JP3278250B2 - How to make an electrophotographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for preparing a lithographic printing plate using an electrophotographic photoreceptor, and more particularly, to a method for producing a lithographic printing plate excellent in transferability and elution removal of a transfer layer. It relates to a good new electrophotographic plate making and printing system.

[0002]

2. Description of the Related Art Today, lithographic offset printing plates include:
Positive photosensitizers containing diazo compounds and phenolic resins as main components, and PS plates using negative photosensitizers containing acrylic monomers or prepolymers as main components have been put into practical use. Therefore, it is necessary to perform plate making by contact exposure of a film master on which an image has been recorded in advance.

On the other hand, due to advances in computer image processing, large-capacity data storage, and data communication technologies, in recent years, computer operation has been consistently performed from document input, correction, editing, layout to page set, and high-speed communication networks and satellite communication As a result, an electronic editing system that can immediately output to a remote terminal plotter has been put to practical use. In particular, the demand for an electronic editing system is high in the newspaper printing field, which requires immediacy. Also, in the field where originals are stored in the form of original films and printing plates are duplicated as necessary, digital data will be stored on ultra-high-capacity recording media such as optical disks. Can be

[0004] However, a direct type printing plate for producing a printing plate directly from the output of a terminal plotter has hardly been put into practical use, and the output is performed on a silver halide photographic film even when an electronic editing system is operating. In fact, a printing plate is indirectly formed on a PS plate by contact exposure based on the above. One of the reasons is that it is difficult to develop a direct printing plate having a sensitivity high enough to produce a printing plate in a practical time by a light source of an output plotter (for example, a He-Ne laser, a semiconductor laser, or the like). Was the cause.

An electrophotographic photoreceptor is considered as a photoreceptor having high photosensitivity capable of providing a direct printing plate. Part 1
First, for electrophotographic lithographic printing using an electrophotographic photoreceptor using photoconductive zinc oxide as a printing plate after forming a toner image by an electrophotographic process and then desensitizing the non-image part with a desensitizing treatment liquid In the original system, a method has been proposed in which a photosensitive member having high sensitivity to semiconductor laser light is used.

[0006] For example, as a combination with a specific spectral sensitizing dye, Japanese Patent Publication No. 2-28143,
No. 124054, No. 63-241561, No. 63-2
No. 6,476,367, and the like. Further, as a technique for improving the binder resin of the photoconductive layer to achieve higher photosensitivity and lower background contamination in the non-image area (that is, improved water retention). For example, JP-A-63-220148,
The techniques described in the publications 116643 and 2-69759 have been proposed.

However, in order to make the printing plate a desensitizing reaction of zinc oxide to develop hydrophilicity, the use of a special desensitizing solution and immersion water requires a specific method. Various printing inks can be used, such as the use of only color inks, the printing durability is extremely reduced when neutral paper is used as the printing paper, and when used together with a printing machine using a PS plate, the printing machine cannot be shared unless the printing machine is thoroughly cleaned. Will occur.

As another electrophotographic lithographic printing plate precursor, there is known a method of removing a photoconductive layer in a non-image portion after forming a toner image. For example, Japanese Patent Publication No. 37-1716
No. 2, No. 38-6961, No. 38-7758, No. 4
Nos. 1-2426, 46-39405, JP-A-50-
19509, 50-19510, 52-243
No. 7, No. 54-145538, No. 54-134632
No. 55-105254, 55-153948
Nos. 55-161250 and 57-147656
And the printing original plate for electrophotographic plate making described in JP-A No. 57-161863 and the like.

In order to use an electrophotographic photosensitive member as a printing plate, it is necessary to remove a non-image portion by etching to expose a hydrophilic surface. In many cases, a separating resin is used. In general, resins soluble or dispersible in these alkaline solvents have poor compatibility with organic photoconductive compounds as compared with polycarbonate resins and the like which are widely used as binding resins for electrophotographic photoreceptors. The amount of the hydrophilic compound introduced into the electrophotographic photosensitive layer is limited. Even if sufficient carriers are generated to cancel the surface potential in the photoconductive layer, if the content of the organic photoconductive compound in the photoconductive layer is low, the moving speed of the carriers in the photoconductive layer is reduced. As a result, the decay rate of the surface potential, that is, the response speed is reduced. For this reason, after the exposure is completed, the surface potential is sufficiently attenuated to such an extent that no fogging is given, and the time required for starting the toner development becomes longer. In order to shorten the process time as much as possible, the response time becomes longer as the exposure illuminance is increased and the exposure time is shortened. Therefore, the high response speed hinders a reduction in the overall process time.

Another problem arises when scanning exposure is performed by a high illuminance light source such as a laser light source. That is, if the response speed is low, the attenuation rate of the surface potential is different between the writing start portion and the writing end portion, so that there is no fog at the writing start portion, but an image with much fog is formed at the writing end portion. A phenomenon occurs that causes inconvenience in the creation of.

A conventionally known binding resin used in an electrophotographic printing plate precursor is disclosed in JP-B-41-2426.
Nos. 37-17162, 38-6961, JP-A-52-2437, JP-A-54-19803, and 54-
No. 134632, No. 55-105254, No. 50-1
Nos. 9509, 50-19510, and the like.
Styrene-maleic anhydride copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-maleic anhydride copolymer, phenol resin and the like are known.

However, it is already known that when these are used for an electrophotographic printing plate precursor using an organic photoconductive compound, they have various problems. That is, when a styrene-maleic anhydride copolymer is used as the binder resin, the formed film is hard and cracks may occur when the printing plate is curved. In addition, the film has poor adhesion and cannot withstand printing on a large number of sheets. When a phenol resin is used as the binding resin, the formed film is fragile and the printing durability is poor. Vinyl acetate-crotonic acid copolymer, vinyl acetate-
The maleic anhydride copolymer still had a problem in printing durability. Furthermore, these resins were insufficient in electrophotographic properties (especially charge retention in darkness and photosensitivity).

As a solution to the above problems, Japanese Patent Application Laid-Open Nos. 57-161863 and 58-76843 disclose a copolymer of an acrylate monomer or a methacrylate monomer and a carboxylic acid-containing monomer. A polymer is disclosed. If these binding resins are used, it can be used as a printing original plate for electrophotographic plate making. However, as described above, the problem that has recently been pointed out due to the slow response speed (that is, insufficient light sensitivity) has not been solved yet.

Furthermore, Japanese Patent Publication No. 1-209458 and the like, which have improved printing durability and photosensitivity, disclose an aromatic ring-containing acrylate or methacrylate with an acidic group-containing carboxylic acid such as carboxylic acid. Copolymers with monomers are disclosed. The use of these binder resins improves the performance described above, but has a problem in that the removal of the photoconductive layer in the non-image portion other than the toner image portion is difficult to proceed promptly, and the conditions for removal are strict. It turned out that the proper management was necessary.

[0015] That is, a printing plate is produced in which a copied image from which only a non-image portion is completely removed is faithfully reproduced without causing elution even in a toner image portion having a small area, and which does not cause printing background stains. The problem that the conditions for this are narrow is unsolved. Furthermore, in this method, in order to elute the entire photoconductive layer which is a non-image portion, these are accumulated in the alkaline processing solution for elution processing, so when processing a large number of processing solutions continuously, Problems such as precipitation of agglomerates and deterioration of the elution removal ability occur.

[0016]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-described various problems of the prior art. Good, long-term and continuous processing,
It is an object of the present invention to provide a novel electrophotographic printing plate making method that can obtain a printing plate having stable performance and is suitable for image formation by scanning exposure with a laser or the like.

It is a further object of the present invention to provide a method for preparing an electrophotographic printing plate which can be used repeatedly and which is effective in reducing running costs. It is another object of the present invention to provide a method for producing a printing plate having good transferability to a material to be transferred in a thermal transfer process and easy removal of a transfer layer.

An object of the invention described in claim 4 of the present invention is to provide a thermoplastic resin having good releasability of a transfer layer. An object of the invention described in claim 5 of the present invention is to provide an electrophotographic photosensitive member suitable for the present invention.

[0019]

According to the first object of the present invention, as described in claim 1, it is removable by a chemical reaction treatment and contains at least the following polymer components (a) and (b). JIS Z0237-1980, "Testing method for pressure-sensitive adhesive tape / pressure-sensitive adhesive sheet" which has a peelable transfer layer as the uppermost layer mainly containing a thermoplastic resin [A], and whose surface is adjacent to the transfer layer. Adhesion of 200gr
A toner image is formed on the transfer layer by an electrophotographic process using an electrophotographic photosensitive member having an am.force (gf) or less, and the toner image is formed on the transfer layer together with a hydrophilic surface capable of being lithographically printed at the time of printing. It has been found that this is achieved by a method for preparing an electrophotographic printing plate, which comprises thermally transferring the material to a transfer material to be transferred, and then removing the transferred layer of the transferred material by a chemical reaction treatment. (I) Polymer component (a): —CO ₂ H group, —CHO group,
—SO ₃ H group, —SO ₂ H group, —P (＝ O) (OH) R ¹
｛R ¹ is a phenolic OH group, a hydrocarbon group or —OR ²
(R ² represents a hydrocarbon group), a group representing a group, a —OH group,
Acid cyclic anhydride-containing group, -CONHCOR ³ (R ³ represents a hydrocarbon group) polymer component containing at least one group of the groups and -CONHSO ₂ R ³ group (ii) polymer component (b) : -CO ₂ H by chemical reaction treatment
Group, -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, and at least one group of an —OH group Component containing at least one functional group that produces

That is, in the method of preparing an electrophotographic printing plate of the present invention, as shown in FIG. 1 showing the outline of the process, an electrophotographic photosensitive member 11 comprising at least a support 1 and a photosensitive layer 2 is formed. An upper layer is provided with a transfer layer 12 which mainly contains a thermoplastic resin [A] having polymer components (a) and (b) and is removable and peelable by a chemical reaction treatment. After the image 3 is formed, the toner image 3 is transferred together with the transfer layer 12 by thermal transfer onto a transfer target material 16 which is a support similar to the support provided for the offset printing plate, to obtain a printing original plate. Next, in the same apparatus as described above or separately from the apparatus, the transfer layer 12 transferred to the transfer target material 16 is subjected to a chemical reaction treatment, and the transfer layer 12 is dissolved or swelled and removed by desorption. Is used as a printing plate.

In the conventional printing plate, the surface of the photoreceptor itself is modified, for example, by hydrophilizing the photosensitive layer or exposing the surface hydrophilic support by eluting the photosensitive layer to form a non-image-forming substrate. On the other hand, in the present invention, after the transfer layer 12 is transferred together with the toner image 3 onto another support (transferred material) 16 having a hydrophilic surface,
The printing plate is prepared by a method completely different from the conventional viewpoint, in which the transfer layer 12 is removed by a chemical reaction treatment.

Here, the transfer layer provided in the present invention does not deteriorate electrophotographic characteristics (such as chargeability, charge retention in darkness, photosensitivity, etc.) until a toner image is formed by an electrophotographic process. Having a thermoplasticity that forms a copied image and is easily transferred to the material to be transferred in the next thermal transfer process. It is necessary that it be easily removed.

As a result of various studies, the above-mentioned thermoplastic resin [A] containing at least the polymer components (a) and (b) was used as the peelable thermoplastic resin which can be removed by the chemical reaction treatment. It has been found that various conditions are satisfied very effectively. Further, as described in claim 3, the transfer layer of the present invention preferably has a layer mainly containing the thermoplastic resin [A] on the photoreceptor on the peelable surface.

As a result, the transferability to the transfer material is further improved, the latitude of the transfer conditions (heating temperature, pressure, transport speed, etc.) is expanded, and the transfer of the hydrophilic surface to be a printing plate is performed. Irrespective of the type of material, it has become possible to transfer easily. When a resin containing the polymer component (a) containing the above-mentioned specific polar group is used as the thermoplastic resin for the transfer layer, the polymer is used to facilitate the removal of the resin by a chemical reaction treatment. When the content of the component (a) in the resin is increased, the electrical insulation of the resin itself is impaired, the electrophotographic characteristics are deteriorated, and the copy image is deteriorated (density reduction, image bleeding, ground in non-image area). Contamination). In addition, since the glass transition point of the resin itself is improved and a high temperature is required to generate thermoplasticity, the transfer conditions during hot-pressure transfer are severe conditions such as high temperature and high pressure and long transfer times. I need. Therefore, in order to satisfy the electrophotographic properties, transferability and removability by chemical reaction,
There is an undesired problem that the size of the transfer device in the transfer process is increased and the time required for preparing a lithographic printing plate is lengthened.

When a resin containing the polymer component (b) which expresses a specific polar group by the above-mentioned chemical reaction is used, the resin itself has sufficient electrical insulation and thermoplasticity. The electrophotographic properties and transferability are good. However, in order to obtain a printing plate, when performing a chemical reaction treatment, the wettability between the treatment liquid and the transfer layer on the material to be transferred is poor, and it takes time to hydrophilize the resin constituting the transfer layer. as a result,
Although the toner image portion has a resist property in the chemical reaction process to be used, a part of a high-definition image portion such as a thin line or a thin character may be partially missing.

Therefore, the resin [A] of the present invention is preferably composed of a copolymer containing at least one polymer component (a) and at least one polymer component (b). As a result, the glass transition point and the electrical insulation of the resin [A] are satisfied, the electrophotographic properties and transferability are significantly improved, and the hydrophilicity of the non-image portion as a printing plate also deteriorates the toner image. And can be quickly and completely removed. As a result, the reproducibility of the copied image transferred to the transfer material with respect to the original image is extremely good, and the transfer conditions are easily peeled and transferred at a low temperature and a low pressure, so that the transfer device can be downsized. . Also, even when used as a printing plate, non-image portions due to the remaining transfer layer are not seen at all, and thin lines / fine characters, halftone dots, lack of high-definition toner image portions such as gradation portions hardly occur, preferable.

Further, as described in claim 4, the thermoplastic resin [A] further contains at least one of a silicon atom and a fluorine atom as a copolymer component (hereinafter referred to as a silicon atom and / or a fluorine atom). It has been found that the use of a copolymer containing the polymer component (c) (containing a fluorine atom) as a block further improves the transferability to a material to be transferred in a thermal transfer process. That is, even if the conditions of the heat pressure at the time of transfer are further relaxed, it is possible to newly provide the effect of improving the releasability of the transfer layer itself, in which the releasability is sufficiently exhibited.

On the other hand, in order to easily peel off the transfer layer, in the present invention, the surface adjacent to the transfer layer of the electrophotographic photosensitive member to be used is coated with JISZ0237-1980 "adhesive tape.
Adhesion test value in the "Adhesive sheet test method"
When the content is 200 gm · force (gf) or less, preferably 150 gf or less, and more preferably 100 gf or less, the releasability between the photoconductive layer and the transfer layer can be exhibited.

In the above JIS adhesion test method,
The electrophotographic photoreceptor of the present invention is used as a “test plate”, and the adhesive strength is measured using a 6 mm-wide adhesive tape at a peeling speed of 120 mm / min. "Adhesive strength" represents a value proportionally converted to a width of 10 mm. The adhesive strength is 200
As a photoreceptor for an electrophotographic printing plate having a gf or less,
Specifically, as described in claim 5, the uppermost layer of the electrophotographic photosensitive member adjacent to the transfer layer or the uppermost layer of the electrophotographic photosensitive member adjacent to the transfer layer has at least one of a silicon atom and a fluorine atom having good releasability. Or a silicon-containing and / or fluorine-containing resin (referred to as polymer [P]) or an amorphous silicon electrophotographic photosensitive member. Thereby, the transfer of the transfer layer is easily and completely achieved.

The layer containing the resin containing silicon atoms and / or fluorine atoms may be a layer adjacent to the transfer layer, and may or may not be a photosensitive layer. A non-photosensitive layer having the releasability may be provided on the photosensitive layer (and thus between the photosensitive layer and the transfer layer) in order to impart releasability from the transfer layer. Further, in the present invention, the polymer [P] is a polymer segment (A) containing at least 50% by weight of a polymer component containing a silicon atom and / or a fluorine atom, and a polymer segment containing a silicon atom and / or a fluorine atom. From the viewpoint of further improving the releasability from the transfer layer, it is preferable that the copolymer is formed by combining at least one type of each with the polymer segment (B) containing 0 to 20% by weight of the united component. .

On the other hand, in the present invention, an electrophotographic photoreceptor having a transfer layer on the surface in advance is not used.
As described, by forming a transfer layer on the surface of the photoreceptor, the photoreceptor after the transfer layer is peeled can be used repeatedly, so that the electrophotographic process can be performed in the apparatus without disposing the photoreceptor. It can be performed continuously, which is advantageous for lowering running cost. The transfer layer is preferably formed on the photoreceptor each time in the same transfer device.

As a method of forming a transfer layer on the surface of the photoreceptor in the transfer device, a method of hot-melt-coating the resin containing the thermoplastic resin [A] on the surface of the photoreceptor,
A method of forming a transfer layer by transferring a transfer layer containing a thermoplastic resin [A] formed on another support material (such as release paper) to the surface of a photoreceptor; And a method in which particles mainly composed of a thermoplastic resin [A] are electrostatically attached or electrodeposited to form a film.

Further, in the above-mentioned electrodeposition method, particles mainly containing the thermoplastic resin are dispersed in an electrically insulating liquid having a relative dielectric constant of 3.5 or less, and supplied.
The thickness of the transfer layer for the release layer can be easily adjusted to a thin film with a uniform thickness. Further, particles mainly containing the thermoplastic resin are supplied between a counter electrode provided opposite to the electrophotographic photosensitive member, and electrophoresed according to a potential gradient applied from an external power supply to the electrophotographic photosensitive member. By forming a film by attaching or electrodepositing it, it becomes easy to adjust a more uniform thin layer.

Hereinafter, the transfer layer of the present invention will be described.
The transfer layer of the present invention, as described above, in order to form a printing plate from the electrophotographic photosensitive member having a releasable surface to a printing plate to obtain a plate-making original plate obtained by release transfer to a transfer receiving material serving as a printing support. This is a layer having a function of eluting and removing the transfer layer by chemical treatment. Therefore, the resin [A] of the main component constituting the transfer layer provided in the present invention is a thermoplastic resin and a resin which is eluted and removed by a chemical treatment.

The resin [A] has a glass transition point (T
g) is 120 ° C. or less or the softening point is 40 ° C. to 15 ° C.
Any material can be used as long as it is in the range of 0 ° C. The weight average molecular weight of the resin is preferably 1 × 1
0 ³ to 1 × 10 ⁶ , more preferably 5 × 10 ³ to 1 × 1
0 is in the range of ^5.

The resin [A] may be, as described in claim 1,-
CO ₂ H group, —CHO group, —SO ₃ H group, —SO ₂ H
Group, —P (＝ O) (OH) R ¹ ｛R ¹ is a phenolic OH
Group representing a group, a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group); —OH group; a cyclic acid anhydride-containing group;
CONHCOR ³ (R ³ represents a hydrocarbon group) group and -
A polymer component (a) containing at least one group selected from CONHSO ₂ R ³ groups and -C
O ₂ H group, —CHO group, —SO ₃ H group, —SO ₂ H group,
—P (＝ O) (OH) R ¹ ｛R ¹ is a phenolic OH group,
A polymer component (b) containing at least one functional group that forms at least one of a 基 group representing a hydrocarbon group or an —OR ² (R ² represents a hydrocarbon group) group and an —OH group Is a copolymer containing at least one of the following.

Here, -P (= O) (OH) R ¹ represents a group represented by the following formula ¹ , wherein R ¹ is -O
Represents an H group, a hydrocarbon group or an —OR ² group (R ² represents a hydrocarbon group); specifically, R ¹ is an optionally substituted aliphatic group having 1 to 12 carbon atoms (eg, a 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, chlorobenzyl, fluorobenzyl, methoxybenzyl, etc.) or an optionally substituted aryl group (phenyl, tolyl, ethylphenyl, propyl-methyl-phenyl, dichlorophenyl, methoxyphenyl) Group, cyanophenyl group,
Acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.), and R ² represents the same content as R ¹ .

[0038]

Embedded image

-CONHCOR ³ group and -CONHSO
R ³ in ₂ R ³ group represents a hydrocarbon group, specifically, represents the same content as R ^2. Further, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride contained include aliphatic dicarboxylic anhydride and aromatic dicarboxylic anhydride. Can be

Examples of aliphatic dicarboxylic anhydrides include:
Succinic anhydride, glutaconic anhydride, maleic anhydride, cyclopentane-1,2-dicarboxylic anhydride, cyclohexane-1,2-dicarboxylic anhydride,
Cyclohexene-1,2-dicarboxylic anhydride ring, 2,
3-bicyclo [2.2.2] octadicarboxylic anhydride rings and the like. These rings include, for example, halogen atoms such as chlorine atom and bromine atom, methyl group, ethyl group, butyl group, hexyl group and the like. An alkyl group or the like may be substituted. Examples of the aromatic dicarboxylic anhydride include a phthalic anhydride ring, a naphthalene-dicarboxylic anhydride ring, a pyridine-dicarboxylic anhydride ring, a thiophene-dicarboxylic anhydride ring, and the like. For example, chlorine atom, halogen atom such as bromine atom, methyl group, ethyl group,
An alkyl group such as a propyl group and a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (an alkoxy group such as a methoxy group and an ethoxy group) may be substituted.

Further, the resin further comprises a polymer component containing at least one silicon atom and / or fluorine atom together with the above-mentioned polymer component (a) and polymer component (b). It is preferable to use a block copolymer obtained by copolymerizing a block type or a graft type. The proportion of each polymer component in the resin [A] is as follows.

In the total polymer component of the resin [A], the polymer component (a) containing a specific polar group is 0.5 to 25% by weight,
Preferably from 1 to 20% by weight, a polymer component (b) containing a functional group which undergoes a chemical reaction to produce the specific polar group
Is 3 to 99.5% by weight, preferably 5 to 50% by weight. When the amount of the polar group-containing copolymerization component (a) is 0.5
When the amount is less than 10% by weight, the processing time for removing the transfer layer by the chemical processing becomes longer, the processing temperature needs to be increased, or a fatal problem of missing of the toner image may occur. If the amount of the copolymer component (a) exceeds 25% by weight, the glass transition point or softening point of the resin [A] will increase, no matter how the other copolymer components of the resin [A] are adjusted. As a result, the transferability of the transfer layer to the material to be transferred is deteriorated.

When the copolymer component (b) containing a functional group that generates a hydrophilic group by the chemical reaction (functional group that expresses a hydrophilic group) is less than 3% by weight, the printing plate and Therefore, the removal of the transfer layer after the chemical reaction treatment becomes insufficient, and the background stain is generated in the non-image portion on the printing plate, which is not preferable. Further, when the polymer component (c) containing a silicon atom and / or a fluorine atom is contained, its content is 1 to 30% by weight, preferably 3 to 20% by weight in the total polymer component of the resin [A]. %. The polymer component (c)
Is characterized in that the resin [A] is bonded to the polymer chains (a) and (b) by a block as a polymer chain. When the content of the polymer segment (c) is 1% by weight or less, the effect of improving the releasability of the resin [A] is diminished.
When the content is 0% by weight or more, the wettability of the resin [A] with the treatment liquid is reduced, and the removal of the transfer layer becomes insufficient.

Next, each polymer component contained in the resin [A] will be described in detail. The polymer component (a) is not particularly limited as a copolymer component containing a specific polar group as described above. Specific examples of the optional polar group-containing copolymer component in the resin [A] may be any vinyl compound containing the polar group,
For example, it is described 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) methyl form, α-chloro form, α-form
-Bromo form, α-fluoro form, α-tributylsilyl form,
α-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid semiamides , 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, vinylbenzene carboxylic acid, vinylbenzene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, vinyl group of dicarboxylic acids or Examples thereof include a half ester derivative of an allyl group, an ester derivative of these carboxylic or sulfonic acids, and a compound containing the polar group in a substituent of an amide derivative.

Hereinafter, the copolymerization component (a) containing a polar group will be exemplified. Wherein, R ₄ represents -H or -CH _3, R ₅ is -H, indicates -CH ₃ or -CH ₂ COOCH _3, R ⁴ represents an alkyl group having 1 to 4 carbon atoms, R ⁵ is R ₆ represents —C _n H _{2n + 1} (n: an integer of 1 to 4), R ₇ represents —C _n H _{2n + 1} , _{-OC n H 2n + 1 (n} : 1~4
E) represents an integer of 1 or 2, and f represents 1 to 2.
3 represents an integer, g represents an integer of 2 to 11, and h represents 1 to
11 represents an integer, i represents an integer of 2 to 4, and j represents 2 to
Indicates an integer of 10.

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

Next, the polymer component (b) will be described. The polymer component (b) has at least one
Number of hydrophilic groups [-CO ₂ H group, -CHO group, -SO ₃ H
Group, -SO ₂ H group, -CHO group, -P (= O) (OH ) R
¹ {R ¹ represents a —OH group, a hydrocarbon group or a —group representing an —OR ² (R ² represents a hydrocarbon group) group and a —OH group]. The number of hydrophilic groups generated from one functional group by a chemical reaction may be one or two or more.

The chemical reaction that can convert a functional group into a hydrophilic group is a treatment solution utilizing a conventionally known hydrolysis reaction, hydrogenolysis reaction, oxygenolysis reaction, β-elimination reaction, nucleophilic substitution reaction, or the like. , Or a decomposition reaction upon irradiation with "chemically active light". First, a functional group that generates at least one carboxyl group by a chemical reaction will be described.

According to one preferred embodiment of the present invention, examples of the carboxyl group-forming functional group include a functional group represented by the following general formula (I). General formula (I) [-COO-L ¹ ] [In general formula (I), L ¹ represents Chemical formula 9. ]

[0056]

Embedded image

However, R ¹¹ and R ¹² may be the same or different and represent a hydrogen atom or an aliphatic group, X represents an aromatic group, Z represents a hydrogen atom, a halogen atom, a trihalomethyl group, an alkyl group, -OH group, -NO ₂ group, -
An SO ₂ -Z ¹ (wherein, Z ¹ represents a hydrocarbon group) group,-
A COO-Z ² (where Z ² represents a hydrocarbon group) group,
O—Z ³ (where Z ³ represents a hydrocarbon group) or —CO 3
—Z ⁴ (wherein, Z ⁴ represents a hydrocarbon group)
n and m represent 0, 1 or 2.

A ¹ and A ² may be the same or different and represent an electron-withdrawing group having a positive Hammett's substituent constant σ value. R ¹³ represents a hydrogen atom or a hydrocarbon group. R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different from each other, and represent a hydrocarbon group or a —O—Z ⁵ (where Z ⁵ represents a hydrocarbon group) 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 represent a hydrogen atom or an aliphatic group, and p represents an integer of 3 or 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 or different from each other, and are preferably a hydrogen atom, or a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group). Group, chloromethyl group, dichloromethyl group, trichloromethyl group, trifluoromethyl group, butyl group, hexyl group, octyl group, decyl group, hydroxyethyl group, 3-chloropropyl group, etc., and X is preferably substituted Represents a phenyl group or a naphthyl group (eg, phenyl group, methylphenyl group, chlorophenyl group, dimethylphenyl group, chloromethylphenyl group, naphthyl group, etc.), and Z is preferably a hydrogen atom, a halogen atom (eg, a chlorine atom) , Fluorine atom, etc.), trihalomethyl group (eg, trichloromethyl group, trifluoromethyl group, etc.), carbon number 1 to 12 optionally substituted linear or branched alkyl groups (for example, methyl, chloromethyl, dichloromethyl, ethyl, propyl, butyl, hexyl, tetrafluoroethyl, octyl) , Cyanoethyl group,
Chloroethyl group, etc.), - CN group, -NO ₂ group, -SO ₂
—Z ¹ [Z ¹ is an aliphatic group (for example, 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) And an optionally substituted aralkyl group having 7 to 12 carbon atoms: specifically, a benzyl group, a phenethyl group,
A chlorobenzyl group, a methoxybenzyl group, a chlorophenethyl group, a methylphenethyl group or the like; or an aromatic group (for example, a phenyl group or a naphthyl group which may contain a substituent: specifically, a phenyl group, a chlorophenyl group, a dichlorophenyl group) , Methylphenyl, methoxyphenyl, acetylphenyl, acetamidophenyl, methoxycarbonylphenyl, naphthyl, etc.)
A —COO—Z ² (Z ² has the same meaning as Z ¹ ),
O—Z ³ (Z ³ has the same meaning as Z ¹ ), or —CO 3
—Z ⁴ (Z ⁴ has the same meaning as Z ¹ above).
n and m each represent 0, 1 or 2.

R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different from each other and are preferably an aliphatic group having 1 to 18 carbon atoms which may be substituted (the aliphatic group may be an alkyl group, an alkenyl group or an aralkyl group). Or an alicyclic group, and examples of the substituent include a halogen atom, a —CN group, a —OH group, and —O—Z ⁶
(Z ⁶ represents an alkyl group, an aralkyl group, an alicyclic group, an aryl group), etc.], and an optionally substituted aromatic group having 6 to 18 carbon atoms (for example, phenyl group, tolyl group, chlorophenyl) group, methoxyphenyl group, acetamidophenyl group, a naphthyl group), or -O-Z ⁵ (Z ⁵
Is an alkyl group having 1 to 12 carbon atoms which may be substituted, an alkenyl group having 2 to 12 carbon atoms which may be substituted, an aralkyl group having 7 to 12 carbon atoms which may be substituted,
8 represents an alicyclic group which may be substituted or an aryl group which may have 6 to 18 carbon atoms and may be substituted).

A ¹ and A ² may be the same or different, and at least one of them is an electron-withdrawing group;
It is sufficient that the sum of the Hammett σ _p values of ¹ and −A ² is 0.45 or more. Examples of the electron withdrawing group here include, for example, an acyl group, an aroyl group, a formyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, an alkylsulfonyl group, an aroylsulfonyl group, a nitro group, a cyano group,
Examples include a halogen atom, a halogenated alkyl group, and a carbamoyl group.

The Hammett's σ _p value is generally used as an index for estimating the degree of electron withdrawing / donating of a substituent, and the larger the value on the + side, the stronger the electron withdrawing group. Specific numerical values for each substituent are described in, for example, Naoki Inamoto, "Hammet Rule-Structure and Reactivity", Maruzen (1984). Also, Ham in this system
The σ _p value of met is considered to be additive, and −
It is not necessary that both A ¹ and -A ² are electron withdrawing groups. Therefore, for example, when -A ¹ is an electron-withdrawing group, the other -A ² substituent is such that the sum of the σ _p values of -A ¹ and -A ² is 0.45 or more. Either one may be used, and there is no particular limitation.

R ¹³ represents an optionally substituted hydrocarbon group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, an allyl group, Examples include a benzyl group, a phenethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 3-methoxypropyl group, and a 2-chloroethyl group.

Y ¹ represents an oxygen atom or a sulfur atom.
R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different from each other, and are preferably a hydrogen atom, an optionally substituted carbon atom having 1 to 1 carbon atoms.
18 linear or branched alkyl groups (for example, a methyl group,
An ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, a chloroethyl group, a methoxyethyl group, a methoxypropyl group, etc., an alicyclic group which may be substituted (for example, a cyclopentyl group) , Cyclohexyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.), and an optionally substituted aromatic group (eg, phenyl group, A naphthyl group, a chlorophenyl group, a tolyl group, a methoxyphenyl group, a methoxycarbonylphenyl group, a dichlorophenyl group, etc. or —O—Z ⁷ (Z ⁷ represents a hydrocarbon group; specifically, R ¹⁷ , R ¹⁸ , R And the same substituents as the ¹⁹ hydrocarbon groups). 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

[0066]

Embedded image

[0067]

Embedded image

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

In the formula (B), R ²⁴ and R ²⁵ may be the same or different and represent the same contents as R ²² and R ²³ . Further, R ²⁴ and R ²⁵ may represent an organic residue which continuously forms an aromatic ring (for example, a benzene ring, a naphthalene ring, etc.). Further, in the general formula (I), R ²⁰ and R ²¹
Represent the same contents as the R ^16.

Another preferred embodiment of the present invention is an oxazolone ring represented by the following general formula (II).

[0071]

Embedded image

In the general formula (II), R ²⁶ and R ²⁷ may be the same or different and each represents a hydrogen atom or a hydrocarbon group, or R ²⁶ and R ²⁷ together form a ring. You may. Preferably, R ²⁶ and R ²⁷ may be the same or different from each other, and each may be a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (eg, a methyl group, an ethyl group, Propyl, butyl, hexyl, 2-chloroethyl, 2-methoxyethyl, 2-
A methoxycarbonylethyl group, a 3-hydroxypropyl group, etc., an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, 4-chlorobenzyl group,
-Acetamidobenzyl group, phenethyl group, 4-methoxybenzyl group, etc.);
2 alkenyl groups (eg, ethylene group, allyl group, isopropenyl group, butenyl group, hexenyl group, etc.) and optionally substituted 5- to 7-membered alicyclic group (eg, cyclopentyl group, cyclohexyl group, chlorocyclohexyl) Group), an aromatic group which may be substituted (for example, a phenyl group,
Chlorophenyl group, methoxyphenyl group, acetamidophenyl group, methylphenyl group, dichlorophenyl group,
A nitrophenyl group, a naphthyl group, a butylphenyl group, a dimethylphenyl group, etc., or a group in which R ¹⁶ and R ¹⁷ together form a ring (eg, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc.) Is also good.

The functional group that forms at least one sulfo group by a chemical reaction includes, for example, a functional group represented by the following general formula (III) or (IV). General formula (III) -SO ₂ -OL ² General formula (IV) -SO ₂ -SL ² [In formula (III) or (IV), L ² represents Chemical formula 13. ]

[0074]

Embedded image

Here, R ¹¹ , R ¹² , X, Z, n, m, Y
^2, R ²⁰ and R ²¹ each represent the same contents. Further, examples of the functional group that generates at least one sulfinic acid group by a chemical reaction include a functional group represented by the following general formula (V).

[0076]

Embedded image

[In the formula (V), A ¹ , A ² and R ¹³ each represent the same contents as described above. ] As the functional group capable of generating a -PO ₃ H ₂ group by chemical reaction, for example, include a functional group represented by the following general formula (VI).

[0078]

Embedded image

[In formula (VI), L ³ and L ⁴ may be the same or different, and each represents the same content as L ¹ . Further, examples of the functional group that generates an —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 reduction 16.

[0080]

Embedded image

Here, R ²⁸ represents a hydrocarbon group, and specifically has the same contents as R ¹¹ . R ^{14 to} R ¹⁹ , Y ¹ and p each represent the same contents as described above. Further, according to another preferred embodiment of the functional group that generates an —OH group by a chemical reaction, the hydroxyl group-forming functional group is
It is a functional group having at least two hydroxyl groups located sterically close to each other in a form protected simultaneously by one protecting group. Examples of the functional group having at least two hydroxyl groups which are sterically close to each other in one protected form include, for example, functional groups represented by the following general formulas (IX), (X) and (XI) be able to.

[0082]

Embedded image

[In the formulas (IX) to (XI), R ²⁹ and R ³⁰ may be the same or different and each represents a hydrogen atom, a hydrocarbon group or —O—Z ¹⁰ (Z ¹⁰ is a hydrocarbon group) ) Represents a group, and U represents a carbon-carbon bond which may be via a hetero atom (provided that the number of atoms between oxygen atoms is within 5). ] Functional In more detail about the functional groups, R ^29, R
³⁰ may be the same or different, and are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, A methoxyethyl group, an octyl group or the like), an optionally substituted aralkyl group having 7 to 9 carbon atoms (such as a benzyl group, a phenethyl group, a methylbenzyl group, a methoxybenzyl group, or a chlorobenzyl group); An alicyclic group (eg, cyclopentyl group, cyclohexyl group, etc.) or an optionally substituted aryl group (eg, phenyl group, chlorophenyl group, methoxyphenyl group, methylphenyl group, cyanophenyl group, etc.) or —O
Z ¹⁰ (Z ¹⁰ has the same meaning as the hydrocarbon group for R ²⁹ and R ³⁰ ). U represents a carbon-carbon bond which may be via a hetero atom, and the number of atoms between oxygen atoms is 5 or less.

The specific examples (b-1) to (b-67) of the functional groups represented by the general formulas (I) to (XI) are described below. However, the content of the present invention is not limited to these. In the following specific examples, each symbol is represented by Chemical Formula 1.
As shown in FIG.

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

According to the present invention, a --CO ₂ H group, a --CHO group, a --SO ₃ H group,
Copolymer component containing a functional group for generating at least one hydrophilic group of -SO ₂ H group, -PO ₃ H ₂ group and -OH group (b) is not particularly limited. Preferably, a polymer in which the hydrophilic group of the polymer component (a) is protected is mentioned as an example.

The -CO ₂ H, -CHO, -SO ₃ H, -PO ₃ H groups as described above which can be used in the present invention.
_The functional groups that express _two groups, —SO ₂ H groups and / or —OH groups by a chemical reaction, are functional groups that protect these hydrophilic groups, and are formed by chemical bonding of these protecting groups to the hydrophilic groups. The introduction can be easily performed by a conventionally known method.

For example, as described in J.I. F. W. McOmie "Protect
ive groups in Organic Chemistry ”(Plenum Pres
s. 1973); W. Greene "Proactive g
roupsin Organic Synthesis "(Wiley-Interscie
nce, 1981), The Chemical Society of Japan, “New Experimental Chemistry Course, Vol. 14, Synthesis and Reaction of Organic Compounds” (Maruzen Co., Ltd.)
Each unit reaction described in, for example, "Reactive Polymers" by Yoshio Iwakura and Keisuke Kurita (Kodansha), 1978) is used.

As a method for introducing these functional groups which can be used in the present invention into the resin [A], -COOH
Group, -CHO group, -SO ₃ H group, -PO ₃ H ₂ group, -S
A method of converting a polymer containing at least one kind of hydrophilic group selected from O ₂ H group, —OH group and the like into a functional group in which each hydrophilic group is protected by a reaction, a so-called polymer reaction method; Alternatively, after synthesizing one or more monomers containing one or more functional groups represented by the above-mentioned general formulas (I) to (XI), any other monomer that can be copolymerized therewith is synthesized. It is obtained by a method of forming a polymer by a polymerization reaction with a monomer.

The latter is preferred because the functional group necessary for the present invention can be arbitrarily adjusted in the polymer, or impurities (in the case of a polymer reaction, a catalyst or a by-product used) are not mixed. (A method in which a desired monomer is obtained in advance and then a polymerization reaction is carried out).
For example, when 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 Is converted into a functional group represented by the general formula (I), and then subjected to a polymerization reaction to produce the compound.

Further, the resin containing an oxazolone ring represented by the general formula (II) as a functional group that generates a carboxyl group by a chemical reaction is obtained by reacting one or more monomers containing the oxazolone ring with Alternatively, it can be obtained by a method of forming a polymer by a polymerization reaction of the monomer and another monomer copolymerizable therewith. This monomer containing an oxazolone ring can be produced by a dehydration ring-closing reaction of N-acyloyl-α-amino acids containing a polymerizable unsaturated bond. Specifically, it can be produced by the method described in the literature in the review article in Chapter 3 of "Reactive Polymers" by Yoshio Iwakura and Keisuke Kurita (published by Kodansha).

Further, the polymer component (c) which has an effect of improving the releasability of the resin [A] itself and which can be contained in the polymer will be described. The polymer component (c) is a polymer component containing a substituent containing a silicon atom and / or a fluorine atom. In the present invention, the substituent includes both those incorporated in the polymer main chain of the polymer and those contained as the substituent of the side chain of the polymer.

The substituent containing a fluorine atom includes, for example, a monovalent organic residue such as Chemical formula 24 and a divalent organic residue such as Chemical formula 25.

[0099]

Embedded image

[0100]

Embedded image

Examples of the silicon atom-containing substituent include a monovalent or divalent organic residue such as that shown in Chemical formula 26.

[0102]

Embedded image

However, R ³¹ , R ³² , R ³³ , R ³⁴ and R
³⁵ may be the same or different and each may be substituted hydrocarbon group or -OR ³⁶ group (R ³⁶ represents the same content as the hydrocarbon group of R ³¹⁾ represent. R ³¹ represents an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, 2
-Chloroethyl group, 2-bromoethyl group, 2,2,2-
Trifluoroethyl group, 2-cyanoethyl group, 3,3
3-trifluoropropylethyl, 2-methoxyethyl, 3-bromopropyl, 2-methoxycarbonylethyl, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl, etc.), carbon An alkenyl group which may be substituted, represented by Formulas 4 to 18 (eg, 2-methyl-1-propenyl, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl Group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc., and optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group) , 2-naphthylethyl, chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl, dimethylbenzyl Dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexyl group, 2-cyclopentylethyl group, etc.) or substituted having 6 to 12 carbon atoms. Aromatic groups (e.g., phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyl) Oxyphenyl group, chlorophenyl group,
Dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamide Phenyl group etc.).

-OR³⁶In the group, R³⁶Is the above R³¹of
Represents the same content as the hydrocarbon group. In addition, the fluorine atom and
Organic residues containing silicon and silicon atoms are combined to form
In that case, it may be directly bonded or further
May be combined via other linking groups. connect
Specific examples of the group include a divalent organic residue,
-, -S-, -N (d¹)-, -SO-, -SO_Two−,
-COO-, -OCO-, -CONHCO-, -NHC
ONH-, -CON (d¹)-, -SO_Two(D ¹)-Etc.
Divalent aliphatic which may have a bonding group selected from
Group or divalent aromatic group, or these divalent residues
It represents an organic residue composed of a combination. here
And d¹Is R³¹Represents the same content as.

As the divalent aliphatic group, there can be mentioned, for example, each group shown in Chemical formula 27.

[0106]

Embedded image

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

As the divalent aromatic group, for example, a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (hetero atoms constituting a heterocyclic ring are selected from oxygen, sulfur and nitrogen atoms. Containing at least one heteroatom). These aromatic groups may have a substituent, for example, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a 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.).

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, a 1,3-
Oxazoline ring and the like. Next, specific examples of the repeating unit having a substituent containing a fluorine atom and / or a silicon atom as described above are shown below. However, the scope of the present invention is not limited to these. The following (c
In each of the specific examples in -1) to (c-32), R
_f represents any one of the following groups (1) to (11), and b represents a hydrogen atom or a methyl group.

[0110]

Embedded image

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

[0112]

Embedded image

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

The polymer component (c) is contained as a block in the resin [A]. Preferred embodiments of the resin [A] as a so-called block copolymer will be described below. In the present invention, in the resin [A], any resin may be used as long as the polymer component containing a fluorine atom and / or a silicon atom is composed of blocks. Here, "consisting of blocks" means that fluorine and / or silicon atoms are 50% by weight.
It means that the polymer segment contained in the polymer is contained, for example, an AB type block, an ABA type block, a BAB type block, a graft type as shown in Chemical formula 34. A block or a star type block is exemplified.

[0118]

Embedded image

These various block copolymers [A] include:
It can be synthesized according to a conventionally known polymerization method. For example, W.S. J. Burlant, A. et al. S. Hoffman "Block an
d Graft polymers "(1986, Reuhold);
J. Cevesa "Block and Graft Copolymers" (196
2 years, Butterworths); C. Allport, W.C. H. J
ames "Block Copolymers" (1972, Applied Sc
i), A. Noshay, J .; E. FIG. McGrath "Block Copolym
ers "(1977, Academymis Press.); Huvter
g, D.C. J. Wilson, G .; Riess, NATO ASI
ser. SerE. 1985 , 149; Perces,
Applide. Polymer Sci. 285 , 95 (1985). For example, for an ionic polymerization reaction using a polymerization initiator such as an organic metal compound (eg, alkyl lithiums, lithium diisopropylamide, alkali metal alcoholates, alkyl magnesium halides, alkyl aluminum halides, etc.),
T. E. FIG. Hogeu-Esch, J.A. Smid "RecentAdvances
in Anion Polymerization "(1987, Elsevier
New York), Yoshio Okamoto, Polymer, 38 , 912 (19
89), Mitsuo Sawamoto, Polymer, 38 , 1018 (198
9), Tadashi Narita, Polymer, 37 , 252 (1988),
B. C. Anderson, et al., Macromolecules 14 ,
1601 (1981); Aoshima, T .; Higasimur
a, Macromolecules 22 , 1009 (1989) and the like.

The ionic polymerization reaction using a hydrogen iodide / iodine system or the like is described in T.I. Higasimura et al., Mak
romol.Chem., Macromol.Symp., 13/ 14, 457
(1988), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Paper Collection 4
6 , 189 (1989). For the group transfer polymerization reaction, see D.S. Y. Sogah et al., Ma
cromolecules, 20 , 1473 (1987); W.
Webster, D.S. Y. Sogah, polymer, 36 , 808 (1
987); T. See Reetg et al., Angew. Chem. I.
ed. Eugl. 25 , 9108 (1986);
No. 3-97609.

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

Further, regarding the ring-opening polymerization reaction of a cyclic compound, S.D. Kobayashi, T .; Saegusa "Ring Opening
Polymerization "(1984, Applied Science)
e Publishers Ltd.); Seeliger et al., Ange
w. Chem. Int. Ed. Engl. 5 , 875 (196)
6), S.P. Kobayashi et al., Poly.Bull. 13 , 4
47 (1985); Chujo et al., Macromolecu
les, 22 , 1074 (1989).

Further, with respect to the living photopolymerization reaction using a dithiocarbamate compound or a xanthate compound as an initiator, Takatsu Otsu, Polymer, 37 , 248 (1)
988), Shunichi Hinomori, Ryuichi Otsu, Polym. Rep. Jap.
37 , 3508 (1988), JP-A-64-111,
JP-A-64-26619; Niwa, Macromolecu
les, 189 , 2187 (1988) and the like.

[0124] On the other hand, a method of synthesizing a block copolymer by radical polymerization reaction to polymeric initiator containing an azo group or a peroxide group, Ueda Akirato, polymer Collected Papers, 3
3 931 (1976), Akira Ueda, Osaka Municipal Technical Research Institute Report 84 (1989), O. Nuyken et al., Macromol.
Chem., Rapid. Commun. 9 , 671 (1988); Yasuo Moriya, "Reinforced Plastics" 29 , 907 (19)
), Ryohei Oda "Science and Industry" 61 , 43 (1987)
And so on.

Regarding the synthesis of the graft type block copolymer, in addition to the above-mentioned books and reviews, Fumio Ide, “Graft Polymerization and Its Application” (1977, Society of Polymer Publishing), edited by The Society of Polymer Science, Japan Polymer Alloy "(1981
Year, Tokyo Chemical Dojin). For example, a method of grafting a polymer chain by a polymerization initiator, a chemical actinic ray (radiation, electron beam, etc.), a mechanochemical reaction in mechanical application, etc., a polymer chain and a functional group of the polymer chain. There are known a method of grafting by utilizing a chemical bond (a so-called interpolymer reaction) and a method of grafting by performing a polymerization reaction using a macromonomer.

As a method of grafting using a polymer, specifically, T.I. Shota et al., J. Mol. Appl. Poly
m. Sci. 13 , 2447 (1969); H. Buck
, Rubber Chemistry and Technology, 50 , 1
09 (1976), Tsuyoshi Endo, Tsutomu Uezawa, Journal of the Japan Adhesive Society,
24 , 323 (1988), Tsuyoshi Endo, ibid. 25 , 40
9 (1989).

As a method of performing a polymerization reaction and grafting using a macromonomer, specifically, a method described in P.S. Dreyfus
s & R. P. Quirk, Encycl. Polym. Sci. En
g., 7 , 551 (1987); F. Rempp, E .;
FraNTA, Adv. Polym. Sci., 58 , 1 (198
4). Percec, Appl. Poly. Sci., 285 , 9
5 (1984); Asami, M .; Takari, Macromo
l. Chem. Suppl., 12 , 163 (1985); R
empp. et al., Macromol. Chem. Suppl., 8 , 3 (1
985), Yusuke Kawakami, Chemical Industry, 38 , 56 (198
7), Yuya Yamashita, Polymer, 31 , 988 (1982),
Shiro Kobayashi, Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of the Adhesion Society of Japan, 18 , 536 (1982), Koichi Ito, Polymer Processing, 35 , 262 (1986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No. 10, 5, edited by Yuya Yamashita, "The Chemistry and Industry of Macromonomers" (1989)
1980, edited by Tsuyoshi Endo, “Molecular Design of New Functional Polymers”, Chapter 4 (1991, CM.
C. Co., Ltd.), Y. Yamashita et al., Polym. Bul
l. 5 , 361 (1981).

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

Further, the resin [A] may be used together with the specific polymer components (a) and (b) and / or (c) together with other polymer components to maintain electrical insulation and thermoplasticity. contains. As the other polymerization component, those having a glass transition point of 120 ° C. or lower of a homopolymer of the polymer component are preferable. Specifically, for example, a component of a repeating unit represented by the following general formula (U) is exemplified. These repeating units may be used alone or in combination of two or more.

[0130]

Embedded image

In the formula (U), V represents —COO—, —OCO
-, - O -, - CO -, - C 6 H 4 -, - (CH 2) n
Represents COO— or — (CH ₂ ) _n OCO—. Where n
Represents an integer of 1 to 4. b ¹ and b ² may be the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom,
Bromine atom, cyano group, trifluoromethyl group, carbon number 1
7 hydrocarbon groups (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group,
A benzyl group or the like or —COOZ ¹¹ (Z ¹¹ represents a hydrocarbon group, specifically the same as those described above for the hydrocarbon group having 1 to 7 carbon atoms).

R ⁶⁰ represents a hydrocarbon group having 1 to 22 carbon atoms. R ⁶⁰ is preferably an alkyl group having 1 to 12 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, 2-chloroethyl group, 2
-Bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-hydroxypropyl group, etc.), having 2 to 18 carbon atoms
Optionally substituted alkenyl group (for example, vinyl group,
Allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), having 7 to 12 carbon atoms
Optionally substituted aralkyl groups (for example, benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.); A cycloalkyl group (e.g., a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc.) or a carbon number of 6 to 12;
Optionally substituted aryl group (for example, phenyl group,
Tolyl, xylyl, mesityl, naphthyl, methoxyphenyl, ethoxyphenyl, fluorophenyl, methylchlorophenyl, difluorophenyl, bromophenyl, chlorophenyl, dichlorophenyl, methylcarbonylphenyl, methoxycarbonyl Phenyl, ethoxycarbonylphenyl, methanesulfonylphenyl, cyanophenyl, etc.).

The content of the copolymer component represented by the above formula (U) is preferably 30 to 97% by weight based on the whole polymer of the resin [A]. Further, the resin [A] may contain, together with the specific polymer component and the copolymer component represented by the general formula (U), other copolymer components copolymerizable with these components. Such other copolymer components include, for example, methacrylates, acrylates, crotonates having substituents other than those described in the general formula (U), α-olefins, carboxylates and the like. Acid vinyl or allyl esters (for example, as carboxylic acid,
Acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalene carboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrene (For example, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene,
Methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compounds, vinylketone-containing compounds, heterocyclic vinyls (for example, vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, Vinyl quinoline, vinyl tetrazole, vinyl oxazine, etc.), but are not limited thereto. These other copolymer components can be used arbitrarily as long as the transferability of the resin [A] is not alienated. Specifically, the resin [A]
Preferably, it does not exceed 20% by weight.

In the transfer layer, other resins may be used together with the resin [A] of the present invention, if necessary. However, by not lowering the performance of elution removal of the transfer layer,
The proportion of the polymer components (a) and (b) according to the present invention in 100 parts by weight of the total resin for forming the transfer layer must satisfy 5% by weight or more. Examples of other resins that can be used in combination include, for example, vinyl chloride resin, polyolefin resin, olefin-styrene copolymer, vinyl alkanoate resin, polyester resin, polyether resin, acrylic resin, methacrylic resin, cellulose resin And fatty acid-modified cellulose resins. These thermoplastic resins may be used alone or in combination of two or more.

More specifically, for example, “Plastic Materials Course Series”, Vol.
961), Kinki Chemical Association Vinyl Subcommittee, “Polyvinyl Chloride”, published by The Nikkan Kogyo Shimbun (1988), Eizo Omori “Functional Acrylic Resin”, Techno System Co., Ltd. (1985)
Eiichiro Takiyama, "Polyester Resin Handbook", published by Nikkan Kogyosha (1988), Kazuo Yuki, "Saturated Polyester Resin Handbook", published by Nikkan Kogyo Shimbun (1989)
), Edited by The Society of Polymer Science, “Polymer Data Handbook <Application>”, Chapter 1, Baifukan (1986), Yuji Harasaki, “Latest Binder Technology Handbook”, Chapter 2, Integrated Technology Center (1985), etc. Is exemplified.

Further, other additives may be used in the transfer layer in order to improve various physical properties such as adhesiveness, film formability and film strength. For example, rosin, petroleum resin, silicone oil, etc. for adjusting the adhesiveness, as a plasticizer and softener for improving the wettability to the photoreceptor and lowering the melt viscosity, such as boribene, DOP, DBP, low molecular styrene resin, low molecular Polyethylene wax, microcrystalline wax, paraffin wax, etc., and high molecular weight hindered polyhydric phenols, triazine derivatives and the like as antioxidants can be added. For more information, see "Hot Melt Adhesion in Practice" (Hiroshi Fukada, Published by The Society of Polymer Publishing, 1983) 29
On page 107.

Next, the electrophotographic photosensitive member of the electrophotographic member to be provided with the transfer layer will be described. As a photoreceptor,
Any conventionally known one can be used. It is important that the surface of the provided photoreceptor (or the uppermost layer of the photoreceptor) be formed so that the transfer layer provided in the transfer device on the photoreceptor can be easily peeled off later. That is, the releasability is given to the surface of the body.

Examples of the photoreceptor having a releasable surface include a photoreceptor using amorphous silicon as a photoconductor. In the case where another photoconductor is used, an overcoat layer is provided on the photoconductor constituting the photoconductor layer, and a method of imparting peelability to the overcoat layer, or a photoconductive layer (photoconductive layer) is used. (Which may be either a single body layer or a photoconductor laminate) in which the surface of the uppermost layer is modified so as to exhibit releasability.

A method for imparting releasability to the overcoat layer or the uppermost photoconductive layer is to use a polymer containing silicon atoms and / or fluorine atoms as the binder resin of the layer, A method is possible in which a small amount of a block copolymer (a surface uneven distribution type copolymer) containing a polymer segment composed of a fluorine atom-containing polymer component is used together with another binder resin. Further, such a resin containing silicon and / or fluorine atoms can be used in combination in the form of particles.

In particular, when an overcoat layer is provided, since the adhesion between the photoconductor layer and the overcoat layer can be sufficiently maintained, the surface uneven distribution type block used in the present invention can be used. A method using a polymer together is preferred. The above surface uneven distribution type copolymer is usually composed of the overcoat layer whole composition 1
It can be used in combination with another binder resin at a ratio of 0.1 to 20 parts by weight in 00 parts by weight.

Specifically, in a PPC photoreceptor using dry toner, a surface layer is formed on the photoreceptor, which is known as one means for maintaining the durability of the photoreceptor surface against repeated use of the photoreceptor. A method similar to the content of the protective layer in the method of providing and protecting can be used. For example, techniques relating to a protective layer using a silicone-based block copolymer include JP-A-61-95358, JP-A-55-83049, JP-A-62-87971, JP-A-61-189559, and Kaisho 62-75461
JP-A-62-75461, JP-A-61-1395
No. 56, JP-A-62-139557, JP-A-62-2
No. 08055 and the like. Examples of the protective layer using a fluorine-based block copolymer include JP-A-61-116362 and JP-A-61-117.
No. 563, JP-A-61-270768 and JP-A-62-270.
No. 14,657 and the like. Further, as a protective layer using a resin containing a fluorine atom-containing polymer component in the form of particles, JP-A-63-249152 discloses a protective layer.
And JP-A-63-221355.

Further, the method of modifying the surface of the uppermost photoconductive layer into a state in which releasability has been developed is described in the case where a so-called dispersion type photoconductor using at least a photoconductor and a binder resin is used. Effectively applied. That is, a block copolymer resin containing, as a block, a polymer segment containing a polymer component containing a fluorine atom and / or a silicon atom in a layer constituting the uppermost layer of the photoconductive layer;
Alternatively, by coexisting at least one of resin particles containing a polymer component containing a silicon atom, these materials are concentrated and migrated to the surface and unevenly distributed, so that the surface can be modified to a peelable surface. Examples of the copolymer and the resin particles are the same as those described in Japanese Patent Application No. 3-249819.

Further, in order to further enhance the uneven distribution of the surface, a polymer segment containing a fluorine atom and / or a silicon atom may be used as a binder resin for the overcoat layer or the photoconductive layer. A block copolymer obtained by bonding at least one kind of polymer segment containing a functional group-containing component with a block can be used. Japanese Patent Application Nos. 3-259430 and 3-2 describe polymer segments containing such heat and / or photocurable group-containing components.
No. 89649 and 3-289648. Alternatively, a light and / or thermosetting resin may be used in combination with the fluorine atom and / or silicon atom containing resin according to the present invention.

In the electrophotographic photoreceptor, in addition to the electrophotographic photoreceptor mainly containing amorphous silicon, the fluorine atom and / or silicon atom of the present invention effective for modifying the surface of the photoreceptor by the above-described method. The polymer containing the polymer component contains the resin [P] and / or the resin particles [L]. When the polymer is a random copolymer, the content of the polymer component containing a fluorine atom and / or a silicon atom is preferably at least 60% by weight or more, more preferably 80% by weight or more of all polymer components. % By weight or more.

More preferably, the polymer contains 50% by weight of a polymer component containing a fluorine atom and / or a silicon atom.
The polymer segment (A) contained above and the fluorine and / or
Alternatively, it is a block copolymer in which a polymer segment (B) containing 0 to 20% by weight of a silicon atom-containing polymer component is bonded by a block. More preferably, the block copolymer comprises at least one polymer component containing at least one light and / or thermosetting functional group in the segment (B) in the block copolymer. is there.

In these block copolymers, it is preferable that the segment (B) does not contain a polymer component containing a fluorine atom and / or a silicon atom at all. In the polymer of the present invention, a block copolymer (polymer having a surface uneven distribution type) containing polymer segments (A) and (B) is used as compared with a random copolymer, so that the releasability of the surface itself is improved. , And the maintenance of the releasability is maintained.

That is, when a coating film is formed by coexisting a small amount of the fluorine-containing and / or silicon-containing resin and / or resin particles of the present invention, the coating film is formed before the drying step after coating.
The resin [P] and the resin particles [L] of the present invention are easily transferred to and concentrated on the surface of the film, and the surface of the film is modified so as to exhibit releasability. As mentioned above, resin [P]
However, when the polymer segment containing a fluorine atom and / or a silicon atom is blocked, the other polymer segment (even if it contains a polymer component containing a fluorine atom and / or a silicon atom) is small. Since the compatibility with the binder resin for forming the film is good, sufficient interaction is performed, and even when forming the coating film of the transfer layer, these resins are
Further transfer to the transfer layer is suppressed or eliminated, and the transfer layer can clearly form and maintain the interface of the photoconductive layer (ie, the anchor effect).

Further, the segment (B) of the block copolymer
By using a polymer containing a curable group therein and crosslinking between the polymers at the time of film formation, the effect that the peelability of the interface between the photoreceptor and the transfer layer is firmly maintained is exhibited. . The polymer may be used as resin particles as described above.
Preferred resin particles [L] are resin particles dispersed in a non-aqueous solvent. Such resin particles contain a polymer segment containing a fluorine atom and / or a silicon atom, and a polymer segment insoluble in the non-aqueous solvent, and a polymer component containing a fluorine atom and / or a silicon atom. Also 20%
The following are those formed by bonding a polymer segment soluble in the non-aqueous solvent.

In the case of the resin particles according to the present invention, transfer and concentration to the surface are carried out by the action of the insolubilized polymer portion. As in the case of the above-mentioned resin, it interacts with the binder resin to perform the effect of the anchor effect. Further, by containing the curable group in the polymer or the binder resin, migration to the transfer layer is eliminated.

Next, the polymer component having a substituent containing a fluorine atom and / or a silicon atom of the present invention will be described. In the present invention, the substituent includes both those incorporated in the polymer main chain of the polymer and those contained as the substituent of the side chain of the polymer. The substituents containing these fluorine atoms and / or silicon atoms, the polymer components containing these, the mode of the polymerization pattern of the block copolymer, and the specific mode of the method of synthesizing the polymer are described in the above resin particles [ A) is the same as described in the polymer component (c) that can be contained in the polymer component (A).

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

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

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

Preferred embodiments of the resin [P] of the present invention as a so-called unevenly distributed copolymer will be described below. That is, in the resin [P], any one may be used as long as the polymer component containing a fluorine atom and / or a silicon atom is composed of blocks. Here, it is composed of blocks.
It means that the polymer has a polymer segment containing 50% by weight or more of a fluorine atom and / or a silicon atom in the polymer.

Next, a preferred embodiment of the resin particles [L] of the present invention will be described. As described above, the resin particles [L] preferably include a fluorine atom and / or silicon atom-containing polymer portion (A) insoluble in a non-aqueous solvent and a fluorine atom and / or silicon atom soluble in the solvent. And a polymer part (B) containing almost no atoms, and the average particle diameter of the particles is minute, not more than 1 μm. Further, the polymer component (A) constituting the insoluble portion of the resin particles may form a crosslinked structure.

As a preferred method for specifically synthesizing the particles [L] as described above, the non-aqueous dispersion polymerization method described for the above-mentioned non-aqueous thermoplastic dispersion particles can be mentioned. The same contents as those described above are included. The non-aqueous solvent used in the production of the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or as a mixture of two or more.

Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol and benzyl alcohol, acetone,
Ketones such as methyl ethyl ketone, cyclohexanone and diethyl ketone; ethers such as diethyl ether, tetrahydrofuran and dioxane; carboxylic esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; hexane, octane, decane, dodecane and tridecane C6-14 aliphatic hydrocarbons such as cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane,
And halogenated hydrocarbons such as trichloroethane. However, the present invention is not limited to the compound examples described above.

By synthesizing the dispersed resin particles by the dispersion polymerization method in these non-aqueous solvent systems, the average particle diameter of the resin particles can be easily reduced to 1 μm or less, and the particle diameter distribution is very narrow and the monodispersed particles are dispersed. It can be. More specifically, a monomer (a) corresponding to the polymer component constituting the block (A) and a monomer (b) corresponding to the polymer component constituting the block (B) are simply The monomer (a) is dissolved in a non-aqueous solvent which becomes insoluble when polymerized, using a peroxide (eg, benzoyl peroxide, lauroyl peroxide, etc.), an azobis compound (eg, azobisisobutyronitrile, azobisiso Heat polymerization may be performed in the presence of a polymerization initiator such as valeronitrile) or an organic metal compound (eg, butyllithium). Alternatively, the polymer [PB] composed of the monomer (a) and the block (B) may be polymerized in the same manner as described above.

Further, the inside of the insolubilized polymer particles of the resin particles [L] of the present invention may have a crosslinked structure.
In order to form these crosslinked structures, any of conventionally known methods can be used. That is, a method of cross-linking a polymer containing the polymer component (A) with various cross-linking agents or curing agents; A method of forming a network structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups, and the polymer component (A) And a polymer containing a component containing a reactive group by a polymerization reaction or a macromolecular reaction.

As the cross-linking agent in the above method, there can be mentioned compounds which are usually used as a cross-linking agent. Specifically, Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents"
Compounds described in Taiseisha (1981), edited by the Society of Polymer Science, “Polymer Data Handbook, Basic Edition”, Baifukan (1986) can be used. For example, an organic silane-based compound (for example, vinyltrimethoxysilane,
Silane coupling agents such as vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc.), polyisocyanate compounds (for example, toluylene diisocyanate) , O-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.), polyol compounds (For example, 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,
1-trimethylolpropane, etc.), polyamine-based compounds (e.g., ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds, and Epoxy resin (for example, “New epoxy resin” edited by Hiroshi Kakiuchi, Shokodo (1985), “Epoxy resin” edited by Kuniyuki Hashimoto
Compounds described in Nikkan Kogyo Shimbun (1969) and the like, melamine resins (for example, compounds described in "Uria Melamine Resin", edited by Ichiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbun (1969)) And poly (meth) acrylate-based compounds (for example, described in "Oligomers" Kodansha (ed. By Ogawara Shin, Takeo Saegusa, Toshinobu Higashimura, published in 1976), Eizo Omori, "functional acrylic resins" Techno System (ed. 1985), etc. Compounds.

The polymerizable functional group of a polyfunctional monomer (hereinafter also referred to as polyfunctional monomer (d)) or a polyfunctional oligomer containing two or more polymerizable functional groups coexisting by the above method. As the group, specifically, CH ₂ ＣＨCH—C
H ₂ —, CH ₂ ＣＨCH—CO—O—, CH ₂ ＣＨCH—,
_{CH 2 = C (CH 3)} -CO-O-, CH (CH 3) =
_{CH-CO-O-, CH 2} = CH-CONH-, CH 2
ＣC (CH ₃ ) —CONH—, CH (CH ₃ ) ＝ CH—
_{CONH, CH 2 = CH-O} -CO-, CH 2 = C (C
_{H 3) -O-CO-, CH} 2 = CH-CH 2 -O-CO
_{-, CH 2 = CH-NHCO-} , CH 2 = CH-CH 2
_{-NHCO-, CH 2 = CH-SO} 2 -, CH 2 = CH
—CO—, CH ₂ ＣＨCH—O—, CH ₂ ＣＨCH—S— and the like can be mentioned. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

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

Examples of the monomer or oligomer having a different polymerizable functional group include carboxylic acids having a vinyl group (for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, allyloyl). A reactant of propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic anhydride, etc. with an alcohol or an amine (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropion) Ester derivatives or amide derivatives containing a vinyl group such as an acid or the like (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate,
Allyl methacrylate, allyl acrylate, alli itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate,
Methacrylic acid vinyloxycarbonyl methyl ester,
Acrylic acid vinyloxycarbonylmethyloxycarbonyl ethylene ester, N-allylacrylamide, N
-Allyl methacrylamide, N-allyl itaconamide, methacryloyl propionic allyl amide, etc.) or amino alcohols (eg, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and vinyl And condensates with carboxylic acids containing groups.

The monomer or oligomer having two or more polymerizable functional groups used in the present invention may be a monomer (a)
And 1 to the total amount of the monomer and other monomers coexisting therewith.
Polymerized using 0 mol% or less, preferably 5 mol% or less,
Form a resin. Furthermore, when a chemical bond is formed by the reaction of reactive groups between polymers in the above-mentioned method to form a bridge between the polymers, the reaction can be performed in the same manner as the reaction of a normal organic low-molecular compound. .

In the dispersion polymerization, monodisperse particles having a uniform particle diameter are obtained, and fine particles having a particle size of 0.5 μm or less are easily obtained. The method using a monomer is preferred. That is, the polymer (P) is mixed with the above-mentioned monomer (a), monomer (b) and / or polymer [PB] to carry out a polymerization granulation reaction. can do.
Further, the polymer [P
When B] is used, the polymer [PB] has a polymerizable double bond group copolymerizable with the monomer (a) at a side chain or one end of the main chain in the polymer main chain. Polymer [PB ']
Is preferred.

The polymerizable double bond group may be any as long as it has a copolymerization with the monomer (a) as described above. As a specific example, CH ₂ ＣC (q)- COO-, C
_{(CH 3) H = CH-} COO-, CH 2 = C (CH 2 C
_{OOH) -COO-, CH 2 = C} (q) -CONH-,
_{CH 2 = C (q) -CONHCOO-} , CH 2 = C
(Q) -CONHCONH-, C (CH 3) H = CH-
_{CONH-, CH 2 = CHCO-, CH} 2 = CH (CH
_{2) g} -OCO- _(g is 0 or an integer of 1 to 3), CH _{2
= CHO-, CH 2 = CH-} C 6 H 4 - ( represent where q is -H or -CH ₃₎ the like.

These polymerizable groups may be directly bonded to the polymer chain, or may be bonded via another divalent organic residue. Specific examples of these polymers are described in, for example, JP-A-61-43775, JP-A-1-257969,
2-74958, 1-282566, 2-1
No. 73667, No. 3-15862, Japanese Patent Application No. 2-177
No. 449 or the like.

The total amount of the polymerizable compound is about 5 to 8 parts by weight based on 100 parts by weight of the non-aqueous solvent, preferably 10 to 10 parts by weight.
50 parts by weight. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compound. The polymerization temperature is 30
To 180 ° C, preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours. Next, a case where a light and / or thermosetting group is contained in the binder resin [P] of the present invention as a polymer component or in combination with the resin [P] as the curable group-containing resin. explain.

Examples of the polymer component containing at least one light and / or thermosetting group which can be contained in the binder resin [P] include those described in the above-mentioned known documents. Possible, more specifically, for example, the same as those described above as the polymerizable functional group. The polymer component containing at least one kind of light and / or curable group contained in these polymers is 1 in 100 parts by weight of the polymer segment [B] of the block copolymer [P].
９５95 parts by weight, preferably 10-70 parts by weight. Further, the total amount of the polymerization components of the entire copolymer [P] is 1
It is preferable to contain 5 to 40 parts by weight based on 00 parts by weight.

When the content is less than the lower limit of the content, the curing after the formation of the photoconductive layer does not proceed sufficiently, and the retention of the film interface with the surface of the photoconductive layer during coating of the transfer layer becomes insufficient.
It adversely affects the peelability of the transfer layer. On the other hand, when the content is more than the upper limit, the electrophotographic characteristics of the binder resin of the photoconductive layer are deteriorated, and the reproducibility of the copied image document is reduced, and the occurrence of background fog in the non-image portion is caused. Occurs.

The light and / or thermosetting group-containing block copolymer [P] is used in an amount of 40 parts by weight based on 100 parts by weight of the total binder resin.
It is preferable to use it by weight% or more. When the resin [P] is 40
If the amount is less than% by weight, the electrophotographic characteristics are deteriorated. Further, in the present invention, a light and / or thermosetting resin [D] together with the above-mentioned fluorine atom and / or silicon atom containing resin is used.
May be used in combination. The light and / or thermosetting group contained in the resin [D] may be any, and specific examples thereof include those having the same content as the curable group contained in the above-described block copolymer.

The light and / or thermosetting resin [D] may be any of conventionally known curable resins.
Examples of the resin include the same functional group-containing resin as the curable group described for the block copolymer [P] of the present invention. These conventionally known binder resins for an electrophotographic photosensitive layer are described, for example, in Ryuji Shibata and Jiro Ishiwatari, Polymer, Vol. 17, No. 278.
Page (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8), Koichi Nakamura, Ed. M. C. Publishing (1
985), edited by the Society of Electrophotography, "Presentation Symposium on Organic Photoreceptors for Electrophotography" (1985), edited by Hiroshi Komon, "Recent development and commercialization of photoconductive materials and photoreceptors", Japan Science Information Co., Ltd. (1986), edited by the Society of Electrophotographic Engineers, “Basics and Application of Electrophotographic Technology,” Chapter 5, Corona Corporation (1988)
Year), D. Tatt, S.M. C. Heidecker, Tappi, 4
9 (No. 10), 439 (1966); S. Bal
tazzi, R.A. G. FIG. Blanclotte et al, Phot. Sci.
Eng. 16 (No. 5), 354 (1972), Nguyen Chan K, Isamu Shimizu, Eiichi Inoue, Journal of the Institute of Electrophotographic Photography 1
8 (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, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers Polymer, acrylate polymer and copolymer, methacrylate polymer and copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, itaconic diester polymer and copolymer , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymer, hydroxyl-modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylate copolymer, ring Rubber-acrylate copolymer, a copolymer containing a nitrogen-free heterocycle (for example, as a heterocycle, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, a benzofuran ring, Benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy resin and the like.

More specifically, Tsuyoshi Endo, "Refinement of Thermosetting Polymer" (CMC Co., Ltd., 1986), Yuji Harasaki, "Handbook of the Latest Binder Technology", Chapter II-1 ( General Technology Center, 1985), Takayuki Otsu "Synthesis and Design of Acrylic Resins and Development of New Applications" (Chubu Management Development Center Publishing Division, 1985), Eizo Omori "Functional Acrylic Resins" (Techno Systems, 1985), etc. Conventionally known resins cited in the general review are used.

As described above, in the present invention, the overcoat layer or the photoconductive layer contains at least one or more types of the binder resin [B] and the block copolymer [P] for the surface boundary, respectively. It is preferable that a small amount of a light and / or thermosetting resin [D] and / or a crosslinking agent coexist to improve the curing of the film. The amount used is 0.1 part by weight based on 100 parts by weight of the total amount of the binder resin [B] and the block copolymer [P].
It is preferably from 0.01 to 20% by weight, and more preferably from 0.1 to 15% by weight. If the amount is 0.01% by weight or less, the effect of improving the hardening of the film is diminished. On the other hand, if it exceeds 20% by weight, it adversely affects the electrophotographic properties.

It is preferable to use a crosslinking agent in combination.
As the cross-linking agent, a compound usually used as a cross-linking agent can be used. Specifically, "Hotbook of Crosslinking Agents", edited by Fuzo Yamashita and Tosuke Kaneko, Taiseisha (1981),
Compounds described in “Polymer Data Handbook Basic Edition”, edited by Optical Branching Society, Baifukan (1986), etc. can be used.

For example, organic silane compounds (for example, vinyltrimethoxysilane, vinyltributoxysilane,
silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropylethoxysilane, etc.), polyisocyanate-based compounds (for example, toluylene diisocyanate, o-toluylene diene) Isocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisoananate, isophorone diisocyanate, polymer polyisocyanate, etc.), polyol compound (for example, 1, 4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine-based compounds (for example, ethylenediamine, γ-hydroxypropyl Ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc., titanate coupling compounds (eg, tetrabutoxytitanate, tetrachlorooxytitanate, isopropyltristearoyl titanate, etc.) aluminum coupling System 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, "Epoxy Resin", edited by Hiroshi Kakiuchi, Shokodo (1985)
Compounds published in Nikkan Kogyo Shimbun (1969), edited by Kuniyuki Hashimoto, etc.), and melamine resins (for example, "Uria Melamine Resin" Nikkan Kogyo Shimbun (1969), edited by Ichiro Miwa and Hideo Matsunaga. Compounds), poly (meth) acrylate-based compounds (for example, “Oligomers” edited by Shin Okawara, Takeo Saegusa, and Toshinobu Higashimura Kodansha (1976), Eizo Omori “Functional acrylic resin” Examples include compounds described in Techno System (published in 1985), etc. Further, monomers having a polyfunctional polymerizable group (eg, vinyl methacrylate, acrylic methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinic acid) Ester, divinyl adipate, diacryl succinate, 2- Chill vinyl methacrylate, trimethylolpropane trimethacrylate, divinylbenzene, pentaerythritol polyacrylate) and the like.

As described above, the uppermost layer of the photoconductive layer of the present invention (the layer adjacent to the transfer release layer in the transfer device) is preferably cured after film formation. The binder resin [B], the block copolymer [P], the curing resin [D], and the cross-linking agent to be provided are preferably used in a combination of functional groups that are easily chemically bonded between polymers. For example, as a polymer reaction by a combination of functional groups, a well-known method can be mentioned, for example, a combination of a functional group of Group A and a functional group of Group B as shown in the following table. However, it is not limited to this.

[0179]

[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. In the case of a reaction mode in which a crosslinking reaction forms a chemical bond between functional groups, for example, organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), phenols (phenol, chlorophenol, Nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc.), organometallic compounds (acetylacetonate zirconium salt,
Acetylacetone zirconium salt, acetylacetocobalt salt, dibutoxytin dilaurate), dithiocarbamic acid compound (diethyldithiocarbamate, etc.),
Tinourum disulfide compounds (such as tetramethyltinouram disulfide), carboxylic anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butyl succinic anhydride, benzophenone dicarboxylic acid 3,3 ', 4,4'-tetracarboxylic acid) Anhydride, trimellitic anhydride, etc.). When the cross-linking reaction is a polymerization reaction mode, a polymerization initiator (a peroxide, an azobis-based compound, or the like) may be used.

The binder resin that can be used in the photoreceptor of the present invention may be any of the resins used in conventionally known electrophotographic photoreceptors, and preferably has a weight average molecular weight of 5 × 10 5
³ to 1 × 10 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10
⁵ things. Further, the glass transition point of the binder resin is preferably from -40 ° C to 200 ° C, more preferably from -10 ° C to
140 ° C. For example, Ryuji Shibata and Jiro Ishiwatari, Polymer, Vol. 17, pp. 278 (1968) Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8) Koichi Nakamura, Ed. Chapter 10, C.I.
H. C. Published (1985) edited by the Society of Electrophotographic Engineers, Preprints of "Current Symposium on Organic Photoconductors for Electrophotography" (1985
Year) edited by Hiroshi Komon, "Recent development and practical application of photoconductive materials and photoreceptors", Japan Scientific Information Co., Ltd. (1986) Ed. (stock)
(1988); Tatt, S.M. C. Heidecker, T
appi, 49 (No. 10), 439 (1966);
S. Baltazzi, R.A. G. FIG. Blanclotte et al, Phot
. Sci. Eng. 16 (No. 5), 354 (197
2), Nguyen Chan K, Isamu Shimizu, Eiichi Inoue, and the compounds described in books and reviews such as Journal of the Institute of Electrographic Photography 18 (No. 2), 22 (1980).

More specifically, olefin polymers and non-polymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Derivatives, polymers and copolymers, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene-unsaturated carboxylic acid ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer Polymer, acrylate polymer and copolymer, methacrylate polymer and copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, itaconic diester polymer and copolymer , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymer, hydroxyl-modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylate copolymer, ring Rubber-acrylate copolymer, a copolymer containing a nitrogen-free heterocycle (for example, as a heterocycle, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, a benzofuran ring, Benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy resin and the like.

In particular, 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, or a phosphono group as a binder resin for the photoconductor, Electrical characteristics can be improved. For example,
Japanese Patent Application Laid-Open No. Sho 63-217354 discloses a resin wherein an acidic group-containing polymer component is randomly present in the polymer main chain.
No. 0761, a resin having an acidic group bonded to one end of a polymer main chain, JP-A-2-67563 and JP-A-2-236.
No. 561, No. 2-238458, No. 2-236562
No. 2-247656 and the like, a resin having an acidic group bonded to the main chain terminal of the graft copolymer or a resin containing an acidic group in the graft portion of the graft copolymer,
An AB type block copolymer containing an acidic group as a block described in JP-A-3-181948 is exemplified. Furthermore, in order to make the mechanical strength of the photoconductive layer insufficient with these low molecular weight resins alone, it is preferable to use other resins of medium to high molecular weight in combination. For example, JP-A-2-685
No. 61, a thermosetting resin forming a crosslinked structure between polymers, JP-A-2-68562, a resin having a partially crosslinked structure, and JP-A-2-69759, a graft type with an acidic group. Resins bonded to the main chain terminals of the copolymer are exemplified. In addition, by using a specific medium to high molecular weight resin, stable performance can be maintained even when the environment fluctuates remarkably.
No. 4, No. 3-77954, No. 3-92961 and No. 3-53257. Resin or acidic group bonding an acidic group to the end of the graft portion of the graft copolymer. Resin contained in graft portion, 3-20
A consisting of an acidic group-containing A block and an acidic group-free B block described in Nos. 6464 and 3-223762.
A graft type copolymer containing a B block type copolymer in a graft portion can be exemplified. By using these specific resins, the photoconductor can be uniformly dispersed, a photoconductive layer having good smoothness can be formed, and a scanning exposure method using a change in environment or semiconductor laser light is used. Even in such a case, excellent electrostatic characteristics can be maintained.

When the binder resin of the present invention contains a photo- and / or thermosetting group, it is preferable that the resin is photo- and / or thermo-cured after the application of the photosensitive layer-forming product. In order to perform thermosetting, for example, the drying conditions are made stricter than the drying conditions at the time of the conventional photoreceptor production. For example, the drying conditions are high temperature and / or long time. Alternatively, it is preferable to further perform a heat treatment after drying the coating solvent. For example, 60 ° C ~
Treat at 150 ° C for 5 to 120 minutes. When the above-mentioned reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As a method of curing a specific functional group in the resin of the present invention by light irradiation, a step of light irradiation with “chemically active light” may be included. The “chemically active light” used in the present invention may be any of visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, γ-ray, α-ray, etc., and preferably includes ultraviolet light. More preferably, it can emit light in the wavelength range of 310 nm to 500 nm. In general, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, halogen lamp, or the like is used. Light irradiation processing is usually performed for 10 seconds to 1 from a distance of 5 cm to 50 cm.
Irradiation for 0 minutes is sufficient.

The constitution and material of the electrophotographic photosensitive member provided in the present invention may be any of conventionally known ones, and are not limited. Examples of photoconductors include “Basics and Application of Electrophotographic Technology” (edited by the Electrophotographic Society of Japan) (Corona Publishing Co., Ltd. (1988)), and Hiroshi Komon “editing recent developments in photoconductive materials and photoconductors.
Various photoconductors described in "Practical Use" (published by Nippon Scientific Information Co., Ltd., 1985).

That is, a single layer composed of the photoconductive compound itself or a photoconductive layer in which the photoconductive compound is dispersed in a binder resin may be mentioned. The dispersed photoconductive layer may be a single layer type, It may be a stacked 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 conventionally known inorganic photoconductive compounds such as zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, selenium, selenium-tellurium, and silicon lead sulfide.

When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used as the photoconductive compound, the binder resin is used in an amount of 10 to 1 based on 100 parts by weight of the inorganic photoconductive compound.
It is used in a proportion of 00 parts by weight, preferably in a proportion of 15 to 40 parts by weight. On the other hand, as the organic compound, any of conventionally known compounds may be used.
No. 17162, No. 62-51462, JP-A-52-2
Nos. 437, 54-19803, 56-107246
And a photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye, and a binding resin as described in JP-A-57-161863 and the like.
146145, 60-17775, 60-1
No. 7752, No. 60-17760, No. 60-2541
No. 42, those having a photoconductive layer mainly comprising a charge generating agent, a charge transporting agent and a binding resin as described in JP-A Nos. 62-54266, and JP-A-60-230147;
As described in JP-A-60-230148 and JP-A-60-2388853, a two-layered photoconductive layer containing a charge generating agent and a charge transporting agent in separate layers is also known.

The electrophotographic photoreceptor of the present invention may take any of the above two types of photoconductive layers. In the case of the second example, the organic photoconductive compound according to the present invention functions as a charge transport agent. Examples of the organic photoconductive compound in the present invention include (a) a triazole derivative described in U.S. Pat. No. 3,121,197, (b) an oxadiazole derivative described in U.S. Pat. No. 3,189,447, and (c) Imidazole derivatives described in JP-B-37-16096, (d) U.S. Pat. No. 3,615,402.
Nos. 3,820,899, 3,542,544, JP-B-45-555, JP-B-51-10983, JP-A-51-93224, and JP-A-55-108667.
Polyarylalkane derivatives described in JP-A-55-156953 and JP-A-56-36656, (e) U.S. Pat. Nos. 3,180,729 and 4,278,746, JP-A-55-88064, and JP-A-55-88064. -88065
No. 49-105537, No. 55-51086,
Nos. 56-80051, 56-88141, 57
No. 45545, No. 54-112637, No. 55-7
No. 4546, pyrazoline derivatives and pyrazolone derivatives, (f) U.S. Pat. No. 3,615,404, JP-B-51-10105, JP-B-46-3712,
Nos. 47-28336 and JP-A-54-83435.
Phenylenediamine derivatives described in JP-A Nos. 54-1110836 and 54-119925, and (g) U.S. Pat. Nos. 3,567,450, 3,180,703, and 3
240597, 3658520, 423210
Nos. 3, 417,961 and 401,376, JP-B-49-35702, and the West German patent (DA
S) No. 1110518, JP-B-39-2775
7, JP-A-55-144250 and JP-A-56-1191.
Nos. 32 and 56-22437, and the arylamine derivatives described in (h) U.S. Pat.
No. 501, etc., amino-substituted chalcone derivatives,
(I) N, N-bicarbazyl derivatives described in U.S. Pat. No. 3,542,546 and the like; (i) U.S. Pat.
An oxazole derivative described in No. 7203, etc.,
(K) styryl anthracene derivatives described in JP-A-56-46234 and the like; (l) JP-A-54-11083
7, fluorenone derivatives, (m) U.S. Pat. No. 3,717,462, JP-A-54-59143 (corresponding to U.S. Pat. No. 4,150,987), JP-A-55-52063, and JP-A-55-52063. -52064, 5
5-46760, 55-85495, 57-1
No. 1350, No. 57-148749, No. 57-104
No. 144 hydrazone derivatives,
(N) U.S. Pat.
Nos. 4,265,990, 4,273,846, 42
No. 99897, No. 4306008 and the like, and benzidine derivatives described in (o) JP-A-58-190953.
No. 59-95540, No. 59-97148, No. 59-195658, No. 62-36674 and the like.
JP-A-4-10966, polyvinyl carbazole and derivatives thereof, (q) JP-B-43-18874 and JP-B-43-18874.
No. 3-19192, polyvinyl pyrene, polyvinyl anthracene, poly-2-vinyl-4- (4′-
Vinyl polymers such as (dimethylaminophenyl) -5-phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole; and (r) polyacenaphthylene, polyindene, and a copolymer of acenaphthylene and styrene described in JP-B-43-19193. Polymers such as polymers, (s)
Condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin described in 3940 Publication
(T) JP-A-56-90833 and 56-16155
No. 0 publications.

In the present invention, the organic photoconductive compound is not limited to the compounds listed in (a) to (t).
All known organic photoconductive compounds can be used. These organic photoconductive compounds may optionally be 2
More than one kind can be used together. As the sensitizing dye contained in the photoconductive layer of the first example, a conventionally known sensitizing dye used in an electrophotographic photoreceptor can be used. These are "electrophotographic" 12 9 (1973), "Synthetic Organic Chemistry" 24 (11), have been described in 1010 (1966) and the like. For example, U.S. Pat.
Each specification No. 83475, JP-48-25658, JP-pyrylium dyes described in JP-62-71965 Patent Publication, Applied Optics Supplement 3 50 (1
969), triarylmethane dyes described in JP-A-50-39548 and the like, cyanine dyes described in U.S. Pat. No. 3,597,196 and the like, and JP-A-60-163.
No. 047, No. 59-164588, No. 60-2525
Styryl dyes described in JP-A No. 17 and each publication are advantageously used.

As the charge generating agent contained in the photoconductive layer of the second example, various organic and inorganic charge generating agents conventionally known in an electrophotographic photosensitive member can be used. For example, selenium, selenium-tellurium, cadmium sulfide, zinc oxide, and the following organic pigments (1) to (9) can be used. (1) U.S. Pat. Nos. 4,436,800 and 4,439,506
JP-A-47-37543, JP-A-58-12
No. 3541, No. 58-192042, No. 58-219
No. 263, No. 59-78356, No. 60-17974
No. 6, No. 61-148453, No. 61-238063
Nos., JP-B-60-5941, JP-B-60-4566.
No. 4, azo pigments such as monoazo, bisazo and trisazo pigments described in each publication, and (2) US Pat.
Nos. 86 and 4666802, JP-A-51-9
Phthalocyanine pigments such as metal-free or metal phthalocyanines described in JP-A-0827 and JP-A-52-55643; (3) perylene-based pigments described in U.S. Pat. No. 3,371,884 and JP-A-47-30330;
(4) UK Patent No. 2237680, JP-A-47
Indigo and thioindigo derivatives described in JP-A-3030331 and the like; (5) Quinaclindone pigments described in British Patent No. 2237679, JP-A-47-30332 and the like; (6) British Patent No. 2237678 And JP-A-59-184348, JP-A-62-28738, and JP-A-42-28738.
Polycyclic quinone-based pigments described in JP-A-7-18544,
(7) JP-A-47-30331 and JP-A-47-18543.
Bisbenzimidazole pigments described in each publication,
(8) U.S. Pat. Nos. 4,396,610 and 4,644,082
And squarium salt pigments described in the specifications of the above-mentioned publications, and (9) azurenium salt pigments described in JP-A-59-53850 and JP-A-61-212542. These can be used alone or in combination of two or more.

The upper limit of the content ratio of the organic photoconductive compound is determined by the compatibility between the organic photoconductive compound and the binding resin. 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 that as much organic photoconductive compound as possible is contained as long as crystallization of the organic photoconductive compound does not occur. The content of the organic photoconductive compound is 5 to 120 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the binder resin. The organic photoconductive compounds can be used alone or in combination of two or more.

The thickness of the photoconductive layer is 1 to 100 μm, especially 1
0 to 50μ is preferred. Further, when a photoconductive layer is used as a charge generation layer of a laminate type photoreceptor having a charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.01 to 5 μm, particularly,
0.05 to 2μ is preferred. In the present invention, various dyes can be used in combination as a spectral sensitizer, if necessary, depending on the type of light source such as exposure to visible light or exposure to semiconductor laser light. For example, Harumi Miyamoto, Hidehiko Takei; Imaging
1973 (No. 8) p. 12, C.I. J. Youung et al .: R
CA Review 15 , p. 469 (1954), Kohei Kiyota: Transactions of the Institute of Telecommunications, J63-C (No. 2),
97 pages (1980), Yuji Harasaki et al., Industrial Chemistry Magazine, 6
6 , 78 and 188 (1963), Tadaaki Tani, Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes, as described in the review articles of Photographic Society of Japan 35 , 208 (1972). And polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, and the like), and phthalocyanine dyes (which may contain a metal).

More specifically, the following are mainly used: carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes.
No. 2, JP-A-50-90334 and JP-A-50-11422
7, Nos. 53-39130 and 53-82353, U.S. Pat. Nos. 3,052,540 and 4,054,450.
And those described in JP-A-57-16456 and the like.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes include those described in F.I. M. Harmmer "The Cyanine Dyes and
The dyes described in "Related Compounds" and the like can be used, and more specifically, US Pat. No. 3,047,384,
No. 3110591, No. 312008, No. 3125
No. 447, No. 3128179, No. 3132942,
No. 3,622,317, British Patent No. 122689
2, 1309274 and 1405898, JP-B-48-7814, and 55-18892.

Further, a long-wavelength near-infrared ray of 700 nm or more
Examples of polymethine dyes that spectrally sensitize the infrared region include JP-A-47-840 and JP-A-47-44180, and JP-B-51-440.
No. 41061, No. 49-5034, No. 49-4512
No. 2, No. 57-46245, No. 56-35141,
No. 57-157254, No. 61-26044, No. 6
Nos. 1-27551 and U.S. Pat. No. 3,619,154.
No. 4,175,956, "Research Discl"
osure ", 1982, 216, pp. 117-118.

The photoreceptor of the present invention is also excellent in that even if various sensitizing dyes are used in combination, the performance is hardly changed by the sensitizing dye. Further, if necessary, various conventionally known additives for electrophotographic photosensitive members can be used in combination. These additives include a chemical sensitizer for improving electrophotographic sensitivity, various plasticizers for improving film properties, and a surfactant.

Examples of the chemical sensitizer include halogen, benzoquinone, chloranyl, fluoranyl, promanyl,
Electron withdrawing compounds such as dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, 2,3-dichloro-5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone, and tetracyanoethylene , Hiroshi Komon et al. “Recent development and commercialization of photoconductive materials and photoconductors” No. 4
Chapters-Chapter 6: Japan Science Information Publishing Co., Ltd. (1986)
Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like described in the above-mentioned References can be used. Also, JP-A-58-65439 and JP-A-58-65439.
Nos. -102239, 58-129439, 62-
Compounds described in each of JP-A-71965 and the like can also be mentioned.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl glycolate, dimethyl glycol Phthalate or the like can be added to improve the flexibility of the photoconductive layer. These plasticizers can be contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer.

The amount of these various additives is not particularly limited, but is usually 0.0
01 to 2.0 parts by weight. The photoconductive layer according to the present invention,
It can be provided on a conventionally known support. Generally , it is preferable that the support of the electrophotographic photosensitive layer is conductive. As the conductive support, a low-resistance substance is formed on a substrate such as a metal, paper, or a plastic sheet in the same manner as in the related art. A substrate subjected to conductive treatment by impregnation or the like, a substrate coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (opposite to the surface on which the photosensitive layer is provided) and further preventing curling, A substrate provided with a water-resistant adhesive layer on the surface of the support, a substrate provided with at least one or more pre-coat layers as required on the surface layer of the support, and a substrate conductive plastic on which Al or the like is deposited is laminated on paper. Can be used.

Specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14 (No. 1),
2-11 (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing Association (1975); F. Hoove
r, J.S. Madromol. Sci. Chem. A-4 (6), 1
Those described in pages 327 to 1417 (1970) and the like are used.

As the developer used in the present invention, conventionally known developers for electrophotography can be used, and any of a dry developer for electrophotography and a liquid developer may be used. For example, the aforementioned “Basics and Application of Electrophotographic Technology”, pp. 497-505, edited by Koichi Nakamura, “Development and Practical Use of Toner Materials”, Chapter 3 (Nippon Kagaku Kagaku Co., 1985), Moto Machida, “Recording Materials And photosensitive resin ", pp. 107-127 (1983), Co., Ltd.
Society Publishing Center, Electrophotographic Society “Imaging No.
2-5 Development / Fixation / Electrification / Transfer of Electrophotography "and the like.

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

[0204] As the basic structure of the material of a specific liquid toner, electrically insulating organic solvent {e.g. isoparaffinic aliphatic hydrocarbon: A b Sopa H, Isopar G (manufactured by Esso Co.) Shellsol 70, Shellsol Sol 71 (manufactured by Shell Co., Ltd.), IP-solvent 1620 (manufactured by Idemitsu Petrochemical) or the like 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, a styrene butadiene resin, It is made by dispersing a resin for imparting dispersion stability, fixing property and chargeability such as rosin, and adding various additives as required to enhance charge properties or improve image properties. is there.

As the coloring agent, known dyes and pigments are arbitrarily selected. For example, benzidine-based, azo-based,
Dyes or pigments such as azomethine, xanthene, anthraquinone, phthalocyanine (including metals), titanium white, nigrosine, aniline black and carbon black. As other additives, those specifically described in, for example, Yuji Harasaki, “Electrophotography,” Vol. 16, No. 2, page 44 can be used. For example,
2-ethylhexylsulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, alkylbenzenesulfonic acid metal salt, alkylphosphate metal salt, lecithin, poly (vinylpyrrolidone), copolymer containing a maleic acid amide component, Malon indene resins, higher alcohols, polyethers, polysiloxanes, waxes and the like. However, it is not limited to these.

The amounts of the main components of these wet developers are usually as follows. The toner particles mainly composed of a resin (and a coloring agent optionally used)
The amount is preferably 0.5 to 50 parts by weight based on 1000 parts by weight of the carrier liquid. If the amount is less than 0.5 parts by weight, the image density becomes insufficient, and if it exceeds 50 parts by weight, fogging to a non-image portion is apt to occur. Further, the carrier liquid soluble resin for dispersion stabilization is also used as needed, and can be added in an amount of about 0.5 to 100 parts by weight based on 1000 parts by weight of the carrier liquid. The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 part by weight based on 1,000 parts by weight of the carrier liquid. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electric resistance of the developer. That is, if the electric resistance of the liquid developer from which the toner particles have been removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a continuous tone image of good quality. ing.

A specific example of a method for producing a wet developer is a method for producing colored particles by mechanically dispersing a colorant and a resin using a disperser such as a sand mill, a ball mill, a jet mill, or an attritor. However, for example, Japanese Patent Publication No. 35-5
No. 511, Japanese Patent Publication No. 35-13424, Japanese Patent Publication No. 50-4
No. 0017, JP-B-49-98634, JP-B-58-
129438 and JP-A-61-180248.

As another method for producing the colored particles, for example, a method in which the dispersed resin particles are produced using a non-aqueous dispersion polymerization method for obtaining fine particles having good monodispersity and coloring the resin particles is used. No. As one of the coloring methods, there is a method of dyeing a dispersion resin with a preferable dye as described in JP-A-57-48738. As another method, a method of chemically bonding a dispersing resin and a dye as disclosed in JP-A-53-54029, or a method of polymerizing as described in JP-B-44-22955 and the like. When producing by a granulation method, there is a method of using a monomer containing a dye in advance to form a dye-containing copolymer.

As the transfer material used in the present invention, a support conventionally used for an offset printing plate can be used as it is. Specifically, a bimetal plate such as a plastic sheet or paper particularly subjected to printing durability, aluminum, a plate, a zinc plate, a copper-aluminum plate, a copper-stainless plate, a chromium-copper plate, a chromium-copper-aluminum plate, a chromium -Lead-iron plate,
A substrate having a hydrophilic surface such as a trimetal plate such as a chromium-copper-stainless plate is used.
mm, particularly preferably 0.1 to 1 mm.

In the case of a support having an aluminum surface, a surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodic oxidation treatment is performed. Is preferred. Also, as described in U.S. Pat. No. 2,714,066, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate is disclosed in
As described in JP-A-7-5125, an aluminum plate that has been subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is also preferably used.

In the anodizing treatment, for example, an aqueous solution or a non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof may be used alone or in combination. It is carried out by flowing a current in the combined electrolyte using the aluminum plate as an anode. Also, silicate electrodeposition as described in U.S. Pat. No. 3,658,662 is effective. The treatment with polyvinyl sulfonic acid described in West German Patent Publication No. 1,621,478 is also suitable.

These hydrophilic treatments are carried out to improve the adhesion to the toner image provided thereon, except that the surface of the support is made hydrophilic. . Further, in order to adjust the adhesion between the support and the transfer layer having the toner image formed thereon, a surface layer may be provided on the surface of the support to improve the characteristics. When a plastic sheet or paper is used as a support, it is a matter of course that a material provided with a surface layer having hydrophilicity is provided because the portions other than the toner image portion layer must be hydrophilic. Specifically, a known original plate for direct drawing type lithographic printing or a transfer material having the same content as the image receiving layer of the original plate can be used.

As a method of preparing the printing plate of the present invention,
First, a copy image is formed on a photosensitive material having the transfer layer through a normal electrophotographic process. That is, each process of charging-exposure-development-fixing is performed by a conventionally known method. As the developer to be subjected to the developing process, any conventionally known developer may be used, and examples thereof include a dry developer and a liquid developer.

More preferably, a combination of a scanning exposure method using a laser beam for exposing based on digital information and a development 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 a flat bed by a register pin method, and then suctioned and fixed by air suction from the back surface. Next, the photosensitive material is charged by a charging device described on page 212 et seq. Of, for example, "Basics and Application of Electrophotographic Technology" (edited by the Society of Electrophotographic Engineers, Corona, published on June 15, 1988). The corotron or scotron system is common. At this time, it is also preferable to control the charging conditions by applying feedback based on the information from the charging potential detecting means of the photosensitive material so that the surface potential always falls within a predetermined range.

Thereafter, for example, 254 of the above cited document is also used.
Scanning exposure with a laser light source is performed by using the method described on and after the page. Next, a toner image is formed using a liquid developer. The photosensitive material charged and exposed on the flatbed can be removed therefrom and used by the direct wet developing method shown on pages 275 et seq. The exposure mode at this time is performed according to the toner image development mode,
For example, in the case of reversal development, a negative image, that is, a laser beam is irradiated to the image area, and a toner having the same charge polarity as that when the photosensitive material is charged is used. To be electrodeposited. Details of the principle are described on page 157 et seq.

In order to remove excess developer after development, squeezing is performed as shown on page 283 of the same document, followed by drying. It is also preferable to rinse only the carrier liquid of the developer before squeezing. Next, the toner image on the photosensitive material is thermally transferred together with the transfer layer to the transfer material. FIG. 2 shows an example of an apparatus for thermally transferring a transfer layer to a material to be transferred.

This is driven while applying a predetermined nip pressure between a pair of rubber-coated metal rollers 4 built in the heating means 5. At this time, the surface temperature of the roller 4 is preferably 50 to 150 ° C, more preferably 80 to 120 ° C.
° C, nip pressure between rollers is preferably 0.2-20
kgf / cm ² , more preferably 0.5 to ¹⁰ kgf /
cm ² , transport speed is preferably 0.1 to 100 mm
/ Sec, more preferably in the range of 1 to 30 mm / sec.
It is natural that these conditions are optimized depending on the physical properties of the photosensitive material used, that is, the materials of the release layer, the photosensitive layer, and the support.

It is preferable that the surface temperature of the roller 4 is kept within a predetermined range by the known surface temperature detecting means 6 and the temperature controller 7. Further, a preheating means for the photosensitive material may be provided before the heating roller portion, and a cooling means after the heating roller portion.
Although not shown in FIG. 2, as an inter-roller pressurizing unit, a spring or an air cylinder using compressed air at both ends of a shaft of at least one roller can be used.

In the present invention, as described in claim 2,
In an apparatus for performing an electrophotographic process, a thermoplastic resin having the resin [A] of the present invention as a main component was coated with an adhesive force of 200 g.
It is preferable to form a transfer layer on an electrophotographic photosensitive member having a surface of f or less. This makes it possible to repeatedly use the electrophotographic photoreceptor in the apparatus, so that the electrophotographic process can be continuously performed without disposing the photoreceptor. As a result, there is an advantage that the cost of the printing plate to be produced can be significantly reduced.

To form a transfer layer on the surface of a photoreceptor in an apparatus for performing an electrophotographic process, a "hot melt" system, a "release paper transfer" system, or an "electrodeposition" system is effective. The "hot-melt" method is to apply a hot-melt coating to the transfer layer composition by a known method.
The mechanism of the hot-melt adhesive hot-melt coating apparatus (hot-melt coater) described on page 15 can be diverted to a photosensitive drum coating specification. Examples include direct roll coaters, offset gravure roll coaters, lot coaters, extrusion coaters, slot orifice coaters, curtain coaters, and the like.

The film thickness of the release transfer layer is suitably from 0.1 to 20 μm, and more preferably from 0.5 to 10 μm. If the film thickness is too thin, transfer failure tends to occur. If the film thickness is too thick, troubles in the electrophotographic process are liable to occur, and sufficient image density cannot be obtained or image quality tends to deteriorate. The melting temperature of the thermoplastic resin at the time of application is optimized depending on the component composition of the thermoplastic resin to be used.
It is in the range of 80 ° C. It is desirable that the preheating is performed using a sealed preheating device having an automatic temperature control means, and then the temperature is raised to an appropriate temperature in a short time at a position where the photoconductor is coated. By doing so, it is possible to prevent deterioration and coating unevenness due to thermal oxidation of the thermoplastic resin.

The coating speed depends on the fluidity of the thermoplastic resin at the time of thermal melting, the coater method, the amount of coating, and the like.
mm / sec is appropriate, and more preferably 5 to 40 mm / sec.
Range of seconds. FIG. 3 is a schematic diagram of an electrophotographic printing plate making apparatus using a method of forming a transfer layer on a photoreceptor by a melt coating (hot melt) method in the apparatus.

The thermoplastic resin 12a is applied by, for example, the hot melt coater 13 to the surface of the photosensitive member 11 on the peripheral surface of the drum, and is cooled to a predetermined temperature by passing under the suction / exhaust unit 15. Hot melt coater 13
After moving to the standby position 13a, the liquid developing unit 14 is moved to that position. This unit 14 comprises a developing device containing a liquid developer. Each of them may be provided with a pre-bath, a rinsing, and a squeezing means in order to prevent the non-image portion from being stained as necessary. As the pre-bath and the rinsing liquid, a carrier liquid of a wet developer is usually used.

The photoreceptor 11, on which the transfer layer 12 made of a thermoplastic resin is formed, then enters an electrophotographic process. The photoreceptor 11 is charged uniformly, for example, positively by a corona charging device 18 and then exposed to light (for example, a semiconductor laser) 1.
When the image is exposed based on the image information in step 9, the potential of the exposed portion is reduced, and a potential contrast is obtained between the exposed portion and the unexposed portion. A developing unit set 14 containing a wet developer dispersed in an electrically insulating dispersion medium having a positive electrostatic charge is brought close to the photosensitive member surface 11 to fix the gap at 1 mm.

First, the photosensitive member 11 is pre-bused by a pre-bus means provided in the developing section. Then, a wet bias is applied to the photosensitive member 11 by applying a developing bias voltage between the photosensitive member and the developing electrode by a bias power supply and an electric connection (not shown). A developer is supplied to the surface of the photoconductor. The bias voltage at this time is connected so that the developing electrode side is positive and the photoconductor side is negative, and the applied voltage is slightly lower than the surface potential of the unexposed portion. If the applied voltage is too low, a sufficient toner image density cannot be obtained.

Thereafter, the developing solution adhering to the surface of the photoreceptor is washed away by a rinsing means built in the developing unit 14, and the rinsing liquid adhering to the surface of the photoreceptor is removed by a squeezing means. Dry by passing through. During this time, the thermal transfer means 17 is placed away from the photoreceptor surface. After the image is formed on the transfer layer of the photoreceptor, a predetermined preheating is performed by a heating unit 17a for thermal transfer, and a rubber roller 17b containing a heating unit having a temperature control unit is transferred via a transfer target material 16. Then, the toner on the surface of the photoreceptor is thermally transferred to the transfer material 16 together with the transfer layer 12, thereby completing a series of steps. Then, as described below, the transfer layer is removed with a desensitizing solution to obtain a printing plate.

The transfer means 17 for thermally transferring the release layer (transfer layer) 12 to the transfer paper 16 comprises a heating means 17a, a heating roller 17b of a metal covered with a rubber with a built-in heating element, and a cooling roller 17c. The heating means 17a uses a non-contact type, for example, an infrared line heater or a flash heater, and preheats the photosensitive layer to a temperature not exceeding the surface temperature of the photosensitive layer obtained by the heating roller 17b. The heating surface temperature of the photosensitive layer by the heating roller 17b is preferably 50 to
The temperature is 150 ° C, more preferably 80 to 120 ° C.

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

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

By stopping the apparatus while the transfer layer is formed, the electrophotographic process can be started immediately when the next apparatus is operated, and the surface of the photosensitive layer is further protected to prevent deterioration of characteristics due to the influence of the external environment. be able to. It is natural that the above-mentioned condition settings are optimized according to the physical properties of the photoreceptor used, that is, the transfer layer, the photosensitive layer and the support, and the material of the transfer paper. In particular, the preheating, roller heating, and cooling conditions in the thermal transfer process are the glass transition point of the transfer layer,
It is necessary to determine in consideration of factors such as softening temperature, fluidity, adhesiveness, film properties, and film thickness. That is, when the transfer layer softened to some extent by the preheating means passes under the heating roller, the adhesiveness increases and the transfer layer adheres to the transfer paper. Then, after passing under the cooling roller, the conditions should be set so that the temperature drops, the fluidity and the tackiness are reduced, and the toner is peeled off from the photosensitive layer surface with the toner adhered to the transfer layer as a film. It is.

Next, the "release paper transfer" system, which is another embodiment of the electrophotographic plate-making and printing original plate producing apparatus which can be used in the present invention, will be described. According to the "release paper transfer" method, a transfer layer is previously formed on a release paper by hot melt coating, solvent coating, latex electrodeposition, etc., and then the transfer layer is thermally transferred to the photosensitive material surface, and an electrophotographic toner image is formed thereon. After the transfer, the transfer layer is thermally transferred to the transfer-receiving material on the releasable surface, and then the transfer layer is removed with a desensitizing solution to form a printing plate.

The release paper having the release layer formed thereon is in the form of a roll,
It can be easily supplied to an electrophotographic plate-making and printing plate making apparatus in sheet form. Any conventionally known release paper can be used for this method. For example, a new adhesive (adhesive) technology and its use / development materials of various applied products (published by the Management Development Center Publishing Department, May 20, 1983), all paper guides, such as the product encyclopedia, Volume 1, Cultural Industries (published by Paper Industry Times, December 1, 1983) No. Specifically, the release paper was made of a release agent mainly composed of silicone, unbleached clupak paper laminated with polyethylene resin, high-grade paper pre-coated with a solvent-resistant resin, kraft paper, and undercoated. PET base or directly applied to glassine paper.

In general, a solvent type silicone is used. The silicone is applied at a concentration of 3 to 7% by a gravure roll or wire bar method, dried, and then heat-treated at 150 ° C. or more to be cured. The coating amount is about 1 g / m ² . Those commercially available from paper manufacturers for tapes, labels, for the forming industry and for the cast coat industry can be used. For example, Separate Paper (Oji Paper), King Leeds (Shikoku Paper), Sun Release (Sanyo Kokusaku Pulp), NK
High release (Nippon Kogyo Paper) and the like.

As an apparatus for easily forming a transfer layer using a release paper on a photoreceptor, there is, for example, a schematic one shown in FIG. That is, the transfer layer 1 containing the resin [A]
The release paper 10 provided with 2 is heated and pressed by a heating roller 17 b to transfer the transfer layer 12 to the surface of the photoconductor 11. The release paper 10 is cooled and collected by the cooling roller 17c. Further, if necessary, the photoreceptor 11 itself may be heated by the preheating means 17a to improve the transferability of the transfer layer 12 by thermocompression bonding.

The apparatus shown in FIG. 4 has basically the same configuration as that of the above-described hot-melt type apparatus (FIG. 3) except for a portion 117 where the transfer layer 12 is formed on the photoconductor 11.
In the part 117 of FIG.
2 is transferred onto the photoconductor 11 and then a toner image is formed by an electrophotographic process.
May be used in place of the portion 17 having
0 to transfer the transfer layer 12 onto the photoreceptor 11;
Both portions for transferring the transfer layer 12 on which the toner image is formed to the transfer material 16 may be incorporated in the apparatus.

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

Next, the “electrodeposition” method that can be used in the present invention will be described. The thermoplastic resin according to the present invention is electrodeposited on the surface of the photoreceptor in a state of resin particles,
For example, a uniform thin film is formed by heating or the like to form a transfer layer. Therefore, the thermoplastic resin particles need to have either a positive charge or a negative charge, and the detectability is arbitrarily determined by the chargeability of the electrophotographic photosensitive member to be combined. .

The resin particles satisfy the above-mentioned physical properties, and usually have an average particle size of 0.01 μm to 0.01 μm.
15 μm, preferably 0.05 μm to 5 μm
m, more preferably in the range of 0.1 μm to 1 μm. . The particles may be in the form of either a particle powder (dry type) or a non-aqueous resin particle (wet type). Preferably, non-aqueous dispersed resin particles are used, in which the thickness of the transfer layer for peeling can be easily adjusted to a thin film with a uniform thickness.

The fine resin particles of the present invention can be produced by a conventionally known mechanical pulverization method or polymerization granulation method. These production methods can use either dry electrodeposition or wet electrodeposition particles. In the case of producing fine particles used in the dry electrodeposition method, as a mechanical pulverization method, directly pulverized by a conventionally known pulverizer,
Fine particles (eg, a method using a ball mill, paint shaker, jet mill, etc.);
If necessary, a material to be resin particles may be mixed, melted, pulverized through kneading, or subjected to classification in order to make the particle size uniform after pulverization or post-treatment of treating the surface of the particles in combination as appropriate. it can. Also, a spray drying method is known.

[0240] Specifically, "Granulation Handbook", edited by Japan Powder Industry Technology Association, Vol. II (Ohm, 1991)
Year), Kanagawa Business Development Center "The latest granulation technology in practice"
(Kanagawa Business Development Center Publishing Division, 1984), edited by Masafumi Arakawa et al., "Latest Powder Design Technology" (Techno System Co., Ltd., 1988), etc. Can be manufactured.

As the polymerization granulation method, conventionally known methods such as an emulsion polymerization reaction, a seed polymerization reaction, a suspension polymerization reaction performed in an aqueous system, and a dispersion polymerization reaction performed in a non-aqueous solvent system are known. Specifically, Soichi Muroi, “Polymer Latex Chemistry,” Polymer Publishing Association (1970), Taira Okuda, Hiroshi Inagaki, “Synthetic Resin Emulsion,” Polymer Publishing Association (1978)
Soichi Muroi "Introduction to Polymer Latex" Kobunsha (19)
1983); Piirma, P .; C. Wang "Emulsion
Polymerization "I. Piirma & J. L. Gavdon,
ACS symp. Sev. 24, p.34 (1974), Fumio Kitahara et al., "Chemistry of Dispersion Emulsification System", Engineering Books (1979
1), supervised by Soichi Muroi, "Advanced technology of ultrafine polymer"
C. M. C. (1991), etc., and then collected and powdered by various methods as described in the mechanical method described above. .

As the method for dry electrodeposition of the obtained fine particle powder, a conventionally known coating method of an electrostatic powder or a developing method of a dry electrophotographic developer can be used. Specifically, J.I. F. Written by Hughes (translated by Hideo Nagasaka and Machiko Midorikawa)
As described in “Electrostatic Powder Coating” and the like, a method of electrodepositing charged fine particles by a method such as corona charging, frictional charging, induction charging, ion wind charging, reverse ionization phenomenon, etc. Development and Practical Use of Photographic Development Systems and Toner Materials ", Chapter 1 (Nippon Scientific Information Inc., 1985)
As described in the written documents such as the year), it can be appropriately performed using a developing method such as a cascade method, a magnetic brush method, a fur brush method, an electrostatic method, an induction method, a touch down method, a powder cloud method, or the like. it can.

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

In addition, as the polymerization granulation method, it can be produced by a conventionally known non-aqueous dispersion polymerization method.
Chapter 2, "Latest Electrophotographic Development System and Development and Practical Use of Toner Materials"
Chapter 3, K. E. FIG. J. Barvett "Dispersion Polymer
ization in Organic Media "John Wiley (197
5 years).

In the polymerization granulation method, the introduction of the polymer component (c) for improving the releasability into the resin [A] corresponds to the polymerization component (a) and / or the polymerization component (b). By conducting a polymerization reaction in the presence of a monomer corresponding to the polymer component (c) together with the monomer, the copolymer is copolymerized in the resin [A], and the resin particles [AR] of the random copolymer can be easily formed. can get.

Further, in order to introduce the polymer component (c) in the form of a polymer block, a method of using at least a block copolymer containing the polymer component (c) as a block in the dispersion stabilizing resin to be used. Or a weight average molecular weight of 1 × 10, wherein the polymer component (c) is a main repeating unit.
^{3 to} 2 × 10 ⁴ (preferably 3 × 10 ^{3 to} 1.5 × 10
⁴ ) The resin [A] can be easily converted into a block copolymer by co-existing with a monofunctional macromonomer and copolymerizing with a monomer corresponding to the polymer component (a) and / or (b). It can be. Another method is to use a polymer initiator (azobis polymer initiator or peroxide polymer initiator) containing the polymer component (c) as a main repeating unit, similarly to the block copolymerization. The combined resin particles [AR] can be obtained.

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

By synthesizing dispersed resin particles by a dispersion polymerization method in these non-aqueous solvent systems, the average particle diameter of the resin particles can be easily reduced to 1 μm or less, and the particle diameter distribution is very narrow and monodispersed. It can be. Since these non-aqueous dispersion resin particles are subjected to a wet electrostatographic development method or a method of being electrophoresed by electrophoresis in a printing field of an electric field, a dispersion medium used at the time of electrodeposition has an electric resistance of 10%.
It is adjusted to a non-aqueous solvent system having a resistivity of not less than ⁸ Ωcm and not more than 3.5.

Specifically, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, and halogenated products thereof can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L (Isoper; a product of Exxon) Name), Shellsol 70, Shellsol 71
(Shelsol; trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits), etc. can be used alone or in combination.

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

As described above, in order to electro-deposit the dispersed particles in the dispersion medium by electrophoresis, the particles are positively or negatively chargeable electrophoretic particles. Is
This can be achieved by appropriately utilizing the technology of a developer for wet electrophotography. Specifically, the above-mentioned “Recent development and practical use of electrophotographic development systems and toner materials” 139 to 148
Page, Electrophotography Society of Japan, "Basic and Application of Electrophotographic Technology", 49
7-505 (Corona Publishing, 1988), Yuji Harasaki "Electrophotography" 16 (No. 2), 44 pages (1977)
And the like, using the electrolysis material and other additives described in the above.

For example, British Patent Nos. 893429 and 9
No. 34038, U.S. Pat.
Nos. 0412 and 4006989, JP-A-60-179
No. 751, No. 60-185963, JP-A-2-139
No. 65 and the like. The composition of the non-aqueous latex to be subjected to electrodeposition usually includes at least 1 to 20 g of particles mainly containing a thermoplastic resin in 1 liter of an electrically insulating dispersion medium, and 0.01 to 20 g of a dispersion stabilizing resin. 5
0 g, the charge control agent added as needed is 0.0001
The range is from 10 to 10 g.

Further, other additives may be added in order to maintain the dispersion stability and charge stability of the particles.
Rosin, petroleum resin, higher alcohols, polyethers, silicone oils, paraffin waxes, triazine derivatives and the like are mentioned. 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 latex for electrodeposition.
That is, when the electric resistance is lower than 10 ⁸ Ωcm, it is difficult to obtain a sufficient amount of the thermoplastic resin particles, and thus the amount of each additive is controlled within this limit.

In this way, the thermoplastic resin particles which have been made into fine particles and which have been charged and dispersed in the electrically insulating liquid have the same behavior as the electrophotographic wet developer. Therefore, for example, electrophoresis can be performed on the surface of the photoreceptor by using a developing device, for example, a slit developing electrode device described in “Basics and Application of Electrophotographic Technology”, pp. 275-285. That is, particles mainly containing a thermoplastic resin are supplied between the opposing electrodes provided so as to face the electrophotographic photosensitive member, and are electrophoresed according to a potential gradient applied from an external power supply, and adhere to the electrophotographic photosensitive member. Alternatively, the film is formed by electrodeposition.

Generally, when the particles are charged positively, a voltage is applied from an external power supply between the conductive support of the photoreceptor and the developing electrode of the developing device so that the photoreceptor side has a negative potential. Then, the particles are electrostatically electrodeposited on the photoreceptor surface. Electrodeposition can also be performed by wet toner development using a normal electrophotographic process. That is, as shown in the premise "Basic and application of electrophotographic technology", pp. 46-79, so-called burn-off, in which the photoreceptor is uniformly charged and no exposure is performed, or only an unnecessary area is exposed, Perform normal wet toner development.

The adhesion amount of the photosensitive resin particles can be arbitrarily adjusted according to the applied voltage of the external bias, the charging potential of the photosensitive member, the developing time, and the like. After the electrodeposition, the developer is wiped off with 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 a thermoplastic resin particle is formed into a film to form a transfer layer.

Hereinafter, a method for forming a transfer layer by an electrodeposition method will be described in detail with reference to the accompanying drawings. FIG. 5 is a schematic view of an electrophotographic transfer device incorporating a device for forming a transfer layer by an electrodeposition method. The apparatus shown in FIG. 5 has basically the same configuration as that of the above-described hot-melt type apparatus (FIG. 3) except for the part where the transfer layer 12 is formed on the photoconductor 11. The dispersion liquid 12a of the thermoplastic resin particles is supplied to the electrodeposition unit 14T in the movable wet developing unit set 14. First, the electrodeposition unit 14T is brought closer to the photoreceptor surface 11, and the distance between the electrodeposition unit 14T and the developing electrode is 1 m.
m. The particle dispersion liquid 12a is supplied between the gaps and rotated while applying a voltage from an external power supply (not shown) so that the particles are electrodeposited on the entire image forming area of the photoreceptor surface 11.

The particle dispersion 12 adhering to the photoreceptor surface 11 by a squeeze device built in the electrodeposition unit 14T
Then, the resin is passed under the suction / exhaust unit 15 and dried, and the thermoplastic resin particles are heated and melted by the heating means 17a to obtain a thermoplastic resin transfer layer 12 formed into a film. Thereafter, if necessary, a cooling device (not shown) similar to the intake / exhaust unit 15 cools the photosensitive member from the outside or the inside of the photosensitive drum to a predetermined temperature.

After lowering the electrodeposition unit 14T, the wet developing unit set 13 is moved. The unit set 13 includes a developing device containing a wet developer.

In the present invention, the transfer layer 12 on the transfer material 16 obtained as described above is subjected to a chemical reaction treatment,
By completely removing the transfer layer 12 by dissolving or swelling and detaching it, an offset printing plate can be prepared. In the treatment for removing the transfer layer 12, a deprotection reaction using chemical optical active rays may be used in addition to the reaction with the treatment solution, or may be used in combination.

As the treatment liquid, an aqueous solution adjusted to a predetermined pH is used. For pH adjustment, a known pH adjuster can be used. The pH range to be applied may be any of acidic to neutral to alkaline, but it is preferable to use in the alkaline range of pH 8 or more in consideration of the rust prevention of the treatment solution or the elution and removal of the transfer layer. The compound used as the alkaline treatment liquid may be any of conventionally known inorganic compounds or organic compounds, for example, carbonate, sodium hydroxide,
Potassium hydroxide, potassium silicate, sodium silicate,
Any of organic amine compounds and the like may be used, and they may be used alone or in combination.

Further, as a compound which can be used in combination for accelerating the hydrophilic reaction, a nucleophilic constant n [R. G. FIG. Pearson, H .; Sobel, J.A. Amer. C
hem. Soc. , 90, 319 (1968)] containing a substituent having a value of 5.5 or more, and hydrolyzing at least 1 part by weight in 100 parts by weight of distilled water.

Specific compounds include, for example, hydrazine, hydroxylamine, sulfite (ammonium salt,
Sodium salt, potassium salt, zinc salt, etc.), thiosulfate, etc., and further contains at least one polar group selected from a hydroxyl group, a carboxyl group, a sulfo group, a phosphono group, and an amino group in the molecule. Mercapto compounds,
Hydrazide compounds, sulfinic acid compounds, primary amine compounds, secondary amine compounds, and the like.

For example, as mercapto compounds, 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 in these treatment solutions is 0.05 to 10 mol / l, preferably 0.1 to 5 mol / l.
l. Further, the pH of the treatment liquid is preferably 8 or more. The conditions of the treatment are as follows.
Minutes are preferred. The treatment liquid may contain other compounds in addition to the nucleophilic compound and the pH adjuster described above. For example, an organic solvent that is soluble in water is added to 100 parts by weight of water.
To 50 parts by weight. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propargyl alcohol, benzyl alcohol, phenethyl alcohol, etc.),
Ketones (acetone, methyl ethyl tetone, cyclohexanone, acetophenone, etc.), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, dimethyl ether, propylene glycol, diethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran Amides) (dimethylformamide,
Pyrrolidone, N-methylpyrrolidone, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, sulfolane, tetramethylurea, etc.), and these may be used alone or in combination of two or more. Good.

Further, 0.1 to 20 parts by weight of a surfactant may be contained in 100 parts by weight of water. Examples of the surfactant include conventionally known anionic, cationic, or nonionic surfactants. For example, Hiroshi Horiguchi "New surfactant" (1975), Sankyo Publishing Co., Ltd., Ryohei Oda,
Compounds described in Kazuhiro Teramura, "Synthesis of Surfactant and Its Application" (1980, published by Maki Shoten) can be used. Further, in order to improve the antiseptic property and the antifungal property during storage of the treatment liquid, a conventionally known antiseptic compound and a fungicidal compound may be used in combination.

Further, at the time of processing, physical operations such as performing under ultrasonic waves or mechanical sliding (rubbing with a brush or the like) may be used together. On the other hand, the light used in the case of performing a deprotection reaction by irradiation with "chemically active light" includes visible light,
Any of ultraviolet rays, far ultraviolet rays, electron beams, X-rays, γ-rays, α-rays and the like may be used, but ultraviolet rays are preferred. More preferably, it can emit light in a wavelength range of 310 nm to 500 nm, and a high-pressure or ultra-high-pressure mercury lamp or the like is generally used. Light irradiation processing is usually 5c
Irradiation for 10 seconds to 10 minutes from a distance of m to 50 cm can be sufficiently performed. After the light irradiation in this manner, the transfer layer is easily removed by dipping in the above water-soluble solution.

[0268]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. [Synthesis Example of Resin [P]] Synthesis Example 1 of Resin [P]: [P-1] 80 g of methyl methacrylate, macromonomer of dimethylsiloxane (FM-0725) (Mw, manufactured by Chisso Corporation)
A mixed solution of 20 g of 1 × 10 ⁴ ) and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. Azobisisobutyronitrile (abbreviation: AIBN) 1.0
g., and reacted for 4 hours. I. B. N. 0.7g
Was added and reacted for 4 hours. The weight average molecular weight (abbreviation: Mw) of the obtained copolymer was 5.8 × 10 ⁴ (G.
P. C. Method measurement).

[0269]

Embedded image

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 a macromonomer (FM-0725), Each polymer was synthesized in the same manner as in Synthesis Example 1 except that each monomer corresponding to the polymer component described in Table-B was used. The Mw of each of the obtained polymers is 4.5 × 10 ^{4 to} 6 ×
The range was 10 ⁴ .

[0271]

[Table 2]

[0272]

[Table 3]

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

[0274]

Embedded image

Synthesis Examples 11 to 15 of Resin [P]: [P-1
1] to [P-15] Instead of the monomers and macromonomers used in Synthesis Example 10 of Resin [P], each monomer and each macromonomer corresponding to the polymer components shown in Table 1C below Each copolymer was synthesized in the same manner as in Synthesis Example 10 except that Mw of the obtained copolymer is 4.5 × 10 ^{4 to} 6.5.
× 10 ⁴ range.

[0276]

[Table 4]

[0277]

[Table 5]

[0278]

[Table 6]

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

[0280]

Embedded image

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

After the mixture was cooled to 0 ° C., methanol 1
0 ml was added and reacted for 30 minutes to terminate the polymerization. The obtained polymer solution was brought to a temperature of 30 ° C. under stirring,
3 ml of 0% ethanol solution of hydrogen chloride was added and stirred for 1 hour. Next, the solvent was distilled off under reduced pressure until the total amount of the reaction mixture was reduced to half, and the reaction mixture was reprecipitated in 1 liter of petroleum ether. The precipitate was collected and dried under reduced pressure to give a polymer having an Mw of 6.8 × 10 ⁴ and a yield of 76 g.

[0283]

Embedded image

Synthesis Example 18 of Resin [P]: [P-18] A mixed solution of 52.5 g of methyl methacrylate, 22.5 g of methyl acrylate, 0.5 g of (tetraphenylporphinato) aluminum methyl and 200 g of methylene chloride was passed through a nitrogen stream. The temperature was 30 ° C. below. 300
W-xenon lamp light is passed through a glass filter for 25 minutes.
Irradiated from a distance of cm and reacted for 20 hours. 25 g of the following monomer (M-2) was further added to this mixture, and
After light irradiation for 2 hours, 3 g of methanol was added to the reaction mixture.
Was added and stirred for 30 minutes to stop the reaction. Next, the reaction mixture was reprecipitated in 1.5 liters of methanol, and the precipitate was collected and dried. The obtained polymer was M in a yield of 78 g.
w 9 × 10 ⁴ .

[0285]

Embedded image

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

[0287]

Embedded image

Synthesis Example 20 of Resin [P]: [P-20] 50 g of methyl methacrylate, ethyl methacrylate 2
A mixture of 5 g and 1.0 g of benzyl isoprusate was sealed in a vessel under a nitrogen stream and heated to a temperature of 50 ° C. This was irradiated with light through a glass filter from a distance of 10 cm with a 400 W high-pressure mercury lamp for 6 hours to carry out photopolymerization.
To this, 25 g of the monomer (M-1) was added, the atmosphere was replaced with nitrogen, and light irradiation was performed again for 10 hours. The obtained reaction product was reprecipitated in 2 liters of methanol, collected and dried. The obtained polymer was 63 g in yield and had a Mw of 6 × 10 ⁴ .

[0289]

Embedded image

Synthesis Examples 21 to 27 of Resin [P]: [P-2
1] to [P-27] Copolymers shown in Table D below were synthesized in the same manner as in Synthesis Example 19 of Resin [P]. Mw of the obtained polymer was 3.5 ×
The range was 10 ^{4 to} 6 × 10 ⁴ .

[0291]

[Table 7]

[0292]

[Table 8]

Synthesis Example 28 of Resin [P]: [P-28] In Synthesis Example 19 of Resin [P], benzyl N, N-
The same reaction as in Synthesis Example 19 was carried out except that 18 g of the compound [I-1] having the following structure was used instead of diethyldithiocarbamate, to obtain a copolymer having an Mw of 4.5 × 10 ⁴ .

[0294]

Embedded image

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 in place of benzylisoplusanthate.
gw, except that g was used.
2.5 × 10 ⁴ copolymer was obtained.

[0296]

Embedded image

Synthesis Example 30 of Resin [P]: [P-30] methyl methacrylate 68 g, methyl acrylate 22
g, glycidyl methacrylate 10 g, an initiator [I-3] having the following structure 17.5 g, and tetrahydrofuran 15
0 g of the mixed solution was heated to a temperature of 50 ° C. under a nitrogen stream.
This solution was irradiated with light through a glass filter from a distance of 10 cm with a 400 W high-pressure mercury lamp for 10 hours to carry out photopolymerization. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain a yield of 72 g and Mw of 4.0.
× 10 ⁴ polymer was obtained.

70 g of this polymer and 30 of monomer (M-2)
g and a mixed solution of 100 g of tetrahydrofuran were irradiated with light at a temperature of 50 ° C. for 13 hours under the same conditions as above under a nitrogen stream. Next, the reaction product was reprecipitated in 1.5 liters of methanol, and the precipitate was collected and dried to obtain 78 g of Mw6.
× 10 ⁴ copolymer was obtained.

[0299]

Embedded image

Synthesis Examples 31 to 38 of Resin [P]: [P-3]
1] to [P-38] In Synthesis Example 30 of resin [P], initiator [I-3] 1
Instead of 7.5 g, the initiator [I] 0.0
The operation was carried out under the same conditions as in Synthesis Example 30 except that 31 mol was used. The yield of each polymer obtained is 70-80 g and Mw
It was 4 × 10 ^{4 to} 6 × 10 ⁴ .

[0301]

[Table 9]

[0302]

[Table 10]

[0303]

[Table 11]

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

[0305]

Embedded image

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

[0307]

Embedded image

Synthesis Examples 3 to 11 of Resin Particles [L]: [L-
3] to [L-11] In Synthesis Example 1 of the resin particles [L], the monomer (LM-
1), Resin particles were produced in the same manner as in Synthesis Example 1 except that each of the compounds shown in the following Table-F was used instead of ethylene glycol dimethacrylate and methyl ethyl ketone. The average particle size of each of the obtained resin particles is 0.15 to 0.30 μm.
Was in the range.

[0309]

[Table 12]

[0310]

[Table 13]

Synthesis Examples 12 to 17 of Resin Particles [L]: [L
-12] to [L-17] In Synthesis Example 2 of the resin particles [L], instead of 5 g of the dispersion stabilizing resin [AB-6], the resin [LP] shown in Table G below.
Each resin particle was synthesized in the same manner as in Synthesis Example 2 except that the above-mentioned was used. The average particle size of each of the obtained particles is 0.10 to 0.25.
μm range.

[0312]

[Table 14]

[0313]

[Table 15]

Synthesis Examples 18 to 23 of Resin Particles [L]: [L
-18] to [L-23] In Synthesis Example 2 of the resin particles [L], the monomer (LM-
2) Instead of 40 g, each monomer of the following Table-H, and instead of 5 g of dispersion stabilizing resin [AB-6], resin [L
P-8] except that 6 g was used in the same manner as in Synthesis Example 2.
Each resin particle was synthesized. The average particle size of each of the obtained particles was in the range of 0.05 to 0.20 μm.

[0315]

Embedded image

[0316]

[Table 16]

[0317]

[Table 17]

[Synthesis Example of Resin [A]] Synthesis Example 1 of Resin [A]: [A-1] 75 g of benzyl methacrylate, 5 g of acrylic acid, 20 g of monomer (b-1) having the following structure and 200 g of toluene The mixed solution was heated to a temperature of 80 ° C. under a nitrogen stream. In addition to this, azobisisobutyronitrile (abbreviation: AIB.
N. 4), and reacted for 3 hours. I. B. N.
1.0 g was added and reacted for 4 hours. The weight average molecular weight (abbreviation: Mw) of the obtained copolymer was 2.5 × 10 ⁴ (GPC method measurement value).

[0319]

Embedded image

Synthesis Example 2 of Resin [A]: [A-2] Mixed solution of 69 g of ethyl methacrylate, 6 g of methacrylic acid, 25 g of monomer (b-2) having the following structure, 2 g of β-mercaptopropionic acid and 200 g of toluene Was heated to 75 ° C. under a stream of nitrogen. A. I. B. N. Add 3g and add 4
Reaction for an additional time. I. B. N. Add 1.0g and add 4
Reacted for hours. Mw of the obtained copolymer was 8.5 × 10
^{Was 3} .

[0321]

Embedded image

Synthesis Example 3 of Resin [A]: [A-3] Phenyl methacrylate 67 g, dimethylsiloxane macromonomer (FM-0725) (Chisso Corporation)
10 g of Mw1 × 10 ⁴ ), 3 g of 3-sulfopropyl methacrylate, 20 g of a monomer (b-3) having the following structure,
A mixed solution of 150 g of tetrahydrofuran and 50 g of ethanol was immediately heated to a temperature of 65 ° C. in an air stream. To this was added 5 g of 2,2'-azobis (isovaleronitrile) (abbreviation: AIVN) and reacted for 4 hours. I. V. N. 1 g was added and reacted for 4 hours. Mw of the obtained copolymer was 1.2 × 10 ⁴ .

[0323]

Embedded image

Synthesis Examples 4 to 20 of Resin [A]: [A-4]
-[A-20] Resins [A] in Table-B below were synthesized in the same manner as in Synthesis Example 2 of resin [A]. Mw of the obtained copolymer was 8 × 1
0 ^{3 to} 9 × 10 ³ .

[0325]

[Table 18]

[0326]

[Table 19]

[0327]

[Table 20]

[0328]

[Table 21]

[0329]

[Table 22]

[0330]

[Table 23]

Synthesis Examples 21 to 31 of Resin [A] [A-2]
1] to [A-31] Resins in Table-C below were synthesized in the same manner as in Synthesis Example 3 of resin [A]. Mw of the obtained copolymer is from 8 × 10 ³ to
The range was 1 × 10 ⁴ . However, the Mw of the macromonomer used was in the range of 5 × 10 ^{3 to} 7 × 10 ³ .

[0332]

[Table 24]

[0333]

[Table 25]

[0334]

[Table 26]

[0335]

[Table 27]

Synthesis Example 32 of Resin [A]: [A-32] phenethyl methacrylate 55 g, acrylic acid 10 g,
20 g of a monomer (b-4) having the following structure, benzyl N, N
-A mixed solution of 12 g of diethyldithiocarbamate and 85 g of tetrahydrofuran was sealed in a vessel under a nitrogen stream, and heated to 50 ° C. This is passed through a glass filter from a distance of 10 cm with a 400 W high-pressure mercury lamp,
Irradiated for hours and photopolymerized.

In addition, a monomer (c-1) 15 having the following structure
g and a mixed solution of 15 g of tetrahydrofuran were added, the atmosphere was replaced with nitrogen, and light irradiation was performed again for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, collected and dried. The obtained copolymer had an Mw of 4.8 × 10 ⁴ in a yield of 73 g.

[0338]

Embedded image

Synthesis Example 33 of Resin [A]: [A-33] In Synthesis Example 32 of Resin [A], 12 g of benzyl N, N-diethyldithiocarbamate as a photopolymerization initiator was used.
Was obtained in the same manner as in Synthesis Example 32 of Resin [A] except that 14 g of an initiator having the following structure was used in place of the above. Mw of the obtained copolymer was 3.5 × 10 ⁴ .

[0340]

Embedded image

Synthesis Examples 34 to 40 of Resin [A]: [A-3]
4] to [A-40] In the synthesis example 32 of the resin [A], except that each monomer corresponding to the polymerization component in Table-D below was used in place of the monomer (c-1), the resin [ Each copolymer was obtained in the same manner as in Synthesis Example 32 of A). The Mw of the obtained copolymer is 2 × 10 ^{4 to} 3.
The range was 5 × 10 ⁴ .

[0342]

[Table 28]

[Production Example of Thermoplastic Resin Particles] Production Example 1 of Thermoplastic Resin Particles: [AR-1] 18 g of dispersion stabilizing resin [Q-1] having the following structure, 48 g of methyl methacrylate, 25 g of methyl acrylate, acrylic acid A mixed solution of 7 g, 20 g of the monomer (B-1) having the following structure, and 542 g of Isopar H was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. 2,2 'as a polymerization initiator
-Azobis (isovaleronitrile) (abbreviated as A.I.V.
N. ) Was added and reacted for 2 hours. Twenty minutes after addition of the initiator, cloudiness occurred and the reaction temperature rose to 88 ° C. After adding 0.5 g of initiator and reacting for 2 hours, 0.3 g of initiator was further added and reacted for 3 hours. 200 after cooling
The resulting white dispersion was passed through a mesh nylon cloth, and was a monodisperse latex having a conversion of 98% and an average particle size of 0.20 μm. The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

[0344]

Embedded image

Production Example 2 of Thermoplastic Resin Particles: [AR-
2] Synthesis of dispersion stabilizing resin [Q-2] A mixed solution of 99.5 g of dodecyl methacrylate, 0.5 g of divinylbenzene and 200 g of toluene was heated to a temperature of 80 ° C. while stirring under a nitrogen stream. 2,2'-azobis (butyronitrile) (abbreviated AIBN) 2 g
And reacted for 3 hours. I. B. N. 0.5 g was added and reacted for 4 hours. The solid content of the obtained polymer is 3
Mw was ⁴ × 10 ⁴ at 3.3% (weight). Synthesis of Particles 18 g (as solid content) of the resin [Q-2], 70 g of vinyl acetate, 5 g of crotonic acid, and the following monomer [B-2] 2
A mixture of 5 g and 382 g of Isopar H was heated to a temperature of 80 ° C. while stirring under a nitrogen stream. A. I. V.
N. 1.6 g was added and reacted for 1.5 hours. I. V.
N. 0.8 for 2 hours and A.P. I. V. N. 0.5
g was added and reacted for 3 hours. Next, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours. After unreacted vinyl acetate was distilled off, the mixture was cooled and passed through a 200-mesh nylon cloth to obtain a white dispersion at a polymerization rate of 87%. It was a monodisperse latex having an average particle size of 0.22 μm.

[0346]

Embedded image

Production Example 3 of Thermoplastic Resin Particles: [AR-3] A mixed solution of 18 g of a dispersion stabilizing resin [Q-3] having the following structure and 546 g of Isopar H was stirred at a temperature of 60 ° C. under a nitrogen stream. did. 50 g of benzyl methacrylate, 7 g of ethyl acrylate, and 1 g of acrylic acid
0 g, 25 g of a monomer (B-3) having the following structure, 2.3 g of 3-mercaptopropionic acid, and A.I. I. V. N. 1.0
g of the mixed solution was added dropwise over 1 hour, and the mixture was reacted for 1 hour. Next, A. I. V. N. 0.8 g was added and reacted for 2 hours. I. V. N. After adding 0.5 g, the mixture was reacted at a temperature of 80 ° C. for 2 hours, and further, 0.5 g of 2,2′-azobis (isobutyronitrile) (abbreviated as AIBN 0.5 g) was added thereto.
Reacted for hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having a degree of polymerization of 98% and an average particle diameter of 0.21 μm and having good monodispersibility.

[0348]

Embedded image

Preparation Example 4 of Thermoplastic Resin Particles: [AR-4] While stirring a mixed solution of 20 g of a dispersion stabilizing resin [Q-4] having the following structure, 135 g of Isopar H and 45 g of ethyl acetate under a nitrogen stream, the temperature was increased. 60 ° C. In this solution, 10 g of 2-phosphonoethyl methacrylate, 65 g of phenethyl methacrylate, a monomer having the following structure (B-4)
25 g, thioglycolic acid 1.5 g, I. V. N.
0.6 g, Isopar H 7.5 g and ethyl acetate 25 g
Was added dropwise over 1 hour.

After reacting for 1 hour as it is, A.I. I. V. N.
Add 0.3 g and add A. I. V. N. 0.3
g was added and reacted for 3 hours. Next, the degree of pressure reduction was 30 mmHg.
Then, ethyl acetate was distilled off, and the same amount of Isopar H as the distilled amount was added. Thereafter, the mixture was cooled and filtered through a 200-mesh nylon cloth to obtain a white dispersion. It was a monodisperse latex having a polymerization rate of 93% and an average particle size of 0.28 μm.

[0351]

Embedded image

Production Examples 5-13 of thermoplastic resin particles: [A
R-5] to [AR-13] In Production Example 3 of the thermoplastic resin particles, the following Table-L
The particles [AR-5] to [AR-17] of the present invention were operated in exactly the same manner as in Production Example 3 except that the monomers described in the above were used.
Was manufactured. The polymerization rate of each obtained latex particle is 90.
９９99%, the average particle size was in the range of 0.15-0.25 μm, and the monodispersity was good.

[0353]

[Table 29]

[0354]

[Table 30]

[0355]

[Table 31]

Preparation Example 14 of Resin Particles: AR-14 14 g of dispersion stabilizing resin [Q-5] having the following structure, 10 g of macromonomer M-1 having the following structure, and Isopar H55
3 g of the mixed solution was stirred at a temperature of 55 ° C. under a nitrogen stream.
Was heated. To this, 75 g of benzyl methacrylate,
Acrylic acid 10 g, monomer [B-14] 15 having the following structure
g, 2-g of 3-mercaptopropionic acid and 1.0 g of 2,2'-azobis (2-cyclopropylpropionitrile) (abbreviation ACP) were added dropwise over 1 hour. After stirring for 1 hour as it is, C. P. P. 0.8
g was added and reacted for 2 hours. Furthermore, 0.5 g of 2,2'-azobis (isobutyronitrile) (abbreviated AIBN) was added, the temperature was set to 80 ° C, and the reaction was performed for 3 hours. After cooling,
The white dispersion obtained through a 200-mesh nylon cloth was a monodisperse latex having a conversion of 97% and an average particle size of 0.17 μm.

[0357]

Embedded image

[0358]

Embedded image

Production Examples of Resin Particles 15 to 23: [AR-1
5] to [AR-23] In the synthesis example of the resin particles [AR-14], instead of 10 g of the macromonomer M-1, each macromonomer M in Table-M below (Mw is 8 × 10 ³ to 1 × 10 Resin particles were synthesized in the same manner as in Synthesis Example 2 except that ( ⁴ ) was used. The polymerization rate of each particle was 98 to 99%, the average particle diameter of the particles was in the range of 0.15 to 0.25 μm, the particle size distribution was narrow, and the monodispersity was good.

[0360]

[Table 32]

[0361]

[Table 33]

[0362]

[Table 34]

Example 1 100 g of photoconductive zinc oxide and a binder resin [B-
1] 20 g, the resin [P-1] 3 g, uranine 0.0
A mixture of 1 g, Rose Bengal 0.02 g, bromophenol blue 0.01 g, maleic anhydride 0.15 g and toluene 150 g was homogenized (Nihon Seiki Co., Ltd.).
) And a rotation speed of 9 × 10 ³ r. p. m. For 10 minutes. To this dispersion, 0.02 g of phthalic anhydride and 0.001 g of o-chlorophenol were added, and the number of revolutions was further increased to 1 × 10 ³ r. p. m. For 1 minute.

[0364]

Embedded image

Next, this dispersion was applied on a 0.2 mm thick paper master for base plate subjected to a conductive treatment and a solvent resistance treatment with a wire bar so as to have an application amount of 25 g / m ² .
After drying to the touch, it was heated at 120 ° C. in a circulating oven for 1 hour. The photoreceptor obtained as described above was subjected to JIS Z-
The adhesive strength of the surface was measured by the “Adhesive tape / sheet test method” of 0237-1980 and found to be 10 gf.

On the other hand, as a comparison,
An electrophotographic photosensitive member was prepared in exactly the same manner except that 3 g of the resin [P-1] was not used, and the surface adhesive strength was 380 g.
f. When a transfer layer was applied in the same manner as in Example 1, and the transfer layer was transferred to a transfer material after toner image formation, the releasability was poor. Further, in order to form a transfer layer on the photosensitive layer, a thermoplastic resin solution of 30 g of resin [A-1], 0.08 g of silicone oil KF-69 (manufactured by Shin-Etsu Silicon Co., Ltd.) and 100 g of toluene was prepared. . This solution was applied with a wire bar so as to have a thickness of 3.0 μm, and oven-dried at 100 ° C. for 20 seconds. The obtained electrophotographic photosensitive member with a transfer layer was allowed to stand overnight (25 ° C., 60% RH).

The ELP-404V plate making machine (manufactured by Fuji Photo Film Co., Ltd.) was used to set the bias voltage of the developing section to 100 V, and ELP-TX (manufactured by Fuji Photo Film Co., Ltd.) was used as the liquid toner. A copied image was actually formed. The copy image formed on the obtained transfer layer is
High-definition image portions such as continuous tone portions composed of fine lines and halftone dots were also clear and excellent, and no background smear was observed in non-image portions.

Next, the photoreceptor made as described above was placed between a pair of heating rollers in which an infrared lamp heater was incorporated inside a hollow roller covered with silicone rubber.
It was passed over a straight master (manufactured by Mitsubishi Paper Mills). The surface temperature of the roller at this time was 100
° C, the nip pressure between the rollers was set at 3 kgf / cm ² , and the transport speed was set at 5 mm / sec.

After the passage, the mixture was cooled to room temperature while being overlapped with the coated paper, and then the photosensitive member and the straight master were separated. At this time, 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 photoconductor before transfer, and no image deterioration was observed. Also, no transfer layer remains on the photoreceptor surface after copying,
The transferability was extremely good.

Next, the plate having the transfer layer transferred to the straight master support was desensitized (that is, the transfer layer was removed), and the printing performance as a printing plate was examined. The plate was immersed in a desensitizing solution (pH 13.1) obtained by diluting a PS plate treating agent DP-4 (manufactured by Fuji Photo Film Co., Ltd.) 7 times with distilled water at a temperature of 25 ° C. for 1 minute. The transfer layer was removed while gently rubbing, and washed thoroughly with water.

The printing plate obtained in this manner was visually observed for a non-image portion and a toner image portion using a 200 × optical microscope. As a result, no transfer layer remained in the non-image portion, and No lack of high-resolution areas such as thin lines and fine characters was observed. This plate was soaked in soaking water for PS plate (SG-23) (manufactured by Tokyo Ink Co., Ltd.) with distilled water.
Using a 30-fold diluted aqueous solution (pH 7.0), Ryobi 3200MCD type (Ryobi Co., Ltd.) was used as a printing machine.
Using neutral paper as the printing paper, printing was performed with various types of offset printing color inks, and the number of printed sheets where a clear image with no background stain was obtained was examined. As a result, 3,000 or more printing endurances were obtained in any case regardless of the type of color ink.

On the other hand, in a known system, a lithographic printing plate is prepared by desensitizing an electrophotographic photosensitive member using zinc oxide with a desensitizing solution containing a chelating agent as a main component under acidic conditions.
When neutral paper is used as printing paper, the number of printings is hundreds of sheets, background stains occur in the non-image area, and when using offset printing color inks other than black, the number of printings is also several hundreds. To the extent, soiling occurred.

As described above, it was found that the method for producing an original plate for offset printing of the present invention has extremely good printing performance, unlike the conventional method, while using the same zinc oxide photoreceptor.

Example 2 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 2
g, a binder resin [B-2] having the following structure, 10 g, a compound [A] having the following structure, 0.15 g, and 80 g of tetrahydrofuran
Was mixed with glass beads in a 500 ml glass container and dispersed for 60 minutes with a paint shaker (manufactured by Toyo Seiki Seisaku-sho), and 0.2 g of resin [P-2] was further added thereto.
0.03 g of phthalic anhydride and 0.1 g of o-chlorophenol.
After adding 001 g and dispersing for 2 minutes, the glass beads were filtered off to obtain a photosensitive layer dispersion.

[0375]

Embedded image

Next, this dispersion was applied with a wire bar onto a 0.2 mm-thick paper stencil master sheet which had been subjected to a conductive treatment and a solvent resistance treatment, and was dried by touching with a finger. Heated for 20 seconds. At 140 ° C
Heated for hours. The thickness of the obtained photosensitive layer was 8 μm. The tackiness of the photoreceptor surface was 5 gf. The photoconductor was used as an electrophotographic photoconductor in the apparatus shown in FIG. For the transfer layer, 120
20 ° C to the surface of photosensitive layer by hot melt coater
After applying the coating at a speed of mm / sec and cooling by blowing cooling air from an air intake / exhaust unit, the surface temperature of the photoreceptor is reduced to 30 mm.
C. At this time, the thickness of the transfer layer was 3 μm.

First, the image-capturing property and transfer property of this photosensitive material were examined. After corona charging the photosensitive material to + 450V,
Read the original in advance with a color scanner,
In the negative mirror mode based on the information stored on the hard disk in the system as digital image data, 5
Using a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) having an mW output, the photosensitive material was exposed to light at an irradiation dose of 30 erg / cm ² at a pitch of 25 μm and a scan speed of 300 cm / sec.

Next, the liquid developer [L
D-1], a bias voltage of +400 V is applied to the photosensitive material side electrode in a developing device having a pair of flat plate developing electrodes, and reversal development is performed so that toner is electrodeposited on the exposed portion. Rinsing was performed in a single bath to remove stains on non-image areas. (Preparation of Liquid Developer [LD-1]) Synthesis of Toner Particles 70 g of methyl methacrylate, 30 of methyl acrylate
g, 20 g of a dispersed polymer having the following structure and Isopar H6
80 g of the mixed solution was stirred at a temperature of 6 under a nitrogen stream.
Warmed to 5 ° C. To this was added 1.2 g of 2,2'-azobis (isovaleronitrile) (AIVIN) to add 2 g
Reaction for an additional time. I. V. N. And add 0.5g
Reaction for an additional time. I. V. N. And add 0.5g
Reacted for hours. Next, the reaction temperature was raised to 90 ° C.
The mixture was stirred under a reduced pressure of mmHg for 1 hour to remove unreacted monomers.

After cooling to room temperature, the mixture was filtered through a 200-mesh nylon cloth to obtain a white dispersion. The conversion of the monomer in the obtained dispersion was 95% by weight, the average particle size of the resin particles was 0.25 μm, and the monodispersibility was good (particle size was CAPA-500: manufactured by Horiba, Ltd.). use).

[0380]

Embedded image

Production of Colored Particles 10 g of a tetradecyl methacrylate / methacrylic acid copolymer (copolymerization ratio: 95/5 by weight), nigrosine 1
0 g and 30 g of Isopar G were placed in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with the glass beads, and dispersed for 4 hours to obtain a fine dispersion of nigrosine. Production of liquid developer 45 g of the resin dispersion of the toner particles, 25 g of the nigrosine dispersion, 0.6 g of hexadecene / half-maleic acid octadecylamide copolymer, and FOC-1800 (manufactured by Nissan Chemical Co., Ltd.); A liquid developer for electrostatography was prepared by diluting to 1 liter of G.

The plate-formed photosensitive material obtained as described above was used to fix an image by a heat roll fixing method. Next, F
uji PS-plate: an aluminum support used for FPD (manufactured by Fuji Photo Film Co., Ltd.) and the developed photosensitive material are superimposed on each other, and the surface temperature in contact with a pressure of 12 kgf / cm ² is always 120 ° C. It passed between a pair of controlled rubber rollers at a speed of 10 mm / sec.

Thereafter, the aluminum support and the light-sensitive material were peeled off after cooling to room temperature with the stack, and the image (fog, image quality of the image) formed on the aluminum support was visually evaluated. In the case of the light-sensitive material of the present invention, all the toner on the light-sensitive material is thermally transferred to the aluminum support side together with the release layer, and a clear image without background fog is obtained. I couldn't see it.

[0384] The above facts indicate that the fluorine atom-containing copolymer coexisting in the photoconductive layer concentrates and transfers to the surface during the formation of the photoconductive layer, and further the binder resin [B] and the resin [P] This is considered to be due to the fact that due to the cross-linking agent, the polymer was sufficiently chemically bonded to each other and a cured film was formed, whereby an interface having good releasability was clearly formed. Next, the plate on which the transfer layer was transferred to the aluminum support was desensitized (that is, the transfer layer was removed), and the printing performance of the printing plate was examined.

The above plate was immersed in a desensitizing solution (E-1) having the following formulation at a temperature of 25 ° C. for 1 minute to remove the transfer layer, washed sufficiently with water, gummed, and printed for offset printing. Created a version. Desensitizing solution (E-1) Mercaptoethanesulfonic acid 10 g Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 8 g N, N-dimethylacetamide 20 g was diluted with distilled water to make a total volume of 1.0 liter, and then water was added. Adjusted to pH 13.0 with sodium oxide.

The printing plate obtained in this manner was visually observed for a non-image portion and a toner image portion using a 200-fold optical microscope. As a result, no transfer layer remained in the non-image portion, and the image portion was not observed. No lack of high resolution areas such as thin lines and fine characters was observed. Immersion water for PS plate (S
G-23) (Tokyo Ink Co., Ltd.) was diluted 130 times with distilled water using an aqueous solution (pH 7.0), Oliver 94 type (Sakurai Seisakusho Co., Ltd.) was used as a printing machine, and printing paper was used. Using neutral paper, printing was carried out with various color inks for offset printing, and the number of printed sheets capable of obtaining a clear image free of background smear was examined. As a result, irrespective of the type of the color ink, a printing endurance of 60,000 or more was obtained in each case.

Further, after printing was performed using the printing plate of the present invention, the PS plate was then printed under the normal operation.
No problems arose. That is, with the same printing press,
It was confirmed that it can 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 extremely good image reproducibility obtained by the semiconductor laser light scanning exposure method and that it is well reproduced on printed matter, and has sufficient color ink suitability. In addition, it was confirmed that the ink had almost no ink selectivity, and exhibited extremely excellent performances, such as that full-color printing was obtained with high printing durability and that it could be easily shared with other offset printing plates.

Example 3 In the apparatus shown in FIG. 5, the following operation was performed using amorphous silicon (adhesive strength: 160 gf) as the electrophotographic photosensitive member. First, a separate paper (manufactured by Oji Paper Co., Ltd.) was used as a release paper, and a paper on which the resin [A-4] was formed with a film thickness of 4 μm was pressed against an amorphous silicon photoreceptor. A transfer layer made of resin [A-4] was transferred to the surface of the photoreceptor.

Next, using the apparatus shown in FIG. 5, after forming and fixing a toner image by an electrophotographic process, the transfer layer is transferred to a PS plate (FPD) and desensitized.
Image reproducibility, transferability and printability were evaluated in the same manner as in Example 2. However, the transferability of the transfer layer from the photoreceptor surface to the aluminum support was 8 mm / sec between a pair of rubber rollers in contact with a pressure of 15 kgf / cm ² and constantly controlled at a surface temperature of 120 ° C. After passing through at a speed (hereinafter referred to as transfer condition I), the aluminum support was cooled at room temperature while being overlapped, and then the photosensitive material was peeled off the aluminum support, and the image formed on the aluminum support obtained was visually evaluated. .

In the desensitization treatment, the plate on which the transfer layer was transferred to the aluminum support was immersed in a desensitization treatment solution (E-2) having the following formulation at a temperature of 30 ° C. for 30 seconds, and then loosened. While rubbing, the transfer layer was removed, washed sufficiently with water, and gummed to prepare a printing plate for offset. Desensitization treatment liquid (E-2) PS plate treatment agent: DP-4 143 g N, N-dimethylethanolamine 100 g diluted with distilled water to make a total volume of 1 liter (pH 13.1) The obtained printing plate was visually observed using a 200-fold optical microscope for the presence or absence of a transfer layer in a non-image portion and the absence of a toner image portion.

[0391] When the photosensitive material provided with the transfer layer of the present invention was used, the imaging performance was good. The transferability of the transfer layer was good and the transfer layer was completely transferred. When the performance as a printing plate was examined, the desensitizing property was good, the transfer layer was completely removed, and no background stain was observed. Further, even in a high-definition image portion such as a fine character, a thin line, and an intermediate portion of halftone dot continuous tone, a lack of a toner image was not observed, and the image portion resistability was good. It was possible to print more than 60,000 sheets, both in actual printing and using various color inks.

Example 4 A printing plate was prepared in the same manner as in Example 3, except that the resin [A-3] was used in place of the resin [A-4] in the transfer layer. As in Example 3, excellent image reproducibility, transferability, desensitizing property, and printing durability were exhibited. That is, at least 60,000 clear prints without background contamination could be printed.

Further, the transfer was carried out by changing the transfer conditions in the method of Example 3 to a pressure of 8 kgf / cm ² , a surface temperature of 80 ° C. and a speed of 10 mm / sec (hereinafter referred to as transfer condition II).
The transferability was evaluated, and it was found that good transferability was still exhibited even under such transfer conditions. Further, by using a thermoplastic resin containing a polymer component containing a silicon atom as a block, transferability was further improved. In particular, it is effective when a transfer layer having good releasability is provided on a photoreceptor such as an aluminum silicon photoreceptor in which the surface of the electrophotographic photoreceptor in contact with the transfer layer is not sufficiently peelable.

Examples 5 to 16 In Example 2, the resin [P-2] and the resin [A-2]
In place of the above, a printing plate was prepared in the same manner as in Example 2 except that each of the resin [P] and the resin [A] shown in Table-N below was used.

[0395]

[Table 35]

The performance of each material was evaluated in the same manner as in Example 2. In each case, the same results as in Example 2 were obtained. That is, it was possible to print at least 60,000 clear prints without background contamination.

Example 17 5 g of 4,4′-bis (diethylamino) -2,2′-dimethyltriphenylmethane was used as an organic photoconductive substance.
4 g of a binder resin [B-3] having the following structure, and the resin [P-1]
9] 0.8 g, 40 mg of dye (D-2) having the following structure, and 0.2% of anilide compound (B) having the following structure as a chemical sensitizer
g was dissolved in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride to obtain a photosensitive solution.

[0398]

Embedded image

The photosensitive solution was applied to a conductive transparent support (a polyethylene terephthalate support having a thickness of 100 μm and a vapor-deposited film of indium oxide; surface resistance: 10 ³ Ω) using a wire round rod. An organic thin film having a 4 μm photosensitive layer was obtained. In addition, 50 ° C 80% R
The photosensitive layer was crosslinked by being left for 3 days under the condition of H. The adhesive strength of the photoreceptor surface was 30 gf.

This photoreceptor was loaded into the apparatus shown in FIG. 3, and the imaging and transfer properties were examined in the same manner as in Example 2. However, exposure was performed using helium-neon laser light having an oscillation wavelength of 630 nm instead of the semiconductor laser light having an oscillation wavelength of 780 nm used in Example 2. The resulting copied image on the aluminum support after transfer was clear without background fog.

Next, the printing plate and the printing performance were examined by desensitizing treatment in the same manner as in Example 2. As in Example 2, the number of printings was 60,000 or more.

Example 18 5 g of a bisazo pigment having the following structure, 95 of tetrahydrofuran
g, polyester resin Byron 200 (Toyobo Co., Ltd.)
5 g) and 30 g of a tetrahydrofuran solution were sufficiently pulverized in a ball mill. Next, this mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was coated on the conductive transparent support used in Example 1 using a wire round rod to form a dispersion having a thickness of about 0.7 μm.
m of the charge generation layer was formed.

[0403]

Embedded image

Next, a hydrazone compound 20 of the following structural formula
g, a mixed solution of 20 g of polycarbonate resin (manufactured by GE, trade name: Lexan 121) and 160 g of tetrahydrofuran are applied on the above-mentioned charge generating layer using a wire round rod, dried at 60 ° C. for 30 seconds, and further dried at a temperature of 100 ° C.
By heating at 20 ° C. for 20 seconds, a charge transport layer having a thickness of about 18 μm was formed, and an electrophotographic photosensitive member having a two-layer photosensitive layer was obtained.

[0405]

Embedded image

Further, in order to form a surface layer for imparting releasability on the photosensitive layer, a resin [P
-39] A mixed solution consisting of 13 g, 0.2 g of phthalic anhydride, 0.002 g of o-chlorophenol and 100 g of toluene was applied using a wire round rod so as to have a thickness of 1 μm. For 1 hour. The tackiness of the surface of the obtained photoreceptor was 0 gf.

[0407]

Embedded image

Using the above photoreceptor, the same operation as in Example 17 was carried out to examine the performance as a printing plate. As a result, a good result equivalent to that of Example 17 was obtained.

Example 19 100 g of photoconductive zinc oxide and a binder resin [B-
5] 19 g, 1 g of the resin [P-32], color of the following structure
[D-3] 0.0020 g, thiosalicylic acid 0.1 g
And a mixture of 300 g of toluene in a homogenizer,
Rotation speed 9 × 10 ^Threer. p. m. For 15 minutes. Next
This dispersion was subjected to a conductive treatment and a solvent resistance treatment.
Wire bar on 0.2mm thick paper master paper
And apply at 2.5 ° C for 20 seconds at 110 ° C.
While drying. The obtained photoreceptor surface has an adhesive strength of 10 gf.
there were.

[0410]

Embedded image

Next, each of the above light-sensitive materials was heated at 25 ° C. and 60% RH.
And the following operation was performed. A paper provided with a layer of resin [A-19] having a thickness of 3 μm on a release paper sun release (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) was loaded on 17 parts of FIG. 5, and the pressure between the rollers was 3 kgf / cm. ^{2. A} transfer layer was formed by transferring a transfer layer on the photosensitive surface under the conditions of a surface temperature of 80 ° C. and a passing speed of 10 mm / sec.

Next, after charging the photosensitive material at -6 kV,
Using a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) with a 5 mW output in a positive mirror image mode based on information previously read from a manuscript by a color caster and stored as a digital image on a hard disk in the system. , 30 erg / on the photosensitive material surface
Exposure was performed at a pitch of 25 μm and a scan speed of 300 cm / sec under an irradiation amount of cm ² .

Next, development was performed using a liquid developer [LD-2] by applying a bias voltage of 150 V, followed by rinsing in a single bath of Isopar H to remove stains on non-image areas. Heat fixing was performed. Using a straight master as a material to be transferred, the material was loaded into 37 parts of FIG. 5, and the transfer conditions (pressure between rolls: 8 kgf / cm ² , surface temperature: 100 ° C.)
The transfer layer was transferred onto a straight master under a temperature of 5 ° C. and a passing speed of 5 mm / sec).

A desensitizing treatment was performed in the same manner as in Example 1 to form a printing plate, and printing was performed. The copied images of the characters and line drawings were reproduced at a level that would cause no practical problems. The transferability and the desensitizing property were good, and there was no remaining non-image portion and no missing toner image portion. The printing durability was 3000 sheets or more.

Example 20 In the preparation of the photoreceptor of Example 19, the binder resin [B-
5] Instead of using 19 g, the binder resin [B
-4] and 3.6 g of the binder resin [B-5], except that 15.4 g of the binder resin was used. The binding strength of the obtained photoreceptor was 10 gf.

Using this photoreceptor, a printing plate was prepared in the same manner as in Example 19. However, the image reproducibility was the same as the environmental conditions (condition I) (25 ° C., 65% RH) performed in Example 19 and the high temperature and high pressure (30 ° C., 80% RH).
(Condition II). The image reproducibility of the copied image was extremely good. In particular, no unevenness occurred even in an image composed of a halftone continuous tone image, and good image reproducibility was exhibited even in a halftone portion. Furthermore, no matter what the environmental condition was either the condition I or the condition II, no omission or the like occurred even in the thin line / fine character portion, and the image reproducibility was very good regardless of the environmental condition. . Therefore, by using a low molecular weight polymer composed of a specific methacrylate component and a specific polar group-containing polymer component as a binder resin of the photoconductor, also in the scanning exposure method using a low output semiconductor laser light. Therefore, an image composed of halftone dot continuous tone images can be favorably reproduced.

Therefore, unlike the case where the electrophotographic photosensitive member is exposed to the entire surface at the same time using a high-output visible light source, the scanning exposure method using a low-output semiconductor laser beam also makes use of a conventionally known electrophotographic photoconductor layer. It can be seen that the printing plate production system of the present invention can exhibit higher performance by combining with a technique for improving characteristics (particularly, charge retention in the dark and light sensitivity).

Examples 21 to 23 In the same manner as in Example 20, except that 3.6 g of each resin [B] shown in Table M below was used instead of 3.6 g of binder resin [B-4]. Thus, each photosensitive material was prepared. Next, a printing plate was prepared in the same manner as in Example 20 using each photosensitive member. All of image reproducibility, transferability and printability showed good performance equivalent to that of Example 20.

[0419]

[Table 36]

Examples 24-36 In Example 1, 20 g of resin [B-1] and resin [P-
1] Instead of 3 g and the crosslinking compound (phthalic anhydride, o-chlorophenol), 2 g of the binder resin [B-6] and the resins [B] and [P] (resin [B] 1
An electrophotographic photoreceptor and a printing plate were prepared in the same manner as in Example 1 except that 5 g of the resin [P] was used and 3 g of the resin [P] were used, and each of the compounds shown in Table P below was used as a crosslinking compound. ,
Image reproducibility and printability were examined in the same manner as in Example 1.
The image reproducibility is good, and the transferability is the same as the transfer conditions I and II.
In any case, the transfer layer was completely transferred to the aluminum support, and was good. Further, when the printability was examined, as in Example 3, more than 60,000 copies of a clear image with no clear image on the non-image area were obtained.

[0421]

[Table 37]

[0422]

[Table 38]

[0423]

[Table 39]

[0424]

[Table 40]

Example 37 Example 37 was repeated except that the electrophotographic photosensitive member was replaced with amorphous silicon by using a photosensitive member having a 1.5 μm-thick releasable surface layer on the amorphous silicon as described below. A printing plate was obtained in the same manner as in Example 3. [Formation of Surface Layer] Using a toluene solution consisting of 1.0 g of resin [P-12], 15 g of a binder resin having the following structure, and 100 g of toluene, coating the amorphous silicon photoreceptor to a thickness of 1.5 μm. After the formation of the film, the film was dried by touch and further cured at 60 ° C. and 80% RH for 24 hours.

[0426]

Embedded image

In the same manner as in Example 3, the image reproducibility, transferability and printability were examined. The image reproducibility was good, and the transferability was good because the transfer layer was completely transferred to the aluminum support under both the transfer conditions I and II. Further, when the printability was examined, as in Example 3, more than 60,000 copies of a clear image with no clear image on the non-image area were obtained.

Example 38 In Example 18, a resin [P-
39] and a crosslinkable compound (phthalic anhydride, o-chlorophenol), 2 g of resin [P-19], 20 g of resin [B-22] having the following structure, 0.1 g of phthalic anhydride,
0.01 g of o-chlorophenol, acetylacetone Z
A printing plate was prepared in the same manner as in Example 18, except that a surface layer composed of 0.005 g of r salt and 100 g of toluene was provided. The tackiness of the surface of the electrophotographic photosensitive member provided with the surface layer was 0 gf.

[0429]

Embedded image

The image reproducibility, transferability and printability were examined in the same manner as in Example 18. The image reproducibility was good, and the transferability was good because the transfer layer was completely transferred to the aluminum support under both transfer conditions I and II. Further, when the printability was examined, as in Example 18, more than 60,000 prints of clear images with no background smear in the non-image area were obtained.

Examples 39 to 52 In Example 38, the resin [P] or the resin particles [L] shown in Table O below was used in place of the resin [P-19] used for forming the peelable surface layer. Example 1 was repeated except that the resin [A-2] shown in the following Table-O was used in place of the resin [A-2] of the transfer layer.
In the same manner as in No. 8, an electrophotographic photosensitive member and a printing plate were prepared.

[0432]

[Table 41]

Image reproducibility, transferability and printability were examined in the same manner as in Example 38. The image reproducibility was good, and the transferability was good because the transfer layer was completely transferred to the aluminum support under both transfer conditions I and II. Further, when the printability was examined, as in Example 38, more than 60,000 prints of clear images with no background smear in the non-image area were obtained.

Example 54 The electrophotographic photosensitive member used in Example 22 was mounted on an apparatus as shown in FIG. 5, and a transfer layer was formed by a wet electrodeposition method. The surface temperature of the photoreceptor was set to 60 ° C., the peripheral speed of the photoreceptor drum was rotated at 10 mm / sec, and a positively charged resin particle dispersion [L-1] having the following content was applied to the photoreceptor surface using a slit electrodeposition device. While supplying, the photoreceptor side was grounded and a voltage of -200 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit and fix the resin particles. At this time, the film thickness was 4 μm.

Resin Particle Dispersion [L-1] Resin Particles [AR-1] 8 g (as solid content) Positive charge control agent CD-1 0.02 g [Octadecyl vinyl ether / N-hexadecylmaleic acid half amide (1 / 1) Weight ratio] Copolymer was adjusted to a total volume of 1.0 liter with Isopar G.

The toner image was formed on the photoreceptor provided with the transfer layer thus obtained in the same manner as in Example 2.
S-plate: Transfer to FPD was performed. In the toner image transferred onto the FPD, almost no deterioration in the image quality of the document was observed. The plate on which the transfer layer was transferred to the aluminum support was heated at 140 ° C. for 5 minutes in order to further strengthen the adhesion between the toner image area and the aluminum support.

The above-mentioned plate was immersed in a desensitizing solution (E-3) having the following formulation at a temperature of 35 ° C. for 1 minute, and the transfer layer was removed while rubbing loosely with a bristle brush. Then, a printing plate for offset was prepared. Desensitizing solution (E-3) PS plate treating agent: DP-4 (Fuji Photo Film Co., Ltd.)
Was diluted 50 times with distilled water (pH 12.5). The printing plate thus obtained was visually observed for a non-image portion and a toner image portion using a 200-fold optical microscope. No transfer layer was observed, and no loss of high-resolution areas such as fine lines and fine characters in the image area was observed.

This plate was soaked in soaking water for PS plate (S
G-23) (Tokyo Ink Co., Ltd.) was diluted 130 times with distilled water using an aqueous solution (pH 7.0), Oliver 94 type (Sakurai Seisakusho Co., Ltd.) was used as a printing machine, and printing paper was used. Using neutral paper, printing was carried out with various color inks for offset printing, and the number of printed sheets capable of obtaining a clear image free of background smear was examined. As a result, irrespective of the type of the color ink, 80,000 or more printing endurances were obtained in each case.

As described above, depending on the type of the toner used as the printing plate, the printing durability is further improved by making the toner image portion more firmly adhere to the support. At this time, the transfer layer which is a non-image portion also adheres more firmly to the support. However, as described above, the transfer layer comprising the resin (A) of the present invention is
It was confirmed that it was easily and completely removed.

Example 55 Using the amorphous silicon photoreceptor provided with a peelable surface layer used in Example 37, the same electrodeposition method as in Example 54 was used instead of the resin particle dispersion liquid [L-1]. A transfer layer having a thickness of 4 μm was formed using the resin dispersion [L-2] having the following content. Resin dispersion liquid [L-2] Resin particles [AR-2] 3 g (as solid content) Resin particles [AR-3] 7 g (as solid content) Positive charge regulator: CD-2 0.015 g

[0441]

Embedded image

[0442] Branched tetradecyl alcohol 10g FOC-1400 (manufactured by Nissan Chemical Industries, Ltd.) was adjusted to a total volume of 1.0 liter with Isopar G. A toner image was formed on this photosensitive member in the same manner as in Example 3.

Next, using a straight master (manufactured by Mitsubishi Paper Mills) as a material to be transferred, the developed photosensitive material is superimposed, and the surface temperature at which the material is in contact with a pressure of 10 kgf / cm ² becomes 100 ° C. It was passed between a pair of rubber rollers which were always controlled at a speed of 10 mm / sec. Thereafter, the support and the photosensitive material were peeled off after being cooled to room temperature while being stacked, and the image (fog, image quality) formed on the obtained straight master support was visually evaluated.

In the case of the photosensitive material of the present invention, all the toner on the photosensitive material is thermally transferred to the support side together with the release layer, and a clear image without background fog is obtained. I could hardly see it.

Next, the plate on which the transfer layer was transferred to the straight master support was desensitized (that is, the transfer layer was removed).
The printing performance as a printing plate was examined. Place the above plate at temperature 2
It was immersed in a desensitizing solution (E-4) having the following formulation at 5 ° C. for 30 seconds to remove the transfer layer while gently rubbing the plate surface, washed sufficiently with water, and gummed to prepare an offset printing plate.

Desensitizing solution (E-4) Mercaptoethanesulfonic acid 10 g Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 5 g N, N-dimethylacetamide 10 g was diluted with distilled water to make a total volume of 1.0 liter. Then, the pH was adjusted to 13.0 with sodium hydroxide.

The printing plate thus obtained was visually observed for a non-image portion and a toner image portion using an optical microscope of 200 times. As a result, no transfer layer remained in the non-image portion, and the image portion was not observed. No lack of high resolution areas such as thin lines and fine characters was observed. This plate was subjected to offset printing in the same manner as in Example 1 to obtain 2,000 sheets of clear images with no background stains.

Examples 56 to 71 In Example 54, 10 g of the resin particles [AR] shown in Table R below were used instead of the resin particles [AR-1] in the dispersion liquid [L-1] of the resin [A]. Except for this, the printing plate was prepared and printed in the same manner as in Example 54.

[0449]

[Table 42]

With the printing plate made of the material of the present invention, 60,000 prints of clear image quality without background fog were obtained. Further, when various printing inks were evaluated in the same manner as in Example 54, the same performance was obtained, and the selectivity of the color ink was not observed.

Examples 72 to 83 Offset printing plates were prepared by performing the desensitization treatment as follows using the plate (plate making original plate) after the transfer to the material to be transferred prepared in Examples 1 to 71. . 0.2 mol of the nucleophilic compound shown in Table S below, 50 g of organic solvent and Newcol B4SN
After adding distilled water to 2 g (manufactured by Nippon Emulsifier Co., Ltd.) to make 1 liter, the pH of each mixture was adjusted to 13.0. Each master plate was immersed in the processing solution at a temperature of 30 ° C. for 1 minute to perform a desensitization treatment. The obtained plate was printed under the same printing conditions as in Example 1.

[0452]

[Table 43]

For each material, when the straight master was used as the material to be transferred, good results were obtained: 3,000 or more printing presses, and when the aluminum support was used as the material to be transferred, more than 60,000 sheets were obtained.

[0454]

According to the method of preparing an electrophotographic plate-making printing plate of the present invention, a printing plate having good plate-making quality and printing quality and having stable performance even after long-term and continuous processing can be obtained. It is suitable for image formation by scanning exposure with a laser or the like. Further, the present invention provides a method for preparing an electrophotographic printing plate which can use a photoreceptor repeatedly and is effective in reducing running cost.

[Brief description of the drawings]

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

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

FIG. 3 is a diagram showing an example of an electrophotographic plate-making printing plate precursor producing apparatus to which a transfer layer forming method by melt coating is applied.

FIG. 4 is a diagram illustrating an example of an electrophotographic plate-making and printing original plate producing apparatus to which a transfer layer forming method using release paper is applied.

FIG. 5 is a diagram illustrating an example of an electrophotographic plate-making and printing original plate producing apparatus to which a transfer layer forming method using an electrodeposition method is applied.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Support body of photoreceptor 2 Photosensitive layer 3 Toner image 4 Rubber coating roller 5 Built-in heating heater 6 Surface temperature detecting means 7 Temperature controller 10 Release paper 11 Photoreceptor 12 Transfer layer 12a Thermoplastic resin 12b Dispersion liquid of thermoplastic resin particles 13 Hot Melt Coater 13a Hot Melt Coater Standby Position 14 Liquid Developing Unit Set 14a Liquid Developing Unit 14b Rinse Bath Unit 15 Suction / Exhaust Unit 15a Suction Unit 15b Exhaust Unit 16 Transfer Material 17 Thermal Transfer Means 17a Preheating Means 17b Heating Roller 17c Cooling Roller 18 Corona charging device 19 Exposure device 117 Thermal transfer means 117b Heating roller 117c Cooling roller

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 13/26-13/32

Claims (5)

(57) [Claims] 1. A releasable transfer layer which can be removed by a chemical reaction treatment and mainly contains a thermoplastic resin [A] containing at least the following polymer components (a) and (b): And the adhesive force of the surface of the photoconductive layer adjacent to the transfer layer according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method” is 200 gram · fo.
A toner image is formed on the transfer layer by an electrophotographic process using an electrophotographic photoreceptor having an rc (gf) or less, and the toner image is transferred onto the transfer layer together with the transfer layer to form a lithographically printable hydrophilic surface during printing. A method for preparing an electrophotographic printing plate, wherein the transfer layer is thermally transferred to a transfer material, and then the transferred layer of the transferred material is removed by a chemical reaction treatment. (I) Polymer component (a): —CO ₂ H group, —CHO group,
—SO ₃ H group, —SO ₂ H group, —P (＝ O) (OH) R ¹
｛R ¹ is a phenolic OH group, a hydrocarbon group or —OR ²
(R ² represents a hydrocarbon group), a group representing a group, a —OH group,
Acid cyclic anhydride-containing group, -CONHCOR ³ (R ³ represents a hydrocarbon group) polymer component containing at least one group of the groups and -CONHSO ₂ R ³ group (ii) polymer component (b) : -CO ₂ H by chemical reaction treatment
Group, -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, and at least one group of an —OH group Component containing at least one functional group that produces 2. Adhesive strength according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method” is 200 g.
A transfer layer containing the thermoplastic resin [A] according to claim 1 is formed on the surface of the electrophotographic photoreceptor having a density of f or less, and a toner image is formed on the transfer layer by an electrophotographic process. An electronic device comprising: thermally transferring a toner image together with a transfer layer to a material to be transferred which becomes a lithographically printable hydrophilic surface during printing, and then removing the transferred layer of the transferred material by a chemical reaction treatment. How to make a photolithographic printing plate. 3. The transfer layer according to claim 1, wherein the transfer layer has a layer mainly containing a thermoplastic resin [A] on a photoreceptor having an adhesive force of 200 gf or less. How to make an electrophotographic printing plate. 4. The thermoplastic resin [A] contains a polymer component (c) containing at least one of a fluorine atom and a silicon atom as a copolymer component. How to make an electrophotographic printing plate. 5. The electrophotographic photoreceptor is a photoreceptor containing amorphous silicon as a main component, or a polymer component containing at least one of a fluorine atom and a silicon atom in a layer adjacent to the transfer layer. 3. The method for preparing an electrophotographic printing plate according to claim 1, which is a photoconductor containing a polymer.