It is possible to provide the resin particles with an electroscopic property by appropriately utilizing the technique of a developer for wet electrostatic photography. Specifically, the above-mentioned "Recent development and practical application of electrophotographic development system and toner material" pp. 139-148, edited by The Institute of Electrophotography "Basics and Applications of Electrophotographic Technology" pp. 497-505 (Corona,
1988), Yuji Harasaki, "Electronic Photography" 16 (No.2), p.44 (19
1977), etc., and using other electro-detection materials and other additives. For example, British Patents 893,429, 934,038, U.S. Pat. Nos. 1,122,397, 3,900,412, 4,606,989, and JP-A-60-179751, 60. -185963, JP-A-2-13965 and the like.

The composition of the non-aqueous latex to be subjected to electrodeposition is usually such that at least 1 liter of the electrically insulating dispersion medium contains 0.1 to 10 particles mainly containing a thermoplastic resin.
20 g, 0.01 to 50 g of the dispersion stabilizing resin, and 0.0001 to 10 g of the charge control agent added as necessary.

Further, other additives may be added in order to maintain dispersion stability of particles, charge stability, and the like.
Examples thereof include rosin, petroleum resin, higher alcohols, polyethers, silicone oils, paraffin waxes, and triazine derivatives. However, it is not limited to these. The upper limit of the total amount of these additives is regulated by the electric resistance of the electrodeposition latex. 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 attached, and therefore the amount of each additive added is controlled within this limit.

The thermoplastic resin particles which have been made into fine particles and imparted with a charge in this way and dispersed in an electrically insulating liquid exhibit the same behavior as an electrophotographic wet developer. Therefore, for example, it is possible to perform electrophoresis on the surface of the photoconductor by using the developing device described in "Basics and Applications of Electrophotographic Technology", pages 275 to 285, for example, the slit developing electrode device. That is, the particles mainly containing the thermoplastic resin (A) are supplied between the counter electrodes that are installed facing the photoconductor, and are electrophoresed according to the potential gradient applied from the external power source to adhere to the photoconductor. Electrodeposited to form a film.

Generally, when the particles are positively charged, a voltage is applied between the conductive support of the photoconductor and the developing electrode of the developing device from an external power source so that the photoconductor 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 on the premise "Basics and Applications of Electrophotographic Technology", pages 46 to 79, the photosensitive member is uniformly charged and then subjected to normal wet toner development.

On the other hand, a preferable medium used when resin particles dispersed in a medium which is liquefied by heating is solid at room temperature and has a heating temperature of 30 to 80 ° C., preferably 4
An electrically insulating organic compound that becomes a liquid at 0 to 70 ° C., and a compound suitable for this is a freezing point of 30 to 80 ° C.
Paraffins, waxes, low-molecular-weight polypropylene having a freezing point of 20 to 80 ° C., beef tallow having a freezing point of 20 to 50 ° C., and hardened oil having a freezing point of 30 to 80 ° C., and these can be used alone or in combination. Other necessary characteristics are the same as those of the electrodeposition resin particle dispersion used in the wet development method.

Furthermore, the resin particles used in this pseudo-wet method are so-called cores in which the resin component having a high glass transition point or a high softening point that does not soften at the liquefying temperature of the medium used constitutes the outer shell of the particles. -By using shell-type particles (a resin having a low Tg in the core portion and a resin having a high Tg in the shell portion), the dispersed resin particles are not fused by heating and are maintained in a stable dispersed state. Is possible.

The amount of the thermoplastic resin particles deposited on the photoconductor can be arbitrarily adjusted by the applied voltage of the external bias, the charging potential of the photoconductor, the processing 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 electrodeposition coating method is preferable because it has the advantages that it can be carried out with a simple device and that a uniform thin layer can be formed stably and easily.

Next, the formation of the transfer layer by the transfer method will be described. The transfer method is a method of transferring a transfer layer formed on a releasable support typified by release paper to the surface of a photoconductor on which a toner image is formed.

The release paper on which the transfer layer is formed is usually roll-shaped or sheet-shaped and can be easily supplied to an electrophotographic plate-making printing plate making apparatus. The release paper to be provided may be any conventionally known release paper, for example, new technology of adhesive (adhesive) and development materials of its application and various applied products (published; Management Development Center Publishing Department, 1978). May 20), Product Encyclopedia of All Paper Guide, Volume 1, Culture Industry Edition) Published;
Paper industry Times, December 1, 1983) and the like are mentioned in the publications. Specifically, the release paper is a non-bleached Clupak paper laminated with a polyethylene resin and a polyethylene resin, a high-grade paper precoated with a solvent resistant resin, a kraft paper, and an undercoated PET base. Or, it is applied directly to glassine paper. Solvent type is generally used for silicone, and it is 3 to 7
Apply with gravure roll and wire bar method at a concentration of
After drying, it is heat-treated at 150 ° C. or higher to be cured. The coating amount is about 1 g / m ² .

As the release paper, those for tape, label, forming industry and cast coat industry which are generally commercially available from paper makers can be used. For example, separate paper (Oji Paper), Kingleys (Shikoku Paper),
Examples include Sun Release (Sanyo Kokusaku Pulp) and NK High Release (Nippon Kogyo Paper Co., Ltd.). In order to form a transfer layer on release paper, a transfer layer composition containing a thermoplastic resin (A) as a main component is applied by bar coating, spin coating,
It is easily performed by applying a film by spray coating or the like. Further, it is also carried out by a hot melt coating method or an electrodeposition coating method.

In order to thermally transfer the transfer layer on the release paper onto the photoreceptor having a toner image on its surface, a usual thermal transfer method can be used. That is, the release paper holding the transfer layer may be pressure-bonded to the photoreceptor on which the toner image is formed, and the transfer layer may be thermally transferred. For this purpose, for example, a device as shown in FIG. 4 described later is used. The conditions for transferring the transfer layer from the release paper to the surface of the photoreceptor on which the toner image is formed are preferably as follows. Roller nip pressure is preferably 0.1-10 kg
f / cm ² , more preferably 0.2 to 8 kgf / cm ² , and the temperature during transfer is preferably 25 ° C to 100 ° C, more preferably 40 ° C to 80 ° C. The conveying speed is preferably 0.5 to 300 mm / sec, more preferably 3 to 200 mm /
Seconds, which may be different from each of the electrophotographic process and the thermal transfer process to the primary receptor.

In the present invention, after the transfer layer is formed on the photoreceptor on which the toner image is formed as described above, the transfer layer is transferred together with the toner image to the primary receptor. Known methods and devices can be used for this thermal transfer. For example, a toner image and a photoreceptor having a transfer layer are brought into close contact with the primary receptor, and the toner image is transferred together with the transfer layer onto the primary receptor by passing it between rollers under heating.

The heating surface temperature of the transfer layer at the time of thermal transfer is preferably 30 to 150 ° C, more preferably 35 to 90 ° C. In order to heat the transfer layer to a desired temperature, it is preferable to use a non-contact heating means such as an infrared line heater or a flash heater. The nip pressure of the roller is preferably 0.2 to 20 kgf / cm ² , more preferably 0.5 to 15 kgf / cm ² . As the roller pressing means, springs or air cylinders using compressed air at both ends of the roller shaft can be used. The transport speed is preferably 0.1 to 300 mm / sec, more preferably 1 to 200 mm / sec. The transport speed may be different between the electrophotographic process and the thermal transfer process.

Next, the primary receptor used in the present invention will be described. It is important that the releasability of the surface of the primary receptor is lower than that of the surface of the photoreceptor, and that the releasability for peeling and transferring to the final transfer material is maintained. That is, the adhesive force on the surface of the primary receptor is larger than the adhesive force on the surface of the photoreceptor, preferably 10 g · f or more, more preferably 30 g / f.
It is necessary to be larger than g · f. On the other hand, the adhesive force on the surface of the primary receptor is preferably at most 250 g · f, more preferably 180 g · f or less.

Any primary receptor satisfying the above conditions may be used. In the present invention, examples of the method used for transferring the toner image from the photoreceptor to the primary receptor include a drum method and an endless belt method that can be repeatedly used. In the drum system, the material of the primary receptor to be provided on the drum may be any material that satisfies the above conditions, but is preferably an elastic layer or a laminated structure including an elastic layer and a reinforcing layer support. It is sufficient that the surface of the laminated structure satisfies the above physical properties. These stacks may be mounted directly on the drum or may be removable so that they can be replaced.

As the elastic body, conventionally known natural resins,
Examples thereof include synthetic resins. These can be used alone or in combination of two or more kinds as a single layer or a plurality of layers. For example, AD Roberts "Natural Rubber Science
and Technology ”Oxford Science Publications (1988), W. Hofmann“ Rubber Technology Handbook ”, Ha
nser Publishers (published in 1989), plastic material structure,
Various resins described in 18 volumes in total, Nikkan Kogyo Shimbun, etc. are used. Specifically, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, cyclized rubber, chloroprene rubber, ethylene-propylene rubber, butyl rubber, chlorosulfonated polyethylene rubber, silicone rubber, fluororubber, polysulfide rubber, natural rubber. , Isoprene rubber, urethane rubber, etc., but not limited thereto, and can be arbitrarily selected in consideration of releasability from the transfer layer, durability and the like. The thickness of the elastic layer is preferably 0.01 to 10 mm.

As the reinforcing layer of the elastic layer, cloth, glass fiber, resin-impregnated special paper, aluminum, stainless steel or the like is used. A sponge-like rubber layer may be provided between the elastic layer and the reinforcing layer. Also in the endless belt system, known members can be used as the primary receptor member, for example, US Pat. Nos. 3,893,761 and 4,684.
No. 238, No. 4,690,539 and the like. A method in which a layer serving as a heating medium is provided in the layer of the belt carrier of the belt type primary receptor is also used, as described in, for example, JP-A-4-503265. The adhesive strength of the surface of the primary receptor can be easily adjusted by the method described with respect to the peelable photoreceptor, for example, the method of applying the compound (S). The average roughness of the surface of the primary receptor is preferably 0.01 mm or less.

Next, in the present invention, the toner image on the primary receptor is thermally transferred together with the transfer layer to the final transfer material.

The material to be transferred used in the present invention may be any one as long as it provides a hydrophilic surface suitable for lithographic printing, and the support conventionally used for offset printing plates can be used as it is. Specifically, a plastic sheet, printing-resistant paper, aluminum plate, zinc plate, copper-aluminum plate,
A substrate having a hydrophilic surface such as a bimetal plate such as a copper-stainless plate or a chrome-copper plate, a chrome-copper-aluminum plate, a chrome-lead-iron plate, or a trimetal plate such as a chrome-copper-stainless plate is used. Its thickness is 0.1-3 mm,
Particularly, 0.1 to 1 mm is preferable.

In the case of a support having an aluminum surface, it has been subjected to surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization treatment. Is preferred. Further, as described in U.S. Pat. No. 2,714,066, an aluminum plate which has been grained and then dipped in an aqueous sodium silicate solution, JP-B-47-51.
As described in No. 25, an aluminum plate subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is also preferably used.

The above anodizing treatment is carried out, for example, by using an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, etc., or an organic acid such as oxalic acid, sulfamic acid, etc., or an aqueous solution or a non-aqueous solution thereof, or two or more thereof. It is carried out by passing an electric current using an aluminum plate as an anode in the combined electrolytic solution. Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. The treatment with polyvinylsulfonic acid described in West German Patent Publication No. 1,621,478 is also suitable. These hydrophilic treatments are performed to make the surface of the support hydrophilic, and also to improve the adhesion to the toner image provided thereon. Further, a surface layer may be provided on the surface of the support in order to adjust the adhesion between the support and the transfer layer on which the toner image is formed. When a plastic sheet or paper is used as the support, it is needless to say that the portion other than the toner image portion must be hydrophilic, so that a surface layer having hydrophilicity is provided. Specifically, a known direct drawing lithographic printing original plate or a transfer material having a layer similar to the image receiving layer of such an original plate can be used.

Known methods and apparatuses can be used for thermal transfer from the primary receptor to the material to be transferred.
The preferable heating temperature range during transfer, the nip pressure range between the primary receptor and the material to be transferred, and the transport speed range are the same as the above thermal transfer conditions for the photoreceptor and the primary receptor. The transfer of the toner image to the primary receptor and the transfer of the transfer layer to the transfer material may be the same or different.

The thermal transfer behavior on the material to be transferred is estimated as follows. That is, for example, the transfer layer, which has been softened to some extent by the preheating means, is further heated by, for example, a heating roller so that the tackiness is increased and the transfer layer is brought into close contact with the material to be transferred. Next, for example, after passing under a cooling roller for peeling, the temperature is lowered, the fluidity and the adhesiveness are reduced, and the toner is peeled from the surface of the primary receptor together with the toner as a film. Therefore, the conditions should be set so that such a state is realized.

It is desirable that the material of the cooling roller is such that a heat conductive metal such as aluminum or copper is coated with silicone rubber, and a cooling means is provided to the inside of the roller or the outer peripheral portion which is not in contact with the material to be transferred to radiate heat. . A cooling fan, a coolant circulation or an electronic cooling element is used as the cooling means, and it is preferable to keep the temperature within a predetermined temperature range in combination with a temperature controller. The transfer of the toner image and the transfer layer from the photoreceptor to the primary receptor and the transfer of the toner image from the primary receptor to the transfer material for each transfer layer may be performed simultaneously within one screen, or may be transferred to the primary receptor. After the transfer of the entire screen is completed, the transfer may be performed on the transfer target material.

In the method for preparing a printing plate of the present invention, the conditions for transferring the toner image and the transfer layer are set such that the photoconductor (photosensitive layer and support) used, the transfer layer, the physical properties of the primary receptor surface, and It is natural to optimize it according to the physical properties of the transfer material. In particular, it is important to determine the temperature condition in the thermal transfer step in consideration of factors such as the glass transition point of the transfer layer, the softening temperature, the fluidity, the tackiness, the film property and the film thickness.

In the present invention, the material to be transferred (printing original plate) having the toner image and the transfer layer obtained as described above is subjected to a chemical reaction treatment so that the transfer layer is completely dissolved by swelling or swelling and desorption. The offset printing plate can be prepared by removing the above. In order to remove the transfer layer, a deprotection reaction by a chemical optical hot line may be used in addition to the reaction by the treatment liquid, or may be used in combination.

As the processing liquid, an aqueous solution adjusted to a predetermined pH is used. A known pH adjuster can be used to adjust the pH. The pH range to be applied may be any of acidic to neutral to alkaline, but considering the rustproof property of the treatment liquid or the elution and removability of the transfer layer, it is preferably used in the alkaline region of pH 8 or more. The compound used as the alkaline treatment liquid may be any conventionally known inorganic compound or organic compound, for example, carbonate, sodium hydroxide,
Potassium hydroxide, potassium silicate, sodium silicate,
Organic amine compounds and the like can be used alone or in combination.

Furthermore, as a compound which can be used in combination to accelerate the hydrophilic reaction, Pearson's nucleophilic constant n [RG Pearson & H. Sobel, J. Amer. Chem. Soc.,
90,319 (1968)] contains a substituent having a value of 5.5 or more and is soluble in 100 parts by weight of distilled water in an amount of 1 part by weight or more. Specific compounds include, for example, hydrazine, hydroxylamine, sulfites (ammonium salt, sodium salt, potassium salt, zinc salt, etc.), thiosulfate salt, and the like, and hydroxyl group, carboxyl group, sulfo group in the molecule. Examples thereof include a mercapto compound, a hydrazide compound, a sulfinic acid compound, a primary amine compound, and a secondary amine compound containing at least one polar group selected from a group, a phosphono group and an amino group.

For example, as a mercapto compound, 2-mercaptoethanol, 2-mercaptoethylamine, N-
Methyl-2-mercaptoethylamine, N- (2-hydroxyethyl) -2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenecarboxylic acid, 2-mercaptoenesulfonic acid, 2-mercaptoethylphosphonic acid, Mercaptobenzenesulfonic acid, 2-mercaptopropionylaminoacetic acid, 2-mercapto-1-aminoacetic acid, 1-mercaptopropionylaminoacetic acid, 1,2-dimercaptopropionylaminoacetic acid, 2,3-dihydroxylopyrmercaptan, 2-methyl 2-mercapto-1-aminoacetic acid or the like as a sulfinic acid compound, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid, Carboxymethyl benzene sulfinic acid, a hydrazide compound, 2- hydrazino ethanol sulfonic acid, 4-hydrazino butanoic acid,
Hydrazinobenzenesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzoic acid, hydrazinobenzenecarboxylic acid, etc. as a primary or secondary amine compound,
For example, N- (2-hydroxyethyl) amine, N, N-
Di (2-hydroxyethyl) amine, N, N-di (2-
Hydroxyethyl) ethylenediamine, tri (2-hydroxyethyl) ethylenediamine, N- (2,3-dihydroxypropyl) amine, N, N-di (2,3-dihydroxypropyl) amine, 2-aminopropionic acid,
Examples thereof include aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2-hydroxyethylmorpholine, 2-carboxyethylmorpholine and 3-carboxypiperazine.

The amount of the nucleophilic compound present in these treatment solutions is preferably 0.05 to 10 mol / liter, more preferably 0.1 to 5 mol / liter. The pH of the treatment liquid is preferably 8 or higher.

The treatment liquid is composed of the above-mentioned nucleophilic compound and pH.
In addition to the regulator, other compounds may be contained. For example,
A water-soluble organic solvent is added in an amount of 1 to 50 in 100 parts by weight of water.
You may contain a weight part. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propanol alcohol, benzyl alcohol, phenethyl alcohol, etc.), ketones (acetone, methyl ethyl tetone, cyclohexanone,
Acetophenone), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol diethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.), amides (dimethylformamide, pyrrolidone,
N-methylpyrrolidone, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, sulfolane, tetramethylurea, etc.) and the like. You may use these individually or in mixture of 2 or more types.

The surfactant may be contained in 100 parts by weight of water in an amount of 0.1 to 20 parts by weight. Examples of the surfactant include conventionally known anionic, cationic or nonionic surfactants. For example, use the compounds described in Hiroshi Horiguchi "New Surfactant" (1975) Sankyo Publishing Co., Ltd., Ryohei Oda, Kazuhiro Teramura "Synthesis of Surfactants and Their Applications" (1980) Maki Shoten. be able to. Furthermore,
In order to improve antiseptic properties and antifungal properties during storage of the treatment liquid, conventionally known antiseptic compounds and antifungal compounds may be used in combination. The treatment conditions are a temperature of 15 to 60 ° C. and an immersion time of 10
Seconds to 5 minutes are preferred. Further, during the treatment, a physical operation such as performing under ultrasonic waves or mechanical sliding (rubbing with a brush or the like) may be used in combination.

On the other hand, the light used in the deprotection reaction by irradiation with chemically active light may be any of visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, γ-ray, α-ray, etc., but is preferable. Is ultraviolet light, more preferably wavelength 31
It is a light ray in the range of 0 nm to a wavelength of 500 nm. Generally, a high pressure or ultra high pressure mercury lamp or the like is used. The light irradiation treatment can be performed sufficiently by irradiating from a distance of 5 cm to 50 cm for 10 seconds to 10 minutes. After irradiating with light in this way,
The transfer layer can be easily removed by immersing in the water-soluble solution as described above.

The method for producing the electrophotographic plate-making printing plate of the present invention will be described in detail below with reference to the accompanying drawings. FIG. 2 is a schematic diagram of an electrophotographic plate-making printing plate making apparatus suitable for carrying out the method of the present invention using a drum system as a primary receptor. As described above, when the electrophotographic photosensitive member whose surface is modified to be peelable is used, a toner image is formed on the photosensitive member by an ordinary electrophotographic process. Also,
When the releasability of the surface of the photoconductor is insufficient, the releasability can be imparted to the surface of the photoconductor by providing a device for applying the compound (S) before entering the electrophotographic process. That is, the compound (S) is supplied to the surface of the photoconductor 11 by the compound (S) applying device 10 using any one of the above-described specific modes. Compound (S) application device 10
May be fixed or movable.

As described above, in the development of the present invention, either a dry type developer or a wet type developer can be used.
An image with higher resolution can be obtained by using a wet type developer. Therefore, the case where a wet type developer is used for toner development will be specifically described below as an example.

First, the photoreceptor 11 is charged with the corona charging device 18
Then, for example, when the exposure device (for example, a semiconductor laser) 19 performs image exposure based on image information after positively uniformly charging, the potential of the exposed portion is reduced and a potential contrast is obtained between the exposed portion and the unexposed portion. The liquid developing unit set 1 includes a liquid developing unit 14L containing a liquid developer in which resin particles having a positive electrostatic charge are dispersed in an electrically insulating dispersion medium.
From the position 4, approach the surface of the photoconductor and fix it with a gap of 1 mm.

First, the photosensitive member 11 is pre-bused by the pre-bus means provided in the developing section, and then a developing bias voltage is applied between the photosensitive member 11 and the developing electrode by a bias power source and electric connection not shown. A liquid 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.

Thereafter, the rinsing means 14R built in the liquid developing unit set 14 wash away the developer adhering to the surface of the photoconductor, and then the squeeze means remove the rinsing liquid adhering to the surface of the photoconductor. Dry by passing under 15. During this time, the primary receptor 20 is placed away from the surface of the photoconductor 11.

Next, a transfer layer is provided by the transfer layer forming device 13 on the photoconductor 11 on which the toner image is formed. Here, the formation of the transfer layer will be described by taking the case of the electrodeposition coating method as an example.

The electrodeposition unit containing the dispersion liquid of resin particles is brought close to the photosensitive member and fixed so that the distance between the electrodeposition unit and the developing electrode is 1 mm. The resin particle dispersion liquid is supplied into this gap and is rotated while applying a voltage from the outside so that the resin particles are adsorbed on the entire surface of the photoreceptor on which the toner image is formed. A squeeze device built in the electrodeposition unit is used to remove the particle dispersion adhering to the surface of the photoconductor, and then the resin particles are thermally melted by a heating means to obtain a film-formed resin transfer layer. At this time, for exhausting the dispersion solvent of the dispersion liquid, the intake / exhaust unit 15 provided for the electrophotographic process of the electrophotographic photosensitive member can be used. A common liquid developer carrier is preferably used for the pre-bath and the rinse liquid. The electrodeposition unit may be separately installed as the transfer layer forming device 13 as shown in FIG. 2, or may be installed side by side in the liquid developing unit set 14 as shown in FIG. 3 (14T).

After the transfer layer is formed, the preheating means 16 for thermal transfer of the photoconductor drum performs a predetermined preheating, and if necessary, the primary receptor 20 is also preheated by the preheating means 16. The toner image on the surface of the photoconductor is transferred to the primary receptor 20 by pressure contact with the transfer layer and transferred by heat.

Next, the toner image completely transferred together with the transfer layer on the primary receptor 20 is further brought into pressure contact with the transfer material 30 to perform thermal transfer. Preheating is performed by the preheating means 16 of the primary receptor 20 and the transfer material 30 is preheated by the transfer backup roller 31, and the toner image on the primary receptor 20 is pressed against the transfer material 30 and then peeled off. To be transferred by the back roller 32 for transfer
The toner image is transferred together with the transfer layer onto 0, and a series of steps is completed. When it is necessary to impart releasability to the surface of the photoconductor 11, by stopping the apparatus with the compound (S) applied in the application apparatus 10, the electrophotographic process starts immediately when the next apparatus is operated. can do.

FIG. 3 is a schematic view of an electrophotographic plate-making printing plate making apparatus suitable for carrying out the method of the present invention using an endless belt system as a primary receptor. Except for the primary receptor, there is essentially no difference from the device shown in FIG.

As the transfer layer forming device 13 on the photosensitive member, a device of a hot melt coating method or a transfer method can be used instead of the electrodeposition coating method. In the hot-melt coating method, for example, the thermoplastic resin (A) is applied to the surface of the photoreceptor, for example, the peripheral surface of the drum, by a hot-melt coater, and is cooled to a predetermined temperature by passing under a suction / exhaust unit to form a transfer layer. Can be formed. After that, the hot melt coater preferably moves to the standby position.

An example of an apparatus for easily forming a transfer layer on a photoconductor by using a release paper in the transfer method is schematically shown in FIG. The release paper 24 provided with the transfer layer 12 is heated and pressed by the heating roller 25b to transfer the transfer layer 12 to the surface of the photoconductor 11. The release paper 24 is cooled by the cooling roller 25c and collected. If necessary, the photoconductor itself may be heated by the preheating means 25a to improve the transferability of the transfer layer by thermocompression bonding. The transfer layer forming unit 120 of FIG. 4 transfers the transfer layer 12 onto the photoconductor 11 by the release paper 24, and then transfers the transfer portion 13 to the transfer material 30 shown in FIG. 2 or 3.
0 may be used for transfer to the transfer material. Alternatively,
A transfer layer forming portion 120 for transferring the transfer layer 12 onto the photoreceptor 11 by the release paper 24, and the transfer layer 1 together with the toner image.
Both of the portions 130 for transferring 2 to the material 30 to be transferred may be incorporated in the apparatus.

When the transfer layer is of a laminated type, the transfer layer forming device may be the same or different.

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 Resin Particles (AR)] Synthesis Example 1 of Resin Particles (AR) 1: (AR-1) A mixed solution of 16 g of the dispersion stabilizing resin (Q-1) having the following structure and 550 g of Isopar H was mixed with nitrogen. Temperature 50 with stirring under air flow
Warmed to ° C. To this, benzyl methacrylate 85.0
g, acrylic acid 15.0 g, methyl 3-mercaptopropionate 2.0 g, 2,2′-azobis (2-cyclopropylpropionitrile) (abbreviation ACPP) 1.2 g and Isopar H
200 g of the mixed solution was added dropwise over 1 hour. After stirring for 1 hour as it was, 0.8 g of ACPP was added and reacted for 2 hours. Furthermore,
2,2'-azobis (isobutyronitrile) (abbreviation AIB
N.) 0.5 g was added, the temperature was set to 80 ° C., and the reaction was carried out for 3 hours. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was a monodisperse latex having a polymerization rate of 97% and an average particle size of 0.17 μm. The particle size was measured by CAPA-500 (manufactured by Horiba, Ltd.) (the same applies hereinafter). A part of the white dispersion was subjected to a centrifuge (rotation speed 1 × 10 ⁴ rpm, rotation time 1 hour) to collect the precipitated resin particles and dried to obtain a weight average molecular weight (Mw) ( The polystyrene conversion value by GPC (the same applies below) and the glass transition point (T
g) was measured. The Mw was 9.8 × 10 ⁴ , and the Tg was 65 ° C.

[0285]

Embedded image

Synthesis Example 2 of Resin Particles (AR): (AR-
2) 14 g of dispersion stabilizing resin (Q-2) having the following structure, 10 g of macromonomer (M-1) having the following structure and 553 g of Isopar H
The mixed solution of (1) was heated to 55 ° C while stirring under a nitrogen stream. To this, a mixed solution of 51.2 g of methyl methacrylate, 30 g of methyl acrylate, 12.5 g of acrylic acid, 1.3 g of methyl 3-mercaptopropionate, 1.2 g of ACPP and 200 g of Isopar H was added dropwise for 1 hour, and the reaction was continued for another 1 hour. did. Next, 0.8 g of 2,2'-azobis (isovaleronitrile) (abbreviation AIVN) was added, immediately after the temperature was set to 75 ° C. for 2 hours, and 0.5 g of AIVN was further added and reacted for 2 hours. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a monodisperse latex having a polymerization rate of 98% and an average particle size of 0.18 μm. The resin particles had Mw of 2 × 10 ⁴ and Tg of 50 ° C.

[0287]

Embedded image

Synthesis Examples 3 to 11 of Resin Particles (AR): (AR
-3) to (AR-11) A mixed solution of 20 g of a dispersion stabilizing resin (Q-3) having the following structure and 480 g of Isopar G was stirred at a temperature of 50 under a nitrogen stream.
Warmed to ° C. A predetermined amount of each monomer shown in Table A below, 2.6 g of methyl 3-mercaptopropionate, A.
A mixed solution of 1.5 g of IVN and 60 g of tetrahydrofuran was added dropwise at a dropping time of 1 hour, and the reaction was continued for another 1 hour. Next, add AIVN 1.0g and set the temperature to 70 ℃.
As it was, after reacting for 2 hours as it was, 0.8 g of AIVN was further added and reacted for 3 hours.

[0289]

[Chemical 38]

60 g of Isopar H was added to the above reaction product, and tetrahydrofuran was distilled off at a temperature of 50 ° C. under reduced pressure of a water jet pump, followed by cooling to obtain a white dispersion through a 200-mesh nylon cloth. Each of the obtained latexes had good monodispersity in the range of average particle diameter of 0.15 to 0.30 μm. The Mw of the resin particles of each latex is 9 × 10 ³
˜1.5 × 10 ⁴ and Tg in the range of 35-80 ° C.

[0291]

[Table 2]

[0292]

[Table 3]

[0293]

[Table 4]

Synthesis Examples of Resin Particles (AR) 12 to 17: (AR
-12) to (AR-17) In Synthesis Example 2 of resin particles (AR), instead of 10 g of the macromonomer (M-1), each macromonomer (Mw is 8 × 10 ³ to 1 × 10 8) shown in Table B below. Each resin particle was synthesized in the same manner as in Synthesis Example 2 except that the range of ⁴ ) was used. The polymerization rate of each particle is 98-99%, the average particle size of those particles is 0.15-0.25
In the range of μm, the particle size distribution of the particles was narrow and the monodispersity was good. The Mw of the resin particles was 9 × 10 ³ to 2 × 10 ⁴ , and the glass transition point was in the range of 40 to 70 ° C.

[0295]

[Table 5]

[0296]

[Table 6]

Synthesis Example 18 of resin particles (AR): (AR-1
8) A mixture solution of 18 g of a dispersion stabilizing resin (Q-4) having the following structure and 560 g of Isopar H was stirred at a temperature of 55 under a nitrogen stream.
Warmed to ° C. 40g of methyl methacrylate, 2
-Propoxyethyl methacrylate 45g, acrylic acid 15
g, methyl 3-mercaptopropionate 1.3 g, AIV
A mixed solution of 0.8 g of N. and 200 g of Isopar H was added dropwise for 1 hour. After stirring for 1 hour as it was, 0.8 g of AIVN was added and reacted for 2 hours. Further, 0.5 g of AIBN was added, the temperature was set to 80 ° C., and the reaction was carried out for 3 hours. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth has a polymerization rate of 97%.
It was a monodisperse latex having an average particle size of 0.17 μm.
The resin particles had Mw of 6 × 10 ³ and Tg of 25 ° C.

[0298]

[Chemical Formula 39]

Synthesis Example 19 of Resin Particles (AR): (AR-1
9) 15 g of the dispersion stabilizing resin (Q-1), 62 g of vinyl acetate,
30g vinyl valerate, 8g crotonic acid and Isopar H 2
75 g of the mixed solution was heated to a temperature of 80 ° C. with stirring under a nitrogen stream. Add AIVN 1.6g and react for 1.5 hours.
IVN (0.8 g) was added for 2 hours, and AIBN (0.5 g) was added for 4 hours. Then, the temperature was raised to 100 ° C. and the mixture was stirred for 2 hours. After distilling off unreacted monomers, the mixture was cooled and passed through a nylon cloth of 200 mesh to obtain a white dispersion with a polymerization rate of 93%. It was a monodisperse latex having an average particle size of 0.25 μm.
The Mw of the resin particles was 8 × 10 ⁴ , and the Tg was 26 ° C.

Synthesis Example 20 of resin particles (AR): (AR-2
0) 20 g of dispersion stabilizing resin (Q-5) having the following structure, 60 g of methyl methacrylate, 30 g of ethyl acrylate, acrylic acid
A mixed solution of 10 g, thioglycolic acid 3 g and Isopar H546 g was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. After adding AIVN 1.0g and reacting for 2 hours, AIVN
0.8 g was added and reacted for 2 hours, 0.5 g of AIBN was further added, and then the temperature was set to 80 ° C. and reacted for 3 hours. After cooling
Polymerization rate of white dispersion 99 through 200 mesh nylon cloth
Earned in%. It was a monodisperse latex having an average particle size of 0.22 μm. The resin particle Mw is 9 × 10 ³ , and the Tg is 23.
° C.

[0301]

[Chemical 40]

Synthesis Example 21 of Resin Particles (AR): (AR-2
1) A mixture solution of 18 g of a dispersion stabilizing resin (Q-6) having the following structure and 500 g of Isopar H was stirred at a temperature of 50 under a nitrogen stream.
Warmed to ° C. To this, methyl methacrylate 35g, 2,
3-dipropoxycarbonylpropyl methacrylate 40
A mixed solution of g, 25 g of 2-sulfoethyl methacrylate, 5.2 g of methyl 3-mercaptopropionate, 1.5 g of AIVN and 120 g of tetrahydrofuran was added dropwise at a dropping time of 1 hour, and the reaction was continued for another 1 hour. Then AIV
N. 1.0 g was added, the temperature was set to 70 ° C. and the reaction was continued for 2 hours, then AIVN 1.0 g was further added and reacted for 3 hours.
120 g of Isopar H was added to this reaction product, the tetrahydro solvent was distilled off under reduced pressure of a water-jet pump at a temperature of 50 ° C., and after cooling.
A white dispersion was obtained through a 200 mesh nylon cloth.
It was a dispersion having an average particle size of 0.18 μm and good monodispersibility. The polymerization rate was 98%. Mw of resin particles is 6 × 1
0 ³ and Tg were 28 ° C.

[0303]

Embedded image

Synthesis Example 22 of Resin Particles (AR): (AR-2
2) 20 g of a dispersion stabilizing resin (Q-7) having the following structure, a monofunctional macromonomer having a repeating unit of dimethylsiloxane (FM-0721 manufactured by Chisso Corporation, Mw6 × 10 ³ ) 15
g, 50 g of methyl methacrylate, 35 g of 2-pentyloxyethyl methacrylate, 15 g of acrylic acid, 6 g of methyl 3-mercaptopropionate and 547 g of Isopar G were heated to a temperature of 60 ° C. with stirring under a nitrogen stream. After adding AIVN 2.0g and reacting for 2 hours, AIVN
1.0 g was added and the reaction was continued for 2 hours. Then AIVN
Immediately after adding 1.0 g, the temperature was set to 75 ° C. for 2 hours, and AIVN 0.8 g was further added and reacted for 2 hours. After cooling, a white dispersion was passed through a 200-mesh nylon cloth to obtain a monodisperse latex having a polymerization rate of 98% and an average particle size of 0.20 μm. The resin particles had Mw of 6.5 × 10 ³ and Tg of 20 ° C.

[0305]

Embedded image

Synthesis Examples of Resin Particles (AR) 23 to 32: (AR
-23) to (AR-32) While stirring a mixed solution of 25 g of a dispersion stabilizing resin (Q-8) having the following structure and 392 g of Isopar H under a nitrogen stream, the temperature
Warmed to 50 ° C.

[0307]

[Chemical 43]

In addition, each monomer shown in Table C below, 3.1 g of methyl 3-mercaptopropionate, and 3 g of initiator ACPP were added.
And a mixed solution of methyl ethyl ketone 150g drop time 1
Drop by time, react for 1 hour as it is, and further ACPP
1.0 g was added and reacted for 2 hours. Then AIVN 1.0g
Immediately after adding, the temperature was set to 75 ° C. and the reaction was carried out for 2 hours. Then, 0.8 g of AIVN was added and the reaction was carried out for 2 hours. After cooling, 20
A white dispersion was obtained through a 0 mesh nylon cloth.
The polymerization rate of each resin particle is 93-99%, and the average particle size is 0.15
The latex had a narrow particle size distribution in the range of ˜0.25 μm. The Mw of the resin component of each particle is 8 × 10 ³ to 1 × 10 ⁴ ,
The Tg was in the range of 10-35 ° C.

[0309]

[Table 7]

[0310]

[Table 8]

[0311]

[Table 9]

Production Example of Resin Particles (ARW) 1: (ARW)
-1) A mixed solution of the total amount of the resin particles (AR-18) (that is, seed particles) synthesized according to Synthesis Example 18 of the resin particles (AR) and 10 g of the dispersion stabilizing resin (Q-1) was stirred under a nitrogen stream. While warming to a temperature of 60 ° C. To this, 85 g of benzyl methacrylate, 15 g of acrylic acid, 2.0 g of methyl 3-mercaptopropionate, 0.8 g of AIVN and Isopar H 200
The mixture of g was added dropwise over 2 hours, and the reaction was continued for another 2 hours. Next, 0.8 g of an initiator was added and the temperature was raised to 70 ° C. to react for 2 hours, and 0.6 g of an initiator was further added and reacted for 3 hours. After cooling, it was passed through a 200-mesh nylon cloth, and the polymerization rate of the obtained white dispersion was 98%, and the latex was a monodisperse powder having an average particle size of 0.24 μm and good monodispersibility.

Next, whether or not the obtained resin particles were formed as independent particles was examined by observing the state of the particles using a scanning electron microscope (SEM). A film prepared by making resin particles dispersed on a PET film was heat-treated at a temperature of 50 ° C. and 80 ° C. for 5 minutes, and then each sample was processed into a JSL-T330 type Scanning Mic.
Observation with a roscope (manufactured by JEOL) at a magnification of 20,000 revealed that the sample at a temperature of 50 ° C had a particle state, but not at a temperature of 80 ° C. That is, the particles were melted by heating.

Similarly, resin particles (AR-1 comprising each of the two resins (copolymers) constituting the particles of the present invention (AR-1
8) and resin particles (AR-1) and dispersed resin particles obtained by mixing the two kinds of resin particles in a 1/1 weight ratio were examined.
In the sample composed of the resin particles (AR-18), the sample not heated was in the particle state, but the particle state was not observed at the temperature of 50 ° C., and the sample of the resin particles (AR-1) had the temperature of 80%.
The particles disappeared at ℃. Furthermore, regarding the sample consisting of mixed particles, when the sample that was not heated and the sample at a temperature of 50 ° C were examined, it was found that the temperature was 50 ° C compared to the unheated sample.
It was confirmed that the particles of No. 1 were invisible.

As described above, as a result of visual observation of the thermal behavior of the particles, the resin particles of the present invention produced as described above are not a mixture of two kinds of resin particles but one kind of particles. Contains two types of resins, in this case, high Tg
It was confirmed that the resin of No. 1 was a core-shell particle in which the resin of low Tg was distributed in the outer layer and the resin of low Tg was distributed in the inner layer.

Production Examples 2-14 of Resin Particles (ARW): (A
RW-2) to (ARW-14) In Production Example 1 of the above resin particles (ARW), the following table-
Particles (ARW-2) to (ARW-14) of the present invention were prepared in the same manner as in Production Example 1 except that each monomer described in D was used.
Was manufactured. The polymerization rate of each latex particle obtained is 95-
The average particle size was 99%, and the monodispersity was good in the range of 0.20 to 0.30 μm.

[0317]

[Table 10]

[0318]

[Table 11]

[0319]

[Table 12]

[Synthesis Example of Resin (P)] Synthesis Example 1: Resin (P) 1: (P-1) 80 g of methyl methacrylate, macromonomer of dimethylsiloxane (FM-0725 manufactured by Chisso Corp., Mw 1 ×).
A mixed solution of 20 g of 10 ⁴ ) and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. AIBN (1.0 g) was added and reacted for 4 hours, and AIBN (0.7 g) was further added and reacted for 4 hours. The Mw of the obtained copolymer was 5.8 × 10 ⁴ .

[0321]

[Chemical 44]

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 the obtained polymer was in the range of 4.5 × 10 ^{4 to} 6 × 10 ⁴ .

[0323]

[Table 13]

[0324]

[Table 14]

Synthesis Example 10 of Resin (P): (P-10) 2,2,3,4,4,4-hexafluorobutylmethacrylate 60
g, macromonomer of methyl methacrylate (AA-6
A mixed solution of 40 g of Mw1 × 10 ⁴ ) manufactured by Toagosei Co., Ltd. and 200 g of benzotrifluoride was heated to 75 ° C. under a nitrogen stream. Add AIBN 1.0g to this and react for 4 hours.
Further, 0.5 g of AIBN was added and reacted for 4 hours. The Mw of the obtained copolymer was 6.5 × 10 ⁴ .

[0326]

Embedded image

Synthesis Examples 11 to 15 of Resin (P): (P-11) to
(P-15) Instead of the monomer and macromonomer (AA-6) used in Synthesis Example 10 of resin (P), each monomer and each corresponding to the polymer component shown in Table F below. Each copolymer was synthesized in the same manner as in Synthesis Example 10 except that the macromonomer was used. The Mw of the obtained copolymer was in the range of 4.5 × 10 ^{4 to} 6.5 × 10 ⁴ .

[0328]

[Table 15]

[0329]

[Table 16]

[0330]

[Table 17]

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

[0332]

Embedded image

Synthesis Example 17 of Resin (P): (P-17) Methyl methacrylate 70 g and tetrahydrofuran 200
The mixed solution of g was thoroughly degassed under a nitrogen stream and cooled to -20 ° C. Add 1,1-diphenylbutyllithium 0.8g 1
The reaction was performed for 2 hours. Further, to this mixed solution, a mixed solution of 30 g of the following monomer (m-1) and 60 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream and added, and the mixture was further reacted for 8 hours. This mixture was brought to 0 ° C and then 10 ml of methanol
Was added and reacted for 30 minutes to terminate the polymerization. The obtained polymer solution was heated to a temperature of 30 ° C. with stirring, 3 ml of 30% hydrogen chloride ethanol solution was added thereto, and the mixture was stirred for 1 hour. Then, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation in 1 liter of petroleum ether. The precipitate was collected and dried under reduced pressure to obtain a polymer having Mw of 6.8 × 10 ⁴
The yield was 76 g.

[0334]

[Chemical 47]

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

[0336]

Embedded image

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

[0338]

[Chemical 49]

Synthesis Example 20 of Resin (P): (P-20) Methyl Methacrylate 50 g, Ethyl Methacrylate 25 g
A mixture of benzyl isopropyl xanthate and 1.0 g 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. To this, 25 g of the monomer (m-1) was added, and the atmosphere was replaced with nitrogen, and light was again irradiated for 10 hours. The obtained reaction product was reprecipitated in 2 liters of methanol, collected, and dried to obtain a polymer having a yield of 63 g and a Mw.
It was 6 × 10 ⁴ .

[0340]

Embedded image

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

[0342]

[Table 18]

[0343]

[Table 19]

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

[0345]

[Chemical 51]

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

[0347]

Embedded image

Synthesis Example 30 of Resin (P): (P-30) 68 g of methyl methacrylate, 22 g of methyl acrylate,
A mixed solution of 10 g of glycidyl methacrylate, 17.5 g of an initiator (I-3) having the following structure, and 150 g of tetrahydrofuran was heated to a temperature of 50 ° C. under a nitrogen stream. 40 in this solution
Photopolymerization was carried out by irradiating with a 0 W high pressure mercury lamp from a distance of 10 cm through a glass filter for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain a polymer having an Mw of 4.0 × 10 ^{4 in} a yield of 72 g.

[0349]

Embedded image

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

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

[0352]

[Table 20]

[0353]

[Table 21]

[0354]

[Table 22]

[Synthesis Example of Resin Particles (PL)] Synthesis Example 1: Resin Particles (PL) 1: (PL-1) 40 g of the monomer (LM-1) having the following structure, 2 g of ethylene glycol dimethacrylate, and the following structure A mixed solution of 4.0 g of the dispersion stabilizing resin (LP-1) and 180 g of methyl ethyl ketone was heated to a temperature of 60 ° C. with stirring under a nitrogen stream.
AIVN 0.3g was added to this and it was made to react for 3 hours. Furthermore,
AIVN 0.1g was added and it 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.

[0356]

[Chemical 54]

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

[0358]

[Chemical 55]

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

[0360]

[Table 23]

[0361]

[Table 24]

Synthesis Examples 12 to 15 of Resin Particles (PL): (PL
-12) to (PL-15) In Synthesis Example 2 of resin particles (PL), the monomer (LM-
2) In the same manner except that each monomer shown in the following Table-J was used instead of 40 g, and 6 g of the dispersion stabilizing resin (LP-8) having the following structure was used instead of 5 g of the dispersion stabilizing resin (AB-6). To synthesize each resin particle. The average particle size of the obtained particles is 0.05 to 0.
It was in the range of 20 μm.

[0363]

[Chemical 56]

[0364]

[Table 25]

Example 1 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 2
g, 8 g of a binder resin (B-1) having the following structure, a resin (P-
1) A mixture of 2 g, 0.15 g of the compound (A) having the following structure and 80 g of tetrahydrofuran was put in a 500 ml glass container together with glass beads and dispersed for 60 minutes with a paint shaker (manufactured by Toyo Seiki Seisakusho), and further phthalic anhydride was added thereto. 0.1
g and 0.02 g of o-chlorophenol were added and dispersed for 5 minutes, and then the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0366]

[Chemical 57]

Next, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, with a wire bar, and was dried by touching with a finger, and then in a 110 ° C. circulation type oven for 20 seconds. Heated. The thickness of the obtained photosensitive layer is 8μ.
m. When the adhesive strength of this photoreceptor was measured by "Adhesive tape / adhesive sheet test method" of JIS Z0237-1980, the value was 2 g · f. On the other hand, in the above-mentioned photosensitive layer, the adhesive force of the surface of the photosensitive member including the photosensitive layer prepared in exactly the same manner except that 2 g of the resin (P-1) was removed was 450 g · f or more and showed no peeling property.

A photoreceptor having the above releasable surface was prepared as shown in FIG.
The electrophotographic photosensitive member 11 is mounted on the apparatus shown in FIG.
-A (adhesive strength 80 g · f / 10 mm width, overall thickness 1.6 mm, made by Meiji Rubber) was attached. However, the liquid developing unit set 14 shown in FIG.
It was used as the liquid developing unit set 14 of the apparatus shown in FIG. That is, the electrodeposition unit 14T was provided in the liquid developing unit set 14.

First, the photoconductor 11 is formed by an electrophotographic process.
A toner image was formed on the top. After passing the photoconductor 11 under the corona charging device 18 in the dark and charging the corona to + 450V, read the original from the color scanner with a color scanner and perform color separation to make corrections related to some system-specific color reproduction. After the addition, based on the information stored in the hard disk in the system as digital image data, using a semiconductor laser drawing device as the exposure device 19, the exposure amount on the photoconductor was 30 erg / cm ² with light of 788 nm. Exposure.

On the other hand, the liquid developer (LD-
1) was prepared.・ Synthesis of toner particles 65 g of methyl methacrylate, 35 g of methyl acrylate,
A mixed solution of 20 g of a dispersion polymer having the following structure and 680 g of Isopar H was heated to a temperature of 65 ° C. while stirring under a nitrogen stream. AIVN 1.2g was added to this and reacted for 2 hours.
Add AIVN 0.5g and react for 2 hours.
0.5 g was added and reacted for 2 hours. Next, set the reaction temperature to 90 ° C.
Then, the mixture was stirred for 1 hour under a reduced pressure of 30 mmHg to remove unreacted monomers.

[0371]

Embedded image

After cooling to room temperature, the mixture was filtered through a 200-mesh nylon cloth to obtain a white dispersion. The reaction rate of the obtained dispersion monomer was 95% by weight, and the average particle size of the resin particles was 0.25.
The particle size was μm and the monodispersity was good. Particle size is CAP
It was measured using A-500. -Production of colored particles Tetradecyl methacrylate / methacrylic acid copolymer (copolymerization ratio; 95/5 weight ratio) 10 g, nigrosine 10 g and Isopar G 30 g were put together with glass beads in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) and 4 It was dispersed for a time to obtain a fine dispersion of nigrosine.

Production of Liquid Developer 45 g of the resin dispersion of the above toner particles, 25 g of the above nigrosine dispersion, 0.2 g of hexadecene / half-maleic acid octadecylamide copolymer and branched octadecyl alcohol (F
15g OC-1800 Nissan Chemical Co., Ltd.
A liquid developer for electrostatic photography (LD-1) was prepared by diluting it to 1 liter.

A bias voltage of +400 V was applied to the developing electrode using the above liquid developer (LD-1), reverse development was carried out so that the toner was electrodeposited on the exposed area, and then rinsed in an Isopar H alone bath. Then, the stain on the non-image area was removed.
An image was fixed on the photosensitive material thus obtained after plate making by a fixing method using a heat roll.

Next, a transfer layer was formed on the photoconductor drum on which the toner image was formed by the electrodeposition coating method using the dispersion liquid (L-1) of the resin (A) having the following content. Dispersion (L-1) of resin (A) Resin particles (AR-4) 5 g (as solid content) Resin particles (AR-18) 5 g (as solid content) Charge control agent (D-1) 0.03 g Octadecyl Vinyl ether / t-octyl maleic acid half amide (1: 1 molar ratio) copolymer Silicon oil (KF-96 Shin-Etsu Silicone Co., Ltd.) 5 g was adjusted with Isopar H so that the total amount became 1 liter.

That is, the peripheral speed of the photosensitive drum is rotated at 10 mm / sec, and while the dispersion liquid is supplied to the surface of the photosensitive member 11 on which the toner image is formed by using the slit electrodeposition device, the photosensitive member side is grounded and the slit electrode is applied. A voltage of 250 V was applied to the electrode side of the deposition device to electrodeposit the resin particles. Next, the dispersion liquid was removed by air squeeze using an intake / exhaust unit, and heated to 80 ° C. by an infrared line heater as a preheating means to melt and film to form a thermoplastic resin transfer layer. The film thickness at this time was 5 μm.

Next, the photoconductor 1 whose surface temperature was adjusted to 80 ° C.
One drum was contacted with 20 drums of the primary receptor whose surface temperature was adjusted to 120 ° C, and heating and pressurization were performed under the conditions of a nip pressure of 5 kgf / cm ² and a drum peripheral speed of 5 mm / sec. The toner image was transferred. All layers were transferred onto the primary receptor 20. Next, between the primary receptor 20 drum whose surface temperature was set to 90 ° C. by the temperature adjusting means 17, the transfer backup roller 31 set to 130 ° C. and the peeling backup roller 32 set to 10 ° C. An aluminum support used for a FujiPS plate FPD (manufactured by Fuji Photo Film Co., Ltd.) as a transfer material 30 was introduced, and heating and pressurization were performed at a nip pressure of 10 kgf / cm ² and a drum peripheral speed of 10 mm / sec. The toner image was transferred together with the transfer layer onto the aluminum support, and a high-quality clear image was obtained.

On the other hand, a toner image was transferred and formed on an aluminum support by a method of transferring without providing a transfer layer and compared with the present invention. The resulting image on the aluminum support was found to have a missing toner image or uneven image density. Further, when fine lines, fine characters, and the like were visually observed with a magnifying glass of 20 times, fine image loss was recognized.
Further, when the surface of the photoconductor was observed, residual toner image was observed. This means that a transfer layer is provided on a photoreceptor on which a toner image is formed, and the toner image is transferred together with the transfer layer onto a transfer material via a primary receptor. It can be seen that the method is very excellent as a method for transferring a toner image to the.

A method of directly transferring to the PS plate without passing through the primary receptor, that is, by interposing the PS plate between the photoreceptor 11 drum and the primary receptor 20,
The toner image on the photoconductor was directly transferred onto the PS plate together with the transfer layer under the same transfer conditions as above. When the image on the obtained aluminum support was visually observed, it was confirmed that a fine image portion was missing and that a toner image and a transfer layer remained on the surface of the photoreceptor.

Next, the printing original plate having the transfer layer transferred to the aluminum support was desensitized (that is, the transfer layer was removed) to prepare a printing plate, and its printing performance was examined. That is, the above plate was treated with a PS plate treating agent (DP-4 manufactured by Fuji Photo Film Co., Ltd.)
Is diluted 50 times with distilled water (pH 12.5) in a desensitizing solution (E-1) at 35 ° C. for 1 minute to remove the transfer layer while gently rubbing the plate surface with a bristle brush. After sufficiently washing with water, gumming was performed to prepare a printing plate for offset.

When the printing plate thus obtained was visually observed using a 200 × optical microscope, no transfer layer remained in the non-image area, and the high density of fine lines and fine characters in the image area. No lack of resolution was observed. Immersion water for the PS plate as the immersion water for this printing plate (SG-23 Tokyo Ink Co., Ltd.)
(Manufactured by Sakurai Manufacturing Co., Ltd.) as a printing machine using an aqueous solution (pH 7.0) diluted 130 times with distilled water.
And using neutral paper as the printing paper, and printing with various color inks for offset printing. As a result, regardless of the type of color ink, in all cases, 60,000 or more printed materials with clear images free of background stains were obtained.

Furthermore, after printing with the printing plate of the present invention, printing was then performed using a normal PS plate with the normal operation, and no problems occurred. That is, it was confirmed that the printing machine could be easily shared with other offset printing plates such as PS plates. As described above, the offset printing plate provided by the present invention has an extremely good image reproducibility obtained by the semiconductor laser light scanning exposure method and that it is well reproduced on a printed matter, and has good color ink suitability, It was confirmed that ink selectivity was hardly seen, full-color printing was obtained with high printing durability, and that it could be easily shared with other offset printing plates, and exhibited extremely excellent performance.

Example 2 An amorphous silicon photoconductor (manufactured by Kyocera) was immersed in a solution prepared by dissolving 1 g of the following releasability-imparting compound (S-1) in 1 liter of Isopar G for 10 seconds and rinsed in Isopar G. Dried. This gives an adhesive strength of 200g ・ f
The surface of the amorphous silicon photoconductor that had been
It was modified to have a peeling surface of gf.

[0384]

Embedded image

This surface-releasing photosensitive member was loaded in the apparatus shown in FIG. Amorphous silicon photoconductor 11
After corona charging to + 700V in a dark place, read the original from a color scanner in advance, color-separate it, and add some corrections related to system-specific color reproduction.
Based on the information stored in the hard disk in the system as digital image data, a semiconductor laser was used to expose with light of 780 nm. The potential of the exposed portion was + 220V and that of the unexposed portion was + 600V.

Then, after pre-bathing with Isopar H (manufactured by Esso Standard Petroleum) by a pre-bathing device incorporated in the developing unit, the liquid developer (L
P-1) 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 exposed 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.

Next, turn on the infrared line heater, pass it under, and measure the surface temperature with a radiation thermometer.
After the temperature was raised to 80 ° C, the following resin (A
-1) is applied to the surface of the photoconductor on which the toner image is formed by the hot melt coater (transfer layer forming device) 13 set at 80 ° C.
The transfer layer was formed by coating at a speed of mm / sec and cooling by blowing cooling air from an intake / exhaust unit. The thickness of the transfer layer at this time was 2.5 μm.

[0388]

Embedded image

On the other hand, as the primary receptor 20, on the roll surface of the blanket 9600-A used in Example 1, 100 g of isoprene rubber and 7 g of the above resin (P-2) were used.
And using 0.001g of phthalic anhydride mixture, 140
A material having a cured film (film thickness 10 μm) formed by heating at 0 ° C. for 2 hours was used (the adhesive force on the surface was 80 g · f). The primary receptor 20 is heated to a temperature of 100 ° C. to form a transfer layer on the toner image.
0, the nip pressure is 4kgf / cm ² , the drum peripheral speed is 5m
The toner image was transferred onto the primary receptor 20 together with the transfer layer under the condition of m / sec.

[0390] Then, the primary receptor drum 20 whose surface temperature was set to 60 ° C by the temperature adjusting means, the transfer backup roller set to 130 ° C and the peeling backup roller set to 10 ° C were covered. Guide the aluminum support for FPD as the transfer material 30, and set the nip pressure to 5 kg.
When heating and pressing were performed at f / cm ² and a drum peripheral speed of 10 mm / sec, all the toner images were transferred onto the aluminum support, and high-quality and clear images were obtained.

On the other hand, for comparison, a toner image was formed on an aluminum support by a method of directly transferring the toner image to the primary receptor without providing a transfer layer on the toner image. In the obtained image, the toner image was missing or the image density was uneven. Further, when fine lines, fine characters, and the like were visually observed with a loupe of 20 times, fine image loss was recognized. Further, when the surface of the photoconductor was observed, residual toner image was observed. This is
In the method of repeatedly using the photoconductor, it is necessary to clean the surface of the photoconductor in order to remove the residual toner, and setting of an apparatus for that purpose or damage to the surface of the photoconductor due to the cleaning becomes a problem.

On the other hand, in the present invention, the toner image is sufficiently peeled from the photosensitive member, and the primary receptor is easily and sufficiently transferred to the transfer material, so that the above problems do not occur. When a printing plate was printed in the same manner as in Example 1, the same good performance as in Example 1 was exhibited.

Example 3 In Example 1, instead of the electrodeposition coating method used for forming the transfer layer on the photosensitive member after forming the toner image, the transfer method from the release paper shown in FIG. 4 was applied. That is, a separate paper (manufactured by Oji Paper Co., Ltd.) is used as the release paper 24, and a film thickness of 4 μm composed of the following resin (A-2) and resin (A-3) in a weight ratio of 1: 1 is used. The paper on which the coating film was formed was applied to a photoreceptor 11 similar to that of Example 1 under the conditions of a roller pressure of 3 kgf / cm ² , a surface temperature of 60 ° C., and a passing speed of 10 mm / sec.
A transfer layer 12 having a film thickness of 4 μm was formed by pressure-bonding on one surface. Thereafter, the same operation as in Example 1 was performed to prepare a printing plate. The image and the number of printable sheets of the obtained printed matter showed the same performance as in Example 1.

[0394]

[Chemical formula 61]

Example 4 2 g of X-type metal-free phthalocyanine, 8 g of a binder resin (B-2) having the following structure, 2 g of a binder resin (B-3) having the following structure,
0.15 g of compound (B) having the following structure and tetrahydrofuran
80g of the mixture is put into a 500ml glass container together with glass beads, and a paint shaker (Toyo Seiki Seisakusho) is used.
After dispersing for 60 minutes, the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0396]

Embedded image

Next, this dispersion was applied with a wire bar onto a 0.2 mm-thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, and was dried by touching with a finger, and then dried in a 110 ° C. circulating oven for 20 seconds. Heated. The thickness of the obtained photosensitive layer is 8μ.
m. The following peelable surface layer was provided on this photoreceptor.

Formation of releasable surface layer A coating material containing 10 g of a silicone resin having the following structure, 1 g of a crosslinking agent having the following structure, and 0.1 g of platinum as a crosslinking catalyst in 100 g of n-hexane was formed using a wire round rod. Thickness
Apply it to 1.5 μm, dry it by touching it, and then at 120 ℃
Heated for 10 minutes. The adhesive strength of the obtained surface was 1 g · f or less.

[0399]

[Chemical formula 63]

A printing plate was prepared in the same manner as in Example 1 using the above-mentioned photosensitive member and was printed. As a result, good performance equivalent to that in Example 1 was obtained.

Example 5 An amorphous silicon photoconductor was mounted as an electrophotographic photoconductor on the apparatus shown in FIG. The adhesive force on the surface of the photoconductor was 200 g · f. The release property was imparted to the photoconductor by immersing it in a solution in which the compound (S) of the present invention was dissolved (immersion method). That is, the photoconductor was rotated in a bath containing a solution prepared by dissolving 1.0 g of the following compound (S-3) in 1 liter of Isopar G for 7 seconds while rotating at a rotational speed of 10 mm / sec. , Dried with air squeeze. The pressure-sensitive adhesive strength of the surface of the photoreceptor thus obtained was measured and found to be 3 g · f, indicating good peelability.

[0402]

[Chemical 64]

After the photoreceptor 11 was corona charged to 700 V, the surface exposure amount was 25 erg / cm ² with light of 780 nm using digital image data and a semiconductor laser based on the information.
Was exposed. The residual potential of the exposed portion was 120V. Subsequently, a liquid developer (LD-2) having the following content was used to apply a bias voltage of 300 V to the developing electrode to perform development so that the toner was electrodeposited on the unexposed area, and then in Isopar H alone bath. Rinsing was performed to remove stains on the non-image area.

Liquid developer (LD-2) Coating resin (octadecyl methacrylate / methyl methacrylate (9/1 molar ratio) copolymer) and carbon black (# 40 Mitsubishi Kasei Co., Ltd.) in a weight ratio of 2: After thoroughly mixing at 1, melt-kneaded with a three-roll mill heated to 140 ° C. A mixture of 12 g of this kneaded material, 4 g of a styrene / butadiene copolymer (Sorprene 1205 manufactured by Asahi Kasei Co., Ltd.), and 76 g of Isopar G was dispersed in a Dynomill. The toner concentrated liquid thus obtained has a solid content of 6 g.
It was diluted with Isopar G to give a liquid developer, and sodium dioctylsulfosuccinate was added to give a liquid developer of 1 × 10 ⁻⁴ mol / liter.

After heat-fixing the toner image, the surface temperature of the photoconductor is set to 50 ° C., the peripheral speed of the photoconductor drum is rotated at 10 mm / sec, and a positive electrode charge resin having the following contents is formed on the surface of the photoconductor using a slit electrodeposition device. Dispersion (L-2) of resin (A) containing particles
While supplying the resin, the photoreceptor side was grounded and a voltage of 130 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit and fix the resin particles. The thickness of the obtained transfer layer was 2.0 μm.

Dispersion (L-2) of resin (A) Resin particles (ARW-1) 10 g (as solid content) Charge control agent (D-1) 0.020 g Branched hexadecyl alcohol 10 g (FOC- 1600 Nissan Chemical Co., Ltd.) is adjusted with Isopar G to a total volume of 1.0 liter.

Next, the photosensitive member 1 whose surface temperature was adjusted to 85 ° C.
One drum and 20 drums of the same primary receptor as in Example 2 whose surface temperature was adjusted to 120 ° C. were brought into contact with each other, and the nip pressure was 3 kg.
When the toner image was heated and pressed under the conditions of f / cm ² and drum peripheral speed of 80 mm / sec, the toner image was transferred to the primary receptor 2 with the transfer layer.
0 was all transferred. Next, the primary receptor 20 drum whose surface temperature is set to 85 ° C. by the temperature adjusting means 17,
An aluminum support used for the FujiPS plate FPD (manufactured by Fuji Photo Film Co., Ltd.) as the transferred material 30 between the transfer backup roller 31 set to 130 ° C. and the peeling backup roller 32 set to 10 ° C. The nip pressure of 3 kgf / cm ² and the drum peripheral speed of 80 mm.
/ Second, heating and pressurization were performed to transfer the toner image together with the transfer layer onto the transfer material.

The printing original plate thus obtained was RICOH
After heating with FUSER Model 592 (manufactured by Ricoh Co., Ltd.) to fix the toner part, visual observation was performed using a 200 × optical microscope. No contamination was observed in the non-image part, and No loss of high-resolution areas such as fine lines and letters was observed. That is, the toner image together with the transfer layer was easily transferred to the material to be transferred by the above heat transfer process, and the toner image portion was not disturbed at all even if the heating operation was further performed after the transfer.

This printing original plate was immersed in a desensitizing solution (E-2) having the following content at 35 ° C., and was rubbed with light to remove it.
The transfer layer was removed by treating for 2 seconds, washed thoroughly with water, and gummed to prepare an offset printing plate. Desensitizing treatment liquid (E-2) PS plate treating agent (DP-4 manufactured by Fuji Photo Film Co., Ltd.) 143 g N, N-dimethylethanolamine 100 g was diluted with distilled water to make the total amount 1 liter. (PH
13.1)

[0410] This printing plate was used as a water for dipping. For the PS plate, an aqueous solution (pH 7.0) obtained by diluting water for dipping (SG-23 Tokyo Ink Co., Ltd.) 130 times with distilled water was used.
A 94 type (manufactured by Sakurai Mfg. Co., Ltd.) was used, and neutral paper was used as the printing paper, and printing was performed with various color inks for offset printing. As a result, regardless of the type of color ink, in all cases, 60,000 or more printed materials with clear images free of background stains were obtained.

As described above, depending on the type of liquid developer used for toner image formation, in order to maintain sufficient adhesion between the toner image portion and the transfer material, and to maintain the toner image strength during printing. Alternatively, the adhesion improving means may be combined after the transfer of the entire transfer layer. The same effect was obtained by a method using flash fixing or a method using heat roll fixing as a means for improving adhesion.

Example 6 A printing plate was prepared in the same manner as in Example 5, except that the peeling property imparting means for the photoconductor was changed to the following contents. The following carboxyl modified silicone oil (TSF
4770 Toshiba Silicon Co., Ltd.) A metalling roll having a silicone rubber layer on the surface in contact with a bath containing an oil of compound (S-4) was brought into contact with the photoconductor to rotate at a peripheral speed of 15 mm / sec. The drum was rotated for 20 seconds. By this treatment, the adhesive force on the surface of the photoconductor became 5 g · f.

[0413]

Embedded image

Also, the same result as above was obtained when the treatment was carried out through a transfer roll having a styrene-butadiene rubber layer on the surface between the metering roll immersed in a silicone oil bath and the photoreceptor. Furthermore, in the method using the above-mentioned metalling roll / transfer roll, the same good result can be obtained by the method of supplying the compound (S-4) between the metalling roll and the transfer roll as shown in FIG. It was When printing was carried out in the same manner as in Example 5 using the above printing plate, the same favorable results as in Example 5 were obtained.

Example 7 A printing plate was prepared and offset printing was carried out in the same manner as in Example 5 except that the means for imparting releasability to the photosensitive member was changed to the following contents. Dimethyl silicone oil (KF-96L-2.0 manufactured by Shin-Etsu Silicone Co., Ltd.) Compound (S-
5) AW treated felt (thickness 15
mm × width 20 mm wool material) was pressed against the photoconductor with a pressure of 200 g, and the photoconductor was rotated at a peripheral speed of 20 mm / sec for 30 seconds. The adhesive force on the surface of the photoreceptor after the treatment was 6 g · f.
The printing results obtained showed good performance as in Example 5.

Example 8 In Example 5, a printing plate was prepared in the same manner as in Example 5 except that the peeling property imparting means for the photoconductor was changed to the following contents, and offset printing was performed. Fluorine type surfactant (Surflon S-141
A roller wound with a cloth impregnated with a compound (S-6) manufactured by Asahi Glass Co., Ltd. is heated to a surface temperature of 60 ° C. and then brought into contact with a photoreceptor, and both drums are rotated at a peripheral speed of 20 mm / sec. It was rotated for 30 seconds. The adhesive force on the surface of the photoconductor became 6 g · f.
The printing results obtained showed good performance as in Example 5.

Example 9 A printing plate was prepared and offset printing was carried out in the same manner as in Example 5 except that the means for imparting releasability of the photoconductor was changed to the following contents. A silicon rubber roller (made by Kinyosha Co., Ltd.) in which a metal core roller is wrapped with silicon rubber is brought into contact with the surface of the photoconductor at a nip pressure of 600 g · f / cm ² , and the peripheral speed is 15
It was rotated for 10 times at a rotation speed of mm / sec. As a result, the adhesive force on the surface of the photoconductor was lowered to 18 g · f. The obtained printing results were as good as those in Example 5.

Examples 10 to 29 Example 1 was repeated except that resin (P) and / or resin particles (PL) shown in Table K below were used instead of 2 g of resin (P-1). An electrophotographic photoreceptor and a printing plate were prepared and printed in the same manner as in. The image quality and printing durability of the printed matter obtained from each printing plate were good as in Example 1.

[0419]

[Table 26]

Examples 30 to 40 Similar to Example 1 except that each compound shown in Table L below was used in place of the resin (P-1), phthalic anhydride and o-chlorophenol. Then, a printing plate was prepared by carrying out the operation and printed. The image quality and printing durability of the printed matter obtained from each printing plate were good as in Example 1.

[0421]

[Table 27]

Examples 41 to 58 In Example 1, the resin particles (AR-4) and (AR-
18) A printing plate was prepared and offset printing was performed in the same manner as in Example 1 except that the resin particles shown in Table M below were used instead of 10 g (1/1 weight ratio). The image quality and printing durability of the printed matter obtained from each printing plate were good as in Example 1.

[0423]

[Table 28]

Examples 59 to 61 In the same manner as in Example 2, except that each resin (A) shown in the following Table-N was used in place of the resin (A-1) used in the hot melt coater. A printing plate was prepared and offset printing was performed. The obtained results were all good as in the case of Example 2.

[0425]

[Table 29]

Examples 62 to 67 In Example 3, instead of the paper provided with the transfer layer on the separate paper, a release paper (manufactured by SunRelease Sanyo Kokusaku Pulp Co., Ltd.) having a film thickness of 4 μm and having a thickness of 4 μm shown in the following Table-O was used. Each resin (A)
A printing plate was prepared and offset printing was carried out in the same manner as in Example 3 except that a paper provided with a layer consisting of was used. As a result, regardless of the type of color ink, 60,000 or more prints with clear images free of background stains were obtained.

[0427]

[Table 30]

[0428]

[Table 31]

[0429]

[Table 32]

Example 68 100 g of photoconductive zinc oxide, a binder resin (B-
4) 17 g, 3 g of binder resin (B-5) having the following structure, 3 g of resin (P-35), 0.01 g of uranine, 0.02 of rose bengal
g, bromphenol blue 0.01 g, maleic anhydride 0.
A mixture of 15 g and 150 g of toluene was placed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) and dispersed at a rotation speed of 9 × 10 ³ rpm for 10 minutes. To this dispersion, 0.02 g of phthalic anhydride and o
-Add 0.001 g of chlorophenol, and further rotate 1 x 1
It was dispersed at 0 ³ rpm for 1 minute.

[0431]

[Chemical formula 66]

Next, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, by a wire bar so as to have a coating amount of 25 g / m ^2, and was dried by touch. Then, it heated at 120 degreeC in the circulation type oven for 1 hour. The adhesive force on the surface of the photoreceptor thus obtained was measured and found to be 4 g · f.

After charging this photosensitive member to a surface potential of 600 V, it was exposed by a surface exposure method for 7 seconds using a halogen lamp of 400 W output, and the bias voltage of the developing section was set to 100 V.
Was developed using a liquid developer (LD-1), then rinsed through a rinse bath of Isopar G, and the image was fixed with a heat roll.

A transfer layer having a two-layer structure was provided on the photoreceptor on which the toner image was formed as follows. First, using a dispersion liquid (L-3) of the following resin (A), a photoreceptor was charged to 150 V and resin particles were electrodeposited to form a first layer having a thickness of 2 μm. Dispersion (L-3) of resin (A) Resin particles (AR-1) 10 g (as solid content) Charge control agent (D-2) of the following structure 0.02 g Branched tetradecyl alcohol 8 g (FOC- 1400 NISSAN CHEMICAL CO., LTD. Is adjusted with Isopar G so that the total volume is 1 liter.

[0435]

Embedded image

Next, a dispersion liquid (L-4) of the following resin (A) was charged on this and charged with 200 V to electrodeposit the resin particles to form a second layer having a thickness of 3 μm. -Dispersion liquid (L-4) of resin (A) In the above dispersion liquid (L-3), resin particles (AR-1)
Adjustment was made in exactly the same manner except that 10 g of resin particles (AR-24) was used instead of 10 g.

The photoconductor prepared as described above was contacted with a heating roller having an infrared lamp heater incorporated inside a hollow roller coated with a silicone rubber layer having a film thickness of 100 μm and a surface adhesive force adjusted to 60 g · f. Then, transcription was performed on this primary receptor. Next, a straight master (manufactured by Mitsubishi Paper Mills Ltd.) was brought into contact with the primary receptor and pressure-bonded with a roller. The surface temperature of the roller at this time is 90 ℃,
Roller nip pressure is 3kgf / cm ² , transport speed is 50m
It was m / sec. After cooling to room temperature, the primary receptor and the straight master were separated. When the state of the transfer layer transferred to the straight master was visually evaluated, it was almost the same as the copied image on the photoreceptor before transfer, and no image deterioration was observed. Further, no transfer layer remained on the surface of the primary receptor after copying, and the transferability was extremely good.

For comparison, the resin (P
-35) An electrophotographic photosensitive member was prepared in exactly the same manner except that 3 g was not used, and the adhesive force on the surface was 400 g · f or more. When a transfer layer was formed and transferred in the same manner as described above, no peeling property was exhibited at the interface between the surface of the photoreceptor and the transfer layer.

Next, the original having the transfer layer transferred on the straight master was immersed in the desensitizing solution (E-3) having the following content at a temperature of 25 ° C. for 30 seconds while gently brushing,
The transfer layer was removed and sufficiently washed with water to obtain a printing plate. Desensitizing treatment liquid (E-3) Mercaptoethanesulfonic acid 10 g Neosoap (Matsumoto Yushi Co., Ltd.) 5 g N, N-dimethylacetamide 10 g was diluted with distilled water to make the total amount 1 liter, and then hydroxylated. Adjust to pH 12.0 with sodium.

When the printing plate thus obtained was visually observed using a 200 × optical microscope, no transfer layer remained in the non-image area, and fine lines and fine characters in the image area were not observed. No lack of high resolution area was observed.

As an immersion water for this printing plate, an aqueous solution (pH 7.0) in which immersion water for PS plate (SG-23 Tokyo Ink Co., Ltd.) was diluted 130 times with distilled water was used as a printing machine.
A 3200MCD type (manufactured by Ryobi Co., Ltd.) was used, and neutral paper was used as the printing paper, and printing was performed with various color inks for offset printing. As a result, regardless of the type of color ink, in each case, more than 1,000 printed materials with clear images free of background stains were obtained. On the other hand, in a known system in which an electrophotographic photoreceptor using zinc oxide is desensitized with a desensitizing liquid containing a chelating agent as a main agent under acidic conditions to form a lithographic printing plate, neutral paper is used as a printing paper. When it was used, the number of printed sheets was several hundred, and background stains were generated in the non-image area, and when color inks for offset printing other than black were used, stains were also generated when the number of printed sheets was about several hundred sheets. As described above, according to the method for producing a printing plate of the present invention, it is possible to provide a printing plate having extremely good printing performance, unlike the conventional method, while using the same zinc oxide photoreceptor. .

Example 69 As an organic photoconductive substance, 5 g of 4,4′-bis (diethylamino) -2,2′-dimethyltriphenylmethane,
Binder resin (B-6) 4g, resin (P-27) 0.
4 g, 40 mg of dye (D-1) having the following structural formula, and 0.2 g of anilide compound (C) having the following structure as a chemical sensitizer were dissolved in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride to prepare a photosensitive layer dispersion liquid. .

[0443]

[Chemical 68]

This photosensitive layer dispersion was applied onto a conductive transparent support (having a vapor-deposited film of indium oxide on a polyethylene terephthalate support having a thickness of 100 μm, surface resistance 10 ³ Ω) using a wire round rod. About 4 μm
A photoreceptor having a photosensitive layer was obtained. The adhesive force on the surface of the photoconductor was 8 g · f. A printing plate was formed and printing was performed in the same manner as in Example 1 except that this photoconductor was used instead of the photoconductor used in Example 1. The image on the obtained printed matter was a clear image without background fog, as in Example 1.
The printing durability was also good.

Example 70 5 g of bisazo pigment having the following structure and 95 g of tetrahydrofuran
And polyester resin (Byron 200 Toyobo Co., Ltd.)
5 g) was thoroughly ground in a ball mill. Next, this mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was coated using a wire round rod on the same conductive transparent support used in Example 69 to form a charge generation layer of about 0.7 μm.

[0446]

[Chemical 69]

Next, a hydrazone compound of the following structural formula 20
g, polycarbonate resin (Lexan 121 GE) 20
60 g of tetrahydrofuran and 60 g of tetrahydrofuran are coated on the charge generation layer using a wire round rod,
Dry for 30 seconds at ℃ and heat at 100 ℃ for 20 seconds, then
A charge transport layer having a thickness of μm was formed to obtain an electrophotographic photoreceptor having a photosensitive layer composed of two layers.

[0448]

Embedded image

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

[0450]

Embedded image

The surface potential of this photosensitive material was -500 V in the dark.
After being charged to, a He-Ne laser was used to expose with light of 633 nm so that the exposure amount on the plate surface would be 30 erg / cm ² . Thereafter, the printing plate was prepared in the same manner as in Example 1, and offset printing was performed. The results obtained were as good as in Example 1.

Examples 71 to 76 Printing was carried out in the same manner as in Example 5 except that each compound (S) shown in Table P below was used in place of 1.0 g / l of the compound (S-3) in Example 5. A plate was made and printed. The results obtained were exactly the same as in Example 5. That is, by using these compounds (S), the releasability of the surface of the photoconductor was effectively exhibited.

[0453]

[Table 33]

[0454]

[Table 34]

Examples 77 to 88 Using the materials to be transferred (plate making original plates) to which the toner images prepared in Examples 1 to 76 were transferred, desensitizing treatment was carried out as follows to prepare offset printing plates. . 0.2 mol of the nucleophilic compound shown in Table Q below, 100 g of organic solvent and Newcol B4S
Distilled water was added to 2 g of N (manufactured by Nippon Emulsifier Co., Ltd.) to make 1 liter, and then the pH of the treatment liquid was adjusted to 12.5. Each material to be transferred was immersed in this treatment liquid at a temperature of 35 ° C. for 1 minute, and desensitized while gently rubbing. When the obtained printing plate was printed under the same printing conditions as in Example 1, all showed the same good performance as in Example 1.

[0456]

[Table 35]

[0457]

According to the present invention, a toner image is formed on the surface of a photoreceptor having releasability by an electrophotographic process, a transfer layer is formed thereon, and then the toner image is transferred together with the transfer layer onto a primary receptor, Further, by transferring to a transfer target material and removing the transfer layer by desensitizing the transfer layer, the transferability of the transfer layer is improved, and a printing plate which gives a printed matter having a high-definition and high-quality image can be obtained. . Furthermore, the transfer conditions and the desensitizing conditions can be relaxed. Further, by using the peelable compound (S) to impart peelability to the surface of the photoreceptor before toner development, a usual electrophotographic photoreceptor can be used.

[Brief description of drawings]

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

[FIG. 2] A drum system is adopted as a primary receptor,
It is a figure which shows the example of an apparatus for implementing the method of this invention.

FIG. 3 is a diagram showing an example of an apparatus for carrying out the method of the present invention, which adopts an endless belt system as a primary receptor.

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

FIG. 5 is a diagram showing an example of an application device of a peelable compound (S).

[Explanation of symbols]

 1 Support for Photoreceptor 2 Photosensitive Layer 5 Toner Image 10 Compound (S) Applying Device 11 Photoreceptor 12 Transfer Layer 13 Transfer Layer Forming Device 14 Liquid Developing Unit Set 14L Liquid Developing Unit 14R Rinse Means 14T Electrodeposition Unit 15 Intake / Exhaust Unit 15a Intake part 15b Exhaust part 16 Preheating means 17 Temperature adjusting means 18 Corona charging device 19 Exposure device 20 Primary receptor 24 Release paper 25a Preheating means 25b Heating roller 25c Cooling roller 30 Transfer material 31 Transfer backup roller 32 Peeling backup roller 110 Compound (S) application part 111 Transfer roll 112 Metering roll 113 Compound (S) 120 Transfer layer forming part 130 Transfer part to transfer material

Claims (5)

[Claims] 1. A toner image is formed on an electrophotographic photosensitive member by an electrophotographic process, and then a peelable transfer layer mainly containing a resin (A) which can be removed by a chemical reaction treatment is formed on the toner image. After that, the toner image and the transfer layer are collectively transferred onto a primary receptor, and the toner image on the primary receptor is transferred together with the transfer layer onto a transfer material which becomes a lithographically printable hydrophilic surface during printing. A method for producing an electrophotographic plate-making printing plate, which comprises transferring and then removing the transfer layer of the transferred material by a chemical reaction treatment. 2. The electrophotographic plate-making printing according to claim 1, wherein the peelable transfer layer is formed by any one of a hot melt coating method, an electrodeposition coating method and a transfer method. How to make a version. 3. The resin (A) constituting the transfer layer is a resin (AH) having a glass transition point of 30 ° C. to 140 ° C. or a softening point of 35 ° C. to 180 ° C. and a glass transition point of 40 ° C. or lower or a softening point of 4.
3. At least composed of a resin (AL) having a temperature of 5 ° C. or lower, and a difference in glass transition point or softening point between the resin (AH) and the resin (AL) is 2 ° C. or more, 3. How to make an electrophotographic plate-making printing plate. 4. The surface of the electrophotographic photoconductor is at least when a toner image is formed, according to JIS Z0237-1980 "Adhesive tape.
Adhesive strength according to "Adhesive sheet test method" is 100 gram
4. The electrophotographic plate-making printing plate according to any one of claims 1 to 3, which has a rce (g · f) or less and an adhesive force on the surface of the primary receptor is larger than an adhesive force on the surface of the photoreceptor. How to make. 5. A means for forming a toner image on an electrophotographic photoreceptor by an electrophotographic process, a means for providing a releasable transfer layer on the photoreceptor having the toner image formed thereon, and a transfer layer for transferring the toner image on a primary receptor. And a means for transferring the toner image together with the transfer layer from the primary receptor onto the material to be transferred.