JPH04188146A - Original form for electrophotographic lithography - Google Patents

Abstract

PURPOSE:To prevent generation of greasing and provide an original form for printing excellent in plate wear by containing resin particles which includes a polymer component having a specified functional group in the surface layer of an opto-conductive layer. CONSTITUTION:In the uppermost surface layer of an opto-conductive layer, resin particles including at least one kind of polymer components having a functional group as expressed by the formula I or the formula II is included. In the formulae,-W1-, W2-: represent-SO2-,-CO-and the like, n1, n2: 0, 1, X: halogen atom. The resin particles in the surface layer reacts with hydrophilic compound including nucleophilic substituent in a processing liquid only when non-image part is etching-processed to show a hydrophilic property. It is thus possible to provide an original form for printing by which no greasing generates with its excellent hydrophilic property of non-image part, and which is excellent in plate wear.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a lithographic printing original plate made by an electrophotographic method, and in particular, a surface layer having specific properties is provided on a photoconductive layer. The present invention relates to an improvement in a composition for forming a surface layer of a lithographic printing original plate.

[Conventional technology]

Currently, various types of offset original plates for direct plate making have been proposed and put into practical use.

In recent years, Japanese Patent Publication No. Sho 45-5606 discloses a method for preparing a printing plate with hydrophilic treatment on the surface of the non-image area, which is easy to make by providing a specific resin layer on an ordinary electrophotographic photoreceptor. That is, a printing plate is disclosed in which a surface layer comprising a vinyl ether-maleic anhydride copolymer and a hydrophobic resin compatible therewith is provided on an electrophotographic photosensitive layer. This layer is a layer that can be made hydrophilic (hydrophilicizable layer) by treating the non-image area with an alkali to open the acid anhydride ring portion with water after the toner image is formed.

The vinyl ether-maleic anhydride copolymer used there becomes water-soluble when the ring is opened and made hydrophilic, so even if it is compatible with other hydrophobic resins, a layer may not be formed. Even if it were, its water resistance was extremely poor, and its printing life was limited to 500 to 600 sheets at most.

Furthermore, JP-A-60-90343 and JP-A-60-159756
, No. 61-217292, etc., disclose a method of providing a surface layer (hydrophilicizable layer) containing silylated polyvinyl alcohol as a main component and also using a crosslinking agent. That is, in this layer, silylated polyvinyl alcohol is hydrolyzed in a non-image area after toner image formation to make it hydrophilic. Furthermore, in order to maintain the film strength after hydrophilization, the degree of silylation of polyvinyl alcohol is adjusted, and the remaining hydroxyl groups are crosslinked using a crosslinking agent. It is also stated that these improve the scumming resistance of printed matter and increase the number of printed sheets.

However, when evaluated in reality, it is still unsatisfactory, especially in terms of background stains.

Furthermore, silylated polyvinyl alcohol is produced by silylating polyvinyl alcohol to a desired ratio with a silylating agent, but since it is a polymer reaction, it is difficult to produce it stably. Furthermore, since the chemical structure of the hydrophilized polymer is limited, it is important to ensure that l) chargeability, 2) quality of copied images (
halftone reproducibility/resolution in image areas, ground blur in non-image areas, etc.)
, 3) It is difficult to prevent the surface layer from affecting photosensitivity, etc.

In order to improve the problems of electrophotographic lithographic printing original plates as described above, the present inventors first developed a resin containing a functional group that generates carboxyl groups upon decomposition as the main component of the surface layer. proposed an original plate for electrophotographic planographic printing using (Japanese Patent Application No. 1983-28345).

Furthermore, we investigated the combination of a resin containing a functional group that generates a hydrophilic group upon decomposition and a compound that crosslinks the resin in the photosensitive layer as the surface layer resin. those containing groups (JP-A-1-254970 and JP-A-1-262556), those containing functional groups that generate carboxyl groups upon decomposition (JP-A-1-283572 and JP-A-1-284860), They have proposed products containing functional groups that generate thiol groups, amino groups, phosphono groups, sulfo groups, etc. upon decomposition (JP-A-1-304465 and JP-A-1-306855).

Furthermore, it is being considered that the surface layer contains a functional group that generates a hydrophilic group by decomposition, and uses a small amount of fine particles that form a higher-order network structure. Those containing a functional group that generates a carboxyl group (JP-A-2-13965), and those that contain a functional group that generates a hydroxyl group by decomposition (JP-A-2-13965).
13966), those containing functional groups that generate sulfo groups, phosphono groups, etc. upon decomposition (JP-A-2-139)
No. 67), etc. are disclosed.

These binder resins or resin particles are subjected to hydrolysis, hydrogenolysis, photolysis, etc. by a desensitizing liquid or soaking water used during printing to generate hydrophilic groups. When these are used as the surface layer resin of a lithographic printing original plate, in any case, it is possible to avoid deterioration of electrophotographic properties (dark charge retention amount and photosensitivity), etc. that occur when hydrophilic groups themselves are included from the beginning. The hydrophilicity of the non-image area, which is rendered hydrophilic by the desensitizing liquid, is enhanced by the hydrophilic groups generated by decomposition in the binder resin in the surface layer or in the resin particles, thereby increasing the hydrophilicity of the image area. The oiliness and hydrophilicity of the non-image area become clear, and the printing ink is applied to the non-image area during printing (;
In addition, by forming a crosslinked structure in the surface layer, the hydrophilic resin becomes water-insoluble, and furthermore, due to the crosslinking effect, it contains water and the hydrophilic crosslinked resin becomes water-insoluble. It swells and develops water-retaining properties, ensuring that the surface layer retains its hydrophilic properties. As a result, it becomes possible to print a large number of prints with clear image quality and no blurring.

[Problem to be solved by the invention]

For binder resins or resin particles that generate hydrophilic groups such as carboxyl groups, hydroxyl groups, sulfo groups, and phosphono groups through the above decomposition reaction, the above-mentioned hydrophilic groups that have been masked with protective groups in advance are decomposed by the treatment liquid. The protecting group is removed by reaction. Therefore, this type of binder resin or resin particles exists stably without being hydrolyzed by the influence of atmospheric humidity (moisture) during storage, and also undergoes a rapid deprotection reaction during hydrophilic treatment. An important property required is that the hydrophilicity of the non-image area can be improved by progressing to generate hydrophilic groups.

However, if we use a hydrophilic group-forming functional group (protecting group) that does not decompose and exists stably even under harsh conditions such as long-term storage in a high-temperature and humid environment, it can be quickly decomposed by the processing solution and quickly develop hydrophilicity. It was found that difficulties arise.

Furthermore, in the scanning exposure method using semiconductor laser light, the zero exposure time is longer than in the conventional simultaneous exposure method of the entire surface using visible light, and there are also restrictions on the exposure intensity, so it is difficult to use a static photoreceptor as an electrophotographic photoreceptor. Higher performance is required in terms of electrical properties, especially dark charge retention and photosensitivity.

In view of the current situation, the present invention further improves the effect of hydrophilicity in non-image areas, is stable even when stored under extremely harsh conditions, and can be easily made hydrophilic in a short period of time during hydrophilic treatment. The object of the present invention was to provide an original plate for electrophotographic lithographic printing that can exhibit the following characteristics and maintain high electrostatic properties even in a scanning exposure method.

In other words, the object of the present invention is to have excellent electrostatic properties (particularly dark charge retention and photosensitivity), reproduce a copy image that is faithful to the original, and, as an offset original, not only be free from surface-like stains. It is an object of the present invention to provide a lithographic printing original plate which does not cause even dotted background stains and has excellent desensitization properties.

A second object of the present invention is to provide a lithographic printing original plate that has a clear and high-quality image even when the environment during copy image formation fluctuates, such as low temperature and low humidity or high temperature and high humidity.

The third objective of the present invention is to provide a lithographic printing original plate that retains sufficient hydrophilicity in non-image areas even when the printing process from etching is accelerated, does not cause scumming, and has high printing durability. It is to provide.

[Means to solve the problem]

The present invention achieves the above object by disposing at least one layer on a conductive support.
In an electrophotographic lithographic original plate comprising a photoconductive layer and a surface layer on the top layer, the surface layer is represented by the following general formula (1) and/or general formula (II). This is achieved by an electrophotographic lithographic printing original plate characterized by containing resin particles containing at least one polymer component having a functional group.

General formula (1) %Formula% General formula (II) Wx-+-CHz-t. -CHzCJ X [However, in the above formula (1) or (II), -W, -, -W, -
each represents -5O2-, -CO- or -0OC-, and n
l + n 2 each represents 0 or l, and X represents a halogen atom] In the present invention, the resin particles are represented by the general formula (I) and/or the general formula (II), and are hydrophilized. The polymer component having a functional group may have a crosslinked structure, and in this case, when it reacts with the hydrophilic treatment liquid and develops hydrophilicity, the resin particles have water resistance and water retention. It is preferable because it has the following.゛In addition, in the present invention, the photoconductive layer has at least a photoconductor and a binder resin, and the binder resin has a coulometric average molecular weight of 1 x 103 to 2 x 10'', and has the following general formula: 30% by weight or more of the repeating unit represented by (III) as a polymer component, -P03Hz, -5O3H, -COOHl-P-R+
[R, represents a hydrocarbon group or -0R2 (R2 represents a hydrocarbon group)] and a cyclic acid anhydride-containing group, a polymer component having at least one kind of polar group 0.5 to 15 weight%
It is particularly preferable to contain at least a resin [A] containing the following.

General formula (n[) CH.

1+CH, -C←oo-Rz [However, in the above formula (II), R3 represents a hydrocarbon group containing a benzene ring or a naphthalene ring.] [Operation] The present invention provides an electrophotographic method having a photoconductive layer. The surface layer which is the uppermost layer of the lithographic printing original plate has the formula (I) and/or the formula (
It is characterized by containing resin particles made of a resin (hereinafter referred to as resin [L]) containing at least one specific functional group shown in II), and the resin particles have nucleophilic reactive substitution. When treated with a treatment liquid containing at least one hydrophilic compound containing groups, the resin particles have the above formula (
A hydrophilic compound containing the nucleophilic substituent is attached to the terminal of the functional group of formula (1) generated by dehydrohalogenation from the functional group of I) or the functional group of formula (n) above. It is capable of addition reaction, and as a result, the resin particles can develop hydrophilicity, so that the surface layer is made hydrophilic, and at the same time, if the resin particles have a crosslinked structure, they have hydrophilicity while at the same time. It is insoluble or sparingly soluble in water and has water-swelling properties.

Furthermore, in the present invention, if the resin particles are crosslinked,
It does not elute with soaking water during printing (and can maintain good printing characteristics even when printing a large number of sheets).

On the other hand, when the binder resin of the photoconductive layer contains resin [A], the resin CA) contains a specific copolymer component and a polar group, and the polar group (hereinafter, not specified herein) (as long as the cyclic acid anhydride-containing group is included) and the photoconductor are properly interacted with, compensating for the trapping of the photoconductor in the photoconductive layer and dramatically improving the humidity properties, while the resin It is believed that the dispersion of the particles is sufficiently uniform to suppress agglomeration and unwanted interactions between the resin particles and the photoconductor.

As a result, the electrophotographic lithographic printing original plate of the present invention can reproduce a copy image that is faithful to the original image even when environmental conditions fluctuate or low-power laser light is used, and the non-image areas can be reproduced. Since it has good hydrophilicity, it does not cause scumming, has a good surface layer smoothness, and has the advantage of excellent printing durability.

Furthermore, the lithographic printing original plate of the present invention is not affected by the environment during plate-making processing, has excellent preservability before processing, and has the characteristics that hydrophilization processing can be carried out quickly.

The mechanism by which the resin particles according to the present invention are made hydrophilic by a hydrophilic compound containing a nucleophilic substituent is shown in the following reaction formula (1) using sulfite ion as a representative example of the nucleophilic hydrophilic compound. . P represents a resin moiety other than the functional group of formula (I) or (II).

OHC) P -W+ CH=CH2CI P"-ga+ CH=CH2HCl General formula (If) General formula (1) That is, the resin particles in the surface layer of the present invention react as described above with the hydrophilic compound containing a nucleophilic substituent in the processing solution only when etching the non-image area as a lithographic printing original plate. By adding a hydrophilic group to the end of the product, it becomes hydrophilic, in other words, it becomes hydrophilic, and since it does not react with moisture in the atmosphere, there are no concerns regarding storage stability. .

Furthermore, since the vinyl sulfone group, vinyl carbonyl group, and acryloxy group represented by the general formula (I) according to the present invention are functional groups that react very quickly with a hydrophilic compound containing a nucleophilic reactive substituent, , it is possible to quickly develop hydrophilic properties.

Furthermore, the functional group represented by the general formula <II) is represented by the reaction formula (1)
As shown in , the dehydrohalogenation reaction easily proceeds by alkali treatment, and it can be converted to the corresponding functional group of general formula (I), and therefore it can be used in the same way as that of formula (I). It is something that can be done.

Further, in the present invention, the above formula (1) and/or the formula (I
If the functional group-containing polymer component f) is a particle having a crosslinked structure, that is, a resin particle forming a higher-order network structure (hereinafter referred to as a network resin particle), the dissolution property in water is further improved. On the other hand, water swelling property is developed, and water retention property becomes even better.

It is important that the resin particles (including network resin particles) exist in the surface layer separately from the binder resin that is the matrix and are dispersed as particles. As a result, the printing original plate of the present invention forms an image area and a non-image area that are faithful to the original image, and provides a high-quality printed image without background stains.

Furthermore, since the resin particles are fixed by the binder resin, they do not peel off during various processing steps, and the binder resin also provides a protective effect. Therefore, it has excellent printing durability, is unaffected by the environment during plate-making processing, and has excellent storage stability before processing.

As described above, the printing original plate for plate making according to the present invention reproduces a copy image that is faithful to the original image, has good hydrophilicity in the non-image area, does not cause scumming, and has a smooth surface layer and electrostatic properties. It has the advantage that it has good properties and printing durability, and is not affected by the environment during plate-making processing and has excellent storage stability before processing.

The resin particles will be further explained below.

The wood-philicity of the resin particles is determined by the contact angle (measured with a goniometer) with distilled water of a film of the resin formed by coating the resin particles dissolved in an arbitrary soluble solvent.
It is hydrophilic and exhibits a value of 50 degrees or less, preferably 30 degrees or less.

Further, in the case of network resin particles, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight or less.

The resin particles (including network resin particles) of the present invention have a maximum particle size of 5 μm or less, preferably 2 μm or less. The average particle diameter of the particles is 0.8 m or less, preferably 0.5 μm or less. If it is larger than 5 μm, the smoothness of the surface layer decreases, causing a decrease in film strength or toner image strength. On the other hand 0
．． If the particle size is smaller than 0.05 μm, it will resemble the case of molecular dispersion, and the effect of being a particle for improving water retention will be diminished.

In the present invention, the resin particles (including network resin particles) are
If the amount is too small, the hydrophilicity of the non-image area will not be sufficient and the effect will be lost.If the amount is too large, the hydrophilicity of the non-image area will be further improved, but the film strength of the surface layer will decrease, so the surface For 100 parts by weight of the matrix resin of the layer, 3
It is preferred to use it in an amount of 0 to 200% by weight, preferably 80 to 150% by weight.

The resin particles used in the present invention will be explained in more detail below.

To explain the resin [L] forming the resin particles, the resin [L] contains at least a functional group represented by the general formula (1) and/or (I[) in its molecular structure. be.

General formula (I) -W+-←CHx-, -CH=CHx General formula (II
) m-2-←CH2-), -CH2CHr-X formula (I),
(II), -1+ + w, - are each 5O2-,
-CO- or -000-, n, , n2 each represent 0 or 1, and X represents a halogen atom.

In the above general formula (I) or (I[), n is more preferably 0. Moreover, the halogen atom of X specifically represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Furthermore, the functional group of the general formula (n) can be easily converted into the corresponding functional group of the formula (1) by dehydrogenation using an alkali treatment, as shown in the reaction formula (1). It can be used in the same way as in I).

As a more specific example of the copolymer component containing the functional group represented by formula (I) and/or (II) of the resin [L],
Examples include those represented by the following formula (IV).

General formula (IV) Bullet Z-Y-1・ In formula (IV), Z is -coo-, -oco-, -o-.

represents a hydrocarbon group), -CONl(COO-, -(
1:0NHCON)I-.

Represents CH2COO, CH20CO, or -(=)'.

Y represents an organic residue that directly bonds or connects -2- and -1. Furthermore, ÷Z-Y+ may directly connect ←C→part and 110.

10 represents a functional group represented by general formula (1) or general formula (II).

al and al may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group, or an aryl group.

General formula (IV) will be explained in more detail.

Preferably Z represents -000-1-0CO-1-0-1.

However, rl is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2
-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, 3-bromopropyl group, etc.), optionally substituted aralkyl groups having 7 to 9 carbon atoms (e.g. benzyl groups, phenethyl groups, 3-phenylpropyl groups, chlorobenzyl groups, bromobenzyl groups, methylbenzyl groups, methoxybenzyl groups, chloro-methylbenzyl groups, dibromobenzyl groups, etc.), optionally substituted aryl groups (e.g. phenyl groups) ,
tolyl group, xylyl group, mesityl group, methoxyphenyl group, chlorophenyl group, bromophenyl group, chloro-methyl-phenyl group, etc.).

Y represents a direct bond or an organic residue connecting -2- and -10.

When Y represents a connecting organic residue, this linking group represents a carbon-carbon bond that may be via a heteroatom; examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom), -( -CH=CH)-, -0-, -3-, -N-, -C
oo-.

-CONH, Sow -, 5O2NH-2NHCOO-
It is composed of bonding units such as 1-NHCONH-, -3i-, etc., singly or in combination (however, r2+ rl.

r'r rs and r@ each represent the same content as rl above).

alo82 may be the same or different, and may be a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group,
Hydrocarbon groups (e.g. methyl, ethyl, propyl,
Butyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group,
an optionally substituted alkyl group having 1 to 12 carbon atoms such as hexyloxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, aralkyl group such as benzyl group, phenethyl group,
represents an aryl group such as a phenyl group, tolyl group, xylyl group, chlorophenyl group, etc.).

Furthermore, 1-Z-Y+ bond ■ in formula (IV) The residue may connect the ←C→ moiety and -W.

Specific examples of polymer components containing functional groups represented by general formula (I) and/or formula (n) of the present invention are shown below. However, the scope of the present invention is not limited to these.

In examples (a-1) to (a-25), a is -H or =
CH, represents R& haCO2CHt, -CHl =
CHz also represents i1 CHzCHJ, and X is -FI
C1+ Br, represents l.

■ (a-1) +CH2-C→- COOCH2CHaSO2-Ra (m: an integer of 1 to 4) General formula (I
) and/or (II) functional groups, when the resin [L) is a copolymer, the content of the polymer component is 30 to 99% by weight, especially 50 to 95% by weight of the total copolymer. % is preferable. Further, the molecular weight of the polymer of the resin CL) is preferably 101 to 10@1, particularly 5×10s to 5×101.

General formula (I) and/or (II) of the present invention as described above
A resin containing a polymer component having a functional group represented by can be synthesized by a conventionally known synthesis method.

That is, a monomer containing a functional group represented by general formula (I) and/or (n) and a polymerizable functional group in the molecule (for example, a monomer corresponding to a repeating unit of general formula (IV)) ) and general formula (1) and/or (II
) and a polymer compound containing a polymer component containing a functional group that chemically reacts with the low-molecular compound (i.e., polymer reaction). It is possible to do this.

Furthermore, after synthesizing a resin having a functional group represented by general formula (II), a dehydrohalogenation reaction is performed by an alkali treatment to synthesize a resin containing a functional group represented by general formula (1). be able to.

As the polymerizable functional group in the monomer synthesis described above, a normal polymerizable double bond group, specifically, CH2=CH-C
Ht-0-C-, CHz=CH-NHCO-.

CH2=CH-CHa-NHCO-, CH2=CH-3
(h-.

CHz=CH-CO-, CHz=CHO-, CH2=C
Examples include H-3-.

The sulfonylation, carbonylation, or carboxylic acid esterification reactions in the monomer synthesis or polymer reaction-based synthesis described above are described in, for example, the Chemical Society of Japan, New Experimental Chemistry Course, Volume 14 [Synthesis and Reactions of Organic Compounds]. ” p. 751, 1
000 pages.

1759 pages (1978) Published by Maruzen ■, S, Patai
.

Z, Rappoport and C, Stirlin
g, ”The Chemistry of 5ulfo
nes and 5 ulfoxides” p. 165 (1988), John Willey & 5
This can be carried out according to the method described in the review published by Ons, et al.

When the resin [L] is a copolymer, examples of other monomers that can be copolymerized with the monomer having a functional group of formula (I) and/or (II) include, for example, α-olefins, Vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls [e.g. vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidacyline, vinylpyrazole, vinyldioxane, vinylfuran, vinylquinoline, vinylthiazole, vinyloxazine, etc.).

In the present invention, at least a portion of the resin particles may be crosslinked.

In a resin in which at least a portion of the polymer has been crosslinked in advance (a polymer having a crosslinked structure in the polymer), the functional group of the formula (I) or (II) contained in the resin is made hydrophilic by treatment. Preferably, the resin is sparingly soluble or insoluble in acidic and alkaline aqueous solutions when the group is formed.

Specifically, the solubility in distilled water at a temperature of 20 to 25°C is preferably 90% by weight or less, more preferably 70% by weight or less.

As a method for introducing a crosslinked structure into a polymer, commonly known methods can be used.

That is, in the polymerization reaction of monomers containing functional groups of the above formulas (I) and/or (If), polyfunctional monomers (monomers containing two or more polymerizable functional groups) or polyfunctional monomers A method of crosslinking between molecules by polymerizing in the coexistence of a functional oligomer; Alternatively, there is a method of crosslinking with a curing agent, or ■
The crosslinkable functional group-containing polymer has the above formula (I) and/or (I
This method includes a method of reacting a polymer with a compound containing a functional group in I).

More specifically, in the method (2) using a polymer reaction, a polyfunctional monomer or a polyfunctional oligomer of the general formula (I) is used.
or a polar group (e.g. -O
R, -Cl, -Br, -Eng.

-N=C=O, -COCI, -5Ch01, etc.)) to form a copolymer, and then - a compound containing a functional group of general formula (I) and/or (II) is introduced through a polymer reaction.

The polyfunctional monomer or oligomer used in the method (2) above may be one having two or more of the same or different polymerizable functional groups. Specifically, for example, as monomers having the same polymerizable functional group, styrene derivatives such as divinylbenzene and trivinylbenzene; polyhydric alcohols (e.g. ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol #200.# 400° #600.1.3-Butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhydroxyphenol (e.g. hydroquinone, resorcinol, catechol, etc.) derivatives) of methacrylic acid, acrylic acid or crotonic esters, vinyl ethers or allyl ethers dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid) vinyl esters, allyl esters, vinylamides or allylamides of polyamines (e.g. ethylenediamine, 1,3-propylene diamine, 1,4-butylene diamine, etc.) and carboxylic acids containing vinyl groups (
Examples include condensates with methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

In addition, polyfunctional monomers or oligomers having different polymerizable functional groups include, for example, vinyl group-containing carboxylic acids [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid,
Reactants of acryloylpropionic acid, itaconilloylacetic acid, itaconiroylpropionic acid, carboxylic acid anhydride, etc. and alcohols or amines (e.g. allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropion) ester derivatives or amide derivatives containing vinyl groups such as vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate,
allyl methacryloylpropionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonyl acrylate ester, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide, allylmethacryloylpropionate, etc.) or amino Alcohols (e.g. aminoethanol, 1-aminopropanol, 1-aminobutanol, ]-aminohexanol, 2
-aminobutanol, etc.) and a carboxylic acid containing a vinyl group.

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is used in an amount of 10% by weight or less, preferably 5% by weight or less of the total monomers, and is polymerized to form a resin.

However, in the case of an electropolymer containing a functional group represented by formula (1), among the above-mentioned polymerizable functional groups, Hz CH2=CH-Coo -, CHz=C-Coo -,
CH2=CH-CONH-.

It is preferable not to use CH2=CH-3Ot- and CH2=CH-Co-.

In the present invention, as the functional group that proceeds with the crosslinking reaction in the method (1) or (2) above, the usual polymerizable double bond groups, such as those described above as polymerizable double bond groups, can be used. In the case of forming a chemical bond and bridging the polymers by the reaction of the reactive groups between the polymers in method (2), it can be carried out in the same manner as the reaction of ordinary organic low-molecular compounds. Specifically, it is described in detail in the bottom notes of Giyu Iwakura, Keisuke Kurita, "Reactive Polymers" Kodansha (published in 1977), Ryohei Oda, "Polymer Fine Chemicals" Kodansha (published in 1976), etc.

For example, a commonly known method is a polymer reaction using a combination of group A (functional group having a dissociable hydrogen atom) and group B functional group shown in Table 1 below.

In addition, R and R' in Table 1 are hydrocarbon groups, and the formula (I
V) r5. Represents the same content as r@.

Table-l Also, -CONHCH20R5(R
5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, hexyl group), and this reactive group is a group that condenses in a self-condensation type reaction. This is known and can also be used.

Furthermore, for example, Endo l@r Refinement of Thermosetting Polymers J
, C, M, C@ (published in 1986), Yuji Harasaki [Latest Binder Technology Handbook] Chapter n-1.

General Technology Center (published in 1985), Otsu Attendance [Synthesis, Design and Development of New Applications of Acrylic Resins J Chubu Business Development Center Publishing Department (published in 1985), Eizo Omori "Functional Acrylic Resin J Techno System (published in 1985), Hideo Inui, Gentabe Nagamatsu, Photosensitive Polymer J Kodansha (1977), Takahiro Tsunoda [New Photosensitive Resin J Printing Society Publishing Department (1981), G, E, reen and B, P,
5tar, R.

J+Macro, Sci, Revs, Macro
, Chem, C21(2), 187-273
Page (1981-82), C, G, Roffey r.
Photopolymerization or 5u
r-face Cortings”, A, Wile
y Interscience Pub.

(published in 1982) and the like can be used.

These crosslinkable functional groups have general formula (I) and/or (I
It may be contained in one copolymer component together with the functional group represented by formula (I) or in a separate copolymer component from the copolymer component containing the functional group of formula (I) and/or (II). It has already been explained that it may be contained in the combined component.

Specific monomers corresponding to the copolymers containing these crosslinkable functional groups include, for example, those represented by the general formula (IV
) may be any vinyl compound containing the functional group that can be copolymerized with the polymer component.

Such vinyl compounds are described, for example, in Polymer Data [Polymer Data Handbook [Basic Edition J], Baifukan (198
6th edition) etc.

Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, a-acetoxymethyl form, α-(2-aminomethyl) form, α-chloro form, α-bromo form, α -fluoro form, α-tributylsilyl form, α-
Cyano form, β-chloro form, β-bromo form, α-chloro-
β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 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, dicarboxylic acid salts. Compounds containing the crosslinkable functional group in a substituent such as half ester derivatives, ester derivatives of these carboxylic acids or sulfonic acids, and amide derivatives are included.

If necessary, a reaction accelerator may be added to the resin [L] of the present invention in order to promote the crosslinking reaction. Examples include acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), peroxides, azobis compounds, crosslinking agents, sensitizers, photopolymerizable monomers, and the like.

As the crosslinking agent, compounds commonly used as crosslinking agents can be used. Specifically, Shinzo Yamashita and Tosuke Kaneko (eds.) [Crosslinking Agent Handbook J Published by Taiseisha (1981),
Compounds described in Polymer Science Golden Wire, "Polymer Data Handbook Basic Edition", Baifukan (1986), etc. can be used.

For example, organic silane compounds (e.g., silane coupling agents such as vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidquinpropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc.) ), polyisocyanate compounds (e.g. toluylene diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisonanate, polymer polyisocyanate, etc.), Polyol compounds (e.g. 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1.1-1-limethylolpropane, etc.), polyamine compounds (e.g. ethylenediamine, γ-hydroxypropylated ethylenediamine) , phenylene diamine, hexamethylene diamine, N-aminoethyl piperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds and epoxy resins (for example, "New Epoxy Resins" edited by Hiroshi Kakiuchi, Shokodo (published in 1985), Hashimoto Compounds described in "Epoxy Resin" edited by Kuniyuki, Nikkan Kogyo Shimbun (published in 1969), melamine resins (for example, Miwa-be,
Compounds described in Hideo Matsunaga (ed.) [Uria Melamine Resin] Nikkan Kogyo Shimbun (published in 1969), etc.), poly(meth)acrylate compounds (for example, Nobu Okawara, Takeo Saegusa, Toshinobu Higashimura (ed.) "Oligomer" Kodansha) (Published in 1976)
, Eizo Omori [Functional Acrylic Resin] Technosystem (
(published in 1985), and specifically, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate, Examples include bisphenol A-diglycidyl ether diacrylate, oligoester acrylate, and methacrylates thereof.

The resin [L] synthesized as described above and containing at least one functional group that generates at least one hydrophilic group when treated with a treatment liquid containing a compound having a nucleophilic substituent is the present invention. In the invention, the maximum particle size is 5 μm or less,
It exhibits a particle state with an average particle size of 1.0 μm or less.

The resin particles of the present invention having such a micro particle size can be made into a desired particle size by allowing the resin powder to coexist as is and dispersing it when preparing the surface layer forming composition. Alternatively, conventionally known dry and wet atomization methods,
Alternatively, a method of using polymer gel latex can be used.

That is, a method of directly pulverizing resin powder into fine particles using a conventionally known pulverizer or dispersing machine (for example, a ball mill, paint shaker, sound mill, hammer mill, jet mill,
(Kedimir, etc.) and a conventionally known method for producing latex particles of a paint or an electrostatic photographic liquid developer can be used. The latter method of producing polymer latex involves dispersing resin powder in combination with a dispersion polymer.The resin powder and dispersion-assisting polymer are kneaded in advance to form a mixed material, which is then crushed and then There are mechanical methods such as a method of dispersing in the coexistence of a dispersed polymer.

Specifically, for example, Kenji Ueki supervised translation [Paint Flow and Pigment Dispersion J Kyoritsu Shuppan (1971), [Solomon, Paint Chemistry J, rPaint and Surface Co.
'ating theory and practice'
, Yuji Harasaki "Coating Engineering" Breakfast Shoten (1971), Yuji Harasaki [Basic Science of Coatings] Maki Shoten (19
Published in 1977), JP-A-62-96954. 62-1)5
171. It is described in 62-75651 publications.

Alternatively, a method for easily obtaining latex particles by a conventionally known polymerization reaction such as a suspension polymerization method or a dispersion polymerization method can also be used. Specifically, the chemistry of So Muroi-r polymer latex.
Polymer Publishing Association (1970), Oku 1) Taira, Hiroshi Taneita “
"Synthetic Resin Emulsion" Kobunshi Publishing Association (published in 1978)
, So Muroi - [Introduction to polymer latex] Kobunsha (1983)
year) etc.

In the present invention, a method of forming polymer latex particles is preferred, and by this method, resin particles having an average particle size of 1.0 μm or less can be easily formed.

By the way, when forming the surface layer in the electrophotographic lithographic printing original plate of the present invention, a method of dispersing in a non-aqueous solvent system is preferable because if water remains in the surface layer, the electrophotographic properties will be impaired. Therefore, in order to sufficiently disperse the latex particles of the present invention in the non-aqueous dispersed surface layer, it is preferable that the latex particles are also non-aqueous latex.

The non-aqueous solvent used in the non-aqueous latex may be any organic solvent as long as it has a boiling point of 200° C. or lower, and may be used alone or in combination of two or more.

Specific examples of this organic solvent include alcohols such as methanol, ethanol, propatool, butanol, fluorinated alcohol, and benzyl alcohol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diethyl ketone, and ethers such as diethyl ether, tetrahydrofuran, and dioxane. carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, aliphatic hydrocarbons having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane, cyclooctane, benzene , aromatic hydrocarbons such as toluene, xylene, and chlorobenzene, methylene chloride,
dichloroethane, tetrachloroethane, chloroform,
Examples include halogenated hydrocarbons such as methylchloroform, dichloropropane, and trichloroethane. However, it is not limited to the compound examples described above.

By synthesizing polymer latex using dispersion polymerization in these non-aqueous solvent systems, the average particle diameter of resin particles can be easily reduced to 1.
It is possible to obtain monodisperse particles with a particle size distribution of .mu.m or less and a very narrow particle size distribution.

Specifically, K, E, J, Barrett I [
1ispersionPolyo+erization
in Organic Media JJohn W
il-eV (published in 1975), Koichi Murata, Polymer Processing.

1), 20 (published in 1974), Tsunetaka Matsumoto, Toyokichi Tange 9 Journal of the Japan Adhesive Association 1.183 (1973), Toyokichi Tange 9 Journal of the Japan Adhesive Association 1. 26 (19B7), D,
J, Walbridge, NATO, Adv.
5 turdy.

In5t, Ser, E, N1)67,40 (19
83), British Patent Nos. 893429 and 934038, U.S. Patent Nos. 1) 22397 and 390041
2. Specifications of 4606989, JP-A-60-179
751) The method is disclosed in Publications No. 60-185963 and the like.

The surface layer of the photoreceptor of the present invention is formed by uniformly dispersing the above-mentioned resin particles in a binder resin of a matrix, and the binder resin will be explained in detail below.

As the binder resin for the surface layer of the present invention, all binder resins conventionally known can be used. Typical examples are vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer, vinyl acetate copolymer, vinyl alkanoate resin, and polyvinyl. These include butyral, alkyd resin, epoxy ester resin, polyester resin, etc.

Specifically, Ryuji Kurita and Tsugube Ishiwata, Kobunshi, Vol. 17, p. 278 (1968), Harumi Miyamoto.

Hidehiko Takei, Imaging, 1973 (Nα8) p.9,
Edited by Takashi Nakamura [Practical technology of binders for recording materials J 1st O
Chapter, C, H, C, Publishing (1985) D, D, T
att, S, C, Heldecker, Tapp
i, 49(N[Llo), 439 (1966),
E, S, Balt-tazzi, R, G, Blan
cloette et al, Photo, Sci
.

Eng, 16 (N(L5), 354 (+972)
, Genin Chan Ke, Isamu Shimizu, Hide Inoue-2 Journal of Electrophotography Society 18 (Nα2), 28 (1980), Tokko Sho 5
0-3101), JP-A-53-54027, JP-A-54-2
0735, 57-202544, 54-68046
Materials disclosed in each publication are listed.

Furthermore, the surface layer may contain a crosslinking compound and a crosslinking promoting compound. Specifically, the same crosslinkable compounds as those used to form the crosslinked structure in the resin particles of the present invention may be mentioned. However, when the surface layer contains particles, the hydrophilicity after desensitization is not inhibited, and the electrophotographic properties as an electrophotographic photoreceptor (e.g. initial potential, charge retention rate in the dark, photosensitivity, residual potential, etc.) must be used within the range that does not have a negative impact on

Specifically, it is preferable to use it within the range of 0005 to IO parts by weight based on the total solid content of the surface layer forming composition.

By using these crosslinking compounds in combination, the surface layer forms a crosslinked structure and becomes a higher-order structure, which improves the film strength after desensitizing the surface layer and controls the water retention property of the entire surface.
Water retention is improved.

Furthermore, fine particles other than the resin particles of the present invention (for example, metal oxides, etc.) may be contained in the surface layer in an amount of 0.001 to 5 parts by weight based on the total amount of the surface layer forming composition. Good too. This improves the film strength or adjusts the surface smoothness due to the filler effect caused by the addition of fine particles.

The resin particles of the present invention described above generate hydrophilic groups by reaction with a hydrophilic compound containing a nucleophilic substituent by treatment with a desensitizing solution or soaking water during printing. Therefore, in the original plate of the present invention containing the resin particles in the surface layer, the hydrophilicity of the non-image area that is made hydrophilic by the desensitizing treatment liquid is due to the sulfo groups, phosphono groups, and carboxyl groups generated by the resin particles. It is expressed for the first time by a hydrophilic group called a group or a hydroxyl group, and the lipophilicity of the image area and the hydrophilicity of the non-image area become clear, and it prevents printing ink from adhering to the non-image area during printing. As a result, it becomes possible to print a large number of prints with clear image quality and no background smear.

Furthermore, in the case of the above-mentioned resin particles that are partially cross-linked, the solubility in water is significantly reduced while maintaining hydrophilicity.
The particles become poorly soluble or insoluble, and the particles themselves become water-swellable.

Therefore, the hydrophilic groups generated in the resin particles exhibit hydrophilicity on the surface of the non-image area, and
The entire surface layer now contains water in a controlled manner, and the effect of the present invention that the hydrophilicity (printing ink repulsion) of the non-image area is further improved is improved, and the durability is also improved.

In terms of more specific effects, even if the amount of the upper functional groups in the resin particles is reduced, the effect of improving hydrophilicity can be maintained unchanged, or if the printing machine size or printing pressure is increased. Even when printing conditions become severe, such as fluctuations in color, it is possible to print a large number of prints with clear image quality and no background smudges.

Conventionally, only a limited number of materials such as zinc oxide could be used because a single layer had to have the properties of photoconductivity and hydrophilicity, but the printing original plate of the present invention has the above-mentioned properties. By forming a surface layer, the photoconductive layer and the hydrophilic layer (surface layer) have functional power (because they are separated,
Compared to conventional systems that rely on the desensitization reaction of zinc oxide, strict controls during printing are significantly relaxed.

In other words, in conventional systems using zinc oxide, a ferrocyan compound is used as the main ingredient in the desensitizing liquid that desensitizes zinc oxide, and this compound requires special handling management to prevent environmental pollution. In addition, since the desensitized hydrophilic substance is attached to the printed matter, the amount that is consumed by printing a large number of sheets is replaced by adding a desensitizing agent to the printing soaking water. However, as a side effect of this, there are problems such as the usable types of color ink are limited and it is difficult to use neutral paper as printing paper.

In contrast, in the system of the present invention, these problems can be easily solved because the principle of desensitization is completely different.

Next, the photoconductive layer of the electrophotographic photosensitive material of the present invention will be explained. The photoconductive layer contains at least a photoconductor and a binder resin, and the binder resin is the following resin CA).
It is particularly preferable to contain at least one kind of.

The resin [A] has a weight average molecular weight of 1 x 103 to 2 x 10', and contains 30% by weight or more of a specific repeating unit represented by the following general formula (II[) as a polymer component, ]I P Oi H2+ SO, H+ C00H, P-
R+ [R+ represents a carbonized "H hydrogen group or -0R2 (R2 represents a hydrocarbon group)]" and at least one selected from a cyclic acid anhydride-containing group
The resin contains 0.5 to 15% by weight of a polymer component having various polar groups.

General formula (III) H3 Thousand CH-C-)- ■ C00-R.

[However, in the above formula (I [), R3 represents a hydrocarbon group containing a benzene ring or a naphthalene ring] In the low molecular weight resin [A], the weight average molecular weight is 1
Xl0"~2X10', preferably 3X10"~1x
1O', and the glass transition point of the resin [A] is preferably -20°C to 1) 0°C, more preferably -10°C to 90°C.
It is ℃.

When the molecular weight of the resin [A) is less than 10', the film forming ability decreases and sufficient film strength cannot be maintained;
When it is larger than X10', even with the original plate of the present invention, dark decay occurs under harsh conditions of high temperature and high humidity, low temperature and low humidity, especially in photoreceptors using near-infrared to infrared spectral sensitizing dyes. Fluctuations in retention rate and photosensitivity become somewhat large, and the effect of the present invention in obtaining stable copied images is diminished.

The presence ratio of the polymer component corresponding to the repeating unit of the general formula (l [ The proportion is between 05 and 15% by weight, preferably between 1 and 10% by weight.

If the content of polar groups in the resin [Δ] is less than 0.5% by weight, the initial potential will be low and sufficient image density cannot be obtained. On the other hand, if the polar group is more than 15% by weight, no matter how low the molecular weight is, the dispersibility decreases, the interaction with the photoconductor becomes uneven, the electrostatic properties worsen, and as a result, the PSJ image This will result in

Next, formula (1) contained at least 30% by weight in the resin [Δ]
The repeating unit shown by is explained.

In the methacrylate component having a substituent of a hydrocarbon group containing a benzene ring or a naphthalene ring, a polymer component of a repeating unit represented by the following general formula (II[a) or general formula (nIb)] is more preferable. .

General formula (n[a) 7H・General formula (I[[b) 1H・c In formulas (IIIa) and (IIIb), T+ and 'rz
independently represent a hydrogen atom, a hydrocarbon group having 1 to 1 o carbon atoms, a chlorine atom, a bromine atom, -CORL, -COOR・(R4 represents a hydrocarbon group having 1 to 10 carbon atoms), L+, Lx is -C00 respectively
- and the number of direct bonds or connected atoms connecting the benzene ring is 1 or more
4 (representing a linking group in 1) In formula (Iffa), preferable 'r+ and 'r' are each independently a hydrogen atom, a chlorine atom, and a bromine atom, as well as a hydrocarbon group having 1 to 10 carbon atoms. , preferably an alkyl group having 1 to 4 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group, etc.)
, an aralkyl group having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group) and aryl groups (e.g., phenyl, tolyl, xylyl, bromophenyl, methoxyphenyl, chlorophenyl, dichlorophenyl, etc.), and -CORa and -COOR.

(Preferable examples of R6 include those described above as preferable hydrocarbon groups having 1 to 10 carbon atoms).

In the formulas (I[[a) and (I[[b), Ll and L
2 is a direct bond connecting -COO- and a benzene ring, or 10H2-+Tr (ns represents an integer of 1 to 3), -CHzOCO-1-CHtCHtOCO-1+, respectively.
cHto-D (rn 1 represents an integer of l or 2), C
A linking group having 1 to 4 linking atoms such as HiCHtO-, more preferably a direct bond or a linking group having 1 to 2 linking atoms.

Formula (n[a) or (I
Specific examples of the copolymer component corresponding to the repeating unit represented by llb) are listed below. However, the present invention is not limited thereto.

In the following (7) (b-1) to (b-20), n is an integer of 1 to 4, m is 0 or an integer of 1 to 3, and p is 1 to 3.
The integers, Rv-R+, all represent -C, Hza++ or -←CHirCdl@ (however, n and m are the same as above), and X+, )h may be the same or different,
Represents a hydrogen atom, -C7l, -Br, or -E.

(b-1) CH.

(b-2) CM.

(b-3) CH) (b-4) CH.

(I1v), I;*Hs (b-5) CH3 (b-6) CH3 (b-7) CI! ■ (b-8) CH3 S-tI! Il-ya.

(b-To) CHs basket (b 1)) CHs (b-12) CF3 I (b13) CHs (b-15) CHs 1←C1, -C→- (b-16) C1i.

(b-17) CHs (b-18) CH3 ■ Next, the polar group-containing polymer component of the low molecular weight resin [A] will be explained.

The polar groups are -PO, H, -5OJ, -COOH.

H One type will be selected.

-P-R+ group means that R+ above represents a hydrocarbon group or H-OR2 (Ri represents a hydrocarbon group), and specifically R1 represents an aliphatic group having 1 to 22 carbon atoms (for example, a methyl group,
Ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, Cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group,
fluorobenzyl group, methoxybenzyl group, etc.), or an optionally substituted aryl group (e.g. phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl- phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.)
etc., and R2 has the same content as R1.

In addition, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride include aliphatic dicarboxylic acid anhydride and aromatic dicarboxylic acid anhydride. It will be done.

Examples of aliphatic dicarboxylic anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclobencune-1,2-dicarboxylic anhydride ring, and cyclohexane-1,2-dicarboxylic anhydride ring. These rings include, for example, chlorine atom, bromine atom, etc. may be substituted with a halogen atom, an alkyl group such as a methyl group, an ethyl group, a butyl group, or a hexyl group.

Examples of aromatic dicarboxylic anhydrides include phthalic anhydride rings, naphthalene-dicarboxylic anhydride rings, pyridine-dicarboxylic anhydride rings, thiophene-dicarboxylic anhydride rings, etc. For example, halogen atoms such as chlorine atom and bromine atom, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hydroxyl group,
It may be substituted with a cyano group, a nitro group, an alkoxycarbonyl group (for example, a methoxy group, an ethoxy group, etc.).

The polar group-containing copolymer component of the present invention can be copolymerized with a monomer corresponding to a repeating unit represented by, for example, general formula (■) [including general formulas (DIa) and (nib)]. Any vinyl compound containing a polar group may be used, and is described in, for example, F Polymer Data No. 1 Handbook [Basic Edition] edited by the Society of Polymer Science and Technology, J Baifukan (published in 1986).

Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-amino)methyl form, α-chloro form, α-bromo form, α -fluoro form, α-tributylsilyl form, α-
Cyano form, β-chloro form, β-bromo form, α-chloro-
β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itafonic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 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, vinyl or allyl group of dicarboxylic acids Examples include half ester derivatives of these, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the polar group in a substituent of an amide derivative.

Examples of polar group-containing copolymer components are shown below. Here, b indicates H or CHff, and bl is H1GHz
or C) 12 C00C) I s, 1'l++
represents an alkyl group having 1 to 4 carbon atoms, and Lx represents an alkyl group having 1 to 4 carbon atoms.
-6 alkyl group, benzyl group or phenyl group,
C represents an integer of 1 to 3, d represents an integer of 2 to 1),
e represents an integer of 1 to 1), f represents an integer of 2 to 4,
g represents an integer of 2 to 10.

(C-1) +CH, -C← 0OH (C-2) cH.

Thousand CH-CH→- (C-3) kl+■ Ten CH2-C→- Coo(CH2)aCOOH (C-4)bl -+-CHx -C← C0NH(CH2), C00H (C-5) blby one +-CH-C→- Coo(CH2)20CO(CH2), C00H(C-
6) bl bzI +CH-C→- Coo(CH2)zOcOcH=cH-COOH(C7
) bl b 2Coo(CHz
)+5O3H OH3 1t+ coo(c)1. )-2-o P-OHH (C-19) C00H+CH,-C
← CHt C0OR mouth.

(C-21) by ■ (C-23) 10CHt-CH→-0sH (C-21)) 10CHt-CH←CH2Cool σ\/″b 1B CONH(CHj), O-P -R+2H υυi Shiri υshiII (C-匈3) +CH-c← Cool eON(CHzCHzCOOH)z(C
JJ5) b+(C-46)
l)+(c-a7)
b.

” ((-aa)bl■蕃OC,Utsu Furthermore, the low molecular weight resin [A) of the present invention has the general formula (III), (IIIa) and/or (Ib) described above.
In addition to the above monomer and the polar group-containing monomer, monomers other than these may be contained as copolymerization components.

As such other copolymerization components, for example, compounds of the general formula (I
In addition to methacrylic esters, acrylic esters, and crotonic esters containing substituents other than those explained in [), α-olefins, vinyl carboxylates, or acrylic esters (for example, as a carboxylic acid, acetic acid,
propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (e.g. dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes ( (e.g. styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N,N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinyl sulfone-containing compounds, vinyl ketone-containing compounds, heterocyclic vinyls (e.g. vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidacillin, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.).

The low molecular weight resin [A) as described above is preferably used in combination with the known resin for the surface layer described above. The ratio of low molecular weight resin to other resins is 5-50/95-50
(weight ratio) is preferable.

Other resins used in combination include weight average molecular weight 3X10'
~1×103, preferably 5×10′ to 5×10′
It is a medium to high molecular weight substance. In addition, the glass transition point of the resin used in combination is -10°C to 120°C, preferably 0°C to 90°C.
It is ℃.

Further, as a medium to high molecular weight resin used in combination, a polymer that satisfies the above-mentioned physical properties and preferably contains 30 parts by weight or more of a repeating unit polymer component represented by the following general formula (V) can be mentioned.

General formula (V) -R-3 In formula (v), ■ is -COO-1-0CO-1-
+-CHz-+-rOCO-1+CH,), -Coo-
Represents 1-0- or -8O2-. However, h represents an integer of 1 to 4] In the general formula (V), bl and bl are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom), cyano groups, or alkyl groups having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.).

Fl+z is an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., 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, 3-hydroxypropyl group, etc.)
, an optionally substituted alkenyl group having 2 to 18 carbon atoms (e.g. vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), a substituted alkenyl group having 7 to 12 carbon atoms; aralkyl groups (e.g. benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), optionally substituted cycloalkyl groups having 5 to 8 carbon atoms; groups (e.g. cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.)
, an optionally substituted aryl group (e.g. phenyl group, tolyl group, xyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, 70 lophenyl group, dichlorophenyl group, bromophenyl group, chlorophenyl group, dichlorophenyl group) , iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, aminophenyl group, nitrophenyl group, etc.).

The medium to high molecular weight binder resin (hereinafter referred to as resin (B)) containing the polymer component represented by general formula (V) is as follows:
For example, a random copolymer resin containing a polymer component represented by formula (V) (JP-A No. 63-49817, No. 63-22
0149, JP 63-220148, etc.), a combination resin of the random copolymer and a crosslinkable resin (JP-A-1-2
1) 766, 1-102573 publications), formula (V)
A copolymer containing a polymer component represented by the formula and partially crosslinked in advance (JP-A-2-34860, JP-A-2-40660, etc.), a monofunctional macromonomer consisting of a polymer component of a specific repeating unit. and a monomer corresponding to the component represented by the formula (V) to obtain a graft type block copolymer (Japanese Patent Applications Nos. 1983-203933 and 1983-20717, Japanese Patent Applications Nos. 163796 and 1989, 212994,
1-229379 and 1-189245 (specifications already pending by the present inventors).

In the present invention, the resin [A] is a copolymer containing at least a methacrylate copolymer component having a specific substituent and a polar group-containing copolymer component, and the polar group is a stoichiometric component of the photoconductor. Because it adsorbs to defects and has a low molecular weight, it improves the coverage of the photoconductor surface, compensating for photoconductor traps and dramatically improving temperature characteristics. It was found that sufficient dispersion was achieved and aggregation was suppressed. As a result, it was found that the electrophotographic properties were significantly improved, and in particular, good properties were exhibited even when a dye for semiconductor laser light spectral sensitization was used in combination.

And if medium to high molecular weight resin [B] is used together, resin [
It was found that the mechanical strength of the photoconductive layer could be sufficiently improved compared to the case of using resin [A] alone, without at all impairing the high performance electrophotographic properties obtained by using resin [A]. That is, the adsorption and coating interaction between the photoconductor and the binder resin is properly performed, and the film strength of the coated conductive layer is maintained.

The photoconductive compound used in the present invention may be either an inorganic photoconductive compound or an organic photoconductive compound.

Examples of the inorganic photoconductive compound used in the present invention include conventionally known inorganic photoconductive compounds such as zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, selenium, selenium-tellurium, and lead sulfide. From this viewpoint, zinc oxide and titanium oxide are preferable.

When using an inorganic photoconductive compound such as zinc oxide or titanium oxide as the photoconductive compound, inorganic photoconductive compound 1
The above-mentioned binder resin is used in a proportion of 10 to 100 parts by weight, preferably 15 to 40 parts by weight, based on 00 parts by weight.

On the other hand, the organic compound may be any conventionally known compound, and specifically, the following two types are conventionally known as examples of electrophotographic planographic original plates. The first is
Japanese Patent Publication No. 37-17162, No. 62-51462, No. 52-2437.54-19803, No. 56-1072
46, 57-161863, etc., which has a photoconductive layer mainly consisting of an organic photoconductive compound, a sensitizing dye, and a binding resin.
-146145, 60-17751 60-1775
2, 60-17760, 60-254142, 6
It has a photoconductive layer mainly containing a charge generating agent, a charge transporting agent, and a binding resin as described in 2-54266 publications. As a special case of the second example,
230147, 60-230148, 60-238
A photoconductive layer having a two-layer structure containing a charge generating agent and a charge transporting agent in separate layers, as described in JP-A No. 853, is also known.

The electrophotographic lithographic printing original plate of the present invention may take the form of either of the above two types of photoconductive layers. In the case of the second example, the organic photoconductive compound referred to in the present invention functions as a charge transport agent.

The organic photoconductive compound in the present invention includes ta+
Triazole derivatives described in US Pat. No. 31)2197, etc., tb+ Oxadiazole derivatives described in US Pat. No. 3,189,447, etc. IcI Imidazole derivatives described in Japanese Patent Publication No. 37-16096, fdl US patent No. 3615402! , 38209
89, 3542544 specifications, Japanese Patent Publication No. 45-55
5, Publications No. 51-10983, Japanese Unexamined Patent Publication No. 51-932
24. 55-108667, 55-156953,
Polyaryl alkane derivatives described in Publications No. 56-36656, etc., tel. US Pat. No. 3,180,729,
4278746, JP 55-88064
, 55-88065, 49-105537, 55
-51086, 56-80051. 56-8814
1. 57-45545, 54-1) 2637, 5
Pyrazoline derivatives and pyrazolone derivatives described in publications such as No. 5-74546, lfl U.S. Pat.
36 publications, JP-A-54-83435, JP-A-54-1)
0836, 54-1) phenylenediamine derivatives described in 9925 publications, etc.,
3240597, 3658520, 423210
3, 4175961. 4012376 specifications,
Special Publication No. 49-35702, West German Patent (DAS)
1) Specification No. 10518, Japanese Patent Publication No. 39-27577,
Japanese Patent Publication No. 55-144250, No. 56-1) No. 9132 No. 5
Arylamine derivatives described in 6-22437 publications, etc. (~ Amino-substituted chalcone derivatives described in U.S. Pat. No. 3,526,501 etc., (il) - Bicalbasil derivatives, ljl Oxazole derivatives described in U.S. Pat. Fluorenone derivatives, - U.S. Pat. No. 3,717,462, JP-A-54-54
No. 9143 (corresponding to U.S. Pat. No. 4,150,987), JP-A-55-52063, JP-A-55-52064
, 55-46760, 55-85495, 57-
1) 350, 57-148749, 57-1041
44 hydrazone rust conductors described in each publication, etc., in) U.S. Patent No. 4047948, U.S. Patent No. 404794
9, 4265990, 4273846, 4299
897, 4306008, etc., benzidine derivatives to+ JP-A-58-190953, JP-A-59-955
40, stilbene derivatives described in Japanese Patent Publications No. 59-97148, No. 59-195658, No. 62-36674, etc., ip+ polyvinylcarbazole and its derivatives described in Japanese Patent Publication No. 34-10966, IQ+ Japanese Patent Publication No. 18674-1974 , 43-1919
2 Polyvinylpyrene, polyvinylanthracene, poly-2-vinyl-4-(4'-dimethylaminophenyl)-5-phenyl-oxazole, poly-3 described in each publication
- Vinyl polymers such as vinyl-N ethylcarbazole, lrl Polymers such as polyacenaphthylene, polyindene, and copolymers of acenaphthylene and styrene described in Japanese Patent Publication No. 19193-1983, +s+ Polymers such as copolymers of acenaphthylene and styrene, etc. Condensation resins such as pyrene-formaldehyde resin, brompyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin described in (TL JP-A-56-9083
3. There are various triphenylmethane polymers described in Patent Publications No. 56-161550.

In the present invention, the organic photoconductive compound is lal~
(It is not limited to the compounds listed in tl, but all conventionally known organic photoconductive compounds can be used. Two or more of these organic photoconductive compounds can be used in combination depending on the case.

As the sensitizing dye contained in the photoconductive layer of the first example, conventionally known sensitizing dyes used in electrophotographic photoreceptors can be used. These are "electrophotography" soil 2 9. (197
3), "Organic Synthetic Chemistry" 1st (1)), 1010. (1
966) etc. For example, U.S. Pat.
41770, 4283475 specifications, JP-A-1978
-Byrylium dyes described in JP-A-25658, JP-A-62-71965, etc., Applied 0pti
cs Supplement i50 (1969),
Triarylmethane dyes described in JP-A No. 50-39548, cyanine dyes described in U.S. Pat. No. 3,597,196, etc., JP-A-60-163047, No. 59-164588, No. 60-252517, etc. Styryl dyes and the like described in JP-A No. 2003-11000 are advantageously used.

The charge generating agent contained in the photoconductive layer of the second example is as follows:
Various conventionally known organic and inorganic charge generating agents can be used in electrophotographic photoreceptors.

For example, selenium, selenium-tellurium, cadmium sulfide, zinc oxide, and the organic pigments shown in (1) to (9) below can be used.

(1) U.S. Pat.
41, 58-192042, 58-219263,
59-78356, 60-179746, 61-
Azo pigments such as monoazo, bisazo, and trisazo pigments described in Japanese Patent Publications Nos. 148453 and 61-238063, Japanese Patent Publications Nos. 60-5941 and 60-45664, etc. (2) U.S. Patent Nos. 3397086 and 466680
2 Specifications, JP-A-51-90827, JP-A-52-55
Phthalocyanine' pigments such as metal-free or metal phthalocyanine, which are described in publications such as No. 643, (3) perylene pigments described in US Pat. ) Indigo and thioindigo derivatives described in British Patent No. 2237680, JP 47-30331, etc.; (5) Cinchona described in GB 2237679, JP 47-30332, etc. Clinton-based pigment (6) British Patent No. 2237678, JP-A-59
-184348, 62-28738, 47-185
44 Polycyclic quinone pigments described in various publications, etc. (7) JP-A No. 47-3033 and No. 47-18543
Bisbenzimidazole pigments described in various publications, etc. (8) U.S. Patent No. 4396610, U.S. Patent No. 464408
2 Squarium salt pigments described in each specification, etc. (9) JP-A-59-53850, JP-A-61-2125
The azulenium salt pigments described in each publication No. 42, etc. These can be used alone or in combination of two or more.

In addition, regarding the mixing ratio of the organic photoconductive compound and the binding resin, the upper limit of the content of the organic photoconductive compound is determined by the compatibility between the organic photoconductive compound and the binding resin, and if an amount exceeding this is added, the organic photoconductive Crystallization of the conductive compound occurs, which is undesirable.

Since the electrophotographic sensitivity decreases as the content of the organic photoconductive compound decreases, it is preferable to include as much of the organic photoconductive compound as possible within a 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, per 100 parts by weight of the binding resin. Further, the organic leading conductive compounds may be used alone or in combination of two or more.

In the lithographic printing original plate of the present invention, the above-mentioned binding resin is used in a proportion of 10 to 100 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the photoconductive compound.

In the present invention, various dyes can be used in combination as spectral sensitizers as necessary depending on the type of light source, such as exposure to visible light or exposure to semiconductor laser light. For example, Harumi Miyamoto,
Hidehiko Takei: Imaging L” Shij2J- (N (18)
Page 12, C. J. Young et al.: RCA Revi
e1ur, p. 469 (1954), Wataru Kiyota: Journal of the Institute of Electrical Communication, 1 length, 1 m (double 2), p. 97 (1980), Yuji Harasaki et al.

Industrial Chemistry Journal, iJL, pages 78 and 188 (1963), Tani Tadaaki 1 Journal of the Japanese Society of Photography 1)゜208 pages (197
carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, phthalein dyes, polymethine dyes (e.g., oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), Examples include phthalocyanine dyes (which may contain metal).

More specifically, carbonium-based dyes, triphenylmethane-based dyes, xanthine-based dyes, and phthalein-based dyes are mainly used in Japanese Patent Publication No. 51-452, JP-A-50-90334, and JP-A-50-1). 4227, 53-3
No. 9130, No. 51-82353, U.S. Patent No. 3
Examples include those described in the specifications of No. 052540 and No. 4054450, and Japanese Patent Application Laid-open No. 16456/1983.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as logcyanine dyes include F, N
+Harmmer rThe Cyanine Dy
Colorants described in esand Related Compounds J, etc. can be used, and more specifically, U.S. Pat.
1008, 3125447, 3128179, 3
132942, 3622317 specifications, British patent box 1226892, 1309274, 140589
8 specifications, Japanese Patent Publication No. 48-7814, No. 55-188
Examples include dyes described in 92 publications and the like.

Furthermore, as a polymethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A-47-840
, No. 47-44180, Special Publication No. 51-41061. Same 4
9-5034. 49-45122, 57-4624
5, 56-35141, 57-157254, 6
1-26044, US Pat. No. 61-27551, US Pat. No. 3,619,154, US Pat. No. 4,175,956, r
Research Disclosure” 1982
Year, 216. Examples include those described on pages 1) 7 to 1) 8.

The photoreceptor of the present invention is also excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together.

Furthermore, various conventionally known additives for electrophotographic photoreceptors may be used in combination, if necessary.

These additives include chemical sensitizers to improve electrophotographic sensitivity, various plasticizers to improve film properties,
Includes surfactants, etc.

Examples of chemical sensitizers include halogen, benzoquinone,
Chloranil, fluorenone, bromanil, dinitrobenzene, anthraquinone, 2゜5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, 2,
Electron-withdrawing compounds such as 3-dichloro-5,6-dichlorobenzoquinone, dinitrofluorenone, trinitrofluorenone, and tetracyanoethylene, Hiroshi Komon et al., "Recent Development and Practical Application of Photoconductive Materials and Photoreceptors" Chapter 4 ~Chapter 6 Nippon Scientific Information ■Polyarylalkane compounds and hindered phenol compounds cited in the review published by Publishing Department (1986)
Examples include p-phenylenediamine compounds. Also,
Japanese Patent Publication No. 58-65439, No. 58-102239, No. 5
Compounds described in Publications No. 8-129439 and No. 62-71965 can also be mentioned.

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

The amount of these various additives added is not particularly limited, but
Usually, the amount is 0,001 to 20 parts by weight per 100 parts by weight of the photoconductor.

The thickness of the photoconductive layer is preferably 1 to 100 microns, particularly 10 to 50 microns.

In addition, when a photoconductive layer is used as a charge generation layer of a photoreceptor with a stack of a charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.01 to Iμ, particularly 0.05 to 0.5μ. is suitable.

The photoconductive layer according to the invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably electrically conductive.As the electrically conductive support, for example, a base material such as metal, paper, or plastic sheet is impregnated with a low-resistance substance in exactly the same manner as conventional methods. The back side of the substrate (the opposite side to the side on which the photosensitive layer is provided)
The support is coated with at least one layer for the purpose of imparting conductivity and preventing curling, etc., the surface of the support is provided with a water-resistant adhesive layer, and the surface layer of the support is coated with at least one layer for the purpose of preventing curling. Depending on the situation, a material provided with at least one precoat layer, a material made by laminating a conductive plastic substrate on which ^1 or the like is vapor-deposited onto paper, etc. can be used.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, electronic photography, 14. (Nal).

2-1) pages (published in 1975), Hiroyuki Moriga, "Introductory Special Paper Chemistry", Kobunshi Publishing Association (published in 1975), M, F, Ho
over, J, Macromol, Sci, C
hew, A-4+61.1327-1417 (1
(published in 1970) etc. are used.

The thickness of the hydrophilic surface layer of the present invention is 10 μm or less, and preferably 0.1 to 5 μm especially for the Carlson process. If it is thicker than 5 μm, disadvantages may occur such as a decrease in sensitivity of the lithographic printing original plate as an electrophotographic photoreceptor and an increase in residual potential.

In order to actually produce the photoreceptor (printing original plate) of the present invention, an electrophotographic photosensitive layer (photoconductive layer) is first formed on a conductive support by a conventional method.

Next, on this layer, the resin particles of the present invention, the binding resin, and if necessary, the above-mentioned additives are dissolved or dispersed in a volatile hydrocarbon solvent with a boiling point of 200°C or less, and this is applied and dried. The surface layer can be formed and manufactured by this method.

Specifically, preferred organic solvents are halogenated hydrocarbons having 1 to 3 carbon atoms, such as dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, dichloropropane, and trichloroethane. Other various solvents used in coating compositions, such as aromatic hydrocarbons such as chlorobenzene, toluene, xylene or benzene, ketones such as acetone or 2-butanone, ethers such as tetrahydrofuran, and methylene chloride, and the above-mentioned solvents. Mixtures of can also be used.

A known method can be applied to the production of a printing plate using the lithographic printing original plate of the present invention obtained as described above. It is created by desensitizing the non-image area. That is, it is charged substantially uniformly in a dark place, and an electrostatic latent image is formed by imagewise exposure. Exposure methods include semiconductor laser,
Examples include scanning exposure using a He--Ne laser or the like, reflection image exposure using a xenon lamp, tungsten lamp, fluorescent lamp or the like as a light source, and contact exposure through a transparent positive film. Next, the electrostatic latent image is developed with toner. As the developing method, various conventionally known methods such as cascade development, magnetic brush development, powder cloud development, liquid development, etc. can be used. Among these, liquid development is capable of forming fine images and is suitable for creating printing plates. The formed toner image can be fixed by a known fixing method, such as heat fixing, pressure fixing, solvent fixing, or the like.

Regarding the lithographic printing original plate having the toner image formed in this way, a printing plate is then created by desensitizing the non-image area.

The desensitization treatment provided in the present invention involves the resin particles of the present invention containing a functional group represented by the general formula (1) containing a compound containing a hydrophilic group that easily reacts nucleophilically with the double bond. This is achieved by treatment with a solution (aqueous solution or mixed solution containing a water-soluble organic solvent).

As a hydrophilic compound that causes a nucleophilic substitution reaction on the double bond of the functional group represented by general formula (I), Par77PearS
The nucleophilic constant n(R, G, Pearson, H
, 5obel, J., Songstad, J.A.
mer, CheIll.

Soc, Jul, 319 (1968)] contains a substituent having a value of 5.5 or more, and distilled water 1
Examples include hydrophilic compounds that dissolve in 1 part by weight or more in 00 parts by weight.

Specific compounds include, for example, hydrazine, hydroxylamine, sulfites (ammonium salts, sodium salts, potassium salts, zinc salts, etc.), thiosulfates, etc.
In addition, at least one group selected from a hydroxyl group, a carboxyl group, a sulfo group, a phosphono group, and an amino group is present in the molecule.
Examples include mercapto compounds, hydrazide compounds, sulfinic acid compounds, primary amine compounds, and secondary amine compounds containing two polar groups.

For example, mercapto compounds include 2-mercaptoethanol, 2-mercaptoethylamine, N-methyl-2-
Mercaptoethylamine, N-(2-hydroxyethyl)2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenedicarboxylic acid, 2-mercaptoethanesulfonic 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-amine acetic acid, etc., as a sulfinic acid compound, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid, dicarboxybenzenesulfinic acid etc. as hydrazide compounds, 2-hydrazinoethanesulfonic acid, 4
-Hydrazibutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenedisulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic 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-dihydroxy propyl)amine, N,N-di(2,3-dihydroxypropyl)amine, 2-aminopropionic acid, aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2
-hydroxyethylmorpholine, 2-carboxyethylmorpholine, 3-carboxypiperazine and the like.

These nucleophilic compounds are used by being included in the above-mentioned desensitizing treatment solution for the photoconductor, or they are included in a treatment solution for separately treating the resin particles.

The amount of the nucleophilic compound present in these treatment solutions is 0.05 mol/1-10 mol/l, preferably 0.1 mol/l to
It is 5 mol/l.

Further, the pH of the treatment liquid is preferably 4 or more.

The conditions for the treatment are preferably a temperature of 15° C. to 60° C. and an immersion time of 10 seconds to 5 minutes.

The treatment liquid may contain other compounds in addition to the above-mentioned nucleophilic compound and pH adjuster.

For example, add 1 part by weight of a water-soluble organic solvent to 100 parts by weight of water.
It may contain up to 50 parts by weight. Examples of such water-soluble organic solvents include alcohols (methanol,
ethanol, propatool, propargyl alcohol, benzyl alcohol, phenethyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol) (monomethyl ether, tetrahydrobilane, etc.), amides (dimethylformamide, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, etc.), and these may be used alone or in combination of two or more. Good too.

Further, 0.1 to 20 parts by weight of a surfactant may be contained in 100 parts by weight of water. Examples of the surfactant include conventionally known anionic, cationic, and nonionic surfactants.

For example, Hiroshi Horiguchi, “New Surfactants,” Sankyo Publishing ■, (197
Compounds described in "Synthesis of surfactants and their applications J Maki Shoten (published in 1980)" by Ryohei Oda and Hiroshi Teramura (published in 1980) can be used.

The method for desensitizing the functional group-containing resin particles of the present invention represented by the general formula (If) is as follows: As shown in the reaction formula (1), after dehydrohalogenation reaction, the produced It is characterized by being made hydrophilic through a nucleophilic reaction of a nucleophilic compound to a heavy bond.

Since the dehydrohalogenation reaction easily proceeds in a treatment solution with a pH of 6 or higher, the dehydrohalogenation reaction can be carried out by setting the pH of the etching treatment solution containing at least the above-mentioned nucleophilic compound to 6 or higher. Hydrophilization is achieved by oxidation and nucleophilic reactions.

More preferably, the pH of the treatment liquid is 8 or higher. Furthermore, after the dehydrohalogenation reaction proceeds with a solution having a pH of 6 or higher, there is no problem in desensitizing the product with a treatment solution containing a hydrophilic group-containing compound that undergoes a nucleophilic reaction.

Furthermore, in the hydrophilic treatment containing the nucleophilic compound, the same effect can be obtained even when the nucleophilic compound is used in the soaking water during printing.

As described above, according to the present invention, any conventionally known electrophotographic photoreceptor can be used as a high-quality lithographic printing original plate. The surface layer in the present invention is a film that exhibits both high hydrophilicity and water resistance after parent wood treatment, and also has extremely good adhesion to the substrate and toner image. It greatly suppresses the occurrence of stains and has high printing durability.

Furthermore, since the printing plate of the present invention can maintain almost the original sensitivity of the electrophotographic photosensitive layer, it is possible to obtain a printing plate with significantly higher sensitivity than conventional printing plates for electrophotographic engraving.

In addition, in the past, only a limited number of materials such as zinc oxide could be used because a single layer had to have the property of being able to be made hydrophilic with the photoconductive layer, but in the printing original plate of the present invention, the photoconductive layer and Since the functions are separated into the hydrophilic layer, the range of selection of the photoconductive layer is expanded, and therefore, for example, if a material with high sensitivity in the long wavelength light region is selected, it is possible to use a He-Me laser, which was previously impossible. It becomes possible to write with a semiconductor laser.

In addition, in the printing original plate of the present invention, the non-image area can be made hydrophilic by simply immersing it in a hydrophilic treatment solution for a few seconds, so it is small and
Plate making becomes possible with a simple device.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Production Example 1 of Resin Particles: A mixed solution of 95 g of CL-13 dodecyl methacrylate, 5 g of acrylic acid, and 200 g of toluene was heated to 70° C. with stirring under a nitrogen stream. To this, 1.5 g of 2.2-azobis(isobutyronitrile) (abbreviation A, engineering, B, N)
was added and reacted for 8 hours.

Add 12 g of glycidyl methacrylate to this reaction mixture solution.
, t-butylhydroquinone Ig and 0.8 g of N,N-dimethyldodecylamine were added and reacted at 100°C for 15 hours to obtain a dispersion resin (P-1) having the following structure.

Dispersion resin CP-1) H Next, 7.5 g (as solid content) of the dispersion resin (P-1)
A mixed solution of 50 g of monomer CM-1 having the following structure and 200 g of methyl ethyl ketone was heated to 65° C. with stirring under a nitrogen stream. To this, 2.2-azobis(isobutyronitrile) (abbreviation A, ■, V,) 1. ) 0.7
g was added and reacted for 6 hours.

Twenty minutes after the addition of the initiators (A, IV, N-), the homogeneous solution began to become cloudy and the reaction temperature rose to 90°C.

After cooling, it was passed through a 200 mesh nylon cloth to obtain a white dispersion. Latex with an average particle size of 0.45 μm [L-1
)Met.

Monomer CM-LE CH CH*=C Coo(CHI hOcO(CHz)zsOtcH=
Production example 2 of CH2 resin particles: (L-23 monomer CM-2 having the following structure) 20 g, dispersion resin [P-1
]8g (as solid content), ethyl acetate 150g, n
- A mixed solution of 150 g of hexane was heated to 55° C. with stirring under a nitrogen stream. A.1. V, N, 0.5g
The mixture was reacted for 4 hours to obtain a white dispersion. After cooling, the resulting dispersion was passed through a 200-mesh nylon cloth, and the resulting dispersion was latex (L-2) with an average particle size of 0.30 μm.

Monomer CM-2] CH3 CH,=C C00CHtCOCH= CHz Production example 3 of resin particles: [L-3] 20 g of monomer [M-3] with the following structure, 5 g of macromonomer CP-2 with the following structure , 150g of methyl ethyl ketone
The reaction was carried out in the same manner as in Production Example 1 for resin particles except that a mixed solution of white latex (
L-3:l was obtained.

Monomer CM-3] 1) Example 4 of manufacturing resin particles: (L-4) Monomer CM-4 with the following structure: 20 g, divinylbenzene lag, the following: The reaction was carried out in the same manner as in Example 1 for the production of resin particles, except that a mixed solution of 6 g of the macromonomer [P-3] with the structure and 150 g of methyl isobutyl ketone was used to obtain a white latex (L-43) with an average particle size of 0.25 μm. Ta.

Monomer (M-4) C.I.

Macromonomer (P-3) C00CaH+%17X103 Production example of resin particles 5: (L-53 Monomer CM-5 with the following structure) 20g, ethylene glycol diacrylate 2.5g, acrylic acid 5g, macromonomer CP -2) 6g and 200g of methyl ethyl ketone
The reaction was carried out in the same manner as in Resin particle production example 1 except that a mixed solution of white latex (L
;-5] was obtained.

Monomer [M-53 Production examples 6 to 13 of resin particles: [L-61 to [L-
13] In Production Example 4 of Resin Particles, resin particles (L-6) to ( L-13] was obtained.

Production examples 14 to 20 of resin particles: [L-14] to (L-2
0) Manufacturing of resin particles except for making a mixed solution of 20 g of monomer CM) in Table 3 below, a predetermined amount of crosslinking monomer, 5 g of macromonomer [P-4) with the following structure, and 200 g of methyl ethyl ketone. The reaction was carried out in the same manner as in Example 1, and each latex (L
-14) to (L-20) were obtained.

Macromonomer CP-4) COOCaHt(n) Synthesis example 1 of binder resin [A): (A-1) Benzyl methacrylate 95g 1 acrylic acid 5g and toluene 2
After heating 00g of the mixed solution to a temperature of 90°C under a nitrogen stream, A, ■, B, N, 5. Qg was added and reacted for 4 hours. Further A.1. 2 g of B and N were added and reacted for 2 hours. The M density of the obtained copolymer CA-1) was 8,500.

Synthesis examples 2 to 28 of binder resin [A]: [A-2) to (A-
28) The following table-
4, each resin 1:A-2) to [A-28] were synthesized.

Synthesis example 29 of binding tree [A): [A-29] 895 g of 2,6-dichlorophenyl methacrylate 1 5 g of acrylic acid,
After heating a mixed solution of 2 g of n-dodecyl mercaptan and 200 g of toluene to a temperature of 80°C under a nitrogen stream, A.
1. B.

Add 2g of N, react for 4 hours, then add A, ■, B, N,
Add 0.5g and wait for 2 hours, then add A, 1. B, N, 0.5
g was added and reacted for 3 hours. After cooling, methanol/water (
The precipitate was collected with a decanterizer and dried under reduced pressure. The yield of the waxy copolymer obtained was 78g, and one piece was 6.3X10”
Met.

Example 1 and Comparative Examples A and B Resin [A-736g (
(as solid content), 34 g of resin [D-1] with the following structure,
200 g of zinc oxide, 0.15 g of hebutamethine cyanine dye [I] having the following structure.

A mixture of 0.05 g of phthalic anhydride and 300 g of toluene was prepared in a homogenizer (manufactured by Nippon Sei Al@) in a 6×1
A photosensitive layer-forming material was prepared by dispersing at a rotational speed of 0'' r, p, m for 15 minutes, and this was applied to conductive treated paper with a wire bar so that the dry adhesion amount was 18 g/rd.
) It was dried for 1 minute at 0°C.

Resin CD-1) Cyanine dye (1) On this photoreceptor, resin particles (L-1) 3% by weight (as solid content), resin CQ-1) having the following structure 2% by weight and 1
A toluene dispersion containing 0.5% by weight of . Next, an electrophotographic light-sensitive material was prepared by leaving it for 24 hours in a dark place at 20° C. and 65% RH.

Resin [Q-1] Comparative Example A A resin with the following structure (R-1
) 3% by weight, resin [Q-1] 2% by weight, and! A toluene solution containing 0.5% by weight of 4-xylylene diisocyanate was applied in the same manner as in Example 1 to produce an electrophotographic light-sensitive material.

Resin [R-1] Comparative Example B Under the conditions for producing the photoconductive layer of the electrophotographic photoreceptor of Example 1, resin [R-2] having the following structure was used instead of resin [A-7] and resin CD-13. ] An electrophotographic light-sensitive material was prepared in the same manner as in Example 1 except that 40 g was used.

Resin [R-2] The film properties (surface smoothness), electrostatic properties, imaging performance, and imaging performance of these photosensitive materials under environmental conditions of 30° C. and 80% RH were investigated. Furthermore, when these photosensitive materials are used as original plates for offset masters, the desensitization property of the photoconductive layer (represented by the contact angle with water of the photoconductive layer after desensitization treatment) and printability (background smudge, The printing durability, etc.) were investigated.

The above results are summarized in Table-5.

(The following is a blank space) The implementation aspects of the evaluation items listed in Table-5 are as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was tested using a Beck smoothness tester (Kumagai Riko ■
The smoothness (
see/cc) was measured.

Note 2) Electrostatic properties: In a dark room at a temperature of 20°C and 65% RH, each photosensitive material was subjected to corona discharge at -6 kV for 20 seconds using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Electric). After that, leave it for 10 seconds, and the surface potential V1 at this time
° was measured. Next, the potential v1-. was measured after being left standing in the dark for 180 seconds, and the retention of the potential after dark decay for 180 seconds, that is, the dark decay retention rate (D, R, R,
(%)], (V+*o/ V+e) xl OO(
%).

In addition, after the surface of the photoconductive layer was charged to -400 V by corona discharge, it was irradiated with monochromatic light with a wavelength of 780 nm, and the time required for the surface potential (V + o) to attenuate to 1/10 was determined.
From this, the exposure amount E tz+e(erg/c+o') is calculated.

Note 3) Imaging properties: Each photosensitive material was left for one day and night under the following environmental conditions. Next, the surface of the photosensitive material was charged at 64 erg using a 2.8 mW output gallium-aluminum-arsenide semiconductor laser (oscillation wavelength 780 nm) as a light source.
Copy image obtained by developing and fixing using ELP-T (manufactured by Fuji Photo Film ■) as a liquid developer after speed exposure at a pitch of 25 μm and a scanning speed of 300 Ill/sec under an irradiation dose of /cmz (Kabri,
Image quality) was visually evaluated.

The environmental conditions during imaging were 20°C, 65% RH and 30°C, 8
It was carried out at 0% RH.

Note 4) Water retention: An electrophotographic light-sensitive material without plate making was immersed in a desensitizing liquid (E-1) prepared according to the following formulation for 3 minutes, and then washed with water.

Desensitizing treatment liquid (E-1) Dissolve this in distilled water and add 1. The pH was adjusted to 1).5 with potassium hydroxide.

This desensitized plate is printed on an offset printing machine (
The degree of scumming on the printed matter was visually evaluated using a Sakurai Seisakusho ■Oliver 52 model).

Note 5) Printing durability: Each photosensitive material is made into a toner image under the same conditions as in 3) above, and desensitized under the same conditions as in 4) above, and this is used as an offset master to form a toner image. This indicates the number of prints that can be printed under the same conditions as , without causing problems with background stains in the non-image areas and image quality of the image areas of the printed matter (the higher the number of prints, the more
(indicates good printing durability).

The electrostatic properties and imaging properties of the photosensitive material of the present invention and the photosensitive materials of the comparative example showed good results even when the environmental conditions changed.

However, the photosensitive material of Comparative Example B, in which a conventional resin was used as the binder resin of the photoconductive layer, had deteriorated electrostatic properties, and the resulting copied images were also unsatisfactory.

Furthermore, when the degree of hydrophilization was examined as an offset master master plate after desensitization treatment, the original plate of the present invention and Comparative Example B were sufficiently hydrophilized before plate making, and no printing ink stains were observed. It showed good water retention.

However, in Comparative Example A, slight staining was observed.

When we actually printed a master plate on which a copy image had been formed using a desensitizing process, we found that the one that gave printed matter with no background smudges in the non-image area from the start of printing and with good print quality was found to be It was only the original version of the present invention.

That is, in Comparative Example A, the water retention ability was insufficient, and in Comparative Example B, the quality of the copied image deteriorated due to a decrease in the electrophotographic properties, so that good printed matter could not be obtained.

As described above, only the photosensitive material of the present invention had excellent electrophotographic properties and printing properties.

Example 2 4,4'bis(diethylamino)-2,2'-dimethyltriphenylmethane 5g1 Bisphenol A polycarbonate (manufactured by GE, trade name) as an organic photoconductive substance
Lexan 121) 5g, spectral sensitizing dye with the following structural formula (■
), and 0.2 g of an anilide compound [A] having 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 solution.

Spectral sensitizing dye (n) Anilide compound [A] This photosensitive solution was transferred using a wire round rod to a conductive transparent support (100 μm polyethylene terephthalate support having a vapor deposited film of indium oxide, surface resistance lO''). Ω) to obtain an organic thin film having a photosensitive layer of about 4 μm.On the surface of this electrophotographic photoreceptor, 3% by weight (as solid content) of resin particles CL-2) and a resin CCl2 having the following structure were applied. ] 2% by weight, phthalic anhydride 0.3% by weight
A toluene dispersion containing 0.01% by weight of 2-chlorophenol was applied with a doctor blade, and then heated at 100°C.
After drying for 20 seconds, the film was further heated at 130° C. for 1 hour to form a surface layer of about 2 μm. Then, in the dark at 20℃, 65
An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under conditions of %RH.

Resin rQ-2) CH, C)l 3 +CHz-C-H47,←C)12-CH-), -mon CH2-C→〒7 "Degreasing treatment liquid prepared from this photosensitive material according to the following formulation (E-2) for 3 minutes to desensitize the sample.

Desensitizing treatment liquid (E-2) These were dissolved in distilled water, the pH was adjusted to 10.0 with sodium hydroxide, and the total amount was 1. It was set as Ol.

A droplet of 2 μl of distilled water was placed on this, and the contact angle with the water formed was measured with a goniometer and was found to be less than 10°. The contact angle before desensitization treatment was 88°,
This clearly shows that the surface layer of this photosensitive material was made very well hydrophilic.

In addition, this desensitized original plate was used in Note 5 of Example 1.
When printing was carried out under these conditions and the printed matter was checked for background stains, no stains were observed.

On the other hand, this electrophotographic light-sensitive material was plate-made using a fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film ■) using a negatively charged liquid developer to form a toner image, and desensitized under the same conditions as above. Processed, this is applied to an offset printing machine (manufactured by Sakurai Seisakusho ■, model 52) as an offset master,
Printed on high quality paper.

The number of prints that could be printed without causing problems with background stains in non-image areas and image quality in image areas was 10,000.

Further, this photosensitive material was left for 3 weeks under the environmental conditions of 45° C. and 75% RH, and then subjected to exactly the same treatment, but there was no change in the overall condition from before aging.

Example 3 5 g of bisazo pigment with the following structure, 95 g of tetrahydrofuran
g, resin [A-6] 0.8% by weight and resin CD-1) 4
．． A mixture of 30 g of 2% by weight tetrahydrofuran solution was thoroughly ground in a ball mill. Next, this mixture was taken out, and 520 g of tetrahydrofuran was added while stirring.

Example 1 This dispersion was prepared using a wire round rod.
It was coated on the conductive transparent support used in
A charge generation layer was formed.

(Bisazo pigment) Next, 20 g of a hydrazone compound having the following structural formula, 20 g of a polycarbonate resin (manufactured by GE, trade name: Lexan 121)
A mixed solution of 160 g of tetrahydrofuran and 160 g of tetrahydrofuran was applied onto the charge generation layer using a wire round rod to form a charge transport layer of about 18 μm, thereby obtaining an electrophotographic photoreceptor having a photosensitive layer consisting of two layers.

(Hydrazone compound) In the surface layer forming dispersion used in Example 2, 3% by weight of resin particles [L-2] was used instead of 3% by weight of resin particles (L-1) on this photoreceptor. Otherwise, a surface layer was formed in the same manner as in Example 2, and an electrophotographic photosensitive material was produced.

A paper analyzer (
The paper analyzer 5P-428 model manufactured by Kawaguchi Electric was charged at -6 kVG, and the initial potential (■・), dark charge retention rate (D, R, R, (%)) and light attenuation exposure (E,
, , ) were measured, and each Ve = -580VS
D, R, R, = 84% and E l/I.

It was 10.0 (1ux-sec).

Furthermore, in the same manner as in Example 1, a fully automatic plate making machine ELP4 was used.
When the plate was made using ELP-T)+- at 04V, the density of the obtained master plate for offset printing was 1.
The image quality was clear when it was 0 or more.

Furthermore, the master plate after plate making was immersed for 30 seconds in a desensitizing liquid (E-3) prepared according to the following formulation, and then washed with water to perform a desensitizing process.

Desensitizing treatment liquid (E-3) These were dissolved in distilled water, and the total amount was 1. The pH of this solution was adjusted to 1) and 0 using sodium hydroxide.

The contact angle of the non-image area with distilled water was 10' or less, indicating that it was sufficiently hydrophilized.

When this original plate for offset printing was printed on a printing machine,
After 10,000 copies were printed, there was no fog in the non-image areas and the images were clear.

The method for measuring the evaluation items of the electrostatic properties described above is as follows.

Electrostatic properties: In a dark room at a temperature of 20°C and 65% RH, each photosensitive material was corona discharged for 20 seconds using a paper analyzer (manufactured by Kawaguchi Denki ■, model 5P-428).
The surface potential at this time is v1. was measured. Then, the potential V after being left undisturbed for 60 seconds in the dark. The potential retention after dark decaying for 60 seconds, i.e.
The dark decay retention rate [D, R, R, (%)] is expressed as (V to
/V+a)xloo(%).

Further, after the surface of the photoconductive layer was charged to -400 V by corona discharge, the photoconductive layer was irradiated with visible light at an illuminance of 2.0 lux, and the surface potential (V+.) was 1/10 or 1/10.
Find the time until it decays to 0, and from this calculate the exposure amount E17
1° or E171°.

Calculate (looks/seconds).

Imaging properties: After each photosensitive material was left for one day and night under the following environmental conditions, it was plate-made using a fully automatic plate-making machine EPL-404V (manufactured by Fuji Photo Film) using EPL-T as a toner, and the resulting copy image was The fog and image quality were visually evaluated. The environmental conditions during imaging were 20°C, 65% RH (I) and 30°C, 8
It was carried out at 0% RH(n).

Example 4 As an organic photoconductive compound, X-type metal-free phthalocyanine (manufactured by Dainippon Ink ■)... 1.9 parts As an additive, the following thiobarbyl acid compound
...0.15 part resin [A-2]
・・・ 2 parts resin CD-1) ・・・
15 parts tetrahydrofuran/cyclohexane (8/2) weight ratio mixed solution...100 parts, 500 parts
The mixture was placed in a mf glass container together with glass beads and dispersed for 60 minutes using a paint shaker, and then the glass beads were filtered off to obtain a photoconductive layer dispersion.

Next, this photoconductive layer dispersion was applied to conductively treated paper using a wire bar so that the dry adhesion amount was 10 g/m'', and 1) it was dried at 0°C for 1 minute. The composition for forming a surface layer used in Example 2 was applied onto the body, and an electrophotographic photosensitive material was produced in the same manner as in Example 2.

The electrostatic properties, imaging properties, and
Printability was examined in the same manner as in Example 1.

Electrostatic properties = 20℃, 65%RH30℃, 80%RHV+
*(-V) 480V -47QvD,R
,R, (%) 85% 83%E+,z+
s(erg/Cm") 33 38 Regarding the imaging performance, there was no background smudge in the non-image area, and the image quality was clear and good. In addition, the water retention as a desensitized offset master master plate had no background smudge. Moreover, the rigidity resistance of the original plate after plate making was 8,000 sheets, which was good.

Furthermore, when the light-sensitive material was left for two weeks at 40° C. and 75% RH and evaluated in the same manner as above, almost no change was observed in any of the items, indicating good properties.

Example 5 8 g of Example (A-3), 1328 g of resin [), 200 g of zinc oxide, and 0.02 g of uranine.

Rose Bengal 0.04g1 Bromephenol Blue 0
．． 03 g, phthalic anhydride 0.04 g and toluene 30
0 g of the mixture in a homogenizer, 1 x to
' r, p, a+, rotation speed Te 5 minutes dispersion L t, knee.

The dry adhesion amount was 18g/m2 on conductive-treated paper.
1) Apply with a wire bar so that it becomes 1) 3 at 0℃
Dry for 0 seconds. On this photoreceptor, the surface layer composition used in Example 2 was applied in the same manner as in Example 2 to produce an electrophotographic photoreceptor.

Example 2 shows the electrostatic properties, imaging properties, and printability of this photosensitive material.
I investigated the same.

This photosensitive material was charged to -6 kV with a paper analyzer, the initial potential (V) was -580 V, the dark charge retention rate (D,
R, R, ) 85%, and light attenuation exposure (El/II)
A value of 15.0 (1ux-see) ty) was obtained for each.

Further, this was plate-made in the same manner as in Example 2, and the density of the obtained offset printing master plate was 1.0 or more and the image quality was clear.

Furthermore, the master original plate after plate making was immersed in the desensitizing liquid (E-2) used in Example 2 for 30 seconds, and then washed with water and desensitized. . The contact angle of the non-image area of the obtained printing original plate with distilled water was 10'' or less, indicating that it was sufficiently hydrophilized.

Next, this offset printing original plate was treated with a treatment liquid (E-2).
Using a solution diluted 50 times with distilled water as soaking water,
When printed with a printing machine, the printed matter after printing 10,000 sheets had no fog in the non-image area and the image was clear.

Examples 6 to 15 In Example 1, instead of 6 g of the photoconductive layer resin [A-7] and 3% by weight of the surface layer resin particles CL-1, each resin [A 16 g (as solid content) in Table 6 below was used. ), each electrophotographic light-sensitive material was prepared in the same manner as in Example 1 except that 3% by weight (solid content) of resin particles [L] was used.

When the front plate was made into a plate using the same apparatus as in Example 1, the density of the obtained offset printing master original plate was 1.0 or more and the image quality was clear. Furthermore, when the image was desensitized and printed using a printing press, the printed matter after printing 10,000 sheets had no capri in the non-image area and the image quality was clear.

Furthermore, this photosensitive material was left for 3 weeks under the environmental conditions of 45° C. and 75% RH, and then treated in exactly the same manner as above.
There was no change at all from before.

Examples 16 to 27 Using each of the photosensitive materials prepared in Examples 1 to 27, an etching process was performed as described below to prepare a master plate for offset printing.

0.5 mol of the nucleophilic compound shown in Table 7 below, 100 mol of organic solvent
g and New Fool B4SN (manufactured by Nippon Nyukazai ■) 10g
After adding distilled water to make 1), the pH of each mixture was adjusted to 100.
Adjusted to. Each photosensitive material was immersed in the above processing solution at 30° C. for 2 minutes.

The obtained plate was printed under the same printing conditions as in Example 1.

In each material, the contact angle with water in the non-image area was 10° or less, making it sufficiently hydrophilic. Furthermore, even though the number of prints was 10,000, the print image quality of the printed matter was good, with no blurring and clear images.

〔Effect of the invention〕

According to the present invention, it has excellent electrostatic properties (especially electrostatic properties under severe conditions), has clear and high-quality images, and can be used as an original plate for offset mastering with good image quality using electrophotography. A printing original plate having good quality and excellent printing durability can be obtained. Further, the lithographic printing original plate of the present invention is effective in a scanning exposure method using semiconductor laser light.

Claims (3)

[Claims] (1) In an electrophotographic lithographic printing original plate comprising at least one photoconductive layer provided on a conductive support and a surface layer provided on the uppermost layer, the surface layer has the following general formula (
1) and/or a polymer component having a functional group represented by general formula (II). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the above formula (I) or (II), -W_1-, -W_2 - is respectively -SO_2-, -C
Represents O- or -OOC-, n_1 and n_2 each represent 0 or 1, and X represents a halogen atom] (2) In the resin particles, the polymer component having a functional group represented by the general formula (I) and/or the general formula (II) has a crosslinked structure. Original plate for photolithographic printing. (3) Claim (1) or (2), wherein the photoconductive layer comprises at least a photoconductor and a binder resin, and contains the following resin [A] as the binder resin: The original plate for electrophotographic lithographic printing described above. Resin [A]: has a weight average molecular weight of 1 x 10^3 to 2 x 10^4,
30% by weight or more of repeating units represented by the following general formula (III) as polymer components, -PO_3H_2, -SO
At least one type selected from _3H, -COOH, ▲mathematical formula, chemical formula, table, etc.▼[R_1 represents a hydrocarbon group or -OR_2 (R_2 represents a hydrocarbon group]] and a cyclic acid anhydride-containing group A polymer component having a polar group of 0
．． 5 to 15% by weight. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the above formula (III), R_3 represents a hydrocarbon group containing a benzene ring or a naphthalene ring]