JPH07325435A - Formation of electrophotographic printing plate for plate making - Google Patents

Abstract

PURPOSE:To improve transferability at the time of transferring a toner image together with a transfer layer to a material to be transferred and to obtain good image quality by still completely transferring the transfer layer and the toner image to the material to be transferred even if the film thickness of the transfer layer in particular is thin and transfer conditions are a low temp. or high speed. CONSTITUTION:Resin particles (AL) contg. a resin (A)) having Tg 10 to 140 deg.C or softening point 35 to 180 deg.C and a resin (A2) having Tg <=45 deg.C or softening point <=60 deg.C and Tg or softening point lower by >=2 deg.C than the Tg or softening point of the resin (A1)) are applied by electrodeposition on the surface of an electrophotographic photoreceptor 11 to form the transfer layer 12. The toner image 3 is formed on the transfer layer 12 by an electrophotographic process. The toner image 3 is transferred together with the transfer layer 12 to the material 16 to be transferred and the transfer layer 12 on the material 16 to be transferred is removed by a chemical reaction treatment, by which the electrophotographic printing plate for plate making is formed.

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 immediately output to a remote end plotter by 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 which directly produces 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 after the toner image is formed, the photoconductive layer in the non-image area is removed 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 area, or the photosensitive layer is eluted and removed to expose the surface of the hydrophilic support. However, there are various restrictions on the photoconductor, especially 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, together with the transfer layer, is thermally transferred to a transfer material that becomes a hydrophilic surface for lithographic printing during 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 is formed at the glass transition point 1
Resin (A ₁ ) having a softening point of 0 to 140 ° C. or a softening point of 35 to 180 ° C.
Identical particles of at least one of at least one and a glass transition point of 45 ° C. or less or a softening point 60 ° C. or less of the resin is an in the resin (A ₁₎ from 2 ℃ higher than the glass transition point or a low softening point resin (A ₂₎ of Thermoplastic resin particles (A
It was found to be achieved by a method for producing an electrophotographic plate-making printing plate, which is characterized in that it is carried out by an electrodeposition coating method using L).

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, at least the surface of the electrophotographic photosensitive member 11 comprising the support 1 and the photosensitive layer 2 is coated with the above resin. A thermoplastic resin particle (AL) containing at least (A ₁ ) and a resin (A ₂ ) in the same particle is electrostatically adhered or electrodeposited to form a film, which enables peeling and chemical reaction treatment. After forming the removable transfer layer 12,
The toner image 3 is formed by a normal electrophotographic process, and the toner image 3 is transferred together with the transfer layer 12 by thermal transfer onto a transfer target material 16 that is a support similar to the support used for the offset printing plate to obtain a printing original plate. Then, the transfer layer 12 on the transfer-receiving material 16 is subjected to a chemical reaction treatment and removed to form a printing plate. The present invention provides the thermoplastic resin particles (A
It is a great feature that L) contains 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.
It forms a good copy image, has the thermoplasticity to easily transfer it to the transfer material in the next thermal transfer step, and has excellent transferability. Furthermore, it has a chemical reaction treatment to make it a printing plate. The feature is that a printing plate having excellent image quality and printing durability can be easily removed by.

If the thermoplastic resin for the transfer layer contains the polymer component (a) containing the above specific hydrophilic group,
It is preferable in that the removal of the transfer layer by the chemical reaction treatment can be easily and quickly achieved, and when the polymer component (b) expressing a specific hydrophilic group in the above chemical reaction is contained, the electrical conductivity of the resin itself is increased. It is preferable because the insulating property is easily maintained, electrophotographic characteristics are not deteriorated, the reproducibility of a copied image is maintained, and the glass transition point of the resin itself can be adjusted within a low temperature range.

Further, by appropriately selecting the polymer components (a) and (b), the glass transition point and the electrical insulation of the resin (A) are satisfied, and the electrophotographic characteristics and transferability are remarkably improved. In addition, the non-image area of the printing plate can be removed quickly and completely without deteriorating the hydrophilicity and the toner image. As a result, the reproducibility of the copied image transferred to the material to be transferred with respect to the original image becomes extremely good, and the transfer conditions are easily peeled and transferred at low temperature and low pressure, so that the transfer device can be downsized. Even when used as a printing plate, no residual non-image portion of the transfer layer was observed, and there was almost no loss of high-definition toner image portion such as fine lines / fine characters, halftone dots, and gradation portions. preferable.

In the present invention, the resin particles (AL) containing the resin (A ₁ ) and the resin (A ₂ ) in the same particle have a relative dielectric constant of 3.
By supplying it by dispersing it in an electrically insulating liquid of 5 or less, the film thickness of the transfer layer can be easily adjusted with a thin film in a uniform thickness. Further, the resin particles (AL) are supplied between the counter electrodes provided so as to face the electrophotographic photosensitive member, and are electrophoresed according to a potential gradient applied from an external power source to adhere or electrodeposit on the electrophotographic photosensitive member. By forming the film by the above method, it becomes easier to adjust the uniform recording layer.

The transfer layer of the present invention will be described below.
As described above, the transfer layer of the present invention is formed by the film formation of the resin particles (AL) by the electrodeposition coating method, and from the electrophotographic photosensitive member having a releasable surface to the transfer material which becomes the support for printing, It is a layer having a function of being removed by a chemical reaction treatment in order to provide a printing original plate by peeling and transferring together with a toner image and to make the printing original plate into a printing plate. 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 used as seeds 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.

As described above, the resin particles (AL) used for forming the transfer layer of the present invention include at least two kinds of resin (A ₁ ) and resin (A ₂ ) having different glass transition points or softening points. It is contained 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 10 to 95/90 to 5 (weight ratio), the transferability is good and the durability of the transfer layer is also good and excellent. It is possible to obtain a printing plate having excellent printing durability. A more preferable ratio of the resin (A ₁ ) / resin (A ₂ ) is 30 to 90/70 to 10
(Weight ratio). Presence of resin (A ₁ ) is 10% by weight
If it is less, a toner image is formed, transferred to a transfer material to be an original plate, and when the original plates are left to overlap until the transfer layer is removed by a chemical reaction treatment, the upper original plate overlapped with the transfer layer is left. The transfer layer may be peeled off due to close contact with the back side, resulting in a missing toner image (poor plate characteristics). On the other hand, when the content of the resin (A ₂ ) is less than 5% by weight, The transferability of the transfer layer tends to deteriorate, which is not preferable.

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.

The weight average molecular weights of the resin (A ₁ ) and the resin (A ₂ ) are preferably in the range of 1 × 10 ^{3 to} 5 × 10 ⁵ , and more preferably 3 × 10 ³ to 8 × 10 ⁴ . Here, the molecular weight is measured by the GPC method and converted into polystyrene, and may be abbreviated as Mw hereinafter.

The resin particles (A
L) is composed of a resin that can be removed by a chemical reaction treatment as described above. Resin (A) that can be removed by chemical reaction treatment
Include a resin which is dissolved and / or swelled by a chemical reaction treatment to be removed, and a resin which is hydrophilized by a chemical reaction treatment and is consequently dissolved and / or swelled and removed.

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 representative example is a resin containing a hydrophilic group protected by a protecting 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 thermoplastic resins (A ₁ ) and (A ₂ ) for the transfer layer 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 {R ¹ represents -OH group, hydrocarbon group or -OR ² (R ² represents hydrocarbon group) group} group, phenolic OH
Polymer component containing at least one group of the groups, acid cyclic anhydride-containing group, -CONHCOR ³ that (R ³ represents a hydrocarbon group) group and -CONHSO ₂ R ³ group. Polymer component (b): -CO ₂ H group in chemical reactions, -CHO
Group, -SO ₃ H group, -SO ₂ H group, -P (= O) (OH ) R
¹ {R ¹ represents an —OH group, a hydrocarbon group or an —OR ² (R ² represents a hydrocarbon group) group} group and at least one functional group forming an —OH group. Seed-containing polymer component.

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

[0026]

[Chemical 1]

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

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

When the amount of the polymer components (a) and (b) present is too small, it becomes difficult to remove the transfer layer by a chemical reaction treatment, and when printed as a printing plate, the non-image area is stained. On the other hand, when the amount is too large, the glass transition point or the softening point of the resin (A) becomes high no matter how the other copolymerization component of the resin (A) is adjusted, and as a result, the material to be transferred to the transfer layer is transferred. However, there is a problem in that the reproducibility of the copied image deteriorates due to the deterioration of the transferability of the transfer layer, the deterioration of the electrical insulation of the transfer layer, and the deterioration of the chargeability of the electrophotographic photosensitive member.

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

Next, each polymer component that can be contained in the resin (A) will be described in detail. The polymer component (a) is not particularly limited as long as it is a copolymer component containing a specific hydrophilic group as described above. The hydrophilic groups may take the form of salts. Specific examples of the hydrophilic group-containing copolymer component include
Any vinyl compound containing such a hydrophilic group may be used, and it is described in, for example, "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 form, α, β-dichloro form, 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 acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half-ester derivatives of vinyl group or allyl group 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.

[0033]

[Chemical 2]

[0034]

[Chemical 3]

[0035]

[Chemical 4]

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8]

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). In the general formula (I) -COO-L ¹ [formula (I), L ¹ represents the following group. ]

[0042]

[Chemical 9]

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

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

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 {Z ¹ is an aliphatic group (eg, an alkyl group having 1 to 12 carbon atoms which may be substituted, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a chloroethyl group, a pentyl group, an octyl group. Group, etc., optionally substituted aralkyl group having 7 to 12 carbon atoms, specifically, benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, chlorophenethyl group, methylphenethyl group, etc., or aromatic group (eg, Phenyl group or naphthyl group which may have a substituent, specifically, phenyl group, chlorophenyl group, dichlorophenyl group, methylphenyl group, methoxyphenyl group, acetylphenyl group, acetamidophenyl group, methoxycarbonylphenyl group, naphthyl group Etc.) group, —COOZ ² (Z ² is the same as the above Z ¹ ) group,
-OZ ³ (Z ³ has the same meaning as Z ¹ ) group or -COZ
⁴ (Z ⁴ has the same meaning as Z ¹ above). n and m each represent 0, 1 or 2. However, when both n and m are 0, Z does not represent a hydrogen atom.

R ¹⁴ , R ¹⁵ , R ¹⁶ and R ²⁰ , R ²¹ may be the same 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 (Z ⁶ represents an alkyl group, an aralkyl group, an alicyclic group, an aryl group) or the like}, and an optionally substituted aromatic group having 6 to 18 carbon atoms (for example, a phenyl group, a tolyl group, Chlorophenyl group, methoxyphenyl group, acetamidophenyl group, naphthyl group, etc.) or -OZ ⁵ (Z ⁵ is an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alkenyl group having 2 to 12 carbon atoms) Represents an optionally substituted aralkyl group having 7 to 12 carbon atoms, an optionally substituted alicyclic group having 5 to 18 carbon atoms, and an optionally substituted aryl group having 6 to 18 carbon atoms) group. .

[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.

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

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

[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 {Z ⁸ is a substituent having the same meaning as the alkyl group, aralkyl group, or alkenyl group of R ²² or R ²³ , or an aryl group which may be substituted (for example, a phenyl group). , Tolyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, ethoxyphenyl group, ethoxycarbonylphenyl group, etc.) or --NHZ ⁹ (Z ⁹ represents the same as Z ⁸ ) . In addition, a residue forming a ring by R ²² and R ²³ may be represented (for example, a 5- or 6-membered monocyclic ring (for example, cyclobenzyl ring, cyclohexyl ring), or 5 or 6
A membered bicyclo ring (for example, a bicycloheptane ring, a bicycloheptane ring, a bicyclooctane ring, a bicyclooctene ring, etc.), and these rings may be substituted, and the substituents are the same as those described above for R ²² and R ²³ . Including the same as the contents}. q represents an integer of 2 or 3.

[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 as 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). In the general formula _{(III) -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]

[Where R ¹¹ , R ¹² , X, Z, n, m,
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]

[Chemical 14]

[In the formula (V), A ¹ , A ² and R ¹³ each have the same meaning 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 the 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]

[Chemical 16]

[Here, R ²⁸ represents a hydrocarbon group, and specifically has the same content as R ¹¹ . R ^{14 to} R ¹⁹ , Y ¹
And p respectively represent the same contents as above. ]

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

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, methylphenyl group, cyanophenyl group) or -OZ ¹⁰ (Z ¹⁰ has the same meaning as the hydrocarbon group of R ^29, R ³⁰⁾ display the group It is. U represents a carbon-carbon bond which may pass through a hetero atom, and the number of atoms between oxygen atoms is 5 or less.

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

[0075]

[Chemical 18]

[0076]

[Chemical 19]

[0077]

[Chemical 20]

[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).

Further, the resin (A) contains a fluorine atom and / or a fluorine atom having an action of improving the releasability of the resin (A) itself together with the above-mentioned polymer components (a) and / or (b). The polymer component (c) containing the substituent may be contained. 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 preferably contained in an amount of 1 to 20% by weight based on the total polymer components of the resin (A).
If the polymer component (c) 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. However, the removal of the transfer layer may be insufficient.

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 electrical 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) or -COOZ ¹¹ (Z ¹¹ represents a hydrocarbon group, specifically, a hydrocarbon group having 1 to 7 carbon atoms) The same as the concrete contents can be mentioned).

R ⁶⁰ is preferably an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, 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 necessary 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-
Examples thereof include styrene copolymers, vinyl alkanoate resins, polyester resins, polyether resins, acrylic resins, methacrylic resins, cellulose resins, and fatty acid-modified cellulose resins.

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.

The total thickness of the transfer layer is preferably 0.1 to 10 μm, more preferably 0.5 to 7 μm. If the film thickness is too thin, transfer defects are likely to occur, and if it is too thick, problems in the electrophotographic process are likely to occur and sufficient image density cannot be obtained, or image quality is likely to deteriorate.

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), electrodeposition is performed on the surface of the photoconductor, and a uniform thin film is formed by, for example, heating to form a transfer layer.
Here, the electrodeposition coating method means that resin particles (A
It means a method of electrostatically attaching or electrodepositing L). Therefore, the thermoplastic resin particles (AL) must have either positive charges or negative charges,
The charge detection 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.
It is in the range of μm to 15 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”, Technosystem Co., Ltd., 1988), etc., and can be easily manufactured by appropriately using the methods described in detail in the textbooks.

As the polymerization granulation method, conventionally known methods such as an emulsion polymerization reaction carried out in an aqueous system, a seed polymerization reaction, a suspension polymerization reaction, and a dispersion polymerization reaction carried out in a non-aqueous solvent system are known. Specifically, Soichi Muroi "Chemistry of Polymer Latex" Polymer Publishing (1970), Taira Okuda, Hiroshi Inagaki "Synthetic Resin Emulsion" Polymer Publishing (1978), Soichi Muroi "Polymer Latex""Introduction" Kobunsha (1983), I.
Piirma, PC Wang "Emulsion Polymerization", I.
Piirma & 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, ion wind charging, reverse ionization, etc. are used. As described in the publications 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. For example, "Flow of Paint and Dispersion of Paint" translated by Kenji Ueki, Kyoritsu Publishing (1971
), 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, and then the fine particles are used as seeds and resin (A The method of producing by feeding and polymerizing the monomers corresponding to (4) is preferable.

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 photography development method or a method of electrophoresing in a pressure field of an electric field, an electrodispersion medium is used as a dispersion medium. A resistance of 10 ⁸ Ω · cm or more and a dielectric constant of 3.
It is adjusted to a non-aqueous solvent system of 5 or less. Specifically, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, and halogen-substituted products thereof can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L
(Isopar; trade name of Exxon), Shersol 7
0, Shelsol 71 (Shellsol; trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco; trade name of American Mineral Spirits Co.) 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 No. 893,42
9, 934,038, U.S. Pat. No. 1,122,3.
97, 3,900,412, 4,606,98
No. 9, JP-A Nos. 60-179751, 60-1859.
63, JP-A-2-13965 and the like.
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 by an infrared lamp or the like, and preferably thermoplastic resin particles are formed into a film to form a transfer layer.

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, according to the present invention, at least when the transfer layer is formed by film-forming the resin particles (AL) by the electrodeposition coating method, the surface of the electrophotographic photosensitive member adjacent to the transfer layer is JIS Z0237- 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. 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” is described in 8.3.1-18.
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 this transfer layer, a method of using a photoreceptor having the surface itself releasability (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.

Examples of the photosensitive material having a peelable surface itself, which can be used in the first method, include a photosensitive material using amorphous silicon as a photoconductor. 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, JP-A-61-95358, JP-A-55-83049, JP-A-62-89771, JP-A-61-189559, and Kaisho 62-75461
JP-A-62-75461, JP-A-62-1395.
56, JP-A-62-139557, JP-A-62-2
Examples thereof include those described in each publication such as 08055. Further, as a protective layer using a fluorine-based block copolymer, there are disclosed in JP-A-61-116362 and JP-A-61-117.
563, JP 61-270768, JP 62-
Examples thereof include those described in each publication such as 14657. 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 is disclosed in JP-A-63-249152.
And those described in JP-A-63-221355.

Further, the method of modifying the surface of the uppermost photoconductive layer to a state in which releasability is manifested is as follows: when a so-called dispersion type photoreceptor using at least a photoconductor and a binder resin is used, 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 strengthen the uneven distribution of the surface, as a binder resin for the overcoat layer or the photoconductive layer, a polymer segment containing a fluorine atom and / or a silicon atom, and a heat and / or photocurable resin are used. It is possible to use a block copolymer obtained by bonding at least one kind of polymer segment containing a functional group-containing component in blocks. 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 in combination with the fluorine atom and / or silicon atom containing resin according to the present invention.

In the electrophotographic photoreceptor, a polymer containing a polymer component containing a fluorine atom and / or a silicon atom of the present invention, which is effective for modifying the surface of the photoreceptor by the above-mentioned method, is Resin (P)] and / or resin particles [hereinafter referred to as resin particles (L)].

When the polymer is a random copolymer, the content of the fluorine-containing and / or silicon-containing polymer component is preferably at least 60% by weight, more preferably at least 60% by weight of the total polymer components. 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 the and segment (β) (surface uneven distribution type copolymer), the peelability of the surface itself is improved compared to the random copolymer, and further the maintenance of the peelability is maintained. To be done. 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 resin particles (L)
Is a substance that 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-releasing 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.

[0132]

[Chemical 25]

[0133]

[Chemical formula 26]

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

[0135]

[Chemical 27]

However, R ³¹ , R ³² , R ³³ , R ³⁴ and R
Each of ^{35, which} may be the same or different, 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.), alicyclic ring having 5 to 8 carbon atoms which may be substituted. 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.

Further, the fluorine atom- and silicon atom-containing organic residues may be constituted in combination, in which case they may be directly bonded or further combined via another connecting group. May be. Specific examples of the group to be linked include a divalent organic residue, and -O-, -S-, -N (d
^{1) -, - CO -,} - SO -, - SO 2 -, - COO-,
-OCO-, -CONHCO-, -NHCONH-,-
CON (d ¹ )-, -SO ₂ N (d ¹ )-, 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.

[0140]

[Chemical 28]

Here, e ¹ and e ² may be the same as or different from each other, and each is a hydrogen atom or a halogen atom (for example,
(Chlorine atom, bromine atom, etc.) or alkyl group having 1 to 12 carbon atoms (for example, methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.) Represents Q is -O
-, - S- or -N (d ²⁾ - represents, d ² is 1 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 (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) can be given as examples of the substituent.
Examples of the heterocyclic group include a furan ring, a thiophene ring, a pyridine ring, a piperazine ring, a tetrahydrofuran ring, a pyrrole ring, a tetrahydropyran ring, and a 1,3-oxazoline ring.

Next, specific examples of the repeating unit having a substituent containing a fluorine atom and / or a silicon atom as described above are shown below. However, the scope of the present invention is not limited to these. 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.

[0144]

[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.

[0146]

[Chemical 30]

[0147]

[Chemical 31]

[0148]

[Chemical 32]

[0149]

[Chemical 33]

[0150]

[Chemical 34]

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, as shown below, A −
Examples thereof include B type blocks, ABA type blocks, BAB type blocks, graft type blocks and star type blocks.

[0152]

[Chemical 35]

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 organometallic compound (eg, alkyllithium, lithium diisopropylamide, alkali metal alcoholates, alkylmagnesium halides, alkylaluminum halides) as a polymerization initiator, TE Hogeu- Esc
h, J. Smid `` Recent Advances in Anion Polymerizatio
n '' (1987, Elsevier New York), Yoshio Okamoto, Polymer, 38 , 912 (1989), Mitsuo Sawamoto, 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 the ring-opening polymerization reaction of a cyclic compound, S. Kobayashi, T. Saegusa “Ring Opening Polym
erization ”(1984, Applied Scence Publishers Lt.
d.), W. Seeliger et al., Angew. Chem. Int. Ed. Eng
l. 5 , 875 (1966), S. Kobayashi et al., Poly. Bul
l. 13 , 447 (1985), Y. Chujo et al., Macromolecules,
22 , 1074 (1989) and the like.

Further, regarding the photo-living 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.

[0159] 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), edited by 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), Takeshi Endo, Tsutomu Uezawa, Journal of Japan Adhesion Society, 24 , 323 (1988), Takeshi Endo, ibid. 25 , 40
9 (1989) etc.

As a method for 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), Toshibu 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. Outside this range,
Both the resin (P) and the resin particles (L) have a reduced concentration effect and 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 or more. 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 preferable method for producing the resin particles (L), there may be mentioned the non-aqueous dispersion polymerization method which will be described later with respect to 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, 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 that constitutes The polymerization may be carried out by heating in the presence of a polymerization initiator such as lauroyl oxide), an azobis compound (eg, azobisisobutyronitrile, azobisisovaleronitrile, etc.), an organometallic compound (eg, butyllithium, etc.). Alternatively, the monomer (a) and the polymer (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 a cross-linking agent can be mentioned. Specifically, "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko.
The compounds described in Taiseisha (1981), "Polymer Data Handbook, Basic Edition", edited by The Polymer Society of Japan, Baifukan (1986), etc. can be used. For example, organic silane compounds (for example, silane coupling agents such as vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane). Etc.), polyisocyanate compounds (for example, toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high molecular polyisocyanate) Nato, etc.), a polyol compound (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxyethylene glycol,
1,1,1-trimethylolpropane, etc.), polyamine compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine,
Modified aliphatic polyamines, etc.), titanate coupling compounds (eg tetrabutoxy titanate, tetrapropoxy titanate, isopropyl tristearoyl titanate etc.), aluminum coupling compounds (eg aluminum butyrate, aluminum acetyl acetate, aluminum oxide octate, Aluminum tris (acetyl acetate), etc., polyepoxy group-containing compounds and epoxy resins (for example, "New Epoxy Resin" by Hiroshi Kakiuchi Shokoido (1985), Kuniyuki Hashimoto "Epoxy Resin" Nikkan Kogyo Shimbun (1969) ) Etc.), melamine resin (for example, Ichiro Miwa,
"Uria Melamine Resin" edited by Hideo Matsunaga, compounds listed in Nikkan Kogyo Shimbun (1969), poly (meta)
Crylate compounds (eg Shin Okawara, Takeo Saegusa, Toshinobu Higashimura, "Oligomer" Kodansha (1976), Eizo Omori "Functional Acrylic Resin" Techno System (1985)
And the like).

In addition, a polyfunctional monomer containing two or more polymerizable functional groups coexisting by the above method [hereinafter also referred to as 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 the same or different polymerizable functional groups may be used.

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

Examples of the monomers or oligomers having different polymerizable functional groups include vinyl group-containing carboxylic acids (for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, and arylloyl). Propionic acid, 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.

Further, in the case of forming a chemical bond by the reaction of the reactive groups between the polymers and bridging the polymers in the above-mentioned method, it is carried out in the same manner as the reaction of a normal organic low molecular compound. be able to. In 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) with a 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 may be any as long as it has copolymerizability with the monomer (a) as described above, but as a specific example, CH ₂ ═C (Q)- COO-, C
_{(CH 3) H = CH-} COO-, CH 2 = C (CH 2 COO
_{H) -COO-, CH 2 = C} (Q) -CONH-, CH 2
= C (Q) -CONHCOO-, CH 2 = C (Q) -C
_{ONHCONH-, C (CH 3) H} = CHCONH-, C
_{H 2 = CHCO-, CH 2 =} CH (CH 2) g -OCO-
(G is 0 or an integer of 1 to 3), CH ₂ = CHO-, CH ₂
═CHC ₆ H ₄ — and the like (wherein Q is —H or —
Represent CH _3).

These polymerizable groups may be directly bonded to the polymer chain or may be bonded via another divalent organic residue. Specific embodiments of these polymers are described in, for example, JP-A 61-43757, JP-A 1-257969,
No. 2-74956, No. 1-282566, No. 2-1
73667, 3-15862, and JP-A-4-706.
It is described in each publication such as No. 69. The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the non-aqueous solvent. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compounds. The polymerization temperature is about 30 to 180 ° C, preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours.

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

Examples of the polymer component containing at least one photo- and / or thermosetting group 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 less than the lower limit, the curing after the film formation of the photoconductive layer does not proceed sufficiently, and the effect of holding the film interface with the surface of the electrophotographic photoreceptor during coating of the transfer layer decreases. On the other hand, when the content is more than the upper limit, the electrophotographic characteristics of the photoconductive layer as the binder resin may be deteriorated, the original reproducibility of the copied image may be deteriorated, and the background fog in the non-image area may occur. Occurs. The resin (P) containing these light and / or thermosetting groups is preferably used in an amount of 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 is contained, and it is preferable that a small amount of the light- and / or thermosetting resin (D) and / or the cross-linking agent coexist in order to improve the curing of the film. The amount used is 0.01 to 20% by weight, preferably 0.1 to 15% by weight, based on the entire binder resin. 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, 20% by weight
If it exceeds the range, 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.

[0185]

[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 cured by light and / or heat after applying the photosensitive layer forming material. In order to carry out heat curing, for example, the drying conditions are set to be more severe than the conventional drying conditions for producing a photoreceptor. For example, the drying conditions may be high temperature and / or 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, a compound (S) exhibiting releasability is adsorbed or adsorbed on the surface of an ordinary electrophotographic photoreceptor before forming a transfer layer, which is a second method for obtaining a photoreceptor having a releasable surface. A method of adhering and imparting releasability to the surface of the photoreceptor will be described.

As the compound (S), 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 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. .

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 (published in 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.

Further, cloth, paper impregnated with the compound (S),
A method in which a felt or the like is brought into close contact with the photoconductor, a method in which a curable resin impregnated with the compound (S) is brought into pressure contact with the photoconductor, and the photoconductor is wetted with a non-aqueous solvent in which the compound (S) is dissolved, and then the solvent is dried. And a method in which a nonaqueous solvent in which the compound (S) is dispersed is electrophoresed and adhered to the photoconductor in the same manner as the 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
Examples include a ton method, an ink-on-demand type pulse jet method, a bubble jet method, and an ink mist type mist method.

In any 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 compound (S) may be appropriately applied according to the photoreceptor 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
State of Science of Adhesive Joints "Academic Press (published in 1961) is sufficient. That is, during formation of the transfer layer, the compound (S) is adsorbed or attached to the electrophotographic photosensitive member and peeled off to the surface thereof. 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 is to add a dispersion containing the resin particles (AL) of the present invention used when the transfer layer is formed by the electrodeposition coating method, The treatment is carried out in the coexistence of a compound (S ') exhibiting peelability. That is, in the conventionally known electrophotographic photoreceptor,
By electrocoating a dispersion for electrodeposition containing the compound (S '), the surface of the photoreceptor 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 to be used 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
”national conference” SPSE (1983), Isao Shinohara, Hidetoshi Tsuchida, Hideaki Kusagawa, “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 and practical application of photoconductive materials and photoconductors" Published by Japan Science Information Co., Ltd. (1985), The Electrophotographic Society of Japan, "Basics of Electrophotographic Technology" And Applications "Corona Publishing Co., Ltd. (1988), The Electrophotographic Society of Japan," Current 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 the conventionally known ones.
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, and the second one is disclosed in JP-A-56-146145.
No. 60, No. 60-17751, No. 60-17752, No. 60-17760, No. 60-254142, No. 62.
-54266, a charge generating agent as described in each publication,
A charge transfer agent, a photoconductive layer containing a binder resin as a main component, and a charge generation agent and a charge transfer agent as described in JP-A Nos. 60-230147, 60-230148, and 60-238853. A photoconductive layer having a two-layered structure in which each of these is contained in a separate layer. 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 the like, (b) US Pat. No. 3,189,
Oxadiazole derivatives described in Japanese Patent No. 447, etc.,
(c) Imidazole derivative described in JP-B-37-16096, (d) U.S. Pat. Nos. 3,615,402, 3,820,989, and 3,542,544, Japanese Patent Publication 45-555 and 51-10983, JP-A-51-93224 and 55-108667.
Nos. 55-156953 and 56-36656, and the like, polyarylalkane derivatives described in (e) U.S. Pat. Nos. 3,180,729 and 4,278,746. 55-88064, 55-880
No. 65, No. 49-105537, No. 55-51086.
No. 56-80051, No. 56-88141, No. 57-45545, No. 54-112637, No. 55.
Pyrazoline derivatives and pyrazolone derivatives described in JP-A-74546, (f) US Pat. No. 3,615,404
Specification, Japanese Patent Publication No. 51-10105, 46-371
2 and 47-28336, JP-A-54-83
No. 435, No. 54-110836, No. 54-1199.
No. 25, etc., 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 and 4,012,376, Japanese Patent Publication No. 49-35702, West German Patent (DA
S) No. 1,110,518, JP-B-39-27
577, JP-A-55-144250 and JP-A-56-11.
9132, 56-22437, and the like, arylamine derivatives described in (h) US Pat.
26,501 and the like, amino-substituted chalcone derivatives, (i) U.S. Pat. No. 3,542,546 and the like, N, N-bicarbazyl derivatives, (j) U.S. Pat. No. 3,257, No. 203, etc., (k) styrylanthracene derivatives, such as those described in JP-A-56-46234, and (l) JP-A-54-110.
Fluorenone derivatives described in 837, etc., (m) U.S. Pat. No. 3,717,462, JP-A-54-591
43 (corresponding to U.S. Pat. No. 4,150,987), JP-A-55-52063, and JP-A-55-5206.
No. 4, No. 55-46760, No. 55-85495,
57-11350, 57-1448749, 5
7-104144, the hydrazone derivatives described in each publication, etc.,

(N) US Pat. Nos. 4,047,948, 4,047,949, 4,265,990, 4,273,846, 4,299,897 and 4 , 306, 008, etc., benzidine derivatives, (o) JP-A-58-190953, 59-59
No. 5540, No. 59-97148, No. 59-1956.
58 and 62-36674, stilbene derivatives described in JP-B-34-10966 and (p) polyvinylcarbazole and derivatives thereof,
(q) Polyvinylpyrene, polyvinylanthracene, poly-2-vinyl-4- (4'-dimethylaminophenyl) -5-phenyl-oxazole, poly- described in JP-B Nos. 43-18674 and 43-19192. Vinyl polymers such as 3-vinyl-N-ethylcarbazole, (r) polymers such as polyacenaphthylene, polyindene, and copolymers of acenaphthylene and styrene described in JP-B-43-19193, (s) JP-B-56 Condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin described in JP-A-13940, etc., (t) JP-A-56-908
No. 33, No. 56-161550, various triphenylmethane polymers, and the like. In the present invention, the organic photoconductive compound is not limited to the compounds listed in (a) to (t), and all known organic photoconductive compounds can be used. Two or more kinds of these organic photoconductive compounds may be used in combination depending on the case.

As the sensitizing dye contained in the photoconductive layer,
Conventionally known sensitizing dyes used for electrophotographic photoreceptors can be used. These are "Electrographs" 12 , 9 (1973),
“Organic Synthetic Chemistry” 24 (11), 1010 (1966) and the like. For example, U.S. Pat. Nos. 3,141,770 and 4,283.
475, each specification of JP-A-48-25658, JP-A-62-71965 and the like, Applied Optics Supplement 3, 50 (1969), JP-A-50-39548 and the like. And the cyanine dyes described in US Pat. No. 3,597,196, JP-A-60-163407, JP-A-59-164588 and JP-A-60-252517. The styryl dyes described in 1) 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) US Pat. Nos. 4,436,800 and 4,439,506, JP-A-47-3754
No. 3, No. 58-123541, No. 58-192042
No. 58-219263, 59-78356,
No. 60-179746, No. 61-148453, No. 61-238063, Japanese Patent Publication No. 60-5941.
And azo pigments such as monoazo, bisazo and trisazo pigments described in JP-A Nos. 60-45664, (2) US Pat. Nos. 3,397,086 and 4,666,802.
Each specification, JP-A-51-90827, JP-A-52-55
Phthalocyanine pigments such as metal-free or metal phthalocyanines described in JP 643, (3) US Pat.
1,884, Japanese Patent Application Laid-Open No. 47-30330, and the like, (4) British Patent No. 2,237,
Indigo and thioindigo derivatives described in Japanese Patent No. 680, JP-A 47-30331 and the like, (5) British Patent No. 2,237,679, JP-A 47-30332
Quinacridone pigments described in Japanese Patent Publication No.

(6) British Patent No. 2,237,678, JP-A-59-184348 and JP-A-62-28738.
No. 47-18544 and polycyclic quinone pigments described in JP-A Nos. 47-30331 and 47-18.
No. 543, bisbenzimidazole-based pigments, (8) U.S. Pat. Nos. 4,396,610 and 4,64
4,082 Squalium salt-based pigments described in each specification, (9) JP-A-59-53850 and JP-A-61-2125.
Azurenium salt-based pigments described in JP-A No. 42, etc. These may be used alone or in combination of two or more.

Further, regarding the mixing ratio of the organic photoconductive compound and the binding resin, the upper limit of the content ratio of the organic photoconductive compound is determined by the compatibility between the organic photoconductive compound and the binding resin. Then, crystallization of the organic photoconductive compound occurs, which is not preferable. Since the electrophotographic sensitivity decreases as the content of the organic photoconductive compound decreases, it is preferable 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 [sometimes referred to as 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. , The weight average molecular weight is preferably 5 × 1
0 ³ to 1 × 10 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10 ^5.
belongs to. The glass transition point of the binder resin is preferably -40 ° C to 200 ° C, more preferably -10 ° C to 1
40 ° C. Examples of these conventionally known binder resins for electrophotographic photosensitive layers include, for example, Ryuji Shibata, Jiro Ishiwata, Polymer, Volume 17, page 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 ( No.8), Koichi Nakamura, "Practical Technology of Binders for Recording Materials," Chapter 10, CMC Publishing (1985
,), Proceedings of "Current Symposium on Organic Photoreceptors for Electrophotography," edited by The Institute of Electrophotography (1985), Hiroshi Komon, "Recent Developments and Practical Applications of Photoconductive Materials and Photoreceptors", Japan Science Information Co., Ltd. (19
1986), "Basics and Applications of Electrophotographic Technology" edited by The Institute of Electrophotography
Chapter 5, Corona Corp. (1988), D. Tatt, SCHeid
ecker, Tappi, 49 (No.10), 439 (1966), ES Baltazz
i, RG Blanclotteet al., Phot. Sci. Eng. 16 (No.
5), 354 (1972), Nguyen Chan Kae, Isamu Shimizu, Eiichi Inoue, Electrophotographic Society of Japan 18 (No.2), 22 (1980), etc. .

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 "Handbook of latest binder technology", Chapter II-1 (General Technology Center 1985)
Annual publication), Takayuki Otsu "Synthesis and design of acrylic resin and new application development" (published by Chubu Business Development Center in 1985), Eizo Omori "Functional acrylic resin" (Technosystem published in 1985), etc. A conventionally known resin is used.

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

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

The thickness of the photoconductive layer is 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, 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.

More specifically, as those mainly containing carbonium type dyes, triphenylmethane type dyes, xanthene type dyes, and phthalein type dyes, Japanese Patent Publication No. 51-45.
2, JP-A-50-90334 and JP-A-50-11422.
No. 7, No. 53-39130, No. 53-82353, U.S. Pat. Nos. 3,052,540 and 4,05.
4,450, each specification, JP-A-57-16456, etc. are mentioned.

As polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes, FM Hamer “The Cyanine Dyes and Related Co
The dyes described in "mpounds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,1.
No. 10,591, No. 3,121,008, No. 3,12
5,447, 3,128,179 and 3,13
2,942, 3,622,317, British Patents 1,226,892, 1,309,274
No. 1,405,898, Japanese Patent Publication No. 48-7
Examples thereof include dyes described in JP-A Nos. 814 and 55-18892. Furthermore, the near-infrared light with a long wavelength of 700 nm or more
As polymethine dyes for spectrally sensitizing infrared light region, JP-A-47-840, JP-A-47-44180 and JP-B-51-
41061, JP-A-49-5034, and JP-A-49-45.
No. 122, No. 57-46245, No. 56-35141.
No. 57-157254, No. 61-26044,
No. 61-27551, U.S. Pat. No. 3,619,
Nos. 154 and 4,175,956, "Resear"
ch Disclosure ”, 1982, 216, pages 117 to 118 and the like. The photoconductor of the present invention is also excellent in that its performance does not easily change depending on the sensitizing dye even when various sensitizing dyes are used in combination.

Furthermore, various conventionally known additives for electrophotographic photoreceptors can be used in combination, if necessary. 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 a review article by the Japanese Scientific Information Co., Ltd. Publishing Department (1986), can 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. Conductively treated, coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and further preventing curling. Those provided with a water-resistant adhesive layer on the surface, those provided with at least one precoat layer on the surface layer of the above-mentioned support, if necessary, those obtained by laminating a substrate conductive plastic having aluminum or the like deposited on paper 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, resin particles (AL) containing at least two kinds of resins having different glass transition points according to the present invention in the same particle are provided on a photoreceptor having a peelable surface developed as described above. After forming a transfer layer by electrodeposition or deposition by an electrodeposition coating method to form a film, a toner image is formed through a normal electrophotographic process. That is, each process of charging-exposure-developing-fixing is performed by a conventionally known method. The formation of the transfer layer and the electrophotographic process may be performed in the same apparatus or different apparatuses. In the present invention, conventionally known methods and apparatuses can be appropriately used for forming a toner image by an electrophotographic process.

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., 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 are arbitrarily selected as the above-mentioned colorants, and for example, benzidine type, azo type,
Examples include dyes or pigments such as azomethine-based, xanthene-based, anthraquinone-based, phthalocyanine-based (including metal-containing), titanium white, nigrosine, aniline black and carbon black. Further, as other additives, those specifically described in Yuji Harazaki "Electrophotography" Vol. 16, No. 2, p. 44 are used. For example, di-2
-Ethylhexyl sulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, alkylbenzene sulfonic acid metal salt, 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.

Further, 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 can be 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. As another method, as disclosed in JP-A-53-54029, a method of chemically bonding a disperse resin and a dye, or a polymerization method described in JP-B-44-22955. 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.

The combination of the scanning exposure method using laser light which is exposed on the basis of digital information and the development method using a liquid developer is an effective process because a high-definition image can be formed. An example is shown below. First, the photosensitive material is positioned on the flat bed by the register pin method, and then sucked and fixed by air suction from the back surface. Then, for example, by "charging device described in" Basics and Applications of Electrophotographic Technology "(edited by The Institute of Electrophotography, Corona Publishing Co., Ltd., June 15, 1988), pages 212 onward,
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 a 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 above cited document can be used. The exposure mode at this time corresponds to the toner image development mode. For example, in the case of reversal development, a negative image, that is, an image portion is irradiated with laser light to charge the photosensitive material with the same charge polarity. The toner having the above is used to apply a developing bias voltage so that the toner is electrodeposited on the exposed portion. The details of the principle are explained on pages 157 and after of the above cited material. After development, in order to remove the excess developer, squeeze as shown on page 283 of the same document is performed, and then dried. It is also preferable to rinse only with the carrier liquid of the developer before squeezing.

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 , and the conveying speed is preferably 0.1 to 300 mm / sec, more preferably 50 to 200 mm / sec. It is natural that these condition settings are optimized depending on the physical properties of the photosensitive material used, that is, the material of the peeling layer, the photosensitive layer and the support. The 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 material to be transferred used in the present invention, the support conventionally used for offset printing plates 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 anodizing 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, Japanese Patent Publication No.
As described in JP-A-7-5125, a sheet obtained by anodizing an aluminum plate and then dipping it in an aqueous solution of an alkali metal silicate is also suitably 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, 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. Treatment with polyvinyl sulfonic 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 material to be transferred thus obtained 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 active 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 range 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.

Further, as a compound which can be used in combination for accelerating the hydrophilic reaction, the nucleophilic constant n [RG Pearson, H. Sobel, J. Amer. Chem. So.
c., 90, 319 (1968)] contains a substituent having a value of 5.5 or more, and is a hydrophilic compound which dissolves 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. Group, phosphono group,
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 amino groups.

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 or 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,
1 to 50 parts of water-soluble organic solvent 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, methylethyl tetone, cyclohexanone,
Acetophenone), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol diethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.), amides (dimethylformamide, pyrrolidone,
N-methylpyrrolidone, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, sulfolane, tetramethylurea, etc.) and the like can be mentioned, and these may be used alone or in combination of two or more.

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 any of visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, γ-ray, α-ray, etc., but is preferable. Is ultraviolet light. More preferably, 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 preparing 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 transfer layer 12 is directly formed on the photosensitive member 11. When the surface of the photoreceptor 11 is insufficiently peeled off, as described above, the transfer layer 1
2 is provided with a device for adsorbing or adhering the compound (S) before the formation of 2 (second method), or in the electrodeposition dispersion liquid containing the transfer layer forming resin particles (AL) of the present invention. By incorporating the compound (S ′) (third method),
Releasability can be imparted to the surface of the photoreceptor 11. Second
In the case of the above method, the compound (S) is supplied to the surface of the photoconductor 11 by appropriately providing the compound (S) supply device 20 using the method of any one of the above-described specific embodiments. The supply device 20 for applying the compound (S) to the surface of the photoreceptor 11 may be fixed or movable.

Dispersion 12a of thermoplastic resin particles (AL)
Is supplied to the electrodeposition unit 13 in the movable liquid developing unit set 14. First, the electrodeposition unit 13 is brought close to the photoreceptor surface 11 and fixed so that the distance between the electrodeposition unit 13 and the developing electrode is 1 mm. The particle dispersion liquid 12a is supplied between the gaps and rotated while applying a voltage from an external power source (not shown) so that the 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 13 is used to remove the particle dispersion 12a adhering to the surface 11 of the photoconductor.
Then, it is passed under the air intake / exhaust unit 15 to be dried, and the thermoplastic resin particles (AL) are thermally melted by the preheating means 17a to obtain a film of the thermoplastic resin transfer layer 12. Then, if necessary, from the outside of the photoconductor or the inside of the photoconductor drum with a cooling device similar to the intake / exhaust unit (not shown),
Cool to the desired temperature.

After lowering the electrodeposition unit 13, the liquid developing unit set 14 is moved. The unit set 14 includes a liquid developing unit 14L containing a wet type developer. Each may be provided with a pre-bath, a rinse and a squeeze means for the purpose of preventing the non-image area from being soiled. A wet developer carrier liquid is usually used as the pre-bath and rinse liquid.

The photosensitive member 11 on which the transfer layer 12 made of a thermoplastic resin is formed, then enters the electrophotographic process. The photoconductor 11 is uniformly charged positively, for example, by the corona charging device 18, and then the exposure device (for example, semiconductor laser) 1
When image exposure is performed based on the image information in 9, the potential of the exposed portion is reduced and a potential contrast is obtained with the unexposed portion. A liquid developing unit 14L containing a liquid developer dispersed in an electrically insulating dispersion medium having a positive electrostatic charge 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 developing unit, and then the developing bias voltage is applied between the photosensitive member and the developing electrode by a bias power source and electric connection which are not shown in the drawing. A developer is supplied to the surface of the photoconductor. At this time, the bias voltage is connected so that the developing electrode side is positive and the photoconductor side is negative, and the applied voltage is slightly lower than the surface potential of the unexposed portion. If the applied voltage is too low, a sufficient toner image density cannot be obtained.

After that, the developing unit set 14 has a built-in rinsing means to wash away the developing solution adhering to the surface of the photoconductor, and a squeeze means to remove the rinsing solution adhering to the surface of the photoconductor. To dry. During this time, the thermal transfer means 17
Is placed away from the surface of the photoconductor.

After the toner image 3 is formed on the transfer layer 12 of the photoreceptor 11, it is thermally transferred to the transfer material 16. That is, the transfer layer 12 holding the toner image 3 is preheated by the preheating means 17a for thermal transfer, and then the transfer material 16 is transferred.
A rubber roller 17b containing a heating element having a temperature control means is pressed against it via a cooling roller 17c, and is passed under the cooling roller 17c to be cooled, and the toner 3 on the surface of the photoreceptor 11 is transferred to the transfer material 16 together with the transfer layer 12. Heat transfer is performed, and a series of printing original plate forming steps is completed.

The transfer means 17 for thermally transferring the transfer layer 12 to the material 16 to be transferred comprises a preheating means 17a, a metal heating roller 17b covered with rubber containing a heating element, and a cooling roller 17c. The preheating means 17a is a non-contact type infrared line heater or flash heater,
Preheating is performed within a range not exceeding the surface temperature of the photosensitive layer obtained by the heating roller 17b. Heating roller 17b
The heating surface temperature of the photosensitive layer is preferably 30 to 150.
C., more preferably 40 to 120.degree.

As the material of the cooling roller 17c, it is preferable 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 which is 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 from 0.2 to
20 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 . Transport speed is 0.1-300 mm / sec, more preferably 50-200 mm
/ Sec, which may be different between the electrophotographic process and the thermal transfer process. 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 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.

[0263]

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

[Production Example of 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, methyl Acrylate 55g, acrylic acid
A mixed solution of 15 g, methyl 3-mercaptopropionate 1.3 g and Isopar H 542 g was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. 0.8 g of 2,2'-azobis (isovaleronitrile) (abbreviation AIVN) was added as a polymerization initiator, and the reaction was carried out for 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. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was a monodisperse latex having a polymerization rate of 99% and an average particle size of 0.18 μm (particle size: CAPA-50.
0 (measured by Horiba, Ltd.).

[0265]

[Chemical 36]

The above resin particle dispersion (that is, seed particles) 650
g and 10 g of the dispersion stabilizing resin (Q-1) were heated to a temperature of 60 ° C. with stirring under a nitrogen stream. To this, a mixture of 85 g of benzyl methacrylate, 15 g of acrylic acid, 1.0 g of 3-mercaptopropionic acid, 0.8 g of AIVN and 200 g of Isopar H was added dropwise for 2 hours, and the mixture was further added as it was.
Reacted for hours. Next, 0.8 g of an initiator was added and the temperature was raised to 70 ° C. to react for 2 hours, and 0.6 g of an initiator was further added and reacted for 3 hours. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the polymerization rate was 98%, and the latex was a monodisperse powder having an average particle size of 0.25 μm and good monodispersibility.

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). A film prepared by making resin particles dispersed on a PET film was heat-treated at a temperature of 50 ° C. and 80 ° C. for 5 minutes, and then each sample was subjected to JSL-T330 type Scanning Microsc
When observed at a magnification of 20,000 using ope (manufactured by JEOL), a particle state was observed in the sample at a temperature of 50 ° C., but a temperature of 80 ° C.
No particles were observed in. That is, the particles were melted by heating.

Similarly, resin particles composed of each of two kinds of resins (copolymers) constituting the particles of the present invention {comparative resin particles (RAL-1) and (RAL- which will be described later, respectively).
2)} and dispersed resin particles obtained by mixing these two kinds of resin particles in a 1/1 weight ratio were investigated. Resin particles (RAL
In the sample consisting of -1), the particle state was not observed at the temperature of 50 ° C., while the unheated sample was in the particle state. The resin particle (RAL-2) sample was in a particle state at a temperature of 50 ° C., but the particles became invisible at a temperature of 80 ° C.
Further, when a sample made up of mixed particles and not heated and a sample at a temperature of 50 ° C. were examined, it was confirmed that the particles at a temperature of 50 ° C. were invisible in comparison with the unheated sample. As described above, as a result of visually observing the thermal behavior of the particles, the resin particles (AL) of the present invention produced as described above are not a mixture of two types of resin particles, It was confirmed that two kinds of resins were contained, and in this case, the high Tg resin was a core-shell particle in which the low Tg resin was distributed in the inner layer and the low Tg resin was distributed in the inner layer.

Production Example 2 of Resin Particles (AL) for Transfer Layer:
(AL-2) Synthesis of dispersion stabilizing resin (Q-2) Dodecyl methacrylate 99.5 g, divinylbenzene 0.5
A mixed solution of g and toluene (200 g) was heated to a temperature of 80 ° C. with stirring under a nitrogen stream. 2 g of 2,2'-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 3 hours, and 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
Met.

Synthesis of Particles A mixed solution of 18 g (as solid content) of the above resin (Q-2), 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 80 ° C. under a nitrogen stream. Warmed to. Add AIVN 1.6g and react for 1.5 hours, add AIVN 0.8g for 2 hours, then AIVN
0.5 g was added and reacted for 3 hours. Next, raise the temperature to 100 ° C. and stir for 2 hours, distill off the unreacted vinyl ester monomer, cool and pass a 200 mesh nylon cloth,
A white dispersion was obtained with a polymerization rate of 87%. It was a monodisperse latex having an average particle size of 0.17 μm.

The above resin particle dispersion (ie, seed particles) 480
g and 20 g of dispersion stabilizing resin particles (Q-2) were heated to a temperature of 60 ° C. while 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 for 2 hours, and the reaction was continued for 1 hour. Next, add 0.8g of initiator and bring the temperature to 75 ℃.
After reacting for a time, 0.6 g of an initiator was further added and reacted for 3 hours.
After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having a polymerization rate of 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 resin (Q-3) for stabilizing dispersion having the following structure and 546 g of Isopar H was stirred at a temperature under a nitrogen stream.
It was set to 60 ° C. Add benzyl methacrylate 50 to this solution.
g, acrylic acid 8 g, monomer (b-1) 42 having the following structure
g, 2-mercaptoethanol 1.8g, AIVN 1.0g
And a mixed solution of 200 g of Isopar H were added dropwise over 1 hour,
The reaction was continued for 1 hour. Next, after adding AIVN 0.8g and reacting for 2 hours, add AIVN 0.5g and add 2 at the temperature of 80 ℃.
After reacting for a time, 0.5 g of AIBN was further added and reacted for 3 hours. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was a latex having a polymerization rate of 98% and an average particle size of 0.17 μm and good monodispersity.

[0273]

[Chemical 37]

A dispersion stabilizing resin (Q-3) was added to the above dispersion.
The temperature of the mixed solution containing 15 g was adjusted to 60 ° C. while stirring under a nitrogen stream. To this, 52 g of methyl methacrylate, 35 g of methyl acrylate, 13 g of acrylic acid, 2 g of 3-mercaptopropionic acid, 0.8 g of AIVN and Isopar H
564 g of the mixture was added dropwise over 2 hours, and the mixture was added as it was for 2 hours. Next, add AIBN 0.8g as an initiator,
The reaction was carried out at a temperature of 80 ° C. for 2 hours, 0.6 g of an initiator was further added, and the reaction was carried out for 3 hours. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion had a polymerization rate of 98% and an average particle size of 0.
The latex was 24 μm and had good monodispersity.

Production Example 4 of Resin Particles (AL) for Transfer Layer:
(AL-4) A mixed solution of 25 g of a dispersion stabilizing resin (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, 27 g of monomer (b-2) having the following structure, 1.5 g of thioglycolic acid, 0.6 g of AIVN and Isopar H 19
A mixed solution of 9.5 g and ethyl acetate 66.5 g was added dropwise over 1 hour. After reacting for 1 hour as it was, AIVN 0.3 g was added for 2 hours, and AIVN 0.3 g was further added for 3 hours. Next, ethyl acetate was distilled off at a reduced pressure of 30 mmHg, and the same amount of Isopar H was distilled off, followed by cooling to 200
A white dispersion was obtained by filtration through a mesh nylon cloth. It was a monodisperse latex having a polymerization rate of 93% and an average particle size of 0.20 μm.

[0276]

[Chemical 38]

The above resin particle dispersion (ie, seed particles) 37
A mixed solution of 2 g and the dispersion stabilizing resin (Q-1) 16 g was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. To this, a mixture of 70 g of vinyl acetate, 25 g of the monomer (b-3) having the following structure, 5 g of crotonic acid, 400 g of Isopar H and 0.9 g of AIVN was added dropwise over 2 hours, and the reaction was continued for another 2 hours. 0.8 g of an initiator was added and the reaction was carried out at a temperature of 85 ° C. for 2 hours. Further, 0.6 g of AIBN as an initiator was added and reacted for 3 hours. After cooling, it was passed through a 200-mesh nylon cloth, and the polymerization rate of the obtained white dispersion was 98%, and the latex was a monodisperse powder having an average particle size of 0.26 μm and good monodispersity.

[0278]

[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 the resin particles for transfer layer (AL), except that each monomer shown in Table B below was used, Production Example 1 described above was used.
The particles (AL-5) to (A-5) of the present invention
L-11) was prepared. The degree of polymerization of each latex particle obtained was 95 to 99%, and the average particle diameter was in the range of 0.20 to 0.30 μm.

[0280]

[Table 2]

[0281]

[Table 3]

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

[0283]

[Table 4]

[0284]

[Table 5]

Production Example 22 of Transfer Layer Resin Particles (AL):
(AL-22) Dispersion stabilizing resin (Q-4) 15 g, methyl methacrylate
A mixed solution of 48 g, 2,3-dipropionyloxypropyl methacrylate 40 g, acrylic acid 12 g, methyl 3-mercaptopropionate 2.0 g and Isopar H 549 g was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. AIVN 0.8 g was added as a polymerization initiator 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. After cooling, pass through a 200-mesh nylon cloth, and the white dispersion obtained had a polymerization rate.
It was a monodisperse latex with an average particle size of 0.18 μm at 98%.

The above resin particle dispersion (ie, seed particles) 260
g, 14 g of the dispersion stabilizing resin (Q-1), 10 g of the macromonomer (m-1) having the following structure, and 553 g of Isopar H were heated to 55 ° C. while stirring under a nitrogen stream. To this, 75 g of benzyl methacrylate, 10 g of acrylic acid,
Monomer (b-11) 15g, 3-mercaptopropionic acid 2
g, 2,2'-azobis (2-cyclopropylpropionitrile) (abbreviation: ACPP) 1.0 g and Isopar H 200 g
The mixed solution of was added dropwise over 1 hour. After stirring for 1 hour as it was, 0.8 g of ACPP was added and reacted for 2 hours. Further AIB
N. 0.5 g was added, the temperature was set to 80 ° C., and the reaction was carried out for 3 hours. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth had a polymerization rate of 97%, and was a latex having an average particle size of 0.24 μm and good monodispersity.

[0287]

[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 (m) in Table D below (Mw was 8). Each resin particle was synthesized in the same manner as in Production Example 22 except that (x10 ³ to 1 × 10 ⁴ ) was used. The polymerization rate of each particle is 98-99%, the average particle size of the particle is 0.20-0.25 μm
Within the range, the particle size distribution of the particles was narrow and the monodispersity was good.

[0289]

[Table 6]

[0290]

[Table 7]

Production Example 29 of thermoplastic resin particles (AL):
(AL-29) 20 g of resin (A-1) having the following structure and resin (A-1) having the following structure
-2) Using 40 g of tetrahydrofuran, temperature of 40 g
After dissolving by heating at ℃, the solvent was distilled off and the residue was dried under reduced pressure. Next, this solid was roughly pulverized using a trio blender (manufactured by Trio Science Co., Ltd.), and then 20 g of this pulverized product, 5 g of a dispersion stabilizing resin (Q-5) having the following structure and 80 g of Isopar G. Were dispersed with a Dynomill. The obtained particle dispersion was a latex having an average particle size of 0.45 μm.

[0292]

[Chemical 41]

Production Example of Comparative Resin Particles 1: (ARL-
1) The dispersion stabilizing resin (Q-1) 10 g, methyl methacrylate 15 g, methyl acrylate 27.5 g, acrylic acid 7.5
A mixed solution of g, methyl 3-mercaptopropionate (0.65 g) and Isopar H (329 g) was heated to a temperature of 60 ° C while stirring under a nitrogen stream. AIVN 0.4 g as a polymerization initiator
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. 0.2g initiator
Add, after reacting for 2 hours, add 0.3 g of initiator and add
Reacted for hours. After cooling, it was passed through a nylon cloth of 200 mesh, and the white dispersion obtained had a polymerization rate of 99% and an average particle size of 0.25μ.
It was a monodisperse latex of m. 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.

Production Example 2 of Comparative Resin Particles: (ARL-
2) A mixed solution of 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,
Reaction was carried out according to the same method as in Production Example 1 (ARL-1) of comparative resin particles to synthesize resin particles. The obtained white dispersion was a monodisperse latex having a polymerization rate of 98% and an average particle size of 0.24 μm. The glass transition point of the resin component was 65 ° C.

[Synthesis Example of Resin (P)] Synthesis Example 1: Resin (P) 1: (P-1) 80 g of methyl methacrylate, dimethylsiloxane macromonomer (FM-0725) (manufactured by Chisso Corporation, Mw 1 × 10 5) ⁴ )
A mixed solution of 20 g and 200 g of toluene was placed under a nitrogen stream at a temperature of 7
Warmed to 5 ° C. To this, 1.0 g of 2,2'-azobis (isobutyronitrile) (abbreviation: AIBN) was added and reacted for 4 hours, and 0.7 g of AIBN was further added and reacted for 4 hours. The weight average molecular weight (abbreviation: Mw) of the obtained copolymer was 5.8 × 1.
It was 0 ⁴ (measured value by the GPC method).

[0296]

[Chemical 42]

Synthesis Examples 2 to 9 of Resin (P): (P-2) to
(P-9) In Synthesis Example 1 of Resin (P), instead of methyl methacrylate and macromonomer (FM-0725), the following Table-E was used.
Other than using each monomer corresponding to the polymer component described in,
Each polymer was synthesized in the same manner as in Synthesis Example 1. The Mw of each polymer obtained was in the range of 4.5 × 10 ^{4 to} 6 × 10 ⁴ .

[0298]

[Table 8]

[0299]

[Table 9]

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

[0301]

[Chemical 43]

Synthesis Examples 11 to 15 of Resin (P): (P-11) to
(P-15) Instead of the monomer and macromonomer (AA-6) used in Synthesis Example 10 of Resin (P), each monomer and each corresponding to the polymer component shown in Table 1F below. Each copolymer was synthesized in the same manner as in Synthesis Example 10 except that the macromonomer was used. The Mw of the obtained copolymer was 4.5 × 10 ^{4 to} 6.5 × 10 ⁴
Was in the range.

[0303]

[Table 10]

[0304]

[Table 11]

[0305]

[Table 12]

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

[0307]

[Chemical 44]

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

[0309]

[Chemical formula 45]

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

[0311]

[Chemical formula 46]

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

[0313]

[Chemical 47]

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

[0315]

[Chemical 48]

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

[0317]

[Table 13]

[0318]

[Table 14]

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

[0320]

[Chemical 49]

Synthesis Example 29 of Resin (P): (P-29) In Synthesis Example 20 of Resin (P), an initiator (I-2) 0.8 having the following structure was used instead of benzyl isopropyl xanthate.
except that g was used, the reaction was performed in the same manner as in Synthesis Example 20, and Mw2.5
A × 10 ⁴ copolymer was obtained.

[0322]

[Chemical 50]

Synthesis Example 30 of Resin (P): (P-30) 68 g of methyl methacrylate, 22 g of methyl acrylate,
A mixed solution of 10 g of glycidyl methacrylate, 17.5 g of an initiator (I-3) having the following structure, and 150 g of tetrahydrofuran was heated to a temperature of 50 ° C. under a nitrogen stream. 40 in this solution
Photopolymerization was carried out by irradiating with a 0 W high pressure mercury lamp from a distance of 10 cm through a glass filter for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain a polymer having an Mw of 4.0 × 10 ^{4 in} a yield of 72 g. 70 g of this polymer, 30 g of monomer (M-2) and tetrahydrofuran
100 g of the mixed solution was heated to a temperature of 50 ° C. under a nitrogen stream and irradiated with light under the same conditions as above for 13 hours. Next, this reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried to obtain a copolymer of Mw 6 × 10 ⁴ with a yield of 78 g.

[0324]

[Chemical 51]

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

[0326]

[Table 15]

[0327]

[Table 16]

[0328]

[Table 17]

[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 A mixed solution of 4.0 g of the dispersion stabilizing resin (LP-1) and 180 g of methyl ethyl ketone was heated to a temperature of 60 ° C. with stirring under a nitrogen stream.
2,2'-azobis (isovaleronitrile) (abbreviation AIV
N.) 0.3 g was added and reacted for 3 hours. In addition, AIVN 0.1
g was added and reacted for 4 hours. After cooling, a white dispersion was obtained through a 200-mesh nylon cloth. Average particle size: 0.25 μm
(The particle size was measured by CAPA-500 (manufactured by Horiba Ltd.)).

[0330]

[Chemical 52]

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

[0332]

[Chemical 53]

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

[0334]

[Table 18]

[0335]

[Table 19]

Synthesis Examples 12 to 17 of Resin Particles (L): (L-1
2) to (L-17) In Synthesis Example 2 of resin particles (L), 5 g of the dispersion stabilizing resin (AB-6) is used instead of the resin (LP) shown in Table J below.
Each resin particle was synthesized in the same manner as in Synthesis Example 2 except that The average particle size of the obtained particles was in the range of 0.10 to 0.25 μm.

[0337]

[Table 20]

[0338]

[Table 21]

Synthesis Examples 18 to 23 of Resin Particles (L): (L-1
8) to (L-23) In Synthesis Example 2 of resin particles (L), the monomer (LM-
2) Instead of 40 g, each monomer in the following Table-K, and resin (AB-6) for stabilizing the dispersion 5 g instead of the resin (L
P-8) was used in the same manner as in Synthesis Example 2 except that 6 g was used,
Each resin particle was synthesized. The average particle size of the obtained particles is 0.
It was in the range of 05 to 0.20 μm.

[0340]

[Chemical 54]

[0341]

[Table 22]

[0342]

[Table 23]

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 together with glass beads in a 500 ml glass container, and a paint shaker (manufactured by Toyo Seiki Seisakusho) 60 Disperse for a minute,
Furthermore, resin (P-2) 2.0g, phthalic anhydride 0.03g
And 0.002 g of o-chlorophenol were added and dispersed for 2 minutes, and then the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0344]

[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 in a 110 ° C. circulation type oven for 20 seconds. It was heated and further heated at 140 ° C. for 1 hour.
The film thickness of the obtained photosensitive layer was 8 μm. The photoconductor surface
When the adhesive strength was measured according to JIS Z-0237-1980 “Adhesive tape / adhesive sheet test method”, it was 3 g · f.

Next, this photosensitive member was loaded into the apparatus shown in FIG. 2 to first form a transfer layer. That is, the surface temperature of the photoreceptor is 60
C. and rotate the photoconductor drum at a peripheral speed of 10 mm / sec. And supply the positively charged resin particle dispersion [L-1] having the following contents to the photoconductor surface using a slit electrodeposition device while grounding the photoconductor side. Then, 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 is 2.5
was 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 / The copolymer was adjusted to a total volume of 1.0 liter with Isopar G.

Next, using this photosensitive member, a toner image was formed, transfer to a transfer material, printing plate preparation and printing were 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) The wavelength of 780 nm) was used to expose the surface of the photosensitive material at a dose of 30 erg / cm ² at a pitch of 25 μm and a scanning speed of 300 cm / sec.

Next, the liquid developer [L
D-1] was used to apply a bias voltage of +400 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. Excluded.

Preparation of Liquid Developer [LD-1] Synthesis of Toner Particles 70 g of methyl methacrylate, 30 g of methyl acrylate,
A mixed solution of 20 g of a dispersion polymer having the following structure and 680 g of Isopar H was heated to a temperature of 65 ° C. with stirring under a nitrogen stream. To this, 1.2 g of 2,2'-azobis (isovaleronitrile) (AIVN) was added and reacted for 2 hours.
0.5 g was added and reacted for 2 hours, and 0.5 g of AIVN was further added and reacted for 2 hours. Next, raise the reaction temperature to 90 ° C,
The mixture was stirred under reduced pressure of 30 mmHg for 1 hour to remove unreacted monomers. After cooling to room temperature, it was filtered through a 200-mesh nylon cloth to obtain a white dispersion. The reaction rate of the monomer of the obtained dispersion was 95% by weight, the average particle size of the resin particles was 0.25 μm, and the monodispersity was good (the particle size was CAPA-500: used by Horiba Ltd. Then measured).

[0350]

[Chemical 56]

Production of colored particles: 10 g of tetradecyl methacrylate / methacrylic acid copolymer (copolymerization ratio; 95/5 weight ratio), 10 g of nigrosine and 30 g of Isopar G together with glass beads, Paint shaker (manufactured by Tokyo Seiki Co., Ltd.) And dispersed for 4 hours to obtain a fine dispersion of nigrosine.

Production of Liquid Developer 45 g of the resin dispersion of the above toner particles, 25 g of the above nigrosine dispersion, 0.6 g of hexadecene / semi-maleic acid octadecylamide copolymer and FOC-1800 (manufactured by Nissan Kagaku Co., Ltd.) 15
A liquid developer for electrostatic photography was prepared by diluting g 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 support used for Fuji PS-Plate FPD (manufactured by Fuji Photo Film Co., Ltd.) and the above-mentioned developed photosensitive material were overlaid, and the surface temperature in contact with them under a pressure of 4 kgf / cm ^2. Was passed at a speed of 100 mm / sec between a pair of rubber rollers whose temperature was constantly controlled at 90 ° C. Then, the aluminum support and the light-sensitive material were peeled off after being cooled to room temperature while being piled up, and the image (fog, image quality of the image) formed on the obtained 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 without background fog was obtained, and almost no deterioration in image quality was observed as compared with the original. As described above, the silicon atom-containing copolymer coexisted in the photoconductive layer is concentrated and transferred to the surface portion during the formation of the photoconductive layer, and the binder resin (B) and the resin (P) are cross-linking agents. It is considered that due to the fact that the polymer was sufficiently chemically bonded to each other and a cured film was formed, so that an interface having good peelability was clearly formed.

On the other hand, as a comparison, in the above photoreceptor,
An electrophotographic photosensitive member was prepared in the same manner except that 2.0 g of the resin (P-2) was not used, and the surface adhesive force was 380 g.
・ It was f. When a transfer layer was applied and transferred in the same manner as in Example 1, no peeling property was exhibited.

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),
The printing performance as a printing plate was examined. The above printing original plate,
30 in the desensitizing solution [E-1] of the following formulation at a temperature of 25 ° C
The transfer layer was removed by immersing for 2 seconds, washed sufficiently with water, and gummed to prepare an offset printing plate. Desensitizing treatment liquid [E-1] Mercaptoethanesulfonic acid 10 g Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 8 g N, N-dimethylacetamide 20 g was diluted with distilled water to make the total amount 1.0 liter, and then hydroxylated. PH adjusted to 12.5 with sodium.

The printing plate thus obtained was visually observed with a 200 × optical microscope for the non-image area and the toner image area. As a result, no transfer layer remained in the non-image area, and No loss of high-resolution area such as fine lines and fine letters was observed.

Immersion water SG for PS plate as immersion water for this plate
An aqueous solution (pH 7.0) prepared by diluting -23 (manufactured by Tokyo Ink Co., Ltd.) 130 times with distilled water was used, Oliver 94 type (manufactured by Sakurai Manufacturing Co., Ltd.) was used as a printing machine, and neutral printing paper was used. Using paper, printing was carried out with various color inks for offset printing, and the number of prints that gave a clear image with no background stain was examined. As a result, regardless of the type of color ink, in any case, a printing durability of 60,000 or more was obtained. Furthermore, after printing with the printing plate of the present invention, the PS plate was printed next with the normal operation, and no problems occurred.
That is, it was confirmed that the same printing machine can be used easily with other offset printing plates such as PS plates.

On the other hand, as a comparison, the case of using a photoconductor in which each of the transfer layers in Comparative Examples 1 to 3 below was used was examined.

Comparative Example 1 Instead of the resin particles (AL-1) in the resin dispersion liquid [L-1] for the transfer layer of Example 1, comparative resin particles (RAL
In the same manner as in the case of the dispersion liquid [L-1] except that -1) was used, a transfer layer was formed on the photoreceptor so that the transfer layer film thickness was 2.5 μm. Other than that, the printing plate was prepared and printed in the same manner as in Example 1 above.

Comparative Example 2 Instead of the resin particles (AL-1) in the resin dispersion liquid [L-1] for the transfer layer of Example 1, the comparative resin particles (RAL
In the same manner as in the case of the dispersion liquid [L-1] except that -2) was used, a transfer layer was formed on the photoreceptor so that the transfer layer film thickness was 2.5 μm. Other than that, the printing plate was prepared and printed in the same manner as in Example 1 above.

Comparative Example 3 Instead of the resin particles (AL-1) in the resin dispersion liquid [L-1] for the transfer layer of Example 1, the comparative resin particles (RAL
-1) and (RAL-2) were used in a 1/1 weight ratio, and the transfer layer film thickness was 2. as in the case of the dispersion liquid [L-1].
A transfer layer was formed on the photoconductor so as to have a thickness of 5 μm. Other than that, the printing plate was prepared and printed in the same manner as in Example 1 above.

Comparative Example 1 which is a transfer layer of resin particles (RAL-1), which is composed of only two kinds of resins constituting the resin particles (AL-1) forming the transfer layer of Example 1 of the present invention. In any of the photoconductors of Comparative Example 2 which is a transfer layer of the resin particles (RAL-2) and under the same transfer conditions as in Example 1, the transfer of the transfer layer was insufficient and a transfer residue was generated on the photoconductor. However, the toner image portion on the printing original plate was missing due to a marked transfer failure.

Comparative Example 3 comprising a transfer layer in which the resin particles (RAL-1) and the resin particles (RAL-2) were mixed at a 1/1 weight ratio was used. The transferability was better than that of, but the transfer was not completed completely. On the other hand, the conditions under which the transfer layer composed of the mixture of the two kinds of resin particles used in Comparative Example 3, which had a relatively good transfer property, were completely transferred were examined. At the slow transfer speed of about 10 mm / sec, transfer of the transfer layer was completely recognized for the first time.

As described above, only the transfer layer of the present invention, in which the resin particles to be electrodeposited contain at least two kinds of resins having different thermoplastic temperatures in the same particle, is a thin layer but is mild. It was transferred rapidly under the transfer conditions. Therefore, the offset printing plate provided by the present invention has an extremely good image reproducibility obtained by the semiconductor laser light scanning exposure method and that it is well reproduced on a printed matter, and has sufficient color ink suitability and ink selection. It was confirmed that there is almost no property, and that full-color printing can be obtained with high printing durability and that it can be shared with other offset printing plates arbitrarily, and that it exhibits extremely excellent performance.

Examples 2 to 15 Resin particles used in the transfer layer in Example 1 (AL-
Instead of 1), each resin particle in Table L below (total amount 8 g)
A printing plate was prepared and offset printing was performed in the same manner as in Example 1 except that the transfer layer was formed to obtain a transfer layer thickness of 2.5 μm. As a result, in all cases, as in Example 1, 60,000 or more printed matters having clear printed images without background stains were obtained.

[0368]

[Table 24]

Example 16 Amorphous silicon electrophotographic photoreceptor (Kyocera Corp.)
Was manufactured by immersing 1 g of the following compound having surface releasability (S-1) in 1 liter of Isopar G for 10 seconds, rinsing in Isopar G, and then drying.
As a result, the surface of the amorphous silicon photoconductor having an adhesive force of 200 g · f was modified to a peelable surface having an adhesive force of 3 g · f.

[0370]

[Chemical 57]

The above photoreceptor was loaded in the apparatus shown in FIG. 2 to form a transfer layer. That is, the surface temperature of the photoconductor is 50 ° C., the peripheral speed of the photoconductor drum is rotated at 10 mm / sec, and a slit electrodeposition device is used on the photoconductor surface to form a positively charged resin particle dispersion liquid [L-2] having the following contents. While supplying, the photosensitive member side was grounded and a voltage of 180 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 2.5 μm.

Resin Particle Dispersion Liquid [L-2] Resin Particles (AL-6) 7 g (as Solid Content) Positive Charge Regulator (CD-2) 0.018 g 1-Hexadecene / N-decyl Maleic Acid Half Amide (1/1 molar ratio) Copolymer Branched tetradecyl alcohol FOC-1400 15 g {manufactured by Nissan Kagaku Co., Ltd.} was adjusted with Isopar G to a total volume of 1.0 liter.

Next, using this photoreceptor, a toner image was formed, transfer to a transfer material, printing plate preparation and printing were carried out as follows. After the photosensitive material is corona charged to +700 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) The wavelength of 780 nm) was used to expose the surface of the photosensitive material at a dose of 30 erg / cm ² at a pitch of 25 μm and a scanning speed of 300 cm / sec. The residual potential of the exposed portion was + 120V. Subsequently, using a liquid developer [LD-2] having the following contents, a bias voltage of 300 V was applied to the developing electrode to perform development so that the toner was electrodeposited on the unexposed area, and then in a bath of Isopar H alone. Rinse to remove stains on non-image area. The toner image was heat-fixed.

Liquid developer [LD-2] Coating resin: poly [octadecyl methacrylate / methyl methacrylate (9/1) molar ratio] copolymer and carbon black # 40 (manufactured by Mitsubishi Kasei Co., Ltd.) in a weight ratio. Then, the mixture was thoroughly mixed at 2: 1 and then melt-kneaded in a three-roll mill heated to 140 ° C. A mixture of 12 g of this kneaded material, 4 g of a styrene-butadiene copolymer (Sorprene 1205 manufactured by Asahi Kasei Co., Ltd.) and 76 g of Isopar G was dispersed in a Dynomill. The concentrated toner solution thus obtained was diluted with Isopar G to a solid content concentration of 6 g / liter, and sodium dioctyl sulfosuccinate was added thereto at a concentration of 1 × 10 ⁻⁴ mol / liter to ^prepare a developer. did.

As the material to be transferred, the image receiving side of OK Master PS type (manufactured by Oji Kako Co., Ltd.) and the photosensitive material after the plate making were superposed, and the surface temperature in contact with each other at a pressure of 4 kgf / cm ^{2 was} measured. It was passed at a speed of 100 mm / sec between a pair of rubber rollers which was constantly controlled at 105 ° C. Then, when the photosensitive member and the OK master were separated from each other after being cooled to room temperature while being piled up, all the toner on the photosensitive material was thermally transferred to the OK master side together with the transfer layer, and the difference in image quality from the plate-making image quality was very small. .

Next, a solution prepared by adding 50 g of dimethylethanolamine to 1 liter of the PS plate treating agent DP-4 (manufactured by Fuji Photo Film Co., Ltd.) and diluting it by 50 times was used as a desensitizing treatment liquid. E-2], at a temperature of 25 ° C, 20
The transfer layer was removed while rubbing gently for 2 seconds. Visual inspection of the non-image area and the toner image area of the printing plate thus obtained using a 200 × optical microscope showed no residual transfer layer in the non-image area, and fine lines in the image area. No loss of high resolution area such as fine letters was observed.

Immersion water SG for PS plate as immersion water for this plate
Ryobi 3 was used as a printing machine by using an aqueous solution (pH 7.0) in which -23 (manufactured by Tokyo Ink Co., Ltd.) was diluted 130 times with distilled water.
A 200 MCD type (manufactured by Ryobi Co., Ltd.) was used, and neutral paper was used as the printing paper, and printing was performed with various color inks for offset printing, and the number of printed sheets from which a clear image with no background stain was obtained was examined. As a result, 3,000 or more durable sheets were obtained regardless of the type of color ink.

Example 17 An amorphous silicon electrophotographic photosensitive member was loaded in the apparatus shown in FIG. The release property imparted to the surface of the photoconductor and the formation of the transfer layer were carried out at the same time by using the resin particle dispersion liquid [L-3] having the following contents. Resin particle dispersion [L-3] Resin particles (AL-8) 8 g (as solid content) Positive charge control agent (CD-1) 0.015 g Compound (S-2) 0.8 g of the following structure is Isopar G The total volume was adjusted to 1 liter.

[0379]

[Chemical 58]

Using the above-mentioned photoreceptor, the toner image formation and the toner image transfer for each transfer layer to the PS plate (FPD) were carried out in the same manner as in Example 1. Visual observation of the plate-making image on the plate for PS plate showed that the entire transfer layer was completely transferred from the photoconductor, and the toner image was good without any omission. That is, as in the present invention, by incorporating a specific releasability-imparting agent into the electrodeposition dispersion liquid for forming the transfer layer and treating it, the surface of the photoreceptor is wetted by the electrodeposition liquid and at the same time dissolved in the dispersion liquid. The releasability-imparting agent that had been used was selectively adsorbed on the surface of the photoconductor, and was then electrophoresed.
It is presumed that L) is attached or adsorbed.

Next, the obtained plate was further subjected to a flash fixing treatment to more sufficiently fix the toner image portion. This plate was immersed in a desensitizing treatment solution [E-3] having the following formulation at a temperature of 30 ° C for 20 seconds, and while gently rubbing the transfer layer, the transfer layer was removed, thoroughly washed with water, gummed, and offset. I made a printing plate. Desensitizing treatment solution [E-3] PS plate treating agent DP-4 (manufactured by Fuji Photo Film Co., Ltd.) 143 g N, N-dimethylethanolamine 100 g was diluted with distilled water to make the total amount 1 liter. Dried (pH 1
3.1)

The printing plate thus obtained was visually observed using 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. When the photosensitive material provided with the transfer layer of the present invention was used, the image pickup property was good. The transferability of the transfer layer was good, and the transfer layer was completely transferred. Further, when the performance as a printing plate was examined, the desensitizing treatment property was good, the transfer layer was completely removed, and no background stain was observed. In addition, even in a high-definition image portion such as a fine character, a thin line in the image portion, and an intermediate portion of continuous gradation of halftone dots, the lack of the toner image was not recognized, and the image portion resistability was good. It was possible to print more than 60,000 sheets whether actually printed or using various color inks.

Examples 18 to 27 The same as Example 17 except that the resin particles for transfer layer (AL-8) in Example 17 were replaced with the resin particles shown in Table M below (total amount 8 g). In the same manner, printing plate preparation and offset printing were performed. For each printing plate, the obtained printed matter was a clear image with no background stain, and 60,000 or more sheets were obtained, and the performance was equivalent to that of Example 17.

[0384]

[Table 25]

Example 28 100 g of photoconductive zinc oxide, a binder resin (B-
2) A mixture of 20 g, resin (P-6) 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 was put in a homogenizer (manufactured by Nippon Seiki Co., Ltd.), Rotation speed 9 × 10
Dispersed at ³ rpm for 10 minutes. To this dispersion, 0.02 g of phthalic anhydride and 0.001 g of o-chlorophenol were added,
Further, dispersion was carried out at a rotation speed of 1 × 10 ³ rpm for 1 minute.

[0386]

[Chemical 59]

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 so that the coating amount was 25 g / m ^2, and was dried by touch to the touch. Then, it heated at 120 degreeC in the circulation type oven for 1 hour. The adhesive force on the surface of the photoreceptor thus obtained was measured and found to be 4 g · f.

A voltage of 200 V was applied while supplying the resin particle dispersion [L-1] used in Example 1 to form a transfer layer on the photosensitive layer using the resin (P-6). By doing so, the resin particles (AL-1) were electrodeposited and dried at 80 ° C. for 1 minute. The obtained electrophotographic photosensitive member with a transfer layer (2.5 μm) was allowed to stand overnight under the conditions of (25 ° C., 60% RH). With this ELP-404V plate-making machine (manufactured by Fuji Photo Film Co., Ltd.), the bias voltage of the developing section was set to 100V,
In addition, a copied image was formed using ELP-TX (manufactured by Fuji Photo Film Co., Ltd.) as a liquid toner, and then rinsed through an Isopar G rinse bath. The copied image formed on the obtained transfer layer is clear and excellent in high-definition image areas such as continuous gradation areas consisting of characters, fine lines, and halftone dots, and scumming in non-image areas is also recognized. I couldn't do it.

Next, the photoconductor prepared as described above was placed between a pair of heating rollers having an infrared lamp heater incorporated inside a hollow roller coated with silicone rubber.
It was passed over a straight master (manufactured by Mitsubishi Paper Mills Ltd.). The surface temperature of the roller at this time is 90 ℃ both above and below,
Nip pressure between rollers is 3kgf / cm ² , transport speed is 1
It was set to 00 mm / sec. After passing, it was cooled to room temperature while being overlapped with the coated paper, and then the photoconductor and the straight master were separated. At this time, when the state of the transfer layer transferred to the straight master was visually evaluated, it was almost the same as the copied image on the photoreceptor before transfer, and no image deterioration was observed. Also,
No transfer layer remained on the surface of the photoconductor after transfer, and the transferability was extremely good.

On the other hand, as a comparison, in the above photoreceptor,
An electrophotographic photosensitive member was prepared in the same manner except that 3 g of the resin (P-6) was not used, and the surface adhesive force was 400 g.
It was f or more. When a transfer layer was applied and transferred,
No peeling property was shown 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 support was subjected to a desensitizing treatment (that is, the transfer layer was removed), and the printing performance as a printing plate was examined. In the desensitizing solution [E-2] (pH 13.1) prepared by diluting the above printing original plate with 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 plate was immersed in the solution for 1 minute, the transfer layer was removed by gentle rubbing, and the plate was thoroughly washed with water. The printing plate thus obtained was visually observed with a 200 × optical microscope for the non-image area and the toner image area, and no residual transfer layer was observed in the non-image area, and fine lines in the image area were observed. -No missing of high resolution area such as fine letters was observed.

Immersion water SG for PS plate as immersion water for this plate
Ryobi 320 was used as a printing machine by using an aqueous solution (pH 7.0) obtained by diluting -23 (manufactured by Tokyo Ink Co., Ltd.) 130 times with distilled water.
A 0MCD type (manufactured by Ryobi Co., Ltd.) was used, and neutral paper was used as the printing paper, printing was performed with various color inks for offset printing, and the number of prints that gave a clear image with no background stain was examined. As a result, it was possible to obtain a printable number of 1,000 or more in any case, regardless of the type of color ink.

On the other hand, in a known system in which an electrophotographic photoreceptor using zinc oxide is desensitized with a desensitizing solution containing a chelating agent as a main component under acidic conditions to prepare a lithographic printing plate,
When neutral paper is used as the printing paper, the number of printed sheets is several hundred, and the non-image area is smeared. Also, when offset color inks other than black are used, the number of printed sheets is several hundred. Occurrence of scumming occurred to some extent. As described above, it was found that the method for producing an offset printing original plate of the present invention has extremely good printing performance, unlike the conventional method, even though the same zinc oxide photoconductor is used.

Example 29 An amorphous silicon photoconductor was mounted as an electrophotographic photoconductor on the apparatus shown in FIG. The adhesive force on the surface of the photoconductor was 200 g · f. The release property was imparted to the photoconductor by immersing it in a solution in which the compound (S) of the present invention was dissolved in the same device (immersion method). That is, the above-mentioned photoreceptor was rotated in a bath containing a solution prepared by dissolving 1.0 g of the following compound (S-3) in 1 liter of Isopar G for 7 seconds while rotating at a rotational speed of 10 mm / sec. Dried with a squeeze. The pressure-sensitive adhesive strength of the surface of the photoreceptor thus obtained was measured and found to be 3 g · f, indicating good peelability.

[0395]

[Chemical 60]

Next, the surface temperature of the photoconductor is set to 50 ° C., the peripheral speed of the photoconductor drum is rotated at 10 mm / sec, and a positive electrode resin particle dispersion liquid [ L-4] was supplied, the photoreceptor side was grounded and a voltage of 130 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit and fix the resin particles to form a transfer layer having a thickness of 2.0 μm.

Resin Particle Dispersion Liquid [L-4] Resin Particles (AL-7) 10 g (as Solid Content) Positive Charge Regulator (CD-1) 0.02 g Branched Hexadecyl Alcohol FOC-1600 10 g { Nissan Kagaku Co., Ltd.} was adjusted to a total volume of 1.0 liter with Isopar G.

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

After the toner image is fixed by heating, 4 is formed on the surface of the photoreceptor.
The material to be transferred (aluminum support for PS plate FPD) is passed at a speed of 100 mm / sec between a pair of rubber rollers which are in contact with each other at a pressure of kgf / cm ² and whose surface temperature is always controlled to 100 ° C. The support was peeled off from the photoreceptor and the toner image was transferred onto the aluminum support together with the transfer layer.

[0400] The printing original plate thus obtained was
The toner portion was fixed by heating for 1 minute in an oven at ℃.
Upon visual observation using a 200 × optical microscope, no loss of high-resolution areas such as fine lines or fine characters in the image area was observed. That is, the toner image together with the transfer layer was easily transferred to the material to be transferred by the above-mentioned heat transfer process, and even if a further heating operation was performed after the transfer, the toner image portion was not disturbed at all.

This printing original plate was dipped in the desensitizing treatment solution [E-3] used in Example 17, and treated with rubbing at 30 ° C. for 30 seconds to remove the transfer layer, and washed thoroughly with water. After that, gumming was performed to prepare an offset printing plate. As an immersion water for this plate, an aqueous solution (pH 7.) was prepared by dipping PS-23 immersion water SG-23 (Tokyo Ink Co., Ltd.) in distilled water.
0), Oliver 94 type (manufactured by Sakurai Mfg. Co., Ltd.) as a printing machine, neutral paper as printing paper, and printing with various color inks for offset printing. The number of prints to obtain the image was examined. As a result, regardless of the type of color ink, in any case, a printing durability of 60,000 or more was obtained.

As described above, depending on the type of liquid developer [LD] used for toner image formation, sufficient adhesion between the toner image portion and the transfer material is maintained to maintain the toner image strength during printing. In order to do so, the adhesion improving means may be combined after the transfer with the transfer layer. As another means of the fixing mode of the present embodiment, the same effect can be obtained by a flash fixing method or a heat roll fixing method.

Example 30 In Example 29, as means for imparting releasability to the photoreceptor,
A printing plate was prepared in the same manner as in Example 29 except that the following contents were replaced. Carboxyl-modified silicone oil (TSF 4770 Toshiba Silicon Co., Ltd.) compound (S
-4) A metering roll having a silicone rubber layer on its surface, which is in contact with a bath containing oil, is brought into contact with the photoconductor,
Both drums were rotated for 20 seconds at a rotation speed of 15 mm / second. By this treatment, the adhesive force on the surface of the photoconductor became 5 g · f.

[0404]

[Chemical formula 61]

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. Furthermore, in the method using the metering roll / transfer roll, as shown in FIG. 3, the compound (S-4) 23 is provided between the metering roll 22 and the transfer roll 21.
Similarly, good results were obtained by the method of supplying. When printing was performed in the same manner as in Example 29 using the above printing plate, the same favorable results as in Example 29 were obtained.

Example 31 A printing plate was prepared and offset printing was carried out in the same manner as in Example 29 except that the means for imparting releasability to the photoconductor was changed to the following contents. Dimethyl silicone oil (KF-96L-2.0, Shin-Etsu Silicone Co., Ltd.) Compound (S-5) 2g uniformly impregnated with AW treated felt [(15mm thick x 20mm wide wool material)] is pressed onto the photoconductor
Pressed at 200 g and the photosensitive drum was rotated at a peripheral speed of 20 mm / sec for 3
It rotated for 0 seconds. The adhesion of the surface of the photoconductor after processing is 6g.
It became f. The obtained printing result showed the same performance as that of Example 29.

Example 32 In Example 29, as means for imparting releasability to the photoconductor,
A printing plate was prepared in the same manner as in Example 1 except that the following contents were replaced, and offset printing was performed. A rubber roller having a built-in heating means was wrapped with a cloth impregnated with a fluorosurfactant (Surflon S-141 Asahi Glass Co., Ltd.) compound (S-6), and the roller was heated to a surface temperature of 60 ° C. Then, the both drums were brought into contact with each other, and both drums were rotated at a peripheral speed of 20 mm / sec for 30 seconds. The adhesive force on the surface of the photoconductor became 4 g · f. The obtained printing result showed the same performance as that of Example 29.

Example 33 A printing plate was prepared and offset printing was carried out in the same manner as in Example 29 except that the peeling property imparting means for the photoconductor was changed to the following contents. 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 800 g · f / cm ² and rotated at a peripheral speed of 15 mm / sec for 10 seconds. . As a result, the adhesive force on the surface of the photoconductor was lowered to 20 · f. The obtained printing result showed the same performance as that of Example 29.

Examples 34 to 53 Example 1 is the same as 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). An electrophotographic photoreceptor and a printing plate were prepared and printed in the same manner as in. The image quality and printing durability of the printed matter obtained from each printing plate were good as in Example 1.

[0410]

[Table 26]

Examples 54 to 64 Examples 54 to 64 were the same as Example 1 except that each compound of the following Table -O was used instead of the resin (P-2), phthalic anhydride and o-chlorophenol. In the same manner, a printing plate was prepared and printed. The image quality and printing durability of the printed matter obtained from each printing plate were good as in Example 1.

[0412]

[Table 27]

Example 65 As an organic photoconductive substance, 5 g of 4,4'-bis (diethylamino) -2,2'-dimethyltriphenylmethane,
Binder resin (B-3) 4g, resin (P-27) 0.
4 g, dye (D-1) 40 mg in the following structural formula, and anilide compound (B) 0.2 g in the following structural formula as a chemical sensitizer were dissolved in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride to prepare a photosensitive layer dispersion liquid. And

[0414]

[Chemical formula 62]

This photosensitive layer dispersion was applied onto a conductive transparent support (a polyethylene terephthalate support having a thickness of 100 μm and a vapor-deposited film of indium oxide having a surface resistance of 10 ³ Ω) using a wire round rod. Then about 4μ
An organic thin film having a photosensitive layer was obtained at m. The adhesive force on the surface of the photoconductor was 8 g · f. A printing plate was formed and printed 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 was also good.

Example 66 Example 16 is the same as Example 16 except that as the electrophotographic photosensitive member, a photosensitive member having a peelable surface layer having a film thickness of 1.5 μm provided on an amorphous silicon photosensitive member as described below is used. A printing plate was prepared in the same manner as in. Printing was carried out in the same manner as in Example 16 using the obtained printing plate.
The same good performance as was obtained.

Formation of releasable surface layer A coating film containing 10 g of a silicone resin having the following structure, 1 g of a crosslinking agent having the following structure, and 0.1 g of platinum as a crosslinking catalyst in 100 g of n-hexane was formed using a wire round rod. Thickness
The coating was applied so as to have a thickness of 1.5 μm, dried by touch with a finger, and heated at 120 ° C. for 10 minutes. The adhesive strength of the obtained surface was 1 g · f or less.

[0418]

[Chemical formula 63]

Example 67 5 g of bisazo pigment having the following structure and 95 g of tetrahydrofuran
And polyester resin Byron 200 (Toyobo Co., Ltd.)
5 g) was thoroughly ground in a ball mill. Next, this mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was applied onto the conductive transparent support used in Example 65 using a wire round rod to form a charge generation layer having a thickness of about 0.7 μm.

[0420]

[Chemical 64]

Next, a hydrazone compound of the following structural formula 20
g, polycarbonate resin (GE company, trade name Lexan
121) A mixed solution of 20 g and tetrahydrofuran 160 g is applied on the charge generation layer using a wire round rod, dried at 60 ° C. for 30 seconds and further heated at a temperature of 100 ° C. 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.

[0422]

[Chemical 65]

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

[0424]

[Chemical formula 66]

The surface potential of this light-sensitive material was +500 V in the dark.
And then charged with a He-Ne laser to expose the plate surface to an exposure amount of 30 erg / cm ² with a light of 633 nm, and the same operation as in Example 1 is repeated to prepare a printing plate. Then, offset printing was performed. The obtained results showed good performance equivalent to that of Example 1.

Example 68 A printing plate was prepared in the same manner as in Example 16 except that a straight master (manufactured by Mitsubishi Paper Mills, Ltd.) was used instead of the OK master PS type used as the material to be transferred. It was created. When the image (fog, image quality of the image) formed on the straight master was visually evaluated, it was completely transferred and a clear image free of background fog was obtained. When offset printing was performed using this plate, 1500 sheets of a clear image printed without background stain were obtained.

Examples 69 to 80 Offset printing plates were prepared by using the plate (printing original plate) after transfer to the materials to be transferred prepared in Examples 1 to 68 and performing the desensitizing treatment as follows. . Nucleophilic compounds of Table-P below
Distilled water was added to 0.2 mol, 100 g of an organic solvent and 2 g of Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) to make 1 liter, and then the pH was adjusted to 12.5 to prepare a treatment liquid. Each printing original plate was immersed in the treatment liquid at a temperature of 35 ° C. for 1 minute, and subjected to a desensitizing treatment while gently rubbing. Using the obtained printing plate, printing was performed under the same printing conditions as in the original example. Good results equivalent to those of the original example were obtained.

[0428]

[Table 28]

Examples 81 to 86 In exactly the same manner as in Example 29, except that each compound (S) shown in Table Q below was used instead of 1.0 g / l of the compound (S-3) in Example 29. I got a printed matter. The results obtained showed exactly the same performance as in Example 29. That is, by using these compounds (S), the releasability of the surface of the photoconductor was effectively exhibited.

[0430]

[Table 29]

[0431]

[Table 30]

[0432]

According to the method for producing an electrophotographic plate-making printing plate using the transfer layer of the present invention, the transferability of the transfer layer is extremely good, the plate-making image quality and the print image quality are good, and the image is continuously transferred for a long period of time. It is possible to obtain a printing plate with stable performance even if the treatment is carried out. It is also suitable for image formation by scanning exposure with a laser or the like.

[Brief description of drawings]

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

FIG. 2 is a view showing an example of an electrophotographic plate-making printing plate making apparatus for carrying out the method of the present invention.

FIG. 3 is a diagram showing an example of a compound (S) supply device that can be used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Support for photoconductor 2 Photosensitive layer 3 Toner image 11 Photoconductor 12 Transfer layer 12a Dispersion liquid of thermoplastic resin particles 13 Electrodeposition unit 14 Liquid developing unit set 14L Liquid developing unit 15 Intake / exhaust unit 15a Intake part 15b Exhaust part 16 Transferred material 17 Thermal transfer means 17a Preheating means 17b Heating roller 17c Cooling roller 18 Corona charging device 19 Exposure device 20 Compound (S) supply device 21 Transfer roll 22 Metering roll 23 Compound (S)

Claims (5)

[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, Formation of the transfer layer,
Glass transition point 10 to 140 ° C or softening point 35 ° C to 180
At least one kind of resin (A ₁ ) having a glass transition point of 45 ° C.
A resin having a softening point of 60 ° C. or less,
₁ ), which has a glass transition point or softening point lower than 2 ° C (A)
_A method for producing an electrophotographic plate-making printing plate, which comprises performing the electrodeposition coating method using thermoplastic resin particles (AL) containing at least one kind of ₂ ) in the same particle. 2. The resin (A ₁ ) and the resin (A ₂ ) contain at least one of the following polymer component (a) and polymer component (b), respectively. Item 1. A method for producing an electrophotographic plate-making printing plate according to Item 1. Polymer component (a): - CO ₂ H group, -CHO group, -SO ₃
H group, -SO ₂ H group, -P (= O) (OH ) R 1 {R 1 is -
OH group, hydrocarbon group or -OR ² (R ² represents a hydrocarbon group) group} group, phenolic OH group, acid cyclic anhydride-containing group, -CONHCOR ³ (R ³ represents a hydrocarbon group ) polymer component polymer component containing at least one group of the groups and -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 {R ¹ is -OH group, hydrocarbon group or -OR ² (R ²
Represents a hydrocarbon group) and a polymer component containing at least one functional group that forms at least one group of an -OH group. 3. The resin particles (AL) have a relative dielectric constant of 3.5.
The method for producing an electrophotographic plate-making printing plate according to claim 1 or 2, which is supplied by being dispersed in the following electrically insulating liquid. 4. The electrophotographic photosensitive member is provided with the resin particles (AL) which are supplied between a counter electrode provided so as to face the electrophotographic photosensitive member and which is electrophoresed according to a potential gradient applied from an external power source. The method for producing an electrophotographic plate-making printing plate according to claim 3, wherein the film is formed by being attached or electrodeposited. 5. When the transfer layer is formed on the surface of the electrophotographic photoconductor by electrodeposition of at least resin particles (AL), adhesion according to JIS Z0237-1980 “Adhesive tape / adhesive sheet test method” The force is 100gram force (gf)
It has the following surface peelability, It is characterized by the above-mentioned.
4. The method for producing an electrophotographic plate-making printing plate as described in 4 above.