JPH0869135A - Production of electrophotographic printing plate - Google Patents

Abstract

PURPOSE: To obtain excellent transfer property when a toner image with a transfer layer is transferred to a transfer material to be transferred, especially to completely transfer a toner image with a transfer layer to the transfer material to be transferred to obtain good image quality even when a film thickness of the transfer layer is thin and transfer is done under conditions of low temp. and high transfer speed. CONSTITUTION: A first transfer layer 12T1 is formed by electrodeposition coating of resin particles (AL) on the surface of an electrophotographic photoreceptor 11. The resin particles (AL) contain a resin (A1 ) having 10 to 140 deg.C Tg or 35-180 deg.C softening point and a resin (A2 ) having <=45 deg.C Tg or <60 deg.C softening point which is lower than the Tg or the softening point of the resin (A.) by >=2 deg.C in one particle. Then a second transfer layer 12T2 containing a resin (A2 ) is formed on the first transfer layer to obtain a transfer layer 12 of a laminated structure. A toner image 3 is formed on the transfer layer 12 by an electrophotographic process. The toner image with the transfer layer 12 is transferred to the material 16 to be transferred. Then the transferred image 12 on the material 16 is removed by chemical reaction processing to obtain a printing plate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing a lithographic printing plate using a transfer layer provided on an electrophotographic photosensitive member, and more specifically, it is excellent in plate transfer image quality and print image quality of transfer layer. Relates to a method for producing an electrophotographic plate-making printing plate having good quality.

[0002]

2. Description of the Related Art A lithographic printing plate, especially an electronic editing system which can be operated by a computer consistently from manuscript input, correction, editing, layout to page setting and can be immediately output to a terminal plotter at a remote place by a high speed communication network or sanitary communication. An electrophotographic photosensitive member is used as a photosensitive member having a high photosensitivity, which can provide a direct type printing plate for directly producing a lithographic printing plate from the output of an end plotter. As a method for preparing a lithographic printing plate using an electrophotographic photosensitive member, after a toner image is formed by an electrophotographic process, a non-image portion is desensitized (hydrophilized) with a desensitizing treatment liquid and used as a printing plate A method is known in which the photoconductive layer in the non-image area is removed after forming a toner image to form a printing plate.

However, the photosensitive layer is hydrophilized to modify the surface of the electrophotographic photosensitive member itself to form a hydrophilic non-image portion, or the photosensitive layer is eluted and removed to expose the surface of the hydrophilic support. In the method, there are various restrictions on the photoconductor, particularly the photoconductive compound and the binder resin used in the photoconductive layer, and there are many problems in terms of image quality and printing durability of the obtained printing plate.

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

[0005]

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

However, in such a method, if the toner image is not completely transferred to the transfer target material together with the transfer layer,
Good plate-making quality cannot be obtained. In particular, when the transfer layer is thin and transfer conditions are relaxed, for example, when the transfer temperature becomes low or the transfer speed becomes high, the transfer layer and the toner image are still satisfactorily applied to the transfer target material. It is desired to be transferred. It is an object of the present invention to solve a new problem relating to transferability in a method for producing a lithographic printing plate using such a transfer layer.

[0007]

The above object of the present invention is to form a transfer layer which can be removed by a chemical reaction treatment and can be peeled off on the surface of an electrophotographic photoreceptor, and the transfer layer can be formed on the transfer layer by an electrophotographic process. A toner image is formed, and the toner image is transferred together with the transfer layer to a transfer material that becomes a hydrophilic surface that can be lithographically printed at the time of printing, and then the transfer layer of the transferred transfer material is removed by a chemical reaction treatment. In the method for producing an electrophotographic plate-making printing plate, the transfer layer has a glass transition point of 10 to 140.
A ° C. or a softening point of 35 ° C. to 180 ° C. Resin (A ₁₎ and a glass transition point of 45 ° C. or less or a softening point 60 ° C. or less of the resin (A _2), the glass transition point or softening point of the resin (A ₁₎ Of the resin (A ₂ ) is higher than that of the resin (A ₂ ) by 2 ° C. or more, and a thermoplastic resin particle (AL) containing at least two kinds of resin in the same particle is formed by an electrodeposition coating method. ₁ ) and a second transfer layer (T ₂ ) mainly containing the above resin (A ₂ ) provided on this layer, which is a laminated structure, and a method for producing an electrophotographic plate-making printing plate. It has been found that

In the method for producing an electrophotographic plate-making printing plate of the present invention, as shown in the outline of the process in FIG. 1, a first layer is formed on the surface of an electrophotographic photosensitive member 11 comprising at least a support 1 and a photosensitive layer 2. As the transfer layer (T ₁ ), the thermoplastic resin particles (A
L) is applied by electrodeposition, that is, electrostatically adhered or electrodeposited to form a film, and a second transfer layer (T ₂ ) mainly containing a thermoplastic resin (A ₂ ) is further provided thereon. After forming a transfer layer 12 which has a laminated structure and is removable and which can be removed by a chemical reaction treatment, a toner image 3 is formed by an ordinary electrophotographic process, and a support similar to the support used for an offset printing plate is formed. Printing is performed by transferring the toner image 3 together with the transfer layer 12 to a transfer material 16 that is a body to form a printing original plate, and then removing the transfer layer 12 transferred to the transfer material 16 by a chemical reaction treatment. It is a version. In the present invention, the transfer layer 12 has a laminated structure and the first transfer layer (T ₁ ) on the photoconductor side.
The thermoplastic resin particles (AL) forming the resin are characterized by containing at least two kinds of resin (A ₁ ) and resin (A ₂ ) having different glass transition points or softening points in the same particle. .

The transfer layer used in the present invention does not deteriorate electrophotographic properties (chargeability, charge retention ratio in the dark, photosensitivity, etc.) until a toner image is formed by an electrophotographic process.
Forming a good copy image, having a thermoplastic property that easily transfers to the material to be transferred in the next thermal transfer step, and having excellent transferability. It is characterized in that it is easily removed and a printing plate having excellent image quality and printing durability can be obtained.

According to the present invention, the transfer layer has the laminated structure as described above, so that the surface of the photoreceptor and the first transfer layer (T ₁ )
The adhesive force at the interface with the
It is presumed that this is due to the synergistic effect of increasing the adhesiveness with the transfer layer (T ₂ ), which dramatically improves the transferability of the transfer layer, which reduces transfer conditions (temperature and pressure) and improves transfer speed. It has become. As a result, the heating and pressurization of the photoconductor are reduced, the deterioration of electrophotographic characteristics is suppressed, the repeated durability of the photoconductor is improved, and the plate-making speed is improved by shortening the time required for the transfer process.

The transfer layer of the present invention will be described below.
The transfer layer of the present invention provides a printing original plate by peeling and transferring together with the toner image from the electrophotographic photosensitive member having a releasable surface to a material to be transferred which becomes a support for printing, and for making the printing original plate a printing plate. Is a layer having a function of being removed by a chemical reaction treatment. Therefore, the resin as the main component that constitutes the transfer layer used in the present invention is a thermoplastic resin and is a resin that is eluted and removed by a chemical reaction treatment. here,
The above resins mainly used in the transfer layer are collectively referred to as a resin (A) (including a resin (A ₁ ) and a resin (A ₂ )).

The transfer layer of the present invention is not particularly limited as long as it is light-transmissive and has a property of transmitting at least a part of wavelength light in the spectral sensitivity region of the electrophotographic photosensitive member. It may be colored instead of the one. Usually, a colorless and transparent transfer layer is used.

The resin particles (AL) used for forming the first transfer layer (T ₁ ) of the present invention are, as described above, two kinds of resins (A _{1 having} different glass transition points or softening points of 2 ° C. or more). ) And the resin (A ₂ ) at least in the same particle. In the present invention, the resin (A ₁ ) and the resin (A ₂ ) whose glass transition point and softening point are within the scope of the present invention can be arbitrarily selected and provided for the present invention.

The resin (A ₁ ) preferably has a glass transition point of 3
0 to 120 ° C. or softening point 38 ° C. to 160 ° C., more preferably glass transition point 35 to 90 ° C. or softening point 40 ° C.
To 120 ° C, the resin (A ₂ ) preferably has a glass transition point of -40 ° C to + 40 ° C or a softening point of 0 ° C to 40 ° C, and more preferably a glass transition point of -20 to + 33 ° C or a softening point of 5. C to 35C. Further, the difference between the glass transition point or the softening point of the resin (A ₁ ) and the resin (A ₂ ) is preferably 5 ° C. or higher, more preferably 10 ° C. or higher. Here, the difference in the glass transition point or the softening point in the case where two or more kinds of the resin (A ₁ ) or the resin (A ₂ ) are contained is the _one having the lowest glass transition point or the softening point in the resin (A ₁ ). And a resin (A ₂ ) having the highest glass transition point or softening point.

Resin (A ₁ ) and resin (A ₂ ) are the same as resin (A ₁ ) /
Since the resin (A ₂ ) is contained in the resin particles (AL) in an abundance ratio of 5 to 90/95 to 10 (weight ratio), electrophotographic characteristics and transferability are good, and durability of the transfer layer is also high. Often,
Moreover, a printing plate having excellent printing durability can be obtained. Furthermore, when a toner image is formed and transferred to a transfer material to form an original plate, and the original plates are left in a stacked state until the transfer layer is removed by a chemical reaction treatment, the transfer layer and the back side of the upper original plate overlapped with each other. There is no peeling of the transfer layer due to the close contact, and as a result, the toner image is not lost (the printing plate characteristics are good). A more preferable ratio is resin (A ₁ ) / resin (A
₂ ) is 10 to 70/90 to 30 (weight ratio).

Further, at least two kinds of resin (A ₁ ) and resin (A ₂ ) contained in the resin particles (AL) of the present invention are
It may be either in a state of being arbitrarily mixed in the particles or in a state of forming a layered structure in which a resin (A ₁ ) main portion and a resin (A ₂ ) main portion are separated (that is, particles having a core-shell structure). In the case of the core-shell structure, whether the core part is the resin (A ₁ ) or the resin (A ₂ ),
It is not particularly limited.

Resin (A₁) And resin (A₂) Weight average molecule
The amount is preferably 1 x 10 ³~ 5 x 10^Five,Than
Preferably 3 × 10³~ 8 × 10^FourRange. here
The molecular weight is measured by the GPC method and converted into polystyrene.
Yes, and may be abbreviated as Mw below.

The transfer layer of the present invention is the first transfer layer (T₁)of
The second transfer layer (T₂) Is the resin (A₂)
It is a further feature that the content is included. First transfer layer (T₁)
Resin (A₂) And the second transfer layer (T₂) Resin (A₂) Is
It may be the same or different. Second transfer layer (T₂) Used for
Resin (A₂) Is the first transfer layer (T₁) Resin particles
Resin in (AL) (A₁) From the glass transition point or softening point
It is preferably 2 ° C. or higher, particularly 5 ° C. or higher. Furthermore, the tree
Resin (A) in oil particles (AL)₁) Is the glass transition temperature of 25 ° C or higher
The upper or softening point is 35 ° C. or higher, and the second transfer layer (T₂)
Resin (A ₂) Is the resin (A₁) From the glass transition point or
The resin has a low softening point in the range of 10 ° C to 40 ° C.
preferable.

The resin (A) forming the transfer layer of the present invention is
As mentioned above, it is a resin that can be removed by a chemical reaction treatment. The resin (A) that can be removed by the chemical reaction treatment is a resin that is dissolved and / or swelled by the chemical reaction treatment to be removed, and a resin that is hydrophilized by the chemical reaction treatment and as a result is dissolved and / or swelled. Includes.

Resin (A) removed by chemical reaction treatment
Is a resin that can be removed with an alkaline treatment liquid, and a particularly useful resin is a resin containing a hydrophilic group in the polymer component.

Another typical example is a resin containing a hydrophilic group protected by a protective group and capable of expressing the hydrophilic group by a chemical reaction. A chemical reaction capable of converting a functional group into a hydrophilic group is a conventionally known hydrolysis reaction,
Hydrophilic decomposition reaction by treatment solution using hydrogenolysis reaction, oxygen-oxygenation reaction, β-elimination reaction, nucleophilic substitution reaction, or hydrolytic reaction by decomposition reaction by irradiation of chemically active light Either is fine.

In particular, as described above, each of the transfer layer thermoplastic resins (A ₁ ) and (A ₂ ) is specified by the following polymer component (a) containing a specific hydrophilic group and a chemical reaction. It is preferable that the copolymer contains at least one of the polymer components (b) having a functional group that produces a hydrophilic group.

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

Here, the -P (= O) (OH) R ¹ group is a group represented by the following.

[0025]

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

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

When a resin containing the above-mentioned polymer component (a) is used as the thermoplastic resin for the transfer layer, the removal of the transfer layer in the chemical reaction treatment is easily and rapidly achieved, while the above-mentioned polymer component is used. When a resin containing (b) is used, it becomes easy to maintain the electric insulation of the resin itself,
It is preferable in that the reproducibility of the copied image can be maintained without deteriorating the electrophotographic characteristics, and the glass transition point of the resin itself can be adjusted within a low temperature range.

The resin (A) may contain the polymer component (a) and the polymer component (b), and by appropriately selecting these polymer components, the resin (A) has good electrical insulation properties. And the glass transition point are satisfied, electrophotographic characteristics and transferability are remarkably improved, and the transfer layer can be removed quickly and completely without deteriorating the hydrophilicity of the non-image area as a printing plate or the toner image. . 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 carried out at low temperature and low pressure, so that the transfer device can be downsized. Even when used as a printing plate, no contamination of the non-image area due to the residual transfer layer was observed, and there was almost no loss of high-definition toner image areas such as fine lines / fine characters and halftone dot areas. preferable.

When the amount of the polymer components (a) and (b) present is too small, it becomes difficult to remove the transfer layer by a chemical reaction treatment, and when the printing plate is printed, the non-image area is stained. On the other hand, if the amount is too large, it will be difficult to control the glass transition point or softening point of the resin (A) to an appropriate range, no matter how the other copolymerization components of the resin (A) are adjusted, resulting in a transfer layer. And the reproducibility of the copied image is deteriorated, resulting in deterioration of the electrical insulation of the transfer layer and deterioration of the chargeability of the electrophotographic photosensitive member.

Therefore, the contents of the polymer component (a) and the polymer component (b) in the resin (A) are preferably as follows. When only the polymer component (a) containing a specific hydrophilic group is contained in the resin (A), preferably 3 to 50% by weight, more preferably 5 to 5% by weight based on the total polymer components of the resin (A). It is 40% by weight. Further, in the case of containing only the polymer component (b) containing a functional group capable of generating a hydrophilic group in the chemical reaction treatment, it is preferably 3 to 100% by weight in the total polymer components of the resin (A), It is preferably 5 to 70% by weight. Further, the polymer component (a) and the polymer component (b)
When the polymer component (a) is contained, the polymer component (a) is preferably 0.5 to 30% by weight, more preferably 1 to 25% by weight, based on the total polymer components of the resin (A). b) is preferably 3 to 99.5% by weight, more preferably 5 to 5
0% by weight.

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

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

[0034]

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[0035]

[Chemical 3]

[0036]

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[0037]

[Chemical 5]

[0038]

[Chemical 6]

[0039]

[Chemical 7]

[0040]

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

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

[0043]

[Chemical 9]

Here, R ¹¹ and R ^{12, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group,
X represents an aromatic group, Z is a hydrogen atom, a halogen atom,
Trihalomethyl group, alkyl group, -CN group, -NO
₂ group, -SO ₂ Z ¹ group (Z ¹ represents a hydrocarbon group), - CO
Represents an OZ ² group (Z ² represents a hydrocarbon group), an —OZ ³ group (Z ³ represents a hydrocarbon group) or a —COZ ⁴ group (Z ⁴ represents a hydrocarbon group), and n and m represent Represents 0, 1 or 2. However, when both n and m are 0, Z does not represent a hydrogen atom. A ¹ and A ² may be the same or different and each represents an electron-withdrawing group having a positive Hammet substituent constant σ value. R ¹³ represents a hydrogen atom or a hydrocarbon group.
R ¹⁴ , R ¹⁵ and R ¹⁶ and R ²⁰ and R ²¹ may be the same or different from each other and each is a hydrocarbon group or —OZ ⁵
Represents a group (Z ⁵ represents a hydrocarbon group). Y ¹ represents an oxygen atom or a sulfur atom, R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different and each is a hydrogen atom, a hydrocarbon group or a —OZ ⁷ group (Z ⁷ represents a hydrocarbon group). And p is 3
Or represents an integer of 4. Y ² represents an organic residue forming a cyclic imide group.

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

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

[0047] A ^1, A ² may be the same or different, are each at least one electron withdrawing group, A ^1,
The sum of Hammet's σ _p values of A ² may be 0.45 or more. Examples of the electron withdrawing group referred to here include, for example, an acyl group, an aroyl group, a formyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, an alkylsulfonyl group,
Examples thereof include aroylsulfonyl group, nitro group, cyano group, halogen atom, halogenated alkyl group, carbamoyl group and the like. Hammet's σ _p value is usually used as an index for estimating the degree of electron withdrawal / donation of a substituent, and the larger it is on the + side, the stronger the electron withdrawing group. Specific numerical values for each substituent are described in Naoki Inamoto's "Hammett's Rule-Structure and Reactivity" Maruzen (1984). Further, it is considered that the Hammett σ _p value in this system is additive, and it is not necessary that both A ¹ and A ² are electron withdrawing groups. Therefore, for example, when A ¹ is an electron-withdrawing group, the other substituent of A ² may be any as long as the sum of the σ _p values of A ¹ and A ² is 0.45 or more,
There are no particular restrictions.

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

R¹⁷, R¹⁸And R¹⁹Are the same as each other but different
May be present, preferably a hydrogen atom, which may be substituted
A straight-chain or branched alkyl group having 1 to 18 carbon atoms (eg,
Methyl group, ethyl group, propyl group, butyl group, hex
Group, octyl group, decyl group, dodecyl group, octadecyl group
Group, chloroethyl group, methoxyethyl group, methoxy group
Ropyl group, etc.), an alicyclic group which may be substituted (eg
Lopentyl group, cyclohexyl group, etc.), may be substituted
An aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group,
Phenethyl group, chlorobenzyl group, methoxybenzyl group
Etc.), an optionally substituted aromatic group (eg, a phenyl group,
Naphthyl group, chlorophenyl group, tolyl group, methoxy group
Phenyl group, methoxycarbonylphenyl group, dichlorophenyl group
Phenyl group) or -OZ⁷Group (Z⁷Represents a hydrocarbon group
And specifically R above¹⁷, R¹⁸, R ¹⁹Same as hydrocarbon group of
Represents one substituent group). p is an integer of 3 or 4
Represent.

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.

[0051]

[Chemical 10]

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

[0053]

[Chemical 11]

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

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

[0056]

[Chemical 12]

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

Examples of the functional group which produces at least one sulfo group by a chemical reaction include functional groups represented by the following general formula (III) or (IV). General formula (III) in -SO ^₂ -O-L ₂ formula _{(IV) -SO 2 -S-L} 2 formula (III) or (IV), L ² represents a group shown below.

[0059]

[Chemical 13]

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

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

[0062]

Embedded image

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

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

[0065]

[Chemical 15]

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

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

[0068]

Embedded image

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

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

[0071]

[Chemical 17]

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

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

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

[0075]

[Chemical 18]

[0076]

[Chemical 19]

[0077]

Embedded image

[0078]

[Chemical 21]

[0079]

[Chemical formula 22]

[0080]

[Chemical formula 23]

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

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

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

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

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

When the resin (A) is used in the first transfer layer (T ₁ ), it improves the releasability of the resin (A) itself together with the above-mentioned polymer components (a) and / or (b). You may contain the polymer component (c) which has a function and which has a fluorine atom and / or a substituent containing a fluorine atom.
In the present invention, the substituent may be incorporated in the polymer main chain of the polymer or may be present as a substituent of the side chain of the polymer. Preferably, the polymer component (c)
Is contained as a block in the resin (A). The polymer component (c) containing a substituent containing a silicon atom and / or a fluorine atom is 1 to 2 in all polymer components of the resin (A).
Those containing 0% by weight are preferable. Polymer component (c)
If it is less than 1% by weight, the effect of improving the releasability of the resin (A) will be weakened, and if it exceeds 20% by weight, the wettability of the resin (A) with the treatment liquid will be reduced and removal of the transfer layer will be inadequate. It may be sufficient.

Specific examples of the polymer component (c) are the same as those of the polymer component (F) containing a substituent containing a fluorine atom and / or a silicon atom which can be contained in the resin (P) described later. I can list things. Furthermore, the aspect of the polymerization pattern of the block copolymer when the polymer component (c) is contained in a block and the method for synthesizing the copolymer are also described in the case of the block copolymer containing the polymer component (F) described below. Is exactly the same as.

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

[0089]

[Chemical formula 24]

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

R ⁶⁰ is preferably an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, Dodecyl group, tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2
-Hydroxypropyl group etc.), alkenyl group having 2 to 18 carbon atoms which may be substituted (for example, vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), carbon number 7 to 12 optionally substituted aralkyl groups (eg, benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group,
Methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), cycloalkyl group having 5 to 8 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.) or substitution having 6 to 12 carbon atoms Aryl groups which may be substituted (for example, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, methylchlorophenyl group, difluorophenyl group, bromophenyl group, chlorophenyl group) Group, dichlorophenyl group, methylcarbonylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, methanesulfonylphenyl group, cyanophenyl group, etc.) and the like.
The polymer component represented by the formula (U) is used alone or in combination of two or more, and the content thereof is 30 to 97 in the resin (A).
It is preferably in the weight%.

The resin (A) may further contain, in addition to the specific polymer component and the polymer component represented by the general formula (U), other copolymerizable components copolymerizable therewith. Examples of such other copolymerization component include, for example, the general formula (U)
In addition to methacrylic acid esters, acrylic acid esters, and crotonic acid esters containing a substituent other than those described above, α-olefins, vinyl carboxylates or allyl acid esters (for example, acetic acid and propionic acid as carboxylic acids). , Butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides,
Methacrylamides, styrenes (for example, styrene, vinyltoluene, chlorostyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.),
Vinyl sulfone-containing compound, vinyl ketone-containing compound,
Heterocyclic vinyls (for example, vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane,
Vinyl quinoline, vinyl tetrazole, vinyl oxazine, etc.), but not limited thereto. These other copolymerization components can be optionally used within a range that does not impair the transferability of the resin (A), but specifically, it is preferable that they do not exceed 20% by weight in the resin (A).

Further, in the transfer layer, together with the resin (A),
You may use together other resin as needed. However, the polymer component (a) according to the present invention is used in 100 parts by weight of the total resin for forming the transfer layer because the performance of elution and removal of the transfer layer is not deteriorated.
It is desirable that the abundance ratios of (b) and (b) satisfy 5% by weight or more. Examples of other resins that can be used in combination include vinyl chloride resin, polyolefin resin, olefin-styrene copolymer, vinyl alkanoate resin, polyester resin, polyether resin, acrylic resin, methacrylic resin, and cellulose resin. , Fatty acid-modified cellulose resins, and the like.

Specifically, for example, Volumes 1 to 18 (1961) of "Plastic Materials Course Series" published by Nikkan Kogyo Shimbun
), "Polyvinyl chloride" edited by the Kinki Chemical Society Vinyl Section, published by Nikkan Kogyo Shimbun (1988), Eizo Omori "Functional Acrylic Resin" Techno System Co., Ltd. (1985), Eiichiro Takiyama "Polyester Resin Handbook" Published by Nikkan Kogyosha (1988
), Kazuo Yuki, "Saturated Polyester Resin Handbook", published by Nikkan Kogyo Shimbun (1989), Polymer Society of Japan, "Polymer Data Handbook <Applications>", Chapter 1 Baifukan (1986
), Yuji Harazaki, "Handbook of Latest Binder Technology," Chapter 2, General Technology Center Co., Ltd. (1985). You may use these thermoplastic resins individually or in combination of 2 or more types.

Further, in the transfer layer, other additives may be used in combination in order to improve various physical properties such as adhesiveness, film forming property and film strength. For example, rosin for adjusting adhesion,
Petroleum resin, silicone oil, etc. as a plasticizer and a softening agent for improving the wettability to the photoreceptor and lowering the melt viscosity, boribten, DOP, DBP, low molecular weight styrene resin, low molecular weight polyethylene wax, microcrystalline wax, paraffin wax, etc. Further, a polymeric hindered polyhydric phenol, a triazine derivative or the like can be added as an antioxidant. For more information, see “Practice of Hot Melt Adhesion” (Hiroshi Fukada, Kobunshi Kobunkai, 1983), 29-107.
There is a description on the page.

If the film thickness of the transfer layer is too thin, transfer defects are likely to occur, and if it is too thick, problems in the electrophotographic process are likely to occur, and a sufficient image density cannot be obtained, or image quality is likely to deteriorate. Therefore, the thickness of the transfer layer as a whole is preferably 0.1 to 15 μm, and more preferably 0.
It is in the range of 5 to 8 μm. The film thickness ratio of the first transfer layer and the second transfer layer is 1 to 8/9 to 2, preferably 2 to 7/8 to 3.

In the present invention, the thermoplastic resin as described above is a resin particle (AL) containing at least two kinds of resin (A ₁ ) and resin (A ₂ ) having a specific glass transition point in the same particle. In the state of 1), it is adhered on the surface of the photoreceptor by the electrodeposition coating method, and a uniform thin film is formed by, for example, heating or the like to form the first transfer layer (T ₁ ). Here, the electrodeposition coating method means a method of electrostatically attaching or electrodepositing the resin particles (AL) on the surface of the photoconductor. Therefore, thermoplastic resin particles (AL)
Must have either a positive charge or a negative charge, and its electroscopic property is arbitrarily determined by the chargeability of the electrophotographic photosensitive member to be combined.

The resin particles (AL) are in a range satisfying the above-mentioned physical properties, and the average particle diameter thereof is usually 0.01.
μm to 10 μm, preferably 0.05 μm
˜5 μm, more preferably 0.1 μm to 1 μm. These particles are either particle powder (dry type), resin particles dispersed in a non-aqueous system (wet type), or resin particles dispersed in an electrically insulating organic substance that is solid at room temperature and becomes a liquid by heating (pseudo-wet type). It may be in a state. Preferably, the non-aqueous dispersion resin particles are capable of easily adjusting the film thickness of the transfer layer for peeling to a thin film with a uniform thickness. The fine resin particles of the present invention can be produced by a conventionally known mechanical grinding method or polymerization granulation method. These production methods can be applied to particles of either dry electrodeposition or wet electrodeposition.

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

As the polymerization granulation method, conventionally known methods such as an emulsion polymerization reaction carried out in an aqueous system, a seed polymerization reaction, a suspension polymerization reaction, and a dispersion polymerization reaction carried out in a non-aqueous solvent system are known. Specifically, Soichi Muroi "Chemistry of Polymer Latex" Polymer Publishing (1970), Taira Okuda, Hiroshi Inagaki "Synthetic Resin Emulsion" Polymer Publishing (1978), Soichi Muroi "Polymer Latex""Introduction" Kobunsha (1983), I.
Piirma, PC Wang "Emulsion Polymerization", I.
Piirma & JL Gardon, ACS symp. Sev. 24, p.34 (1
974), Fumio Kitahara et al. "Chemistry of Dispersion Emulsion System" Engineering Book (1
979), Soichi Muroi, "Cutting-edge technology of ultrafine particle polymer" CMC (1991), etc. It can be produced by collecting and pulverizing by various methods.

As a method of dry electrodeposition of the obtained fine particle powder, a conventionally known coating method of electrostatic powder or a developing method of dry electrostatic photographic developer can be used. Specifically, as described in "Electrostatic Powder Coating" by JF Hughes (Translated by Hideo Nagasaka and Machiko Midorikawa), corona charging, friction charging, induction charging, ionic wind charging, reverse ionization, etc. are used. As described in the textbooks such as "Method of Electrodepositing Charged Fine Particles", Koichi Nakamura, "Development and Practical Use of Recent Electrophotographic Development System and Toner Material", Chapter 1 (Japan Science Information Co., Ltd., 1985). , Cascade method, magnetic brush method, fur brush method, electrostatic method, induction method,
This can be appropriately performed using a development method such as a touchdown method or a powder cloud method.

When producing the non-aqueous latex used in the wet electrodeposition method, either the mechanical method or the polymerization granulation method can be used as described above. For example, a method in which a dispersion polymer is used in combination and further dispersed by a wet disperser (for example, a ball mill, a paint shaker, a eddy mill, a dyno mill, etc.), a material serving as a resin particle component and a dispersion assisting polymer (or a coating polymer) are kneaded in advance. And the like, and then pulverized, and then a dispersing polymer is coexisted and dispersed. Specifically, a method for producing a paint or a developer for electrostatic photography can be used.
), DH Solomon "The Chemistry of Organic Fil
m Formers '' John Wiles & Sons (1967), `` Paint and Su
rface Coating Theory and Practice ", Yuji Harazaki" Coating Engineering "Asakura Shoten (1971), Yuji Harasaki" Basic Science of Coating "Asakura Shoten (1977), etc.

Further, as a polymerization granulation method, a seed polymerization method can be easily used. Specifically, the above-mentioned "state of the art of ultrafine particle polymer", Chapter 2, "Recent electrophotographic development" can be used. Development and practical application of systems and toner materials "
Chapter, KEJ Barvett “Dispersion Polymerization in
Organic Media "John Wiley (1975) et al., A conventionally known non-aqueous dispersion polymerization method is used to first synthesize fine particles of a resin (A ₁ ) or a resin (A ₂ ). It is preferable to use the above as a seed and to carry out the polymerization by feeding and polymerizing the resin (A ₂ ) or monomers corresponding to the resin (A ₁ ) in the same manner as above.

In the polymerization granulation method, in order to introduce the polymer component (c) into the resin particles for improving the releasability, a single amount which is soluble in the organic solvent forming the resin particles and which is insolubilized by polymerization is used. By carrying out a polymerization reaction in the presence of a monomer corresponding to the polymer component (c) together with the polymer, the resin is copolymerized in the resin (A), and the resin particles of the random copolymer are easily obtained.

Furthermore, in order to introduce the polymer component (c) in blocks, a method of using at least a block copolymer containing the polymer component (c) in blocks in the dispersion stabilizing resin to be used, or the polymer component ( A monomer having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ (preferably 3 × 10 ^{3 to} 1.5 × 10 ⁴ ) composed of c) as a main repeating unit is allowed to coexist. It can be easily carried out by a method of copolymerization. Further, as another method, a polymer initiator containing the polymer component (c) as a main repeating unit (azobis polymer initiator or peroxide polymer initiator) may be used to similarly obtain the block copolymer. Resin particles of can be obtained.

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

Since these non-aqueous dispersion resin particles are subjected to a wet electrostatic electrophotographic development method or a method of electrophoresing in a pressure field of an electric field, a dispersion medium used at the time of electrodeposition has an electric resistance of 10 It is preferable to adjust to a non-aqueous solvent system having a dielectric constant of 3.5 or less and ⁸ Ω · cm or more. Specifically, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, and halogen-substituted products thereof can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane,
Cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L (Isopar; trade name of Exxon), Shersol 70, Shersol 71 (Shellsol; trade name of Shell Oil), Amsco OMS, Amsco 46
0 solvent (Amsco; trade name of American Mineral Spirits, Inc.) and the like can be used alone or in combination. Therefore, the above-mentioned insulating organic solvent is preferably used from the beginning as the solvent used for the polymerization granulation, but it can also be adjusted by granulating with a solvent other than these solvents and then substituting the dispersion medium.

In order to electrophoretically disperse dispersed particles in a dispersion medium, the particles must be positively or negatively charged electrophoretic particles. Providing the particles with electroscopic properties can be achieved by appropriately utilizing the technique of a developer for wet electrostatic photography. Specifically, "Recent Development and Practical Use of Electrophotographic Development Systems and Toner Materials" 139-148, "Basics and Applications of Electrophotographic Technology" edited by The Institute of Electrophotography, 497-505 (Corona Publishing Co., 1988 Annual), Yuji Harasaki "Electronic Photography" 16 (No.2), 44
Page (1977), etc. are used by using the electrophotographic material and other additives. For example, British Patent 893,429
No. 934,038, U.S. Pat. No. 1,122,397.
Issue 3,900,412, Issue 4,606,989
No. 60-179751, JP-A 60-18596.
3 and JP-A-2-13965. The composition of the non-aqueous latex used for electrodeposition is usually at least 0.1 to 20 g of particles mainly containing a thermoplastic resin in at least 1 liter of an electrically insulating dispersion medium, and 0.01 to 100 g of a dispersion stabilizing resin. 50 g, and the charge control agent to be added as necessary is in the range of 0.0001 to 10 g.

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

Thermoplastic resin particles (AL) which have been made into fine particles in this way and given an electric charge and dispersed in an electrically insulating liquid
Shows a behavior similar to that of the electrophotographic wet developer. Therefore, for example, it is possible to perform electrophoresis on the surface of the photoconductor by using the developing device described in "Basics and Applications of Electrophotographic Technology", pages 275 to 285, for example, the slit developing electrode device. That is, particles mainly containing a thermoplastic resin, are supplied between the counter electrode placed facing the electrophotographic photoreceptor,
Electrophoresis is performed according to a potential gradient applied from an external power source to adhere or electrodeposit on the electrophotographic photosensitive member to form a film.

In general, when the particles are positively charged, a voltage is applied from an external power source between the conductive support of the photoconductor and the developing electrode of the developing device so that the photoconductor has a negative potential. Then, the particles are electrostatically electrodeposited on the surface of the photoreceptor. It is also possible to perform electrodeposition by wet toner development by a usual electrophotographic process. That is, as shown on the premise "Basics and Applications of Electrophotographic Technology", pages 46 to 79, so-called burn-off is performed in which the photosensitive member is uniformly charged and then not exposed or only unnecessary areas are exposed. Perform normal wet toner development.

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

Further, in the resin particles of the present invention to be subjected to this pseudo-wet method, the resin component having a high glass transition point or a high softening point which does not soften at the liquefying temperature of the medium to be used constitutes the outer shell of the particles. , So-called core-shell type particles (resin having a low glass transition point in the core portion and resin having a high glass transition point in the shell portion) are used, so that the dispersed resin particles are not fused by heating and stably. It is possible to maintain a dispersed state.

The amount of the thermoplastic resin particles deposited on the photosensitive member can be arbitrarily adjusted by the applied voltage of the external bias, the charging potential of the photosensitive member, the developing time, and the like. After electrodeposition, the developer is wiped off by a squeeze using a known rubber roller, gap roller, reverse roller or the like. Methods such as corona quiz and air squeeze are also known. In addition, cold or warm air,
Alternatively, it is dried with an infrared lamp or the like, and preferably the thermoplastic resin particles are formed into a film to form the first transfer layer (T ₁ ).

First transfer layer formed on the surface of this photoreceptor
(T₁) A second transfer layer (T ₂) Is a normal solvent coating
Although it may be formed according to the cloth method, it is formed in the electrophotographic apparatus.
The embodiment is preferable in terms of lower running cost.
Second transfer layer (T₂) Is the first transfer layer (T₁) Those who form on the surface
As the method, a hot melt coating method, an electrodeposition coating method and a transfer method are preferable.
It is used well. By these methods, electrophotographic apparatus
Inside the first transfer layer (T₁) The second transfer layer (T
₂) Can be easily formed.

Hereinafter, each method will be described in detail. In the hot melt coating method, the transfer layer composition is hot melt coated by a known method. For this purpose, a mechanism of a solventless coating machine, for example, a hot melt coating machine for hot melt adhesives (hot melt coater) described in "Actual of hot melt bonding" on pages 197 to 215 is used for the first transfer layer (T ₁ ) Can be used as a coating specification. Examples include direct roll coaters, offset gravure roll coaters, rod coaters, extrusion coaters, slot orifice coaters, curtain coaters and the like.

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

Next, the formation of the transfer layer by the transfer method will be described. In this method, a transfer layer (T) held on a releasable support typified by release paper (hereinafter simply referred to as release paper) is used.
₂ ) is transferred onto the surface of the first transfer layer (T ₁ ). The release paper on which the transfer layer is formed can be easily supplied to the transfer device in the form of a roll or a sheet. As the release paper used in the present invention, any conventionally known release paper can be used. For example, “new technology of adhesive (adhesive) and its application / development material for various applied products”
(Issue: Management Development Center Publishing Department, May 20, 1978)
Sun), “All Paper Guide Paper Product Encyclopedia, First Volume / Culture Industry Edition” (Published; Paper Industry Times Co., Ltd., 1983 12)
Those described in (1st of a month) and the like.

Concretely, the release papers are unbleached Kurupack papers laminated with a polyethylene resin as a release agent mainly composed of silicone, high-grade papers precoated with a solvent-resistant resin, kraft papers, and undercoated PET. It is applied on a base or a substrate such as glassine paper. A silicone of a solvent type is generally used, and a gravure roll, a reverse roll, or a roll having a concentration of 3 to 7% is used on the substrate.
After coating and drying with a wire bar or the like, it is heat-treated at 150 ° C or higher to be cured. The coating amount is about 1 g / m ² .

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

To form the transfer layer (T ₂ ) on the release paper,
This can be easily carried out by applying a transfer layer composition containing a resin constituting the transfer layer as a main component by bar coating, spin coating, spray coating or the like according to a conventional method. The transfer layer (T ₂ ) on the release paper is replaced with the first transfer layer (T ₁ ) on the electrophotographic photosensitive member.
For thermal transfer onto the surface, a conventional thermal transfer method can be used. That is, it is sufficient thermal transfer layer (T ₂₎ transfer layer release paper holding the (T ₂₎ and pressed on the first transfer layer on the electrophotographic photosensitive member (T _1). Transfer the release layer (T ₂ ) from the release paper to the first transfer layer (T ₁ ).
The conditions for transferring to the surface are preferably as follows. The roller nip pressure is 0.1 to 10 kgf / cm ² , more preferably 0.2 to 8 kgf / cm ² , and the transfer temperature is 25.
C. to 100.degree. C., more preferably 40.degree. C. to 80.degree.
The conveying speed is 0.5 to 200 mm / sec, more preferably 3 to 150 mm / sec.

The electrodeposition coating method is substantially the same as that described for the formation of the first transfer layer (T ₁ ). First transfer layer (T
Instead of the resin particles (AL) forming ₁ ), the thermoplastic resin (A ₂ ) may be used as the resin particles (A ₂ L).

Next, the electrophotographic photosensitive member used in the present invention will be described. As the electrophotographic photoreceptor, any conventionally known one can be used. What is important is that the surface of the photoconductor has releasability when the transfer layer is formed so that the transfer layer provided on the surface of the photoconductor can be easily peeled later together with the toner image.

That is, in the present invention, JIS Z0237- on the surface of the electrophotographic photosensitive member which is adjacent to the transfer layer at least when the transfer layer is formed by the electrodeposition coating method of the resin particles (AL). 1980 "Adhesive tape / adhesive sheet test method", the adhesive force is preferably 100 gram force
(g · f) or less, more preferably 80 g · f or less, and particularly preferably 50 g · f or less. Thereby, the releasability between the photoconductor and the transfer layer can be better exhibited, and the transfer layer can be easily peeled off from the photoconductor at the time of transfer to the transfer material.

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

As a method for obtaining a photoreceptor having releasability on the surface adjacent to the transfer layer, a method using a photoreceptor having a releasability on the surface itself (first method), or expressing releasability Method (second method) in which the compound (S) to be applied is applied to the surface of the photoreceptor before the transfer layer is formed, and in a dispersion liquid in which the resin particles (AL) of the present invention are dispersed in an insulating organic solvent. A method (third method) in which a compound (S ') exhibiting releasability is coexistent and electrodeposition is performed. Also, any of these methods can be used in combination.

The photoconductor in which the surface of the photoconductor which can be used in the first method has releasability is a photoconductor obtained by modifying the surface of amorphous silicon to have releasability. As a method for modifying the peelability, fluorine atoms and /
Alternatively, there is a method of treating the surface of amorphous silicon with a coupling agent containing a silicon atom (for example, a silane coupling agent, a titanium coupling agent, etc.).
-89844, JP-A-4-231318, JP-A-6
0-170860, 59-102244, 60
No. 17750 and the like. Further, as another method, a compound (S) described later, particularly a fluorine atom and / or
Alternatively, a compound containing a component containing a silicon atom as a substituent in a block (for example, polyether, carboxylic acid,
Examples include a method of adsorbing and fixing modified polydialkylsilicones such as amino groups and carbinol groups. Further, when another photoconductor is used, a method of providing an overcoat layer on the photoconductive layer constituting the photoreceptor and imparting releasability to the overcoat layer, or a photoconductive layer (photoconductor There may be mentioned a method of modifying the surface of the uppermost layer (which may be either a single layer or a photoconductor laminate) to a state where peelability is exhibited.

To impart releasability to the overcoat layer or the uppermost photoconductive layer, a polymer containing a silicon atom and / or a fluorine atom is used as a binder resin for the layer, or a silicon atom and / or a fluorine atom is used. There is a method of using a small amount of a block copolymer containing a polymer segment composed of the contained polymer component (surface uneven distribution type block copolymer) together with another binder resin. The resin containing silicon and / or fluorine atoms may be used in the form of resin particles. Among them, when the overcoat layer is provided, the adhesion between the photoconductive layer and the overcoat layer can be sufficiently maintained,
A method of using the above-mentioned surface unevenly distributed block copolymer in combination is preferable. The surface unevenly distributed copolymer is preferably used in combination with another binder resin in a proportion of usually 0.1 to 20 parts by weight based on 100 parts by weight of the total composition of the overcoat layer.

Specifically, in a PPC photosensitive member using a dry toner, a surface layer is formed on the photosensitive member, which is known as one means for maintaining durability of the photosensitive member surface against repeated use of the photosensitive member. A method similar to the content of the protective layer in the method of providing and protecting can be used. For example, as a technique relating to a protective layer using a silicone block copolymer, there are disclosed in JP-A-61-95358 and JP-A-6-95358.
5-83049, 62-89771, 61-1
89559, 62-7541, 62-754.
No. 61, No. 62-139556, No. 62-13955.
No. 7, No. 62-208055, etc. are mentioned. Further, as a protective layer using a fluorine-based block copolymer, there are disclosed in JP-A-61-1116362 and JP-A-61-161.
No. 17563, No. 61-270768, No. 62-14
No. 657 etc. are mentioned. Further, as a protective layer in which a resin containing a fluorine atom-containing polymer component is also used in the form of particles, there are disclosed in JP-A-63-249152 and JP-A-63-152152.
The thing described in No. 221355 is mentioned.

Further, the method of modifying the surface of the uppermost photoconductive layer to a state in which releasability is exhibited is a method of using a so-called dispersion type photoconductor containing at least a photoconductor and a binder resin. It is applied particularly effectively. That is, in the layer constituting the uppermost layer of the photoconductive layer, a resin of a block copolymer containing a polymer segment containing a polymer component containing a fluorine atom and / or a silicon atom in a block, and a fluorine atom and / or By coexisting at least one of the resin particles containing a polymer component containing a silicon atom,
Since these materials are concentrated / migrated to the surface and unevenly distributed, the material can be modified to have a peelable surface. As for the copolymer and the resin particles, the same as those described in JP-A-5-197169 can be mentioned.

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

In the electrophotographic photosensitive member, the polymer containing the polymer component containing a fluorine atom and / or a silicon atom of the present invention, which is effective for modifying the surface of the photosensitive member by the above-mentioned method, is It is configured in the form of resin (P) and / or resin particles (hereinafter referred to as 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 based on the total polymer components, more preferably Is 80% by weight or more.

More preferably, the polymer segment (α) containing 50% by weight or more of the polymer component containing a fluorine atom and / or a silicon atom and 0 to 20% by weight of the polymer component containing a fluorine and / or silicon atom. It is a block copolymer in which the polymer segments (β) contained therein are linked by blocks. More preferably, it is a block copolymer containing at least one polymer component containing at least one photo- and / or thermosetting functional group in the segment (β) in the block copolymer. In these block copolymers, the segment (β) preferably contains no fluorine atom and / or silicon atom-containing polymer component.

In the above polymer, the segment (α)
By using a block copolymer containing (1) and a segment (β) (a surface unevenly distributed copolymer), the peelability of the surface itself is improved as compared with the random copolymer, and further the maintenance of the peelability is maintained. It That is, when a coating film is formed by coexisting a small amount of the above-mentioned resin (P) and / or resin particles (L) containing a fluorine atom and / or a silicon atom, the resin can be easily formed before the drying step after coating. (P) and the resin particles (L) are
It is transferred to and concentrated on the surface of the film and is modified so that the film surface can exhibit releasability.

As described above, when the polymer segment (α) containing a fluorine atom and / or a silicon atom is blocked, the other polymer segment (β) (containing a fluorine atom and / or a silicon atom). However, even if it contains a small amount of the polymer component), the resin has a good compatibility with the binder resin for film formation, and therefore interacts sufficiently with this, and these resins are Further transfer to the layer can be suppressed or eliminated, and the interface between the transfer layer and the electrophotographic photosensitive member can be clearly formed and maintained (that is, the anchor effect). By using a polymer containing a curable group in the segment (β) of the block copolymer to crosslink between the polymers during film formation, the peeling property at the interface between the photoreceptor and the transfer layer is further strengthened. The effect is maintained. In particular, when the surface-peeling photoreceptor is repeatedly used and used in combination with a liquid developer, it is preferably in a crosslinked film state.

The polymer is the resin particles (L) as described above.
May be used as. Preferred resin particles (L) are
Resin particles dispersed in a non-aqueous solvent. Such resin particles include a polymer segment (α) insoluble in a non-aqueous solvent containing a polymer component containing a fluorine atom and / or a silicon atom, and a polymer component containing a fluorine atom and / or a silicon atom. And a polymer segment (β) soluble in a non-aqueous solvent of 20% or less is included. In the case of resin particles (L), the action of the insolubilized polymer portion causes migration and concentration on the surface,
Further, the non-aqueous solvent-soluble polymer portion bonded to the particles interacts with the binder resin to perform an anchor effect, as in the case of the resin (P). Furthermore, by containing a curable group in the polymer or in the binder resin, transfer to the transfer layer is eliminated.

The substituent containing a fluorine atom and / or a silicon atom, the polymer component (F) containing these, the aspect of the polymerization pattern of the block copolymer and the method for synthesizing the polymer will be specifically described.

The polymer component (F) is a polymer component containing a substituent containing a silicon atom and / or a fluorine atom. This substituent may be incorporated in the polymer main chain of the polymer or may be contained as a substituent of the side chain of the polymer. Examples of the substituent containing a fluorine atom include the following monovalent or divalent organic residues.

[0140]

[Chemical 25]

[0141]

[Chemical formula 26]

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

[0143]

[Chemical 27]

However, R ³¹ , R ³² , R ³³ , R ³⁴ and R
^{35, which} may be the same or different, each represents an optionally substituted hydrocarbon group or an -OR ³⁶ group (R ³⁶ represents an optionally substituted hydrocarbon group).

Specific examples of the hydrocarbon group represented by R ^{31 to} R ³⁶ include an alkyl group having 1 to 18 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group,
Hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 2-cyanoethyl group, 3,3,3-trifluoropropyl group Ethyl group,
2-methoxyethyl group, 3-bromopropyl group, 2-methoxycarbonylethyl group, 2,2,2,2 ', 2',
2'-hexafluoroisopropyl group, etc., 4 to 4 carbon atoms
18 optionally substituted alkenyl groups (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.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group,
2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic ring having 5 to 8 carbon atoms Formula group (for example, cyclohexyl group, 2-cyclohexyl group, 2-cyclopentylethyl group, etc.) or C6 to C1
2 optionally substituted aromatic groups (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, Butoxyphenyl group, decyloxyphenyl group,
Chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc. ) And the like.

The fluorine atom- and silicon atom-containing organic residues may be constituted in combination, in which case they may be directly bonded or may be combined via another linking group. May be. Specific examples of the group to be linked include divalent organic residues, and -O-, -S-, -N (d
^{1) -, - CO -,} - SO -, - SO 2 -, - COO-,
-OCO-, -CONHCO-, -NHCONH-,-
CON (d ¹ )-, -SO ₂ N (d ¹ )-, etc., a divalent aliphatic group or a divalent aromatic group which may intervene a bonding group selected from these groups, or a divalent group thereof. Represents an organic residue composed of a combination of residues. Where d ¹ is the R
Indicates the same contents as ³¹ .

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

[0148]

[Chemical 28]

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

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

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

[0152]

[Chemical 29]

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

[0154]

[Chemical 30]

[0155]

[Chemical 31]

[0156]

[Chemical 32]

[0157]

[Chemical 33]

[0158]

Embedded image

The polymer component (F) is preferably contained in the resin (P) in blocks. The block copolymer, which is a preferred embodiment of the resin (P), will be described below. This block type copolymer has a fluorine atom and /
Alternatively, any polymer may be used as long as the silicon atom-containing polymer component is composed of blocks. Here, to be composed of blocks means that the polymer has a polymer segment containing 50% by weight or more of a polymer component containing a fluorine atom and / or a silicon atom, for example, A as shown below. −
Examples thereof include B type blocks, ABA type blocks, BAB type blocks, graft type blocks and star type blocks.

[0160]

Embedded image

These various block copolymers can be synthesized by a conventionally known polymerization method. For example,
WJ Burlant, AS Hoffman `` Block and Graft poly
mers ”(1986, Reuhold), RJ Cevesa“ Block and
Graft Copolymers "(1962, Butterworths), DC
Allport, WH James "Block Copolymers" (1972,
Applied Sci), A. Noshay, JE McGrath `` Block Copo
lymers '' (1977, Academicis Press.), G. Huvterg, D.
J. Wilson, G. Riess, NATO ASIser. SerE. 1985 , 14
9, V. Perces, Applied. Polymer Sci. 285, 95 (198
It is described in the books and reviews such as 5).

For example, regarding the ionic polymerization reaction using an organic metal compound (eg, alkyllithium, lithium diisopropylamide, alkali metal alcoholate, alkylmagnesium halide, alkylaluminum halide, etc.) as a polymerization initiator, TE Hogeu- Esc
h, J. Smid `` Recent Advances in Anion Polymerizatio
n '' (1987, Elsevier New York), Okamoto Yoshio, Polymer, 38 , 912 (1989), Sawamoto Mitsuo, Polymer, 38 , 1018 (198)
9), Tadashi Narita, Polymer, 37 , 252 (1988), BC Anderson
et al., Macromolecules 14 , 1601 (1981), S. Aoshim
a, T. Higasimura, Macromolecules 22 , 1009 (1989) and the like.

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

Regarding the living polymerization reaction using a metalloporphyrin complex, see T. Yasuda, T. Aida, S. Inoue, Mac.
romolecules, 17 , 2217 (1984), M. Kuroki, T. Aida,
S. Inoue, T. Ann. Chem. Soc. 109, 4737 (1987), M. Kur
oki et al., Macromolecules, 21 , 3115 (1988), M. Kur
oki, I. Inoue, Synthetic Organic Chemistry, 47 , 1017 (1989).

Further, regarding ring-opening polymerization reaction of cyclic compounds, S. Kobayashi, T. Saegusa "Ring Opening Polym
erization ”(1984, Applied Scence Publishers Lt.
d.), W. Seeliger et al., Angew. Chem. Int. Ed. Eng
l. 5 , 875 (1966), S. Kobayashi et al., Poly. Bul
l. 13 , 447 (1985), Y. Chujo et al., Macromolecules,
22 , 1074 (1989) and the like.

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

[0167] 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 Proceedings, 33
931 (1976), Akira Ueda, Osaka City Research Institute Report 84 (198)
9), O. Nuyken et al., Macromol. Chem., Rapid. Comm.
un. 9, 671 (1988), Yasuo Moriya et al. "Reinforced plastic" 2
9 , 907, Ryohei Oda, "Science and Industry" 61 , 43 (1987).

Regarding the synthesis of the graft type block copolymer, in addition to the above-mentioned textbooks and reviews, Fumio Ide “Graft polymerization and its applications” (1977, Polymer Society of Japan), The Society of Polymer Science, eds. Polymer Alloy "(1981, Tokyo Kagaku Dojin) and the like. For example, a method of grafting a polymer chain with a polymerization initiator, chemical actinic rays (radiation, electron beam, etc.), mechanochemical reaction in mechanical application, etc., polymer chains and functional groups of polymer chains A method of grafting by utilizing chemical bonding (so-called interpolymer reaction),
Also known is a method of carrying out a polymerization reaction using a macromonomer and grafting.

As a method of grafting using a polymer, specifically, T. Shota et al., J. Appl. Polym. S
ci. 13 , 2447 (1969), WH Buck, Rubber Chemistry a
nd Technology, 50 , 109 (1976), Tsuyoshi Endo, Tsutomu Uezawa, Journal of Japan Adhesive Society, 24 , 323 (1988), Tsuyoshi Endo, ibid. 25 , 40
9 (1989) etc.

As a method of carrying out a polymerization reaction and grafting using a macromonomer, specifically, P. Dreyfuss
& RP Quirk, Encycl. Polym. Sci. Eng., 7 , 551
(1987), PF Rempp, E. Franta, Adv. Polym. Sci.,
58 , 1 (19894), V. Percec, Appl. Poly. Sci., 285,
95 (1984), R. Asami, M. Takari, Macromol. Chem. Sup
pl., 12 , 163 (1985), P. Rempp. et al., Macromol. C
hem. Suppl., 8, 3 (1985), Yusuke Kawakami, Chemical Industry, 38 , 5
6 (1987), Yuya Yamashita, Polymer, 31 , 988 (1982), Kobayashi Shiro, Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of Japan Adhesive Society, 18 , 536 (1982), Koichi Ito, Polymer processing, 35 , 262
(1986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No.10,
5, Yuya Yamashita, "Chemistry and Industry of Macromonomers" (198
9 years, IPC Co., Ltd., Takeshi Endo "Molecular design of new functional polymers" Chapter 4 (1991, CMC Co., Ltd.),
Y. Yamashita et al., Polym. Bull. 5, 361 (1981).

The synthesis method of the star type block copolymer is as follows:
For example, MT Reetz, Angew. Chem. Int. Ed. Engl.,
27 , 1373 (1988), M. Sgwarc `` Carbanions, Living Poly
mersand Electron Transfer Processes "(1968, Wil
ey. New York), B. Gordon et al., Polym. Bull. 11 , 3
49 (1984), RB Bates et al., J. Org. Chem. 44 , 3
800 (1979), Y. Sogah, ACS Polym. Rapr. 1988 , N
o.2, 3, JW Mays. Polym. Bull. 23 , 247 (1990), I.
M. Khan et al., Macromolecules, 21 , 2684 (1988),
A. Morikawa, Macromolecules, 24 , 3469 (1991), Akira Ueda, Toru Nagai, Kogaku, 39 , 202 (1990), T. Otsu, Poly
m. Bull. 11 , 135 (1984), etc. However, the method for synthesizing the block copolymer is not limited to these methods.

The case where the resin (P) and the resin particles (L) are so-called surface unevenly distributed copolymers will be described. In the segment (α) containing a silicon atom and / or a silicon atom-containing polymer component, the polymer component (F) contains at least 50% by weight, preferably 70% by weight, of the total amount of the entire segment (α). % Or more, more preferably 80% by weight or more. In the segment (β), the content of the fluorine atom and / or silicon atom-containing polymer component (F) is 20% by weight or less, preferably 0% by weight, of the total amount of the segment (β).

The weight ratio of the segment (α) to the segment (β) is preferably 1 to 95: 5 to 99, more preferably 5 to 90:10 to 95. In this range, both the resin (P) and the resin particles (L) can effectively exert the concentration effect and the anchor effect on the surface of the uppermost layer.

The weight average molecular weight of the resin (P) is preferably 5 × 10 ³ to 1 × 10 ⁶ , and more preferably 1 × 1.
It is 0 ^{4 to} 5 × 10 ⁵ . On the other hand, the weight average molecular weight of the segment (α) in the resin (P) is at least 1 × 1.
It is preferably 0 ³ . The average particle diameter of the resin particles (L) is preferably 0.001 to 1 μm, more preferably 0.05 to 0.5 μm.

Next, a preferable embodiment of the resin particles (L) will be described. As described above, the resin particles (L) are
Preferably, it is composed of a segment (α) containing a fluorine atom and / or a silicon atom which is insoluble in a non-aqueous solvent, and a segment (β) containing almost no fluorine atom and / or a silicon atom, which is soluble in this solvent. is there. Furthermore, the segment (α) part constituting the insoluble portion of the resin particle (L) may form a crosslinked structure.

As a preferred method for producing the resin particles (L), there may be mentioned the non-aqueous dispersion polymerization method which will be described later on the production of the non-aqueous dispersion resin particles. The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles has a boiling point of 200.
Any organic solvent may be used as long as it is at a temperature of not more than 0 ° C., and they can be used alone or in combination of two or more.

Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, and benzyl alcohol, acetone,
Ketones such as methyl ethyl ketone, cyclohexanone, diethyl ketone, ethers such as diethyl ether, tetrahydrofuran, dioxane, carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, hexane, octane, decane, dodecane, tridecane , Aliphatic hydrocarbons having 6 to 14 carbon atoms such as cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane,
Examples include halogenated hydrocarbons such as trichloroethane. However, it is not limited to the above-mentioned compound examples. By synthesizing dispersed resin particles in these non-aqueous solvent systems by a dispersion polymerization method, the average particle diameter of the resin particles easily becomes 1 μm or less, and the particle diameter distribution is very narrow and monodisperse particles are obtained. You can

Specifically, the monomer (a) and the segment (β) corresponding to the polymer component constituting the segment (α)
And a monomer (b) corresponding to the polymer component constituting the monomer, and a non-aqueous solvent in which the monomer (a) dissolves but becomes insoluble when polymerized, using a peroxide (for example, benzoyl peroxide, peroxide). It may be carried out by heat polymerization in the presence of a polymerization initiator such as lauroyl oxide), an azobis compound (eg azobisisobutyronitrile, azobisisovaleronitrile etc.), an organometallic compound (eg butyllithium etc.). Alternatively, the monomer (a) and the polymer (Pβ) composed of the segment (β) may be polymerized in the same manner as above.

Furthermore, the inside of the insolubilized polymer particles of the resin particles (L) may have a crosslinked structure. Any conventionally known method can be used to form these crosslinked structures. That is, a method of cross-linking a polymer containing a segment (α) with various crosslinking agents or curing agents, and a polymerization reaction when a monomer (a) corresponding to the segment (α) is contained in the polymerization reaction. A method for forming a network structure between molecules by allowing a polyfunctional monomer or polyfunctional oligomer containing two or more functional groups to coexist, and a component containing a segment (α) and a reactive group. It can be carried out by a method of cross-linking the contained polymers with a polymerization reaction or a polymer reaction.

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

In addition, a polyfunctional monomer containing two or more polymerizable functional groups coexisting in the above method [hereinafter also referred to as a polyfunctional monomer (d)] or a polyfunctional oligomer polymerizable functional group. As the group, specifically, CH ₂ ═CHCH
_{2 -, CH 2 = CHCOO-,} CH 2 = CH-, CH 2 = C
_{(CH 3) -COO-, CH (} CH 3) = CHCOO-, C
_{H 2 = CHCONH-, CH 2 =} C (CH 3) -CONH
_{-, CH (CH 3) =} CHCONH-, CH 2 = CHOC
_{O-, CH 2 = C (CH} 3) -OCO-, CH 2 = CHCH
_{2 OCO-, CH 2 = CHNHCO-,} CH 2 = CHCH 2
_{NHCO-, CH 2 = CHSO 2 -} , CH 2 = CHCO
-, CH ₂ = CHO-, can be mentioned CH ₂ = CHS-like. Any monomer or oligomer having two or more of these same or different polymerizable functional groups may be used.

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

Examples of the monomers or oligomers having different polymerizable functional groups include vinyl group-containing carboxylic acids (for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, and arylloyl). Propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic acid anhydride, etc.) and ester or amide derivatives containing vinyl groups such as alcohol or amine reactants (eg vinyl methacrylate, vinyl acrylate, vinyl itaconic acid) , Allyl methacrylate, allyl acrylate, allyl itaconate, methacryloyl vinyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyl oxycarboxyl methyl acrylate, vinyl acrylate Luoxycarbonylmethyloxycarbonylethylene ester, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconic acid amide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (eg aminoethanol, 1-aminopropanol, 1-amino) Butanol,
1-aminohexanol, 2-aminobutanol, etc.) and a condensate of a carboxylic acid containing a vinyl group. The monomer or oligomer having two or more polymerizable functional groups used in the present invention is 10 mol% or less, preferably 5 mol% or less based on the total amount of the monomer (a) and other coexisting monomers. Polymerization is carried out using less than mol% to form a resin.

Furthermore, in the case of forming a chemical bond by the reaction of reactive groups between polymers and bridging between polymers in the above-mentioned method, it is carried out in the same manner as the reaction of a normal organic low molecular compound. be able to. In dispersion polymerization, since monodisperse particles having a uniform particle size are obtained and fine particles of 0.5 μm or less are easily obtained, a polyfunctional monomer is used as a method for forming a network structure. The method used is preferred. That is, the above-mentioned monomer (a), monomer (b) and /
Alternatively, it can be synthesized by polymerizing the polymer (Pβ) further with the polyfunctional monomer (d) to carry out a polymerization granulation reaction. Further, when the polymer (Pβ) composed of the above-mentioned segment (β) is used, the monomer (a) is attached to a side chain in the polymer main chain of the polymer (Pβ) or one end of the main chain. A polymer having a polymerizable double bond group copolymerizable with (P
β ′) is preferred.

The polymerizable double bond group is a single bond as described above.
Any one may be used as long as it has copolymerizability with the monomer (a).
As a physical example, CH₂= C (Q) -COO-, C
(CH₃) H = CH-COO-, CH₂= C (CH₂COO
H) -COO-, CH₂= C (Q) -CONH-, CH₂
= C (Q) -CONHCOO-, CH₂= C (Q) -C
ONHCONH-, C (CH₃) H = CHCONH-, C
H₂= CHCO-, CH₂= CH (CH₂)_g-OCO-
(G is 0 or an integer of 1 to 3), CH₂= CHO-, CH ₂
= CHC₆H_FourAnd the like (wherein Q is -H or-)
CH₃Represents).

These polymerizable groups may be directly bonded to the polymer chain or may be bonded via another divalent organic residue. Specific embodiments of these polymers are described in, for example, JP-A 61-43757, JP-A 1-257969,
No. 2-74956, No. 1-282566, No. 2-1
No. 73667, No. 3-15862, No. 4-70669.
No. etc. The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the non-aqueous solvent. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compounds. The polymerization temperature is about 30 to 180 ° C., preferably 40 to
It is 120 ° C. The reaction time is preferably 1 to 15 hours.

Next, when a photo and / or thermosetting group is contained in the resin (P) as a polymer component, or when a photo and / or thermosetting group-containing resin is used in combination with the resin (P) Will be explained.

Examples of the polymer component containing at least one photo- and / or thermo-curable group which can be contained in the resin (P) include those described in the above-mentioned known documents, More specifically, for example, the same as those described as the polymerizable functional group can be mentioned. The content of the polymer component containing at least one light and / or curable group that can be contained in these polymers is such that the polymer segment (β) 1 of the resin (P) which is a block copolymer.
The amount is preferably 1 to 95 parts by weight, more preferably 10 to 70 parts by weight, out of 00 parts by weight. Furthermore, it is preferable to contain 5 to 40 parts by weight in the total 100 parts by weight of the polymer component of the entire resin (P). When the content is within the above range, the curing of the photoconductive layer after the film formation is sufficiently advanced, the effect of holding the film interface with the surface of the electrophotographic photoreceptor at the time of coating the transfer layer is sufficient, and the transfer layer is good. It becomes peelable. In addition, the electrophotographic characteristics of the photoconductive layer as the binder resin can be kept good.
Resin (P) containing these light and / or thermosetting groups
Is preferably 40 parts by weight or less based on 100 parts by weight of the total binder resin. When the amount of the resin (P) exceeds 40 parts by weight, electrophotographic characteristics may deteriorate.

Further, a light and / or thermosetting resin (D) may be used in combination with the fluorine atom and / or silicon atom containing resin. The light and / or thermosetting resin (D) may be any conventionally known curable resin, for example,
The resin containing a curable group as described in the above block copolymer may be mentioned. Further, conventionally known resins can be used together. Each of the resins specifically described as the binder resin that can be used in the photoreceptor described below can be given as an example.

As described above, as one embodiment of the pre-peeling photoreceptor of the present invention, the uppermost layer of the photoreceptor, for example, the overcoat layer or the photoconductive layer, is a resin containing a silicon atom and / or a fluorine atom. , And, if necessary, other binder resin (hereinafter sometimes referred to as binder resin (B)), but further contains light and / or light in order to improve the curing of the film.
Alternatively, it is preferable to allow a small amount of the thermosetting resin (D) and / or the crosslinking agent to coexist. The amount used is 0.0 in all binder resins.
It is 1 to 20% by weight, preferably 0.1 to 15% by weight. If the amount used is less than 0.01% by weight, the effect of improving the hardening of the film will be diminished. On the other hand, if it exceeds 20% by weight, electrophotographic characteristics may be adversely affected.

Further, it is preferable to use a crosslinking agent in combination,
The compound normally used as a crosslinking agent can be used. Specifically, compounds that have been described in "Crosslinking Agent Handbook" edited by Fuzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), and "Polymer Data Handbook Basic Edition" edited by the Polymer Society of Japan, Baifukan (1986). Can be used. Specific examples thereof include the compounds described as the cross-linking agent, and further, a monomer having a polyfunctional polymerizable group (for example, vinyl methacrylate, acryl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinic acid). Ester, divinyl adipate ester, diacryl succinate ester, 2-methyl vinyl methacrylate, trimethylol propane trimethacrylate, divinyl benzene, pentaerythritol polyacrylate and the like).

The uppermost layer of the photoreceptor (layer adjacent to the transfer layer)
Is preferably cured after film formation. The binder resin (B), the surface unevenly distributed copolymer (P), the curable resin (D), and the cross-linking agent used in the present invention are used in a combination of functional groups in which polymers are easily chemically bonded to each other. Is preferred. For example, a well-known polymer reaction due to a combination of functional groups can be mentioned, and specifically, a combination of a functional group of group A and a functional group of group B as shown in the following group table-A is exemplified. . However, it is not limited to this.

[0193]

[Table 1]

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

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

In order to cure the specific functional group in the resin of the present invention by irradiation with light, a step of irradiation with chemically active light may be included. Examples of the chemical actinic rays used in the present invention include visible rays, ultraviolet rays, far ultraviolet rays, electron beams, and X rays.
Any of rays such as rays, γ rays and α rays may be used, but ultraviolet rays are preferable. More preferably, it is a light ray having a wavelength of 310 nm to a wavelength of 500 nm. Generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp or the like is used.
The light irradiation process is usually 10 seconds to 1 from a distance of 5 cm to 50 cm.
Irradiation for 0 minutes is sufficient.

Next, before the transfer layer formation, which is the second method for obtaining a photoreceptor having a releasable surface, a compound (S) exhibiting a releasability is adsorbed or adsorbed on the surface of an ordinary electrophotographic photoreceptor. A method of adhering and imparting releasability to the photoreceptor surface will be described.

The compound (S) includes a fluorine atom and /
Or a compound containing at least a silicon atom, and the structure thereof is not particularly limited as long as it improves the releasability of the surface of the electrophotographic photoreceptor, and may be a low molecular compound, an oligomer or a polymer. . In the case of an oligomer or a polymer, the substituent containing a fluorine atom and / or a silicon atom may be incorporated in the main chain of the polymer, or may be present as a substituent on the side chain of the polymer. Preferred are oligomers and polymers that contain the repeating unit containing the substituent in a block, and the adsorbability and the releasability on the surface of the electrophotographic photosensitive member are particularly effectively exhibited.

Examples of these substituents containing a fluorine atom and / or a silicon atom are the same as those described in relation to the resin (P) that can be used in the above-mentioned photoreceptor.

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

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

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

By applying the compound (S) to the surface of the electrophotographic photosensitive member, the surface is modified so as to have a desired releasability. Applying the compound (S) to the surface of the electrophotographic photosensitive member means supplying the compound (S) to the surface of the electrophotographic photosensitive member to form a state in which the compound (S) is adsorbed or attached to the surface of the photosensitive member. .

In order to apply the compound (S) as described above to the surface of the electrophotographic photosensitive member, any conventionally known method may be used. For example, Yuji Harazaki "Coating Engineering" Asakura Shoten Co., Ltd. (published in 1971), Yuji Harazaki "Coating Method" Maki Shoten (1979), Hiroshi Fukada "Practice of Hot Melt Adhesion"
Air doctor coater, blade coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, spray coater, curtain described in Polymer Publishing Co., Ltd. (1979). Each method such as a coater or a calendar coater can be used.

Also, cloth, paper impregnated with the compound (S),
A method in which a felt or the like is brought into close contact with the photoconductor, a method in which a curable resin impregnated with the compound (S) is brought into pressure contact with the photoconductor, and the photoconductor is wetted with a non-aqueous solvent in which the compound (S) is dissolved, and then the solvent is dried. And a method in which a nonaqueous solvent in which the compound (S) is dispersed is electrophoresed and adhered to the photoconductor in the same manner as the above-mentioned electrodeposition coating method.

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

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

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

In the present invention, these methods are not particularly limited, and various methods are selected depending on the state of the compound (S) to be used (liquid, waxy substance, solid), and if necessary, a heating medium is used in combination. Thus, the fluidity of the compound (S) used can be adjusted. The application of the compound (S) may be appropriately performed according to the photoconductor to be used and the ability to maintain the releasability by adsorption or adhesion of the compound (S) and the means thereof. The compound (S) is preferably applied in such a manner that it can be easily incorporated in the electrophotographic apparatus used in the present invention.

The amount of the compound (S) applied to the surface of the photoconductor is not particularly limited, and may be set within a range where the adverse effect on the electrophotographic characteristics of the photoconductor does not pose a practical problem. Usually, a coating film thickness of 1 μm or less is sufficient, and “Weak boundary Layer” (Bikerman “The
The state of "Science of Adhesive Joints" Academic Press (defined in 1961) is sufficient. That is, during formation of the transfer layer, the compound (S) is adsorbed or adhered on the electrophotographic photosensitive member and peeled off on its surface. It is sufficient that the surface adhesion is 100 g · f or less, and it is not always necessary to repeat this step in the method of the present invention.

In the present invention, the third method for imparting releasability to the photoreceptor comprises the resin particles (AL) of the present invention used when the first transfer layer (T ₁ ) is formed by the electrodeposition coating method. The compound (S ') exhibiting releasability is coexisted in the dispersion liquid. That is, a conventionally known electrophotographic photoreceptor is electrodeposited with an electrodeposition dispersion liquid containing a compound (S ′), whereby the photoreceptor surface exhibits releasability.

Specifically, the compound (S ') exhibiting releasability in an electrically insulating organic solvent having a relative dielectric constant of 3.5 or less.
Containing at least one of the resin particles of the present invention (A
L) is used to disperse the resin particles (A
By depositing L) onto the surface of the electrophotographic photosensitive member by electrophoresis to form a film, it is possible to impart releasability to the photosensitive member and form a transfer layer capable of peeling. The compound (S ′) contained in the electrocoating dispersion liquid for forming the transfer layer is adsorbed or attached to the photoreceptor before the dispersed resin particles (AL) are electrophoresed and electrodeposited on the photoreceptor surface. Therefore, as a result, a photoreceptor having a peeling property before the formation of the transfer layer is obtained.

The compound (S ') may be the same as the compound (S) used in the second method, and more specifically, the dispersion solvent 1 in which the resin particles (AL) are dispersed. Any substance that can be dissolved in 0.05 g or more in liter may be used. Preferably, 0.1 g or more is dissolved in 1 liter of the dispersion solvent. The addition amount of the compound (S ′) in the electrically insulating organic solvent varies depending on the compound (S ′) and the electrically insulating organic solvent used, but adversely affects the electrophoresis of the resin particles (reduction of liquid resistance, viscosity It is added to the extent that it does not increase). It is preferably about 0.05 g / liter to 20 g / liter.

The constitution and materials of the electrophotographic photosensitive member provided in the present invention may be any conventionally known ones and are not limited. For example, RM Schaffert, “Electrophoto
graphy '' Focal Press London (1980), SW Ing, MD
Tabak, WE Haas, `` Electrophotography Fourth Int
"Ernational Conference" SPSE (1983), Isao Shinohara, Hidetoshi Tsuchida, Hideaki Kusakawa "Recording Materials and Photosensitive Resins" Published by Japan Society Publishing Center (1979), Hiroshi Komon, Kagaku to Kogyo, 39 (3),
161 (1986), Comprehensive technical data collection Photoconductor "Recent development of photoconductive materials and photoconductors" And Applications ”Corona Publishing Co., Ltd. (1988), Electrophotographic Society of Japan,“ Presentation Symposium on Organic Photoreceptors for Electrophotography ”Proceedings (1985
Years) etc. and various photoconductors described in reviews.
That is, a single layer composed of the photoconductive compound itself or a photoconductive layer in which the photoconductive compound is dispersed in a binder resin can be mentioned. The dispersed photoconductive layer may be a single layer type or a laminated type. But it's okay.

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

On the other hand, the photoconductive layer using an organic compound may be any of those known in the art.
7-17162, 62-51462, JP-A-52
-24437, 54-19803, 56-1072.
No. 46, No. 57-161863, etc.,
A photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye, and a binder resin, JP-A-56-146145 and 60-17.
No. 751, No. 60-17752, No. 60-17760
No. 60-254142, No. 62-54266, and the like, and a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent, and a binding resin, and JP-A-60-230147.
No. 60-230148, No. 60-238853, and the like, and a photoconductive layer having a two-layer structure containing a charge generating agent and a charge transporting agent in separate layers.
The electrophotographic photoreceptor of the present invention may have any form of a photoconductive layer.

Examples of the organic photoconductive compound in the present invention include (a) triazole derivatives described in US Pat. No. 3,112,197 and (b) oxadiazoles described in US Pat. No. 3,189,447. Derivative, (c) Japanese Patent Publication No.37-1
Imidazole derivatives described in 6096, (d) U.S. Pat. Nos. 3,615,402, 3,820,989, 3,542,544, and JP-B-45-555 and 51.
No. 10983, JP-A Nos. 51-93224 and 55-
108667, 55-156953, 56-3
Polyarylalkane derivatives described in No. 6656,
(e) US Pat. Nos. 3,180,729 and 4,278,7
46, JP-A-55-88064 and JP-A-55-8806.
5, No. 49-105537, No. 55-51086.
No. 56-80051, No. 56-88141, No. 57-45545, No. 54-112637, No. 55.
-74546 and other pyrazoline derivatives and pyrazolone derivatives, (f) U.S. Pat. No. 3,615,404, Japanese Patent Publication Nos. 51-10105, 46-3712 and 47-
28336, JP-A-54-83435, and JP-A-54-1.
No. 10836, No. 54-119925 and the like, phenylenediamine derivatives,

(G) US Pat. Nos. 3,567,450, 3,180,703, 3,240,597, 3,658,520, 4,232,103, and 4, 175,961; 4,012,376; JP-B-49-35702; West German Patent (DAS) 1,11.
0,518, Japanese Examined Patent Publication No. 39-27577, JP-A-55.
-144250, 56-119132, 56-
22437 and the like, arylamine derivatives, (h) U.S. Pat. No. 3,526,501 and the like, amino-substituted chalcone derivatives, (i) U.S. Pat. No. 3,542,546 and the like, N, N-bicarbazyl Derivative, (j) US Patent 3,2
57,203, etc., (k) styrylanthracene derivatives described in JP-A-56-46234, (l) fluorenone derivatives described in JP-A-54-110837, (m) United States Patent 3,717,46
No. 2, JP-A-54-59143 (U.S. Pat.
0-987), JP-A-55-52063, JP-A-55-52064, JP-A-55-46760, and JP-A-55-520.
No. 85495, No. 57-11350, No. 57-148.
749, 57-104144 and the like, hydrazone derivatives,

(N) US Pat. Nos. 4,047,948, 4,047,949, 4,265,990, 4,273,846, 4,299,897, and 4, Benzidine derivatives described in No. 306,008,
(o) JP-A-58-190953 and 59-95540
No. 59-97148, 59-195658,
Stilbene derivatives described in JP-A-62-36674,
(p) Polyvinylcarbazole and its derivatives described in JP-B-34-10966, (q) JP-B-43-18674
, Polyvinylpyrene described in No. 43-19192,
Polyvinyl anthracene, poly-2-vinyl-4-
Vinyl polymers such as (4'-dimethylaminophenyl) -5-phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole; (r) polyacenaphthylene, polyindene, acenaphthylene described in JP-B-43-19193. Polymers such as copolymers of styrene and styrene, (s) JP-B-56-
Condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin and ethylcarbazole-formaldehyde resin described in 13940 and the like, and (t) various triphenylmethanes described in JP-A-56-90833 and 56-161550. Polymers, etc.
In the present invention, the organic photoconductive compound, (a) ~ (t)
The compound is not limited to the compounds listed in 1 above, and all known organic photoconductive compounds can be used. Two or more kinds of these organic photoconductive compounds may be used in combination depending on the case. Organic photoconductive compounds are also used as charge transport agents.

As the sensitizing dye contained in the photoconductive layer,
Conventionally known sensitizing dyes used for electrophotographic photoreceptors can be used. These are "Electrographs" 12 , 9 (1973),
“Organic Synthetic Chemistry” 24 (11), 1010 (1966) and the like. For example, U.S. Patents 3,141,770 and 4,28
3,475, JP-A-48-25658, 62-7.
Pyrylium dyes described in 1965, Applied Opti
cs Supplement 3, 50 (1969), JP-A-50-39548
Triarylmethane dyes described in U.S. Pat.
Cyanine dyes described in JP-A No.
0-163047, 59-164588, 60
The styryl dyes described in No. 252517 and the like are advantageously used.

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

(1) U.S. Pat.
8-219263, 59-78356, 60-
179746, 61-148453, 61-2
No. 38063, Japanese Patent Publication No. 60-5941, No. 60-45
Azo pigments such as monoazo, bisazo, and trisazo pigments described in US Pat. No. 664, (2) US Pat. No. 3,397,086,
No. 4,666,802, JP-A-51-90827,
Phthalocyanine pigments such as metal-free or metal phthalocyanines described in JP-A No. 52-55643, (3) US Pat.
371,884, perylene pigments described in JP-A-47-30330, (4) British Patent 2,237,680
And indigo and thioindigo derivatives described in JP-A-47-30331, (5) British Patent 2,237,679
And quinacridone pigments described in JP-A-47-30332

(6) British Patent 2,237,678, JP-A-59-184348, 62-28738 and 4
7-18544 and other polycyclic quinone pigments, (7) JP-A-47-30331, JP-A-47-18543 and other bisbenzimidazole pigments, (8) US Pat.
396,610, 4,644,082, and the like, squalium salt pigments, (9) JP-A-59-53850
And the azurenium salt-based pigments described in JP-A-61-212542 and the like. These may be used alone or in combination of two or more.

In addition, the mixing ratio of the organic photoconductive compound and the binding resin determines the upper limit of the content of the organic photoconductive compound due to 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 to include as many organic photoconductive compounds as possible within the range where crystallization of the organic photoconductive compound does not occur. The content of the organic photoconductive compound is 5 to 120 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the binder resin.

The binder resin (B) other than the above-mentioned specific resin that can be used in the photoreceptor of the present invention may be any of the resins used in conventionally known electrophotographic photoreceptors, and the weight average molecular weight is preferably 5 × 10 ³ ~1 × 10 ^6, and more preferably from ^{2 × 10 4 ~5 × 10 5} . The glass transition point of the binder resin is preferably -40 ° C to 200 ° C, more preferably -10 ° C to 140 ° C. Examples of conventionally known binder resins for electrophotographic photosensitive layers include, for example, Ryuji Shibata, Jiro Ishiwatari, Kogaku, Vol. 17, p. 278 (1968).
), Miyamoto Harumi, Takei Hidehiko, Imaging, 1973 (No.
8), Koichi Nakamura, "Practical Technology of Binders for Recording Materials", Part 1
Chapter 10, CMC Publishing (1985), Proceedings of "Current State Symposium on Organic Photoreceptors for Electrophotography" edited by The Institute of Electrophotography (1985)
), Hiroshi Komon, "Recent Development and Practical Use of Photoconductive Materials and Photoconductors", Japan Science Information Co., Ltd. (1986), Electrophotographic Society, "Basics and Applications of Electrophotographic Technology", Chapter 5, Corona Co., Ltd.
(1988), D. Tatt, SCHeidecker, Tappi, 49 (No.1
0), 439 (1966), ES Baltazzi, RG Blanclotteet
al., Phot. Sci. Eng. 16 (No. 5), 354 (1972), Nguyen
Jang Kae, Isamu Shimizu, Eiichi Inoue, The Journal of The Institute of Electrophotography 18 (N
o.2), 22 (1980) and the like, compounds and the like described in reviews.

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

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

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

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

The thickness of the photoconductive layer is preferably 1 to 100 μm, particularly preferably 10 to 50 μm. When the photoconductive layer is used as the charge generation layer of the laminated type photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is preferably 0.01 to 5 μm, and particularly preferably 0.05 to 2 μm. Is.

In the present invention, various dyes can be used together as a spectral sensitizer depending on the kind of light source such as visible light exposure or semiconductor laser light exposure. For example, Harumi Miyamoto, Hidehiko Takei; Imaging 1973 (No.8) No. 12
Page, CJ Young et al .: RCA Review 15 , 469 pages (1954
,) Kyohei Kiyota: Transactions of the Institute of Electrical Communication, J63-C (No.
2), p. 97 (1980), Yuji Harasaki et al., Journal of Industrial Chemistry, 66 ,
78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 3
5 , Carbonate dyes, diphenylmethane dyes, triphenylmethane dyes, etc.
Examples thereof include xanthene dyes, phthalein dyes, polymethine dyes (eg, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain a metal), and the like.

[0232] More specifically, as those mainly containing carbonium dyes, triphenylmethane dyes, xanthene dyes and phthalein dyes, Japanese Patent Publication No. 51-45.
2, JP-A-50-90334 and JP-A-50-11422.
No. 7, No. 53-39130, No. 53-82353,
US Pat. Nos. 3,052,540 and 4,054,450
And JP-A-57-16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include FM Hamer “The Cyanine Dyes and Related Co
The dyes described in "mpounds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,11.
0,591, 3,121,008, 3,12
5,447, 3,128,179 and 3,13
2,942, 3,622,317, British Patent 1,
No. 226,892, No. 1,309,274, No. 1,4
05,898, Japanese Patent Publication No. 48-7814, 55-1
Examples thereof include dyes described in No. 8892. Furthermore, 700
Polymethine dyes that spectrally sensitize the near infrared to infrared light region having a long wavelength of not less than nm are disclosed in JP-A-47-840 and 47-4.
No. 4180, Japanese Patent Publication No. 51-41061, Japanese Patent Laid-Open No. 49-
No. 5034, No. 49-45122, No. 57-4624.
No. 5, No. 56-35141, No. 57-157254.
No. 61-26044, No. 61-27551, and U.S. Pat. Nos. 3,619,154 and 4,175,956.
Issue, "Research Disclosure", 1982, 216, 117-118.
Examples include those described on pages. The photoconductor of the present invention is also excellent in that its performance does not easily change depending on the sensitizing dye even when various sensitizing dyes are used in combination.

If desired, various conventionally known additives for electrophotographic photoreceptors can be used in combination. These additives include chemical sensitizers for improving electrophotographic sensitivity, various plasticizers for improving film properties, surfactants and the like. As a chemical sensitizer,
For example, halogen, benzoquinone, chloranil, fluoranyl, bromanil, dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, phthalic anhydride, maleic anhydride, N-hydroxymaleimide, N-hydroxyphthalimide, Electron-withdrawing compounds such as 2,3-dichloro-5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone, tetracyanoethylene, nitrobenzoic acid, dinitrobenzoic acid, Hiroshi Komon et al. "Recent Photoconductive Materials and Photosensitization Development and practical use of the body ”Chapters 4 to 6:
A polyarylalkane compound, a hindered phenol compound, a p-phenylenediamine compound, and the like, which are cited as references in the publication of Japan Scientific Information Co., Ltd. (1986), may be mentioned. Further, JP-A-58-65439 and JP-A-58-102239.
No. 58-129439, No. 62-71965, and the like.

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

The photoconductive layer can be provided on a conventionally known support. Generally, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, just as in the conventional case, for example, a substrate such as metal, paper or plastic sheet is impregnated with a low resistance substance. And conductive treatment is applied to the back surface (the surface opposite to the surface on which the photosensitive layer is provided) of the substrate, and at least one layer is coated for the purpose of preventing curling. Those provided with a water-resistant adhesive layer on the surface, those provided with at least one precoat layer as required on the surface layer of the above-mentioned support, those obtained by laminating electroconductive plastic substrate on which aluminum or the like is deposited on paper, etc. Can be used. Specifically,
As an example of a conductive substrate or conductive material, Yukio Sakamoto,
Electrophotography, 14 (No.1), pp. 2-11 (Published in 1975), Hiroyuki Moriga "Introduction to Special Paper Chemistry" Polymer Publishing (1975), M.
F. Hoover, J. Macromol. Sci. Chem, A-4 (6), 1327 ~ 1
Those described on page 417 (published 1970) can be used.

In the present invention, the peelable surface is formed as described above.
On the developed photoreceptor, the difference in glass transition point according to the present invention is
A resin containing at least two kinds of resins in the same particle
Particles (AL) are formed by electrodeposition or adhesion by the electrodeposition coating method.
By forming a film, the first transfer layer (T ₁) Is formed, and further on this
Resin (A₂Second transfer layer (T)₂), Then usually
To form a toner image. Immediately
The charging-exposure-developing-fixing process is conventionally known.
By method. First transfer layer (T₁) And / or second roll
Layer (T₂) Formation and electrophotographic process in the same equipment
It may be performed by a separate device. In the present invention, the electronic
To form a toner image by the photographic process
Known methods and devices can be used as appropriate.

The developer used in the present invention may be a conventionally known developer for electrostatic photography, and may be either a dry developer for electrostatic photography or a liquid developer. For example, "Basics and Applications of Electrophotographic Technology", pages 497 to 505, "Development and Practical Use of Toner Material", supervised by Koichi Nakamura, Chapter 3 (published by Nihon Kagaku Information Co., Ltd., 1985), Moto Machida "Recording Materials" And photosensitive resin "
Practical modes are shown in pages 107 to 127 (published in 1983), Academic Society Publishing Center, Electrophotographic Society, "Imaging No. 2 to 5, electrophotographic development, fixing, charging and transfer". As the dry developer, a one-component magnetic toner, a two-component toner, a one-component non-magnetic toner, a capsule toner and the like have been put into practical use, and any of these can be used.

The basic constitution of a concrete liquid developer is as follows.
Electrically insulating organic solvent {for example, isoparaffin-based aliphatic hydrocarbon: Ansoper H, Isopar G (manufactured by Esso) Shellsol 70, Shellsol 71 (manufactured by Shell Oil), IP-solvent 1620 (manufactured by Idemitsu Petrochemical)
Etc. as a dispersion medium, a resin for imparting dispersion stability, fixability and chargeability to an inorganic or organic pigment or dye as a colorant and an alkyd resin, an acrylic resin, a polyester resin, a styrene butadiene resin, a rosin, etc. Is dispersed, and various additives are added, if desired, for the purpose of enhancing charging characteristics or improving image characteristics.

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

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

As a specific example of the method for producing a liquid developer, a method for producing colored particles by mechanically dispersing a colorant and a resin using a disperser such as a sand mill, a ball mill, a jet mill or an attritor. However, for example, Japanese Patent Publication 35-
5511, 35-13424, 50-4001.
No. 7, No. 49-98634, No. 58-129438.
And JP-A-61-180248.

As another method for producing colored particles, for example, a method of producing dispersed resin particles by a non-aqueous dispersion polymerization method which gives fine particles having good monodispersity and coloring the resin particles is used. Can be mentioned. As one of the coloring methods, there is a method of dyeing a dispersed resin with a preferable dye as described in JP-A-57-48738. Further, as another method, as disclosed in JP-A-53-54029, a method of chemically bonding a dispersion resin and a dye, or a polymerization method as described in JP-B-44-22955 and the like. In the case of producing by a granulation method, there is a method of using a dye-containing monomer in advance to obtain a dye-containing copolymer.

A combination of the scanning exposure method using laser light which is exposed based on digital information and the developing method using a liquid developer is an effective process because a high-definition image can be formed. An example is shown below. First, the photosensitive material is positioned on the flat bed by the register pin method, and then sucked and fixed by air suction from the back surface. Then, for example, by using the charging device described in "Basics and Applications of Electrophotographic Technology" (edited by the Electrophotographic Society, Corona Publishing Co., Ltd., June 15, 1988), pages 212 and thereafter.
Charge the photosensitive material. The corotron or scotron system is common. At this time, it is also preferable to control the charging condition by giving feedback so that the surface potential is always within a predetermined range based on the information from the charging potential detection means of the photosensitive material. After that, for example,
Scanning exposure with a laser light source is performed using the method described on page 254 and thereafter.

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

Next, the toner image on the photoconductor is thermally transferred together with the transfer layer to the transfer material. The thermal transfer of the transfer layer to the material to be transferred may be performed in the same apparatus as the transfer layer forming step and the electrophotographic step or in a separate apparatus. For example, the transfer layer together with the toner image can be easily thermally transferred onto the transfer target material by driving while applying a predetermined nip pressure between a pair of rubber-coated metal rollers having a built-in heating means.

The surface temperature of the rollers at this time is preferably 30 to 150 ° C., more preferably 40 to 120 ° C., and the nip pressure between the rollers is preferably 0.2 to 20 kgf / c.
m ² , more preferably 0.5 to 10 kgf / cm ² , transport speed is preferably 10 mm / sec or more, more preferably 50 mm
/ Sec or more. It is natural that these condition settings are optimized depending on the physical properties of the photosensitive material used, that is, the material of the peeling layer, the photosensitive layer and the support. The surface temperature of the roller is preferably kept within a predetermined range by a known surface temperature detecting means and temperature controller. Further, a preheating means for the photosensitive material may be provided in front of the heating roller portion, and a cooling means may be provided afterwards. Further, as the inter-roller pressing means, a spring or an air cylinder using compressed air at both ends of the shaft of at least one roller can be used.

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 plastic sheet or a paper with a particularly printing durability, aluminum, a plate, a zinc plate, a copper-aluminum plate, a copper-stainless plate, a bimetal plate such as a chromium-copper plate, a chromium-copper-aluminum plate, a chromium plate. A substrate having a hydrophilic surface such as a lead-iron plate, a chrome-copper-stainless plate, or a trimetal plate is used, and the thickness thereof is 0.1.
-3 mm is preferable, and 0.1-1 mm is particularly preferable.

In the case of a support having an aluminum surface, it is subjected to surface treatment such as graining treatment, dipping treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization treatment. Is preferred. Further, as described in U.S. Pat. No. 2,714,066, an aluminum plate which has been grained and then dipped in an aqueous sodium silicate solution, JP-B-47-5.
As described in No. 125, an aluminum plate subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is also preferably used.

The anodizing treatment is carried out, for example, by using an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid or the like, or an organic acid such as oxalic acid, sulfamic acid or the like, or an aqueous solution or a non-aqueous solution of one or more of them. It is carried out by passing an electric current using an aluminum plate as an anode in the combined electrolytic solution. Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. The treatment with polyvinylsulfonic acid described in West German Patent Publication No. 1,621,478 is also suitable.

These hydrophilization treatments are carried out to improve the adhesion to the toner image provided thereon, in addition to the treatment for making the surface of the support hydrophilic. . Further, in order to adjust the adhesion between the support and the transfer layer on which the toner image is formed, 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 the support, it is needless to say that a layer other than the toner image part layer must be hydrophilic, so that a surface layer having hydrophilicity is provided. Specifically, a known transferable lithographic printing plate precursor or a transfer material having the same contents as the image receiving layer of the plate can be used.

In the present invention, the transfer layer on the transfer material obtained as described above is subjected to a chemical reaction treatment to completely remove the transfer layer, whereby an offset printing plate can be prepared. . In order to remove the transfer layer, a deprotection reaction by a chemical optical hot line may be used in addition to the reaction by the treatment liquid, or may be used in combination.

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

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

For example, as a mercapto compound, 2-mercaptoethanol, 2-mercaptoethylamine, N-
Methyl-2-mercaptoethylamine, N- (2-hydroxyethyl) -2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenecarboxylic acid, 2-mercaptoenesulfonic acid, 2-mercaptoethylphosphonic acid, Mercaptobenzenesulfonic acid, 2-mercaptopropionylaminoacetic acid, 2-mercapto-1-aminoacetic acid, 1-mercaptopropionylaminoacetic acid, 1,2-dimercaptopropionylaminoacetic acid, 2,3-dihydroxypropylmercaptan, 2-methyl- 2-Mercapto-1-aminoacetic acid and the like as a sulfinic acid compound, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid The dicarboxylate benzene sulfinic acid, a hydrazide compound, 2- hydrazino ethanol sulfonic acid, 4-hydrazino butanoic acid,
Hydrazinobenzenesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzoic acid, hydrazinobenzenecarboxylic acid, etc. as a primary or secondary amine compound,
For example, N- (2-hydroxyethyl) amine, N, N-
Di (2-hydroxyethyl) amine, N, N-di (2-
Hydroxyethyl) ethylenediamine, tri (2-hydroxyethyl) ethylenediamine, N- (2,3-dihydroxypropyl) amine, N, N-di (2,3-dihydroxypropyl) amine, 2-aminopropionic acid,
Examples thereof include aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2-hydroxyethylmorpholine, 2-carboxyethylmorpholine and 3-carboxypiperazine. The amount of the nucleophilic compound present in these treatment liquids is 0.05 to 10 mol / liter, preferably 0.1 to 5 mol / liter. Also, the pH of the treatment liquid
Is preferably 8 or more.

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

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

On the other hand, the light used in the deprotection reaction by irradiation with chemically active light may be visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, γ-ray, α-ray or the like, but is preferable. Is ultraviolet light. More preferably, it is a light beam having a wavelength of 310 nm to a wavelength of 500 nm. Generally, a high pressure or ultra high pressure mercury lamp or the like is used. The light irradiation treatment can usually be performed sufficiently by irradiation for 10 seconds to 10 minutes from a distance of 5 cm to 50 cm. After irradiating with light in this way, the transfer layer can be easily removed by immersing in the water-soluble solution as described above.

The method for producing the electrophotographic plate-making printing plate of the present invention will be described in detail below with reference to the accompanying drawings. FIG. 2 is a schematic view of an electrophotographic plate-making printing plate making apparatus, which is a preferred embodiment for carrying out the method of the present invention, in which the transfer layer formation, the electrophotographic process and the thermal transfer of the transfer layer can be performed in the same apparatus. It is a figure.

As described above, when the electrophotographic photosensitive member 11 whose surface is modified to have peelability is used, the first transfer layer 12T ₁ is directly formed on the photosensitive member 11. If the surface of the photoreceptor 11 is not sufficiently peeled, as described above,
An apparatus for adsorbing or adhering the compound (S) before the formation of the first transfer layer 12T ₁ is provided (second method), or electrodeposition dispersion containing the transfer layer-forming resin particles (AL) of the present invention. By containing the compound (S ′) in the liquid (third method), it is possible to impart releasability to the surface of the photoreceptor 11. In the case of the second method, the compound (S) coating apparatus 10 using any one of the methods of the specific embodiments described above.
Is appropriately provided to supply the compound (S) to the surface of the photoreceptor 11. The device 10 for applying the compound (S) to the surface of the photoreceptor may be fixed or movable.

Dispersion 12a of thermoplastic resin particles (AL)
Is supplied to the first transfer layer electrodeposition unit 13a in the movable liquid developing unit set 14. First, the electrodeposition unit 13a is brought close to the photoreceptor surface 11 and fixed so that the distance between the electrodeposition unit 13a and the developing electrode is 1 mm. The dispersion liquid 12a is supplied into this gap and rotated while applying a voltage from an external power source (not shown) so that the resin particles (AL) are electrodeposited on the entire surface of the image forming area on the surface 11 of the photoconductor. The squeeze device built in the electrodeposition unit 13a removes the dispersion liquid 12a adhering to the surface 11 of the photoconductor, and then passes it under the intake / exhaust unit 15 for drying, and the thermoplastic resin particles (A
L) is heat-melted to obtain a first transfer layer 12T ₁ of thermoplastic resin which is formed into a film.

First transfer layer 12T _{1 made of} thermoplastic resin
The photoreceptor 11 on which is formed is then subjected to the second transfer layer 12 by any one of a hot melt coating method, an electrodeposition coating method and a transfer method.
Form T ₂ . Thermoplastic resin particles (A
₂ L) of the dispersion liquid 12b is used, as shown in FIG. 2, the second transfer layer electrodeposition unit 13b is provided in the liquid developing unit set 14, and the same process as the formation of the first transfer layer 12T ₁ is performed. You can Thereafter, if necessary, a cooling device (not shown) similar to the intake / exhaust unit 15 is used to cool the photosensitive member from the outside or the inside of the photosensitive drum to a predetermined temperature.

First transfer layer and second layer made of thermoplastic resin
The photoconductor on which the transfer layer is formed then enters an electrophotographic process. When the photoconductor 11 is uniformly charged positively, for example, by the corona charging device 18, and then imagewise exposed by the exposure device 19, for example, a semiconductor laser based on image information, the potential of the exposed portion is reduced and the unexposed portion is exposed. A potential contrast is obtained during the period. A liquid developing unit 14L containing a liquid developer in which particles having a positive electrostatic charge are dispersed in an electrically insulating dispersion medium is brought close to the photoreceptor surface 11 and fixed with a gap of 1 mm.

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

After that, the developing solution attached to the surface of the photoconductor is washed off by the rinsing means built in the developing unit set 14, and subsequently the rinsing solution adhering to the surface of the photoconductor is removed by the squeeze means. To dry. During this time, the thermal transfer means 17
Is placed away from the surface of the photoconductor. A carrier liquid of a liquid developer is usually used as the prebath liquid and the rinse liquid.

The toner image 3 is transferred onto the transfer layer 12 of the photoconductor 11.
After forming on (12T ₁ and 12T ₂ ), transfer means 17
Is thermally transferred to the transfer material 16. That is, toner image 3
The transfer layer 12 holding the pre-heating means 17 for thermal transfer.
A predetermined preheating is carried out by a, and then a metal roller coated with a rubber containing a heating element having a temperature control means is pressed as a transfer backup roller 17b through the transfer target material 16, and further, a peeling backup roller 17
As c, the photoconductor 1 is cooled by passing under a cooling roller.
The toner image 3 on 1 is transferred together with the transfer layer 12 to the transfer material 16, and a series of printing original plate forming steps is completed.

As the preheating means 17a, a non-contact type infrared line heater or flash heater is used, and preheating is performed within a range not exceeding the surface temperature of the photosensitive layer obtained by the heating roller 17b. The surface temperature of the photosensitive layer heated by the heating roller 17b is preferably 30 to 150 ° C, more preferably 40 to 120 ° C.

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

The nip pressure of these rollers is 0.2 to 2
0 kgf / cm ^2, more preferably 0.5~10kgf / cm ^2, as the have not but roller pressing means shown in Figure can be used an air cylinder using a spring or compressed air to both ends of the roller shaft . The conveying speed is preferably 10 mm / sec or more, more preferably 50 mm / sec or more, and may be different in the electrophotographic process and the thermal transfer process.

The above conditions are set according to the photosensitive member used,
It is natural to optimize the transfer layer and the physical properties of the material to be transferred. In particular, it is important to determine the preheating, roller heating, and cooling conditions in the thermal transfer step in consideration of factors such as the glass transition point of the transfer layer, the softening temperature, the fluidity, the tackiness, the film property, and the film thickness. That is, the transfer layer, which has been softened to some extent by the preheating means, passes under the heating roller to increase the tackiness and adhere to the material to be transferred. Then, after passing under the cooling roller, conditions should be set so that the temperature is lowered, the fluidity and the adhesiveness are reduced, and the toner as a film is peeled off from the surface of the photosensitive layer together with the toner. Further, by stopping the apparatus with the transfer layer 12 formed, the electrophotographic process can be started immediately when the apparatus is next operated, and the photosensitive layer surface can be protected and the characteristic deterioration due to the influence of the external environment can be prevented. it can.

The transfer layer formed on the transfer-receiving material as described above is then removed by a chemical reaction treatment to obtain an offset printing plate.

Another example of a suitable apparatus for carrying out the method of the present invention is shown in FIG. In this example, the second transfer layer is formed by a hot melt coating method. In FIG. 3, after the liquid developing unit set 14 has moved to the standby position, the hot melt coater 13 is moved to that position from the standby position 13w. The thermoplastic resin 12c for the second transfer layer is applied by the hot melt coater 13 onto the first transfer layer 12T ₁ on the photoconductor 11 on the peripheral surface of the drum, and the intake / exhaust unit 15
It is cooled down to a specified temperature by passing under the second
The transfer layer 12T ₂ is formed.

Yet another suitable apparatus example is shown in FIG. The second transfer layer is formed according to the transfer method. FIG.
In the above, the second transfer layer 12T ₂ is simply formed on the first transfer layer 12T ₁ on the photoconductor 11 by the second transfer layer transfer device 117. That is, the release paper 20 provided with the second transfer layer 12T ₂ is heated and pressed by the heating roller 117b to transfer the second transfer layer 12T ₂ to the surface of the first transfer layer 12T ₁ .
The release paper 20 is cooled by the cooling roller 117c and collected. If necessary, the photoconductor 11 itself is heated by the preheating means 17a.
May be heated to improve the transferability of the second transfer layer 12T ₂ by thermocompression bonding.

The position where the second transfer layer transfer device 117 is incorporated is not particularly limited. As a movable type, the transfer layer 12T ₁
And 12T ₂ may be replaced with the thermal transfer means 17 for transferring 12T ₂ to the transfer material 16. Alternatively, this device 117 is first used to form the second transfer layer 12T ₂ and then the transfer layer 1
It can also be used for transferring 2T ₁ and 12T _{2 to} the transfer material 16. Other configurations in FIGS. 3 and 4 are essentially the same as those in FIG.

[0275]

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

[Production Example of Transfer Layer Resin Particles] Production Example of Transfer Layer Resin Particles (AL) 1: (AL-1) 20 g of a dispersion stabilizing resin (Q-1) having the following structure, 30 g of methyl methacrylate, and methyl. Acrylate 55 g, acrylic acid 15 g, methyl 3-mercaptopropionate 1.
A mixed solution of 3 g and Isopar H542 g was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. 2,2'-azobis (isovaleronitrile) as a polymerization initiator (abbreviation AIV
N.) 0.8 g was added and reacted for 2 hours. Twenty minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88 ° C. After adding 0.5 g of the initiator and reacting for 2 hours, 0.3 g of the initiator was further added and reacted for 3 hours. 200 after cooling
The white dispersion obtained by passing through a mesh nylon cloth was a monodisperse latex having a polymerization rate of 99% and an average particle size of 0.18 μm. The particle size was measured by CAPA-500 (manufactured by Horiba, Ltd.) (the same applies hereinafter).

[0277]

Embedded image

A mixed solution of the entire amount of the above resin particle dispersion (that is, seed particles) and 10 g of the dispersion stabilizing resin (Q-1) was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. to this,
Benzyl methacrylate 85g, acrylic acid 15g, 3
-Mercaptopropionic acid 1.0 g, AIVN 0.8
g and 200 g of Isopar H were added dropwise over 2 hours, and the reaction was continued for another 2 hours. Next, the initiator was added to 0.
8 g was added and the temperature was raised to 70 ° C. to react for 2 hours, and 0.6 g of an initiator was further added and reacted for 3 hours. After cooling, a 200 mesh nylon cloth was passed through, and the polymerization rate of the obtained white dispersion was 9
The latex was 8% and had an average particle size of 0.25 μm and good monodispersity.

Next, whether or not the obtained resin particles were formed as individual particles was examined by observing the state using a scanning electron microscope (SEM). After heat-treating the film produced so that the resin particles are dispersed on the PET film at a temperature of 50 ° C. and 80 ° C. for 5 minutes,
JSL-T330 Scanning Microscope for each sample
When observed at 20,000 times using (manufactured by JEOL), a particle state was observed in the sample at a temperature of 50 ° C., but a temperature of 80
Not observed at ° C. That is, the particles were melted by heating.

Similarly, the resin particles of the present invention (AL-
1) Resin particles composed of each of two kinds of resins (copolymers) constituting {1) (Comparative resin particles (1) and (2) described below respectively) and these two kinds of resin particles in a 1/1 weight ratio. The mixed dispersed resin particles were investigated. In the sample composed of the resin particles (1), the sample not heated was in a particle state, but the particle state was not observed at the temperature of 50 ° C.
The resin particle (2) sample was in a particle state at a temperature of 50 ° C., but no particles were visible at a temperature of 80 ° C. Further, when a sample made up of mixed particles and a sample not heated and a temperature of 50 ° C. were examined, it was confirmed that particles were not visible in the sample having a temperature of 50 ° C. as compared with the unheated sample.

As described above, as a result of visual observation of the thermal behavior of the particles, the resin particles (AL of the present invention produced as described above (AL
-1) is not a mixture of two types of resin particles,
Two kinds of resins were contained in one particle, and in this case, it was confirmed that the resin having a high Tg was a core-shell particle in which the resin having a low Tg was distributed in the inner layer.

Production of Comparative Resin Particles (1) 10 g of dispersion stabilizing resin (Q-1), 15 g of methyl methacrylate, 27.5 g of methyl acrylate, 7.5 g of acrylic acid, 0.65 of methyl 3-mercaptopropionate.
A mixed solution of g and Isopar H329 g was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. As a polymerization initiator,
AIVN 0.4g was added and reacted for 2 hours. Twenty minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88 ° C. After adding 0.2 g of the initiator and reacting for 2 hours, 0.3 g of the initiator was further added and reacted for 3 hours. 20 after cooling
The white dispersion obtained through a 0-mesh nylon cloth was a monodisperse latex having a polymerization rate of 99% and an average particle size of 0.25 μm. A part of the above-mentioned dispersion was allowed to settle with a centrifugal settling machine, and then the settled component was taken out and dried by vacuum drying. The glass transition point of the obtained resin component was measured and found to be 38 ° C.

Preparation of Comparative Resin Particles (2) 10 g of the dispersion stabilizing resin (Q-1), 42.5 g of benzyl methacrylate, 7.5 g of acrylic acid, 0.5 g of 3-mercaptopropionic acid and 326 g of Isopar H were mixed. The resin particles were synthesized by reacting in the same manner as in the production of the comparative resin particles (1). The obtained white dispersion was a monodisperse latex having a polymerization rate of 98% and an average particle size of 0.24 μm. Further, the glass transition point of the resin component is 65
° C.

Production Example 2 of Resin Particles (AL) for Transfer Layer:
(AL-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 80 ° C while stirring under a nitrogen stream. Add 2 g of 2,2'-azobis (isobutyronitrile) (abbreviation AIBN),
After reacting for 3 hours, 0.5 g of AIBN was further added and reacted for 4 hours. The solid content of the obtained polymer was 33.3% (by weight), and the Mw was ⁴ × 10 ⁴ .

Synthesis of Particles A mixed solution of 18 g (as solid content) of the above resin (Q-2) for stabilizing dispersion, 72 g of vinyl acetate, 8 g of crotonic acid, 20 g of vinyl propionate and 382 g of Isopar H was stirred at a temperature of nitrogen while flowing. Warmed to 80 ° C.
Add AIVN 1.6g and react for 1.5 hours.
0.8 g was added for 2 hours, and AIVN 0.5 g was added for 3 hours. Next, the temperature was raised to 100 ° C. and the mixture was stirred for 2 hours to distill off unreacted monomers, and then cooled to 20
Polymerization rate of the white dispersion was 8 through a 0 mesh nylon cloth.
Obtained at 7%. It was a monodisperse latex having an average particle size of 0.17 μm.

A mixed solution of the entire amount of the resin particle dispersion (that is, seed particles) and 20 g of the dispersion stabilizing resin (Q-2) was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. To this, a mixture of 50 g of methyl methacrylate, 35 g of 2-butoxyethyl methacrylate, 15 g of acrylic acid, 2.6 g of methyl 3-mercaptopropionate, 0.8 g of AIVN and 200 g of Isopar H was added dropwise over 2 hours, and the reaction was continued for 1 hour. Next, 0.8 g of an initiator was added, the temperature was raised to 75 ° C., and the reaction was performed for 2 hours. Further, 0.6 g of the initiator was added, and the reaction was performed for 3 hours. After cooling, a 200 mesh nylon cloth was passed through to obtain a white dispersion, which was a latex having a polymerization rate of 98% and an average particle size of 0.23 μm and good monodispersity.

Production Example 3 of Transfer Layer Resin Particles (AL):
(AL-3) A mixed solution of 25 g of a dispersion stabilizing resin (Q-3) having the following structure and Isopar H546 g was heated to 60 ° C. while stirring under a nitrogen stream. 50 g of benzyl methacrylate, 8 g of acrylic acid, and a monomer (b-
1) 42 g, 2-mercaptoethanol 1.8 g, A.
A mixed solution of 1.0 g of IVN and 200 g of Isopar H was added dropwise over 1 hour, and the reaction was continued for 1 hour. Then A.
IVN 0.8g was added and reacted for 2 hours, then AIVN
0.5g was added and reacted at a temperature of 80 ° C for 2 hours.
AIBN 0.5g was added and reacted for 3 hours. After cooling, 2
The white dispersion obtained through a 00 mesh nylon cloth was a latex having a polymerization rate of 98% and an average particle size of 0.17 μm and good monodispersity.

[0288]

Embedded image

Dispersion-stabilizing resin particles (Q-
3) The temperature was set to 60 ° C while stirring the mixed solution containing 15 g under a nitrogen stream. To this, 52 g of methyl methacrylate, 35 g of methyl acrylate, 13 acrylic acid
g, 3-mercaptopropionic acid 2 g, AIVN 0.
A mixture of 8 g and Isopar H564 g was added dropwise for 2 hours, and the reaction was continued for another 2 hours. Then as an initiator
AIBN 0.8 g was added, the temperature was raised to 80 ° C., and the reaction was performed for 2 hours. Further, 0.6 g of an initiator was added, and the reaction was performed for 3 hours. After cooling, a 200-mesh nylon cloth was passed through, and the obtained white dispersion was a latex having a polymerization rate of 98% and an average particle size of 0.24 μm and good monodispersity.

Production Example 4 of Resin Particles (AL) for Transfer Layer:
(AL-4) A mixed solution of 25 g of dispersion-stabilizing resin particles (Q-4) having the following structure, 300 g of Isopar H, and 100 g of ethyl acetate was stirred at a temperature of 60 ° C. under a nitrogen stream. In this solution, 8 g of 2-hydroxyethyl methacrylate, 65 g of phenethyl methacrylate, a monomer of the following structure (b-
2) 27 g, thioglycolic acid 1.5 g, AIVN
A mixture of 0.6 g, Isopar H (199.5 g) and ethyl acetate (66.5 g) was added dropwise over 1 hour. After reacting for 1 hour, AIVN 0.3g was added for 2 hours, then
AIVN 0.3g was added and it reacted for 3 hours. Next, ethyl acetate was distilled off under a reduced pressure of 30 mmHg, and the same amount of distilled off Isopar H was added, followed by cooling and filtering with a 200-mesh nylon cloth to obtain a white dispersion. Polymerization rate 93
%, And the average particle size was 0.20 μm.

[0291]

[Chemical 38]

The above resin particle dispersion (that is, seed particles) 3
A mixed solution of 72 g and 16 g of the dispersion stabilizing resin (Q-1) was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. To this, 70 g of vinyl acetate and the monomer (b-3) 2 having the following structure
5 g, crotonic acid 5 g, Isopar H 400 g and A.
A mixture of 0.9 g of IVN was added dropwise over 2 hours, and the reaction was continued for another 2 hours. Add 0.8g of initiator, temperature 85
React for 2 hours at ℃, then AIBN as an initiator
0.6 g was added and reacted for 3 hours. After cooling, a 200 mesh nylon cloth was passed through, and the polymerization rate of the obtained white dispersion was 9
The latex was 8% and had an average particle size of 0.26 μm and good monodispersity.

[0293]

[Chemical Formula 39]

Production Examples 5-1 of Resin Particles (AL) for Transfer Layer
1: (AL-5) to (AL-11) In Production Example 1 of resin particles for transfer layer (AL), except that each monomer shown in the following Table-B was used, the above Production Example 1 was used at all. Perform the same operation to make resin particles (AL-5) to (AL-11).
Was manufactured. The degree of polymerization of each latex particle obtained was 95.
.About.99%, and the average particle size was in the range of 0.20 to 0.30 .mu.m.

[0295]

[Table 2]

[0296]

[Table 3]

Production Examples 12 to 2 of Transfer Layer Resin Particles (AL)
1: (AL-12) to (AL-21) In Production Example 3 of resin particles (AL) for transfer layer, instead of the monomer (b-1), each monomer shown in Table C below. Particles (AL-12) to (AL-21) of the present invention were produced by the same procedure as in Production Example 3 except that the above was used. The degree of polymerization of each latex particle obtained was 95 to 99%, and the average particle diameter was in the range of 0.18 to 0.28 μm.

[0298]

[Table 4]

[0299]

[Table 5]

Production Example 22 of Transfer Layer Resin Particles (AL):
(AL-22) 15 g of dispersion stabilizing resin (Q-4), 48 g of methyl methacrylate, 40 g of 2,3-dipropionyloxypropyl methacrylate, 12 g of acrylic acid, 2.0 g of methyl 3-mercaptopropionate and 549 g of Isopar H.
The mixed solution of 1 was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. AIVN 0.8 was added as a polymerization initiator and reacted for 2 hours. 20 minutes after the addition of the initiator, a cloudiness was formed,
The reaction temperature rose to 88 ° C. After adding 0.5g of initiator and reacting for 2 hours, add 0.3g of initiator and add 3g.
Reacted for hours. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a monodisperse latex having a polymerization rate of 98% and an average particle size of 0.18 μm.

The above resin particle dispersion (that is, seed particles) 2
60 g, dispersion stabilizing resin (Q-1) 14 g, macromonomer (m-1) 10 g having the following structure, and Isopar H5
A temperature of 55 ° C. while stirring 53 g of the mixed solution under a nitrogen stream.
Warmed to. To this, 75 g of benzyl methacrylate,
Acrylic acid 10 g, monomer (b-11) 15 g, 3-mercaptopropionic acid 2 g, 2,2'-azobis (2-cyclopropylpropionitrile) (abbreviation: ACPP)
A mixed solution of 0 g and 200 g of Isopar H was added dropwise for 1 hour. After stirring for 1 hour as it was, 0.8 g of ACPP was added and reacted for 2 hours. Then add 0.5 g of AIBN,
The temperature was set to 80 ° C. and the reaction was performed for 3 hours. 20 after cooling
The white dispersion obtained through a 0 mesh nylon cloth had a polymerization rate of 97% and was a latex having an average particle size of 0.24 μm and good monodispersity.

[0302]

[Chemical 40]

Production Examples 23-2 of Resin Particles (AL) for Transfer Layer
8: (AL-23) to (AL-28) In Production Example 22 of resin particles (AL), instead of 10 g of macromonomer (m-1), each macromonomer (Mw is 8 × 10 ³ ) shown in Table D below. Each resin particle was synthesized in the same manner as in Production Example 22 except that the resin particles were used in the range of 1 × 10 ⁴ to 1 × 10 ⁴ . The degree of polymerization of each particle was 98 to 99%, the average particle diameter of the particles was in the range of 0.20 to 0.25 μm, the particle size distribution of the particles was narrow, and the monodispersibility was good.

[0304]

[Table 6]

[0305]

[Table 7]

Production Example 29 of thermoplastic resin particles (AL):
(AL-29) 20 g of the resin (A-1) having the structure shown below and 30 g of the resin (A-2) having the structure shown below were dissolved by heating with 100 g of tetrahydrofuran at a temperature of 40 ° C., the solvent was distilled off, and the residue was dried under reduced pressure. . Next, after roughly pulverizing this solid substance using a trio blender (manufactured by Trio Science Co., Ltd.), a mixture consisting of 20 g of this pulverized substance, 5 g of a dispersion stabilizing resin (Q-5) having the following structure and 80 g of Isopar G is used. It was dispersed with a dyno mill. The obtained particle dispersion has an average particle size of 0.45μ.
m latex.

[0307]

Embedded image

Synthesis Example 1 of Thermoplastic Resin Particles (A ₂ L) 1:
(A ₂ L-1) A mixed solution of 10 g of the dispersion stabilizing resin (Q-4), 20 g of the macromonomer (m-10) having the following structure and 560 g of Isopar H was heated to a temperature of 65 ° C while stirring under a nitrogen stream. Methyl methacrylate 28g, 3-ethoxypropyl methacrylate 40g, acrylic acid 12g, 3
-2.6 g mercaptopropionic acid, AIVN 0.8
and a mixed solution of 200 g of Isopar H were added dropwise over 1 hour. After stirring for 1 hour as it was, 0.8 g of AIVN was added and reacted for 2 hours. Furthermore, add 0.5 g of AIBN,
The temperature was set to 80 ° C. and the reaction was performed for 3 hours. 20 after cooling
The white dispersion obtained by passing through a 0 mesh nylon cloth was a monodisperse latex having a polymerization rate of 97% and an average particle size of 0.20 μm. Further, the Mw of the resin particles is 9 × 10 ³ ,
The glass transition point was 20 ° C.

[0309]

Embedded image

Synthesis Example 2 of thermoplastic resin particles (A ₂ L):
(A ₂ L-2) 15 g of dispersion stabilizing resin (Q-1) (as solid content),
A mixed solution of 67 g of vinyl acetate, 25 g of vinyl propionate, 8 g of crotonic acid and 275 g of Isopar H was heated to a temperature of 80 ° C. with stirring under a nitrogen stream. AIVN
Add 1.6g and react for 1.5 hours, AIVN 0.8g
Was added for 2 hours, and AIBN 0.5 g was further added for 4 hours. Then, the temperature was raised to 100 ° C. and the mixture was stirred for 2 hours to distill off unreacted monomers, then cooled and passed through a nylon cloth of 200 mesh to obtain a white dispersion with a polymerization rate of 88%. It was a monodisperse latex having an average particle size of 0.25 μm. The Mw of the resin particles was 5 × 10 ⁴ , and the glass transition point was 18 ° C.

Synthesis Example 3 of thermoplastic resin particles (A ₂ L):
(A ₂ L-3) 18 g of dispersion stabilizing resin (Q-4) and Isopar H56
0 g of the mixed solution was heated to a temperature of 55 ° C. with stirring under a nitrogen stream. 48g of benzyl methacrylate, 2
-Methoxyethyl methacrylate 40 g, acrylic acid 1
2 g, methyl 3-mercaptopropionate 3.2 g,
A mixed solution of 0.8 g of AIVN and 200 g of Isopar H was added dropwise for 1 hour. After stirring for 1 hour, AI
0.8 g of VN was added and reacted for 2 hours. Furthermore, AIBN
0.5 g was added, the temperature was set to 80 ° C., and the reaction was performed for 3 hours. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth had a polymerization rate of 97% and an average particle size of 0.20 μm.
It was a monodisperse latex of m. The Mw of the resin particles was 8.5 × 10 ³ , and the glass transition point was 18 ° C.

Synthesis Examples 4-1 of Thermoplastic Resin Particles (A ₂ L)
5: (A ₂ L-4) to (A ₂ L-15) Each monomer shown in the following Table-E was used in place of each monomer used in Synthesis Example 3 of resin particles (A ₂ L). Others were the same as in Synthesis Example 3 above to produce each resin particle. The polymerization rate of each particle is 93 to 99%, and the average particle diameter of the particles is 0.15.
Within the range of ˜0.25 μm, the particle size distribution of the particles was narrow and the monodispersity was good. Mw of resin particles is 8 × 10 ³
˜1 × 10 ⁴ and Tg ranged from 10 ° C. to 35 ° C.

[0313]

[Table 8]

[0314]

[Table 9]

[0315]

[Table 10]

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

[0317]

[Chemical 43]

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

[0319]

[Table 11]

[0320]

[Table 12]

Synthesis Example 10 of Resin (P): (P-10) 2,2,3,4,4,4-hexafluorobutylmethac
60 g of relate, macromonomer of methyl methacrylate
-(AA-6, manufactured by Toagosei Kagaku Co., Ltd., Mw 1 x 10^Four)
A mixed solution of 40 g and benzotrifluoride 200 g is nitrified.
The temperature was raised to 75 ° C. under an elementary air stream. A.I.B.N.
1.0g was added and reacted for 4 hours, 0.5g of A.I.B.N.
Was added and reacted for 4 hours. The Mw of the obtained copolymer is
6.5 x 10 ^FourMet.

[0322]

[Chemical 44]

Synthesis Examples 11 to 12 of Resin (P): (P-11) to
(P-12) Instead of the monomer and macromonomer used in Synthesis Example 10 of Resin (P), each monomer and each macromonomer corresponding to the polymer components shown in Table G below were used. The other is
Each copolymer was synthesized in the same manner as in Synthesis Example 10 above. The Mw of the obtained copolymer was 4.5 × 10 ^{4 to} 6.5 × 10 ^4.
Was in the range.

[0324]

[Table 13]

Synthesis Example 13 of resin (P): (P-13) methyl methacrylate 67 g, methyl acrylate 22
A mixed solution of g, methacrylic acid 1 g and toluene 200 g was heated to a temperature of 80 ° C. under a nitrogen stream. To this, 10 g of a polymeric azobis initiator (PI-1) having the following structure was added and reacted for 8 hours. After the reaction was completed, the precipitate was reprecipitated in 1.5 liter of methanol, and the obtained precipitate was collected and dried to obtain a copolymer of Mw 3 × 10 ^{4 in} a yield of 75 g.

[0326]

[Chemical formula 45]

Synthesis Example 14 of Resin (P): (P-14) A mixture of 50 g of ethyl methacrylate, 10 g of glycidyl methacrylate and 4.8 g of benzyl N, N-diethyldithiocarbamate was sealed in a container under a nitrogen stream,
The temperature was raised to 50 ° C. This was irradiated with light from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 6 hours for photopolymerization. Tetrahydrofuran 100
After being dissolved in g, 40 g of the following monomer (M-1) was added, the atmosphere was replaced with nitrogen, and light irradiation was again performed for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, collected and dried. The polymer obtained had a yield of 73 g and a Mw of 4.8 × 10.
^{Was 4} .

[0328]

[Chemical formula 46]

Synthesis Examples 15-18 of Resin (P): (P-15)-
(P-18) In the same manner as in Synthesis Example 14 of Resin (P), each copolymer shown in Table H below was synthesized. The Mw of the obtained polymer is 3.5 × 1.
It was in the range of 0 ^{4 to} 6 × 10 ⁴ .

[0330]

[Table 14]

Synthesis Example 19 of Resin (P): (P-19) In Synthesis Example 14 of Resin (P), 18 g of an initiator (I-11) having the following structure was used instead of benzyl N, N-diethyldithiocarbamate. Was synthesized in the same manner as in Synthesis Example 14 except that was used to obtain a copolymer having Mw of 4.5 × 10 ⁴ .

[0332]

[Chemical 47]

Synthesis Example 20 of Resin (P): (P-20) Methyl Methacrylate 68 g, Methyl Acrylate 22
g, 10 g of glycidyl methacrylate, 17.5 g of an initiator (I-12) having the following structure and 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 from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 10 hours to perform photopolymerization.
The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to give a yield of 72 g and a Mw of 4.0 × 10.
A polymer of ⁴ was obtained. 70 g of this polymer, monomer (M-
2) A mixed solution of 30 g and 100 g of tetrahydrofuran was heated under a nitrogen stream at a temperature of 50 ° C. under the same conditions as above.
Irradiated for hours. Next, the reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried to obtain a yield of 78 g.
Thus, a copolymer having Mw of 6 × 10 ⁴ was obtained.

[0334]

[Chemical 48]

Synthesis Examples 21 to 25 of Resin (P): (P-21) to
(P-25) In the synthesis example 20 of the resin (P), the initiator (I-12) 1
Instead of 7.5 g, the initiator (I) 0.0
Operation was carried out under the same conditions as in Synthesis Example 20 except that 31 mol was used. The yield of each polymer obtained was 70 to 80 g and Mw4.
It was x10 ^{4 to} 6x10 ⁴ .

[0336]

[Table 15]

[0337]

[Table 16]

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

[0339]

[Chemical 49]

Synthesis Example 2 of Resin Particles (L): (L-2) Monofunctional macromonomer consisting of butyl acrylate unit (AB-6, Toagosei Co., Ltd.) as a dispersion stabilizing resin.
5 g) and 140 g of methyl ethyl ketone were mixed and heated to a temperature of 60 ° C. with stirring under a nitrogen stream. 40 g of a monomer (LM-2) having the following structure, 1.5 g of ethylene glycol diacrylate, AIVN 0.2
g and a mixed solution of 40 g of methyl ethyl ketone were added dropwise over 1 hour. After reacting for 2 hours, AIVN 0.
1 g was added and reacted for 3 hours to obtain a white dispersion. After cooling, the resulting dispersion was passed through a nylon cloth of 200 mesh, and the average particle size was 0.35 μm.

[0341]

Embedded image

Synthesis Examples 3 to 6 of Resin Particles (L): (L-
3) to (L-6) In Synthesis Example 1 of the resin particles (L), the monomer (LM-
Resin particles were produced in the same manner as in Synthesis Example 1 except that 1), ethylene glycol dimethacrylate, and methyl ethyl ketone were replaced with the compounds shown in Table J below. The average particle diameter of the obtained resin particles is 0.15 to 0.30 μm.
Was in the range.

[0343]

[Table 17]

Example 1 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 2
g, a mixture of 8 g of the binder resin (B-1) having the following structure, 0.15 g of the compound (A) having the following structure, and 80 g of tetrahydrofuran was placed in a 500 ml glass container together with glass beads, and a paint shaker (manufactured by Toyo Seiki Seisakusho) was used. Disperse for 60 minutes, and further add 2.0 g of resin (P-2), 0.03 g of phthalic anhydride and 0.002 of o-chlorophenol.
After adding g and dispersing for 2 minutes, the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0345]

[Chemical 51]

Next, this dispersion was degreased to a density of 0.
Apply on a 2mm thick aluminum plate with a wire bar,
After being dried by touch, it was heated in a circulating oven at 110 ° C. for 20 seconds and further at 140 ° C. for 1 hour. The film thickness of the obtained photosensitive layer was 8 μm. The surface of the photoreceptor is JIS Z0237-19
When the adhesive force was measured by 80 "adhesive tape / adhesive sheet test method", it was 3 gf.

This photoconductor was loaded into a device as shown in FIG. 2 to first form a first transfer layer (T ₁ ). That is, the surface temperature of the photoconductor is 60 ° C., and the peripheral speed of the photoconductor drum is 10 mm /
It is rotated for 2 seconds and a resin particle dispersion liquid (L-
While supplying 1), the photoreceptor side was grounded and a voltage of 150 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit and fix the resin particles. The film thickness at this time was 1.2 μm. Resin particle dispersion liquid (L-1) Resin particles (AL-1) 8 g (as solid content) Positive charge control agent (CD-1) 0.02 g Octadecyl vinyl ether / N-hexadecyl maleic acid half amide (1 (1 mol ratio) Copolymer Charge control aid 0.1 g Dodecyl methacrylate / methacrylic acid (94/6 weight ratio) Copolymer was adjusted with Isopar G to a total volume of 1.0 liter.

On the first transfer layer (T ₁ ), in the above dispersion liquid (L-1), 8 g of resin particles (A ₂ L-1) (as solid content) was used in place of 8 g of resin particles (AL-1). In the same manner as above, a second transfer layer (T ₂ ) having a film thickness of 1.2 μm was prepared by using a resin particle dispersion liquid (L-2) containing positively charged resin particles prepared in the same manner as described above. Formed.

Next, using this photosensitive material, a toner image was formed, transferred to a transfer material, a printing plate was prepared and printing was carried out as follows. After the photosensitive material is corona charged to +450 V, it is read from the original by a color scanner in advance, and based on the information stored in the hard disk in the system as digital image data, a 5 mW output gallium-aluminum-arsenic semiconductor laser (oscillation) 30 erg on the surface of the photosensitive material using a wavelength of 780 nm)
Exposure was performed at a pitch of 25 μm and a scanning speed of 300 cm / sec under an irradiation amount of / cm ² .

Next, the liquid developer (L
D-1) was used to apply a bias voltage of +200 V to the developing electrode to carry out reversal development so that the toner was electrodeposited on the exposed area, and then rinsed in a bath of Isopar H alone to stain the non-image area. I removed it.

Preparation of liquid developer (LD-1) -Synthesis of toner particles Methyl methacrylate 70 g, methyl acrylate 30
g, 20 g of a dispersion polymer having the following structure and Isopar H6
80 g of the mixed solution was stirred under a nitrogen stream at a temperature of 6
Warmed to 5 ° C. To this, 1.2 g of 2,2'-azobis (isovaleronitrile) (AIVN) was added and reacted for 2 hours, 0.5 g of AIVN was further added and reacted for 2 hours, and 0.5 g of AIVN was added and further reacted for 2 hours. Reacted next,
The reaction temperature was raised to 90 ° C. and the mixture was stirred under reduced pressure of 30 mmHg for 1 hour to remove unreacted monomers. After cooling to room temperature, 20
Filtration through a 0 mesh nylon cloth gave a white dispersion. The reaction rate of the monomers in the obtained dispersion was 95% by weight, the average particle size of the resin particles was 0.25 μm, and the dispersibility was good (the particle size was CAPA-500: used by Horiba, Ltd. Then measured).

[0352]

[Chemical 52]

Production of colored particles Tetradecyl methacrylate / methacrylic acid (95/5
(Weight ratio) 10 g of the copolymer, 10 g of nigrosine and 30 g of Isopar G were put together with glass beads in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

Manufacture of Liquid Developer 45 g of the resin dispersion of the toner particles, 25 g of the nigrosine dispersion, 0.6 g of hexadecene / semi-maleic acid octadecylamide copolymer and branched octadecyl alcohol (FOC-1800, manufactured by Nissan Chemical Co., Ltd. A liquid developer for electrostatic photography was prepared by diluting 15 g of the above) to 1 liter of Isopar G. An image was fixed on the photosensitive material after plate making obtained as described above by a fixing method using a heat roll.

Next, the aluminum used for the Fuji PS plate FPD (manufactured by Fuji Photo Film Co., Ltd.) was placed between the photosensitive material after the above development at a temperature of 60 ° C. and the rubber roller whose surface temperature was constantly controlled at 100 ° C. Support 4kgf
After passing under a pressure of / cm ² at a speed of 200 mm / sec, the aluminum support was peeled off from the light-sensitive material. The toner image was transferred onto the aluminum support together with the transfer layer. The image (fog, image quality of the image) formed on the aluminum support was visually evaluated. The toner on the photosensitive material was thermally transferred to the aluminum support side together with the transfer layer, and a clear image with no background fog was obtained, and almost no deterioration in image quality was observed as compared with the original.

As described above, the fluorine atom-containing copolymer coexisting in the photoconductive layer is concentrated and transferred to the surface portion of the photoconductive layer during the formation of the photoconductive layer, and the binder resin (B) and the resin (P) are further added. Are sufficiently chemically bonded to each other by a cross-linking agent to form a cured film, so that an interface with good releasability is clearly formed, and the first transfer layer (T ₁ ) and the photoconductive layer are separated from each other. The adhesive strength is small and the second transfer layer (T ₂ ) and the transferred material (aluminum support)
It is thought that this is because the adhesive strength with On the other hand, as a comparison, 10 g of the binder resin (B-1) except for 2.0 g of the resin (P-2) in the above photoreceptor
An electrophotographic photosensitive member was prepared in exactly the same manner as above, except that the surface adhesive force was 420 g · f. A transfer layer was formed and transferred in the same manner as above, but showed no peeling property at all.

Next, the plate (printing original plate) on which the transfer layer was transferred to the aluminum support was desensitized (that is, the transfer layer was removed), and the performance as a printing plate was examined. That is, 30% of this printing original plate was placed in a desensitizing solution (E-1) having the following formulation at a temperature of 25 ° C.
After dipping for 2 seconds to remove the transfer layer and washing thoroughly with water, gumming was performed to prepare an offset printing plate. Desensitizing treatment liquid (E-1) Treatment liquid for PS plate (DP-4 manufactured by Fuji Photo Film Co., Ltd.) 100 g N-methylaminoethanol 10 g was diluted with distilled water to a total volume of 1.0 liter and pH 12.
Adjusted to 5.

When the printing plate thus obtained was visually observed using a 200 × optical microscope, no transfer layer remained in the non-image area, and high density of fine lines and fine characters in the image area was observed. No lack of resolution was observed. Immersion water for this PS plate as PS water (SG-23, Tokyo Ink Co., Ltd.)
Produced by diluting 130 times with distilled water (pH 7.
0), Oliver 94 type (manufactured by Sakurai Seisakusho Co., Ltd.) was used as a printing machine, and neutral paper was used as printing paper, and printing was performed with various color inks for offset printing. As a result, regardless of the type of color ink, in all cases, 60,000 or more clear image prints with no background stain were obtained. Furthermore,
After printing with the printing plate of the present invention, printing was then performed using a normal PS plate with the normal operation, and no problem occurred. That is, it was confirmed that the same printing machine could be easily shared with other offset printing plates such as PS plates.

For comparison, the case of using the photoconductors having the respective transfer layers of the following Comparative Examples 1 to 5 was examined.

Comparative Example 1 Resin particles (AL-1) of Example 1 and resin particles (A ₂ L-
The same as Example 1 except that a single-layer transfer layer composed only of resin particles (AL-1) was formed in a thickness of 2.5 μm instead of the transfer layer composed of the two-layer (laminated) structure of 1). A printing plate was prepared by operating the above and printed.

Comparative Example 2 Instead of the transfer layer having the two-layer structure of Example 1, a single-layer transfer layer consisting of resin particles (A ₂ L-1) alone was used.
A printing plate was prepared in the same manner as in Example 1 except that a film having a thickness of 5 μm was formed, and printing was performed.

Comparative Example 3 A dispersion liquid (Comparative Resin Particle (1) was used in place of the resin particles (AL-1) in the first transfer layer resin particle dispersion liquid (L-1) of Example 1). In the same manner as in L-1), a transfer layer having a two-layer structure was formed on the photoconductor so that the transfer layer had a total film thickness of 2.5 μm. Thereafter, the printing plate was prepared and printed in the same manner as in Example 1.

Comparative Example 4 A dispersion liquid (Comparative Resin Particle (2)) was used in place of the resin particles (AL-1) in the first transfer layer resin particle dispersion liquid (L-1) of Example 1, except that the dispersion liquid ( In the same manner as in L-1), a transfer layer having a two-layer structure was formed on the photoconductor so that the transfer layer had a total film thickness of 2.5 μm. After that, the printing plate was prepared and printed in the same manner as in Example 1.

Comparative Example 5 Comparative resin particles (1) were used in place of the resin particles (AL-1) in the resin dispersion (L-1) for the first transfer layer of Example 1.
And the dispersion (L-
In the same manner as in 1), a transfer layer having a two-layer structure was formed on the photoconductor so that the total thickness of the transfer layer was 2.5 μm. Then Example 1
A printing plate was prepared and printed in the same manner as in.

In Comparative Examples 1 to 5, under the transfer conditions of Example 1 of the present invention, the transfer of the transfer layer was insufficient, and the transfer residue was generated on the photosensitive member, and the toner image portion on the printing original plate was formed. Drops occurred due to poor transfer. In particular, in Comparative Examples 2, 3 and 4, remarkable transfer failure occurred.

Next, the conditions under which the transfer layer of each comparative example was completely transferred were examined. Comparative Example 1 of Example 1 comprising a 2.5 μm transfer layer containing only the resin particles (AL-1) constituting the first transfer layer (T ₁ ) is a heating temperature on the photoreceptor side of 70 ° C., a transfer speed of 100 mm / sec. Completely transcribed. Further, the resin particles (AL- that form the first transfer layer (T ₁ ) of Example 1 of the present invention are used.
1.2 μm of the first transfer layer, which is a mixture of the resin particles (1) and the resin particles (2) in a weight ratio of 1/1, and which is composed of each of the two types of resins constituting the resin particles (A ₂ L). Comparative Example 5, which is a transfer layer having a total film thickness of 2.5 μm and composed of the second transfer layer consisting of -1), completely transferred at a temperature of 70 ° C. on the photoreceptor side and a transfer speed of 80 mm / sec.

On the other hand, in the case of Comparative Examples 2, 3 and 4, the conditions for complete transfer did not exist in the method of separating the photosensitive member and the aluminum support during heating as in Example 1. Therefore,
In the above Comparative Examples 2 to 4, the total thickness of the transfer layer was 5.0 μm.
Was carried out. The photoreceptor of Comparative Example 2 having a transfer layer thickness of 5.0 μm was heated to a temperature of 60 ° C., and an aluminum support was placed between the rubber roller and a temperature of 100 ° C. under a pressure of 4 kgf / cm ² to 5.0 mm. It was passed at a speed of / second. Then, after cooling to room temperature and peeling off the photosensitive member and the aluminum support at a speed of 5.0 mm / sec, the toner image was completely transferred to the aluminum support together with the transfer layer. Similarly, in Comparative Examples 3 and 4 having a film thickness of 5.0 μm, complete transfer was performed by this method. Further, in Comparative Example 4 in which the film thickness was 5.0 μm, complete transfer was possible up to a speed of 10 mm / sec. In these cases,
Not only the transfer time but also the cooling time was needed.

From the above, as compared with Example 1 of the present invention, Comparative Example 1 mainly lacks the adhesive force between the transfer layer and the material to be transferred, and Comparative Example 2 shows the adhesion between the photoreceptor and the transfer layer. In Comparative Examples 3 to 5, the adhesive force of the photoconductor and the adhesive force to the material to be transferred are unbalanced and the cohesive failure of the resin in the transfer layer is caused, which deteriorates the transferability. Is presumed to be the cause. The second transfer in which the resin particles to be electrodeposited as the first transfer layer in contact with the photoreceptor side contain at least two kinds of resins having different glass transition points or softening points in the same particle, and in contact with the transfer material side. Only the transfer layer of the laminated structure of the present invention composed of a resin having a low Tg as a layer is a thin layer and is rapidly transferred at a low temperature.

As described above, the offset printing plate provided by the present invention has an extremely good image reproducibility obtained by the semiconductor laser light scanning exposure method, that it is well reproduced on a printed matter, and it is suitable for color ink. It has been confirmed that the ink composition is sufficiently excellent, almost no ink selectivity is observed, and that full-color printing can be obtained with high printing durability, and that it can exhibit an extremely excellent performance such as being able to optionally use a printing machine with other offset printing plates.

Example 2 An amorphous silicon photoconductor (manufactured by Kyocera Corp.) was mounted as an electrophotographic photoconductor on the apparatus shown in FIG. The adhesive force on the surface of the photoconductor was 200 g · f. In this device, the compound (S) of the present invention is added to the photoreceptor so that it can be peeled off.
Was immersed in a solution in which was dissolved (immersion method). That is, the photoreceptor was rotated at a peripheral speed of 10 mm / sec in a bath containing a solution prepared by dissolving 1.0 g of the following compound (S-1) in 1 liter of Isopar G (manufactured by Esso Corporation). It was treated by touching for 2 seconds and dried by air squeeze. The pressure-sensitive adhesive strength of the surface of the photoreceptor thus obtained was measured and found to be 3 g · f and good peelability.

[0371]

Embedded image

Next, the surface temperature of the photoconductor is set to 50 ° C., the photoconductor drum is rotated at a peripheral speed of 10 mm / sec, and the positive electrode resin particles having the following contents are contained on the photoconductor surface using a slit electrodeposition device. While supplying the resin particle dispersion (L-3),
The photoconductor side is grounded and 130V is applied to the electrode side of the slit electrodeposition device.
Voltage was applied to electrodeposit and fix the resin particles. The film thickness of the obtained first transfer layer (T ₁ ) was 1.0 μm. Resin particle dispersion (L-3) Resin particles (AL-3) 7 g (as solid content) Positive charge control agent (CD-2) 0.018 g 1-hexadecene / N-decyl maleic acid half amide (1 / 1) Molar ratio) Copolymer Branched tetradecyl alcohol 5 g (FOC-1400, manufactured by Nissan Kagaku Co., Ltd.) was adjusted with Isopar G to a total volume of 1.0 liter.

Furthermore, on the first transfer layer (T ₁ ), 7 g of resin particles (AL-3) in the resin particle dispersion liquid (L-3) was used.
In place of the resin particles (A ₂ L-2) 7 g (as solid content), except that the resin particle dispersion liquid (L
-4) was used to form a second transfer layer (T ₂ ) having a film thickness of 1.5 μm in the same manner as above with an applied voltage of 170V.

Next, after corona-charging the above photosensitive material to +700 V, the original is read by a color scanner in advance, color separation is performed, and some corrections relating to the color reproduction peculiar to the system are added. It was exposed to light of 780 nm using a semiconductor laser based on the information stored in the hard disk. The potential of the exposed portion was + 220V and that of the unexposed portion was + 600V. Then, after pre-bathing with Isopar G (manufactured by Esso Standard Petroleum) using a pre-bath device incorporated in the developing unit, a liquid developer (LD-
2) was supplied from the developing unit to the surface of the photoconductor. At this time, a developing bias voltage of 50 V was applied to the developing unit side to perform development. Then, the non-image area was cleaned by rinsing in a bath of Isopar G alone, and dried in an intake / exhaust unit.

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

Then, the infrared line heater was turned on and passed under the infrared line heater to measure the surface temperature of the light-sensitive material with a radiation thermometer to about 60 ° C., and then contacted with the aluminum support for PS plate FPD, It was passed under a rubber roller controlled at a temperature of 105 ° C. under the conditions of a nip pressure of 4 kgf / cm ² and a drum peripheral speed of 250 mm / sec, and then the photoreceptor and the aluminum support were peeled off. The toner image was transferred together with the transfer layer onto an aluminum support. The printing original plate thus obtained was used as a RICOH FUSER model 59.
2 (manufactured by Ricoh Co., Ltd.) was further heated to fix the toner portion. Upon visual observation using a 200 × optical microscope, no contamination was observed in the non-image area, and no loss of high-resolution areas such as fine lines and fine characters in the image area was observed.

This printing original plate was immersed in a desensitizing solution (E-2) having the following formulation at a temperature of 30 ° C. for 20 seconds, and during that time, the transfer layer was removed by gently rubbing, followed by thorough washing with water and gumming. , An offset printing plate was created. Desensitizing treatment liquid (E-2) PS plate treating agent (DP-4, manufactured by Fuji Photo Film Co., Ltd.) 143 g N, N-dimethylethanolamine 15 g was diluted with distilled water to make a total amount of 1 liter. (PH 1
3.1).

The printing plate thus obtained was visually observed with a 200 × optical microscope for the presence or absence of the transfer layer in the non-image area and the absence or absence of the toner image area. The desensitizing treatment was good, the transfer layer was completely removed, and no background stain was observed. Further, no toner image loss was observed in the high-definition image portion such as fine characters, fine lines and halftone dot continuous gradation in the image portion, and the resist property in the image portion was good. Immersion water for this PS plate as PS water (SG-23, Tokyo Ink Co., Ltd.)
Produced by diluting 130 times with distilled water (pH 7.
0), Oliver 94 type (manufactured by Sakurai Seisakusho Co., Ltd.) was used as a printing machine, and neutral paper was used as printing paper, and printing was performed with various color inks for offset printing. As a result, regardless of the type of color ink, in all cases, 60,000 or more printed materials with clear images free of background stains were obtained.

As described above, depending on the type of liquid developer used for toner image formation, the toner may be used in order to maintain sufficient adhesion between the toner image area and the transfer material and maintain the toner image strength during printing. After transferring the image and transfer layer together,
Adhesion improving means may be combined. A similar effect was obtained by a method using flash fixing or heat roll fixing as a means for improving adhesion.

As a method of imparting releasability to the surface of the photoconductor by applying the compound (S) to the surface of the photoconductor in the apparatus for performing the electrophotographic process, the following (1) to (4) are used instead of the dipping method.
Method.

(1) In the compound (S) coating apparatus 10,
A compound having the following structure (S-2) for imparting releasability to the photoreceptor
The peripheral speed of 15 mm is obtained by contacting the photoconductor with a metering roll that has a silicone rubber layer on the surface that is in contact with a bath containing oil.
Both drums were rotated for 20 seconds at a rotation speed of / sec.
By this treatment, the adhesive force on the surface of the photoconductor became 5 g · f.

[0382]

[Chemical 54]

Also, the same result as above was obtained when the treatment was carried out through a transfer roll having a styrene-butadiene rubber layer on the surface between the photoconductor and the metering roll immersed in the silicone oil bath. .

Further, in the method using the above-mentioned metering roll / transfer roll, the method of supplying the compound (S-2) 113 between the metering roll 112 and the transfer roll 111 as shown in FIG. Similarly good results have been obtained.

(2) AW-treated felt (thickness 15 mm × width 20 mm) uniformly impregnated with 2 g of the compound (S-3), that is, dimethyl silicone oil (KF-96L-2.0, manufactured by Shin-Etsu Silicone Co., Ltd.). Wool material) was pressed against the photoconductor with a pressure of 200 g and the photoconductor was rotated for 30 seconds at a peripheral speed of 20 mm / sec. The adhesion of the surface of the photoconductor after processing is 5g
・ It became f.

(3) To a rubber roller having a built-in heating means,
A roller wound with a cloth impregnated with compound (S-4), that is, a fluorosurfactant (Surflon S-141, manufactured by Asahi Glass Co., Ltd.) is heated to a surface temperature of 60 ° C. and then contacted with a photoreceptor. Both drums were rotated for 30 seconds at a peripheral speed of 20 mm / second rotation speed. The adhesive force on the surface of the photoconductor became 12 g · f.

(4) A silicone rubber roller (manufactured by Kinyo Co., Ltd.) in which a silicone rubber is wound around a metal core roller is brought into contact with the surface of the photoconductor at a nip pressure of 500 gf / cm ² , and the peripheral speed is 15 mm / sec. It spun for a second. As a result, the adhesive force on the surface of the photoconductor was lowered to 10 g · f.

In the same manner as the above-mentioned method except that the dipping method for imparting releasability to the surface of the photoreceptor is imparted with the releasability to the surface of the photoreceptor by the methods (1) to (4) above. When toner image formation, transfer to a transfer material, printing plate preparation and printing were carried out, all showed similarly good results.

Example 3 2 g of X-type metal-free phthalocyanine, 8 g of a binder resin (B-2) having the following structure, 2 g of a binder resin (B-3) having the following structure,
A mixture of 0.15 g of the compound (B) having the following structure and 80 g of tetrahydrofuran is put in a 500 ml glass container together with glass beads, dispersed for 60 minutes with a paint shaker (manufactured by Toyo Seiki Seisakusho), and the glass beads are filtered off to disperse the photosensitive layer. And

[0390]

[Chemical 55]

Next, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, with a wire bar, and was dried by touch with a finger, and then was dried in a 110 ° C. circulation type oven at 20 ° C. Heated for seconds. The film thickness of the obtained photosensitive layer was 8 μm. A peelable surface layer having a film thickness of 1.5 μm was provided on the photosensitive layer as follows. -Formation of easily peelable surface layer 10 g of silicone resin having the following structure, 1 g of crosslinking agent having the following structure
And 0.1 g of platinum as n-hexane 10 as a crosslinking catalyst.
The coating material contained in 0 g was coated using a wire round rod, dried by touch with a finger, and further heated at 120 ° C. for 10 minutes. The adhesive strength of the obtained surface was 1 g · f or less.

[0390]

[Chemical 56]

This photoconductor was mounted in the same apparatus as in Example 1 and operated in the same manner as in Example 1 to prepare and print a printing plate. As with Example 1, 60,000 or more printed matters having clear printed images without scumming were obtained.

Example 4 The same amorphous silicon photoconductor as that used in Example 2 was mounted in the apparatus shown in FIG. 3, and the electrophotographic coating method was used to simultaneously impart the releasability to the photoconductor and to form the first transfer layer. I did.
That is, the following resin particle dispersion (L-5) was used to form a first transfer layer (T ₁ ) having a film thickness of 1.0 μm on a photoconductor in the same manner as in Example 1. Resin particle dispersion liquid (L-5) Resin particles (AL-4) 8 g (as solid content) 0.02 g of the following charge adjusting compound (D-2) Compound (S-5) 0.8 g It was adjusted with Isopar G so that it became 1 liter.

[0395]

[Chemical 57]

Next, in order to form the second transfer layer (T ₂ ),
The resin (A ₂ ), which has the following structure, is used as the resin (A ₂ ).
The transfer layer surface was coated at a speed of 20 mm / sec, and cooling air was blown from the intake / exhaust unit 15 to cool it. The thickness of the obtained second transfer layer (T ₂ ) was 2.0 μm.

[0397]

[Chemical 58]

Using this photosensitive material, a toner image was formed, transfer to a transfer material, printing plate preparation and printing were carried out in the same manner as in Example 2. As with Example 2, 60,000 or more prints with clear images free of background stains were obtained.

Example 5 5 g of bisazo pigment having the following structure and tetrahydrofuran 95
and 5 g of a polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) were sufficiently pulverized in a ball mill. Then, this mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was placed on a conductive support using a wire round rod (thickness 100 μm
A polyethylene terephthalate support has a vapor deposited film of indium oxide. It was coated on a surface resistance of 10 ³ Ω) to form a charge generation layer of about 0.7 μm.

[0400]

Embedded image

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

[0402]

Embedded image

In order to form a surface layer for imparting releasability on this photosensitive layer, a resin having the following structure (P-26)
A solution 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 to a film thickness of 1 μm, dried by touch, and further heated at 120 ° C. for 1 hour. . The adhesive force on the surface of the obtained photoreceptor was 5 g · f.

[0404]

[Chemical formula 61]

The above-mentioned photoreceptor was loaded into an apparatus incorporating a transfer layer forming apparatus as shown in FIG. 4, and a resin particle dispersion liquid (L) containing positively charged resin particles having the following contents was prepared in the same manner as in Example 1.
-6) was used to form a first transfer layer (T ₁ ) having a thickness of 1.2 μm. Resin particle dispersion liquid (L-6) Resin particles (AL-4) 8 g (as solid content) Charge adjusting compound (CD-1) 0.018 g Branched tetradecyl alcohol 10 g (FOC-1400, Nissan Chemical Co., Ltd.) Was manufactured by Isopar G so that the total amount was 1 liter.

A second transfer layer (T ₂ ) was formed on this by a transfer method from a release paper. That is, FIG. 4 shows a paper in which a resin (A ₂ -2) having the following structure is formed into a coating film with a thickness of 2 μm by using Sun release (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) as the release paper 20. pressed to on the first transfer layer (T ₁₎ to a roller pressure of 3 kgf / cm ^2, thickness 2μm on the first transfer layer under the conditions of a surface temperature 60 ° C. and passed through speed 10 mm / sec (T ₁₎ The second transfer layer (T ₂ ) of was formed.

[0407]

Embedded image

This photosensitive material was charged to a surface potential of 500 V and then exposed to light of 633 nm using a He-Ne laser so that the exposure amount on the plate surface became 30 erg / cm ² , and the same as Example 1. Was operated to prepare a printing plate, and offset printing was performed. The results obtained showed good performance equivalent to that of Example 1.

Example 6 100 g of photoconductive zinc oxide, a binder resin (B-
4) 20 g, resin (P-23) 3 g, uranine 0.01
g, rose bengal 0.02 g, bromphenol blue 0.01 g, maleic anhydride 0.15 g and toluene 150 g, a homogenizer (Nippon Seiki Co., Ltd.)
Manufactured) and dispersed at a rotation speed of 1 × 10 ⁴ rpm 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 1 × 1.
Dispersed at 0 ³ rpm for 1 minute.

[0410]

[Chemical formula 63]

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

On the above-mentioned photosensitive layers, in the same manner as in Example 1, the first transfer layer (T ₁ ) 1.3 μm and the second transfer layer (T ₂ ) 1.
A transfer layer having a laminated structure of 5 μm was formed. The transfer layer electrophotographic photosensitive material thus obtained was allowed to stand overnight under the conditions of 25 ° C. and 60% RH. The bias voltage of the developing portion of this photoconductor was set to 100 V by an ELP-404V plate making machine (manufactured by Fuji Photo Film Co., Ltd.), and the liquid developer was used as the above (LD-
1) was used to form a duplicate image and then rinsed through an Isopar G rinse bath. The copied image formed on the obtained transfer layer is clear and good even in high-definition image areas such as continuous tone areas consisting of characters, fine lines, and halftone dots, and scumming in non-image areas is also recognized. There wasn't.

The photosensitive material plate-made as described above was laminated with a straight master (manufactured by Mitsubishi Paper Mills Co., Ltd.) and covered with silicone rubber. A hollow roller covered with an infrared lamp heater was provided between a pair of heating rollers. Let it pass. At this time, the surface temperature of the rollers is 60 ° C both above and below, the nip pressure between the rollers is 3 kgf / cm ² , and the conveying speed is 2
It was set to 00 mm / sec. After passing, the photoreceptor and the straight master were separated, and the state of the transfer layer transferred to the straight master was visually evaluated. As a result, there was almost no difference from the copied image on the photosensitive material before transfer, and no image deterioration was observed. Further, no transfer layer remained on the surface of the photoreceptor after the transfer, and the transferability was extremely good.

On the other hand, as a comparison, an electrophotographic photosensitive member was prepared in the same manner except that 3 g of the resin (P-23) was not used in the above photosensitive member, and the surface adhesive force was 400 g.
・ F or more. A transfer layer was formed and transferred in the same manner as above, but no peeling was observed at the interface between the surface of the photoreceptor and the transfer layer.

Next, the printing original plate having the transfer layer transferred to the straight master was desensitized (that is, the transfer layer was removed) to obtain a printing plate, and its printing performance was examined. That is, the above printing plate was placed 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. The transfer layer was removed by immersing for 20 seconds while gently rubbing, and thoroughly washed with water. When the printing plate thus obtained was visually observed using a 200 × optical microscope, no transfer layer remained in the non-image area, and the high-resolution area such as fine lines and fine characters in the image area was observed. Was not observed.

[0416] This plate was used as the immersion water for the PS plate.
An aqueous solution (pH 7.0) obtained by diluting G-23 and Tokyo Ink Co., Ltd. with distilled water 130 times was used, and Ryobi 320OMCD type (manufactured by Ryobi Co., Ltd.) was used as a printing machine.
Using neutral paper as the printing paper, printing was performed with various color inks for offset printing. As a result, regardless of the type of color ink, over 1,000 sheets of printed matter with clear images with no background stain were obtained. On the other hand, in a known system in which an electrophotographic photoreceptor using zinc oxide is desensitized with a desensitizing liquid containing a chelating agent as a main component under acidic conditions to form a lithographic printing plate, neutral paper is used as a printing paper. As a result, the number of printed sheets was several hundred, and the non-image area was stained, and when a color ink for offset printing other than the black ink was used, the number of printed sheets was about several hundred and the background was stained. On the other hand, the offset printing plate producing method of the present invention can provide a printing plate having extremely good printing performance, unlike the conventional method, while using the same zinc oxide photoreceptor.

Example 7 4,4'-bis (diethylamino) -2,2'-dimethyltriphenylmethane (5 g) as an organic photoconductive substance, 4 g of a binder resin (B-5) having the following structure, and a resin (P- 12)
1.0 g, 40 mg of the dye (D-1) having the following structural formula, and 0.2 g of the anilide compound (C) having the following structure as a chemical sensitizer, 30 ml of methylene chloride and 30 ml of ethylene chloride.
To obtain a photosensitive layer dispersion liquid.

[0418]

[Chemical 64]

This photosensitive layer dispersion was applied onto the conductive transparent support described in Example 5 using a wire round rod to obtain an organic thin film having a photosensitive layer of about 4 μm. The adhesive force on the surface of the photoconductor was 8 g · f. A printing plate was formed in the same manner as in Example 1 except that this photoconductor was used instead of the photoconductor used in Example 1. The printed image on the obtained printed matter was clear without background fog, and the printing durability of the printing plate was good as in Example 1.

Examples 8 to 22 Example 2 is different from Example 2 except that the first transfer layer (T ₁ ) and the second transfer layer (T ₂ ) are formed by using the resin particles shown in Table K below. In the same manner as described above, a printing plate was prepared and offset printing was performed. The image quality and printing durability of the obtained printed matter were as good as in Example 2.

[0421]

[Table 18]

Examples 23 to 25 The resin (A) used for the second transfer layer (T ₂ ) in Example 4 was used.
₂ -1) was used following Table -L resin (A ₂₎ in place in the same manner as in Example 4 to create a printing plate was subjected to offset printing. The image quality and printing durability of the obtained printed matter were as good as in Example 4.

[0423]

[Table 19]

Examples 26 to 29 Resins (A) used in the second transfer layer (T ₂ ) in Example 5 were used.
_2-2) except for using the following table -M resin (A ₂₎ in place in the same manner as in Example 5 to create a printing plate was subjected to offset printing. The image quality and printing durability of the obtained printed matter were as good as in Example 5.

[0425]

[Table 20]

Examples 30 to 37 In Example 1, except that the resin (P) and / or the resin particles (L) shown in Table N below were used in place of 2.0 g of the resin (P-2), respectively. An electrophotographic photosensitive member and a printing plate were prepared and printed in the same manner as in 1. The image quality and printing durability of the obtained printed matter were as good as in Example 1.

[0427]

[Table 21]

Examples 38 to 45 In the same manner as in Example 1 except that each compound of the following Table -O was used in place of the resin (P-2), phthalic anhydride and o-chlorophenol in Example 1. The operation was performed to prepare a printing plate, and printing was performed. The image quality and printing durability of the obtained printed matter were as good as in Example 1.

[0429]

[Table 22]

Examples 46 to 57 Using the plate (printing original plate) transferred to the transfer material prepared in Examples 1 to 45, desensitizing treatment was carried out as follows to prepare offset printing plates. Nucleophilic compounds of Table-P below.
Distilled water was added to 2 mol, 30 g of an organic solvent and 1.0 g of Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) to make 1 liter, and then the pH of the mixture was adjusted to 12.5. Each printing original plate was immersed in the treatment liquid at a temperature of 35 ° C. for 30 seconds and rubbed gently to perform desensitization. The obtained plate was printed under the same printing conditions as in the original example. Each printing plate showed good performance equivalent to that of the original example.

[0431]

[Table 23]

Examples 58 to 74 In the same manner as in Example 4, except that each compound (S) shown in the following Table-Q was used in place of 0.8 g / l of the compound (S-5) in Example 4. I got a print. Good results similar to those in Example 4 were obtained. That is, by using these compounds (S), the releasability of the surface of the photoconductor was effectively exhibited.

[0433]

[Table 24]

[0434]

[Table 25]

[0435]

[Table 26]

[0436]

[Table 27]

[0437]

[Table 28]

[0438]

According to the present invention, the transfer layer has a good transfer, no transfer residue is left on the photosensitive member, and a toner image is not missing due to a transfer failure. A printing plate can be easily obtained. Furthermore, sufficient transferability can be obtained even if the transfer conditions are relaxed. Also,
An ordinary electrophotographic photoreceptor can be used by imparting releasability to the surface of the photoreceptor with the release compound (S).

[Brief description of drawings]

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

FIG. 2 is a diagram showing an example of an apparatus for carrying out the method of the present invention using an electrodeposition coating method as a method for forming a second transfer layer (T ₂ ).

FIG. 3 is a diagram showing an example of an apparatus for carrying out the method of the present invention using a hot melt coating method as a method for forming a second transfer layer (T ₂ ).

FIG. 4 is a diagram showing an example of an apparatus for carrying out the method of the present invention using a transfer method as a method for forming a second transfer layer (T ₂ ).

FIG. 5 is an apparatus diagram showing an example of applying a peeling compound (S).

[Explanation of symbols]

1 Support of Photoreceptor 2 Photosensitive Layer 3 Toner Image 10 Compound (S) Coating Device 11 Photoreceptor 12 Transfer Layer 12a Dispersion of Thermoplastic Resin Particles 12b Dispersion of Thermoplastic Resin Particles 12c Thermoplastic Resin 12T ₁ First Transfer Layer 12T ₂ Second transfer layer 13a First transfer layer electrodeposition unit 13b Second transfer layer electrodeposition unit 13 Hot melt coater 13w Hot melt coater standby position 14 Liquid developing unit set 14L Liquid developing unit 15 Air intake / exhaust unit 15a Air intake Part 15b Exhaust part 16 Transferred material 17 Thermal transfer means 17a Preheating means 17b Transfer backup roller 17c Separation backup roller 18 Corona charging device 19 Exposure device 20 Release paper 110 Compound (S) coating device 111 Transfer roll 112 Metalling roll 113 Compound (S) 117 second transfer layer transfer device 117b heating roller 117c cooling roller

Claims (6)

[Claims] 1. A transfer layer which is removable by a chemical reaction treatment and which can be peeled off is formed on the surface of an electrophotographic photoreceptor, a toner image is formed on the transfer layer by an electrophotographic process, and the toner image is transferred. In the method for producing an electrophotographic plate-making printing plate, in which each layer is heat-transferred to a transfer material that becomes a lithographically printable hydrophilic surface during printing, and then the transfer layer of the transferred transfer material is removed by a chemical reaction treatment, a transcription layer is the glass transition point 10 to 140 ° C. or a softening point 35 ° C. to 180 ° C. of the resin (a ₁₎ and a glass transition point of 45 ° C. or less or a softening point 60 ° C. or less of the resin (a _2), the resin ( The thermoplastic resin particles (AL) containing at least two kinds of resins in which the glass transition point or softening point of A ₁ ) is higher than that of the resin (A ₂ ) by 2 ° C. or more by the electrodeposition coating method. first transfer layer formed by film with (T _1), the Electrophotographic plate making printing plate creation and wherein the second is a laminated structure comprising a transfer layer (T ₂₎ which contains mainly the above resin (A ₂₎ provided on the. 2. The resin (A ₁ ) and the resin (A ₂ ) each contain at least one of the following polymer component (a) and polymer component (b): 1. A method for producing the electrophotographic plate-making printing plate described in 1. Polymer component (a): - CO ₂ H group, -CHO group, -SO ₃
H group, -SO ₂ H group, -P (= O) (OH ) R 1 group {R ¹ represents a -OH group, a hydrocarbon group or -OR ² group (R ² represents a hydrocarbon group)} , phenolic OH groups, acid cyclic anhydride-containing group, -CONHCOR ³ group (R ³ represents a hydrocarbon group) and a polymer component polymer component containing at least one of the radicals -CONHSO ₂ R ³ group (b): -CO ₂ H group in a chemical reaction process, -C
HO group, -SO ₃ H group, -SO ₂ H group, -P (= O) (O
H) R ¹ group {R ¹ represents an -OH group, a hydrocarbon group or an -OR ² group (R ² represents a hydrocarbon group)} and a functional group forming at least one group of an -OH group. Polymer component containing at least one 3. The electrophotographic printing plate according to claim 1, wherein the second transfer layer (T ₂ ) is formed by any one of a hot melt coating method, an electrodeposition coating method and a transfer method. How to make a print version. 4. Resin particles (AL) and second transfer layer (T ₂ ).
4. The resin particles (A ₂ L) used when the resin is formed by the electrodeposition coating method are dispersed in an electrically insulating liquid having a relative dielectric constant of 3.5 or less and supplied. How to make an electrophotographic printing plate. 5. Resin particles (AL) and resin particles (A
₂ L) is supplied between the counter electrodes which are respectively installed facing the electrophotographic photosensitive member, and is electrophoresed according to the potential gradient applied from the external power source to be adhered or electrodeposited on the electrophotographic photosensitive member. The method for producing an electrophotographic plate-making printing plate according to claim 4, wherein the film is formed. 6. The electrophotographic photoreceptor has an adhesive force of 100 gram · force (g) according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method” when the first transfer layer (T ₁ ) is formed.
F) The method for producing an electrophotographic plate-making printing plate according to any one of claims 1 to 5, which has the following surface releasability.