JPH01283572A - Master plate for planographic printing - Google Patents

Abstract

PURPOSE:To obviate the generation of scumming and to provide the master plate having high plate wear by incorporating a resin which has a functional group to form at least one carboxyl group by decomposition and is partly crosslinked as the essential component of the surface layer into said plate. CONSTITUTION:The master plate for planographic printing formed by utilizing an electrophotographic sensitive body provided with at least one photoconductive layer on a conductive base and further provided with the surface layer on the uppermost layer thereof contains at least one kind of the resin which contains at least one kind of the functional group forming at least one carboxyl group by decompositiion and is at least partly crosslinked as the essential component of the surface layer thereof. The master plate for electrophotographic planographic printing having the layer which contains such resin and can be imparted with a hydrophilic property on the surface layer is the film with which the high hydrophilic property and water resistance are compatible after the processing for imparting the hydrophilic property; in addition, the adhesiveness to a toner image is extremely good and, therefore, the resulted master plate for planographic printing has the excellent quality in terms of both the prevention of scanning and the printing resistance.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to an electrophotographic lithographic printing original plate made by an electrophotographic method, and in particular, a surface having specific properties on a photoconductive layer. This invention relates to a lithographic printing original plate having layers.

(Prior art and its problems) Currently, various kinds of offset original plates for direct plate making have been proposed and put into practical use. A photoreceptor with a photoconductive layer mainly composed of is subjected to a normal electrophotographic process to form a highly lipophilic toner image on the surface of the photoreceptor, and then the surface is coated with a non-lipidizing liquid known as an etchant. A widely used technique is to obtain an offset master plate by selectively making non-image areas hydrophilic.

In order to obtain good printed matter, first, the original image is faithfully copied onto the offset master plate, the surface of the photoreceptor is easily compatible with the anti-fat treatment liquid, and the non-image area is made sufficiently hydrophilic, and at the same time it has water resistance. In addition, during printing, the photoconductive layer with the image does not separate, has good compatibility with dampening water, and has sufficient hydrophilicity in the non-image area to prevent staining even if a large number of prints are made. It is necessary to have performance such as the ability to maintain

In particular, as an offset master plate, background smearing due to insufficient desensitizing properties is a major problem, and in order to improve this problem, the development of a zinc oxide binding resin that improves desensitizing properties has been studied. For example, Tokuko Sho 50-3101
No. 1, JP-A-53-54027, JP-A-54-207
No. 35, JP-A-57-202544, JP-A-58-6
It is disclosed in the specification of No. 8046 and the like. However, even if these resins are said to be effective in improving desensitization properties, when actually evaluated, they are still unsatisfactory in terms of scumming and printing durability.

On the other hand, using an organic photoconductive compound as the photoconductive particle,
It is also possible to use an electrophotographic body in which a photoconductive layer is provided together with a binder resin on a textured aluminum substrate.

To make this type of master plate, as described above, a toner image is formed on the photosensitive layer by a normal electrophotographic method, and then the non-image area is dissolved and removed using a processing liquid. As a result, the non-image portion becomes an aluminum substrate and becomes hydrophilic. For example, Special Publication No. 37-17162, Special Publication No. 17162, Special Publication No. 17162
-39405, JP-A-52-2437, JP-A-56
When using a photosensitive layer in which an oxadiazole compound or an oxazole compound is bound with an alkali-soluble resin such as a styrene-maleic anhydride copolymer, as shown in Japanese Patent Application Laid-open No. 105254-10724, etc.
No., JP-A-55-16125, JP-A-58-1509
It is known that a photosensitive layer comprising a phthalocyanine pigment or an ab pigment and an alkali-soluble phenol resin is used, as shown in Japanese Patent Application Laid-open No. 58-162961 and the like.

However, in this plate-making process, the photosensitive layer in the non-image area must be removed by dissolution, which requires a large-scale apparatus, takes time, and slows down the plate-making speed. Furthermore, since ethylene glycol, glycerin, methanol, ethanol, etc. are used as processing liquids (organic solvents), problems with this plate-making method remain in terms of cost, safety, pollution, and occupational health. There is.

Furthermore, Japanese Patent Publication No. 5606/1983 discloses a method of preparing a printing plate of the type in which the surface of the non-image area is hydrophilized, which is easy to make by providing a specific resin layer on an ordinary electrophotographic photoreceptor. That is, vinyl ether is deposited on the electrophotographic photosensitive layer.
A printing plate provided with a surface layer comprising a maleic anhydride copolymer and a hydrophobic resin compatible therewith is disclosed.

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 rigidity was limited to 500 to 600 sheets at most.

Furthermore, JP-A-60-90343, JP-A-60-159
No. 756, JP-A No. 61-217292, etc.,
A method of providing a surface layer (hydrophilicizable layer) containing silylated polyvinyl alcohol as a main component and also using a crosslinking agent is disclosed.

That is, in this layer, silylated polyvinyl alcohol is hydrolyzed in the non-image area after toner image formation to make it hydrophilic. In addition, 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 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 silyl and other agents, but it is difficult to produce stably because it is a molecular reaction. Furthermore, since the chemical structure of the hydrophilic polymer is limited, it is important to ensure that it does not inhibit its function as an electrophotographic photoreceptor: 1) charging properties, 2) quality of copied images (knitting point reproducibility, resolution, There were problems such as it was difficult to prevent the surface layer from affecting the image area (ground blur, etc.), 3) exposure sensitivity, etc.

Furthermore, as the surface layer resin, resins containing functional groups that generate hydrophilic groups upon decomposition are being considered; for example, resins containing functional groups that generate hydroxyl groups upon decomposition (Japanese Patent Application No. 1982 No. 106417, patent application No. 106417
2-15' No. 1507) and those containing functional groups that generate carboxyl groups upon decomposition (Japanese Patent Application No. 62-226).
No. 694, Japanese Patent Application No. 62-28345), etc. are disclosed.

These resins are resins that are hydrolyzed or hydrolyzed by desensitizing liquid or dampening water used during printing to generate hydrophilic groups, and when these resins are used as surface layer resins of planographic printing original plates, they are The generated hydrophilic group improves the hydrophilicity of the non-image area, makes the lipophilicity of the image area and the hydrophilicity of the non-image area clear, and prevents printing ink from adhering to the non-image area during printing. It is stated that as a result, it becomes possible to print a large number of prints with clear image quality and no background smear.

However, even when these resins are used, they are still not satisfactory in terms of scumming and printing durability, and even when using resins containing hydrophilic group-forming functional groups such as those mentioned above, hydrophilicity in non-image areas is In order to further improve the content, if the content is increased, the hydrophilicity will increase due to the hydrophilic groups generated by decomposition, and the surface layer resin will become water-soluble, which causes problems especially in terms of its sustainability. I found out something.

Therefore, it is desired to develop a technique that further improves the effect of hydrophilicity in non-image areas and further improves durability.

Further, in the conventional technology, there were problems such as a narrow allowable range of material composition when achieving a comprehensive balance of electrophotographic properties, film properties, etc.

The present invention is intended to improve the problems of electrophotographic lithographic printing original plates as described above.

The object of the present invention is to provide an insensitizing, dry planographic plate that reproduces a copy image that is faithful to the original image, and that does not cause not only uniform background smudges on the entire surface but also dotted smudges as an offset original plate. The purpose is to provide original printing plates.

Another object of the present invention is to provide a lithographic printing original plate which maintains sufficient hydrophilicity in non-image areas even when the number of printed sheets increases, does not cause scumming, and has good stiffness.

Another object of the present invention is to provide a lithographic printing original plate having a resin that can be used in the surface layer, can be made hydrophilic in non-image areas, and is easy to manufacture.

Another object of the present invention is to provide a lithographic printing original plate having a wide range of material composition tolerances when achieving a comprehensive balance of electrophotographic properties, film properties, etc.

(Means for Solving the Problems) The above-mentioned method is based on lithographic printing using an electrophotographic photoreceptor comprising at least one photoconductive layer on a conductive support and a surface layer on the top layer. In the original plate, the surface layer preferably contains at least one functional group that generates at least one carboxyl group upon decomposition and at least one resin that is at least partially crosslinked. It has been found that this can be achieved by an electrophotographic lithographic printing original plate having the following characteristics.

Below, at least one functional group that decomposes to produce at least one carboxyl group used in the present invention will be described.
species-containing resin (hereinafter simply referred to as "carboxyl group-forming agent f7")
(sometimes referred to as "iJ-containing resin") will be explained in detail.

The functional group contained in the carboxyl group-forming functional group-containing resin of the present invention generates a carboxyl group by decomposition.
The number of carboxyl groups generated from one functional group may be one or two or more.

According to one preferred embodiment of the present invention, the carboxyl group-generating functional group-containing resin is a resin containing at least one functional group represented by the general formula (1): (-COO-L').

In general formula (1) [Coo-L'), LIR
l R1! is -(-C-)ko "IX1-) 了Z', -M-R'
, RZ R5 -N=CH-Q', -C-Q2, -NO-OH.

1'1 υ represents.

However, R1 and RZ may be the same or different and represent a hydrogen atom or an aliphatic group; Xl represents a divalent aromatic group; ZI represents a hydrogen atom, a halogen atom, a trihalomethyl group, an alkyl group , -CN, NOz, So□
R2+, -COOR", 0 1 (2j or -Co-R2
4 (wherein R", Rzz, R2'3, and R24 each represent a hydrocarbon group); n and m represent Oll or 2.

R", R', and R5 may be the same or different and represent a hydrocarbon group or -Ql'; 12s (wherein, R2S represents a hydrocarbon group); M is Si, Sn, or T
represents i.

Q' and Q'' each represent a hydrocarbon group.

Yl represents an oxygen atom or a sulfur atom; R11, R7
, R8 may be the same or different and each represents a hydrogen atom, a hydrocarbon group or -0R16 (wherein RZ& represents a hydrocarbon group); p represents an integer of 5 or G;

Y2 represents an organic residue forming a cyclic imide group.

The functional group of the general formula (-Coo-L') generates a carboxyl group upon decomposition, and will be explained in more detail below.

Ll is -+C-)? When representing -(X'-)-TZ', R1 and R2 may be the same or different and represent a hydrogen atom or an aliphatic group.

The aliphatic group represented by R1 and R2 is preferably a linear or branched alkyl group having 1 to 12 carbon atoms that may be substituted (for example, a methyl group, an ethyl group, a propyl group, a chloromethyl group, a dichloro methyl group, trichloromethyl group, trifluoromethyl group, butyl group, hexyl group, octyl group, decyl group, hydroxyethyl group, 3-chloropropyl group, etc.).

Xl represents a divalent aromatic group, preferably a divalent phenylene group or naphthylene group that may be substituted (for example, a phenylene group, a methylphenylene group, a chlorophenylene group, a dimethylphenylene group, a chloromethylphenylene group,
naphthylene group, etc.).

ZI preferably has a hydrogen atom, a halogen atom (for example, a chlorine atom, a fluorine atom, etc.), a trihalomethyl group (for example, a trichloromethyl group, a trifluoromethyl group, etc.), or a carbon number of 1.
~12 optionally substituted linear or branched alkyl groups (e.g., methyl group, chloromethyl group, dichloromethyl group, ethyl group, propyl group, butyl group, hexyl group, tetrafluoroethyl group, octyl group) , cyanoethyl group,
(chloroethyl group, etc.), -CN, -NO2, -SO□Rz
+.

-COOR", Q-R13 or -Co-R" (wherein RZI, R22, R", RZ4 each represent a hydrocarbon group). As a hydrocarbon group represented by R21, R2!, Ral, RZ4, is preferably an aliphatic group [for example, an optionally substituted alkyl group having 1 to 12 carbon atoms (specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a chloroethyl group, a pendel group, an octyl group, etc.), Carbon number 7
~12 optionally substituted aralkyl groups (specifically benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, chlorophenethyl group, methylphenethyl group, etc.)] or aromatic group [e.g. optional phenyl group or naphthyl group (specifically, phenyl group, chlorophenyl group, dichlorophenyl group, methylphenyl group, methoxyphenyl group, acetylphenyl group, acetamidophenyl group, methoxycarbonylphenyl group, naphthyl group, etc.)] Can be mentioned.

n and m represent Oll or 2.

The Ll described above is -(-C→-7-(X'),
To explain more specifically the case where Z' is represented, the following examples of substituents can be given.

For example, β, β, β-trichloroethyl group, β.

β, β-trifluoroethyl group, hexafluoro-1-
Propyl group, -CH□+CF2CF2+-? -H group (n
' indicates 1 to 5), 2-cyanoethyl group, 2-nitroethyl group, 2-methanesulfonylethyl group, 2-ethanesulfonylethyl group, 2-butanesulfonylethyl group,
Benzenesulfonylethyl group, 4-nitrobenzenesulfonylethyl group, 4-cyanohenzenesulfonylethyl group, 4-methylbenzenesulfonylethyl group, Wt91
A benzyl group that may contain a group (e.g. benzyl group, methoxyhensyl group, 1-limethylbenzyl group, pentamethylbenzyl group, nitrobenzyl group, etc.), a phenacyl group that may contain a substituent (e.g. phenacyl bromophenacyl group, etc.), and phenyl groups which may contain substituents (eg, phenyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group, trifluoromethylphenyl group, dinitrophenyl group, etc.).

When Ll represents -M-R', R3, R',
R5 may be the same or different from each other, and is a hydrocarbon group or -o-R2S (wherein R25 represents a hydrocarbon group)
represents. The hydrocarbon group represented by R3, R', and R5 is preferably an optionally substituted aliphatic group having 1 to 18 carbon atoms [the aliphatic group is an alkyl group, an alkenyl group,
It represents an aralkyl group or an alicyclic group, and examples of substituents include a halogen atom, -CNi, -08 group, -0-Q3
(Q' represents an alkyl group, an aralkyl group, an alicyclic group, an aryl group)], an optionally substituted aromatic group having 6 to 18 carbon atoms (for example, a phenyl group, a tolyl group,
(chlorophenyl group, methoxyphenyl group, acetamidophenyl group, naphthyl group, etc.). The hydrocarbon group represented by R2S is preferably an optionally substituted argyl group having 1 to 12 carbon atoms, an optionally substituted alkenyl group having 2 to 12 carbon atoms, or an optionally substituted alkenyl group having 7 to 12 carbon atoms. Aralkyl group, optionally substituted with 5 to 5 carbon atoms
Examples include 18 alicyclic groups and optionally substituted aryl groups having 6 to 18 carbon atoms.

M represents each atom of Si, Ti, or Sn, and more preferably represents a Si atom.

When Ll represents -N=CH-Q' or -CQ2, Q' and Q2 each represent a hydrocarbon group. The hydrocarbon groups represented by Q' and Q'' are preferably optionally substituted aliphatic groups each having 1 to 18 carbon atoms (the aliphatic groups include alkyl groups, alkenyl groups, aralkyl groups, alicyclic groups, etc.). Examples of substituents include halogen atoms, -CN groups, alkoxy groups, etc.), optionally substituted aryol groups having 6 to 18 carbon atoms (e.g. phenyl group, methoxyphenyl group, tolyl group, chlorophenyl group, naphthyl group, etc.)
can be mentioned.

In 'Yl represents an oxygen atom or a sulfur atom.

R6, R7, and R8 may be the same or different from each other, and each represents a hydrogen atom, a hydrocarbon group, or 0RZ6 (however, R''
represents a hydrocarbon group). Rh, R? , Ra
The hydrocarbon group represented by is preferably a linear or branched alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic groups (e.g. cyclopentyl group, cyclohexyl group, etc.), substituted Aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, chlorobenzyl group, chlorohensyl group, methylbenzyl group, methoxybenzyl group, 3-phenylpropyl group, etc.), optionally substituted aromatic groups ( Examples include phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl W, etc.).

Specifically, the hydrocarbon group represented by RZ& is,
The same hydrocarbon groups as those represented by R6, R7, and R6 above can be mentioned.

p represents an integer of 5 or 6.

Y2 represents an organic residue forming a cyclic imide group. Preferably, it represents an organic residue represented by -stratification (II) or (III).

General formula (II) General formula (III) In formula (It), R' and R'' may be the same or different, and each is a hydrogen atom, a halogen atom (for example, a chlorine atom,
bromine atom, etc.), an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, 3-
chloropropyl group, 2-(methanesulfonyl)ethyl group, 2-(ethoxyoxy)ethyl group, etc.), carbon number 7-1
2 optionally substituted aralkyl groups (e.g., hensyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group,
chlorobenzyl group, bromobenzyl group, etc.), carbon number 3~
an optionally substituted alkenyl group (e.g. allyl group, 3-methyl-2-propenyl group, 2-hexenyl group)
, 4-propyl-2-pentenyl group, 12-octadecenyl group, etc.), -3-R"(R" is the above R9 or RIG
A substituent having the same content as an alkyl group, aralkyl group, or alkenyl group, or an optionally substituted aryl group (
For example, phenyl group, tolyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, ethoxyphenyl group, ethoxycarbonylphenyl group, etc.). ],
or -NHR"(R"l: is the same as R" above). It may also represent a residue that forms a ring with R9 and RIll [for example, a 5- to 6-membered ring]. Monocyclic (e.g. cyclopentyl ring, cyclohexyl ring), or 5-6
membered bicyclo rings (e.g., bicyclohebutane ring, bicycloheptene ring, bicyclooctane ring, bicyclooctene ring, etc.)]. The ring condensed with R9 and R'' may be further substituted, and substituents include groups other than hydrogen atoms among those listed above for R9 and R10, i.e., halogen atoms,
Alkyl group, aralkyl group, alkenyl group, 3-R2
'? and -NHR28, with alkyl groups and aralkyl groups being particularly preferred.

9 represents an integer of 2 or 3.

In the formula (I[[), RII and RI2 may be the same or different and represent the same content as R9 and RIo above. Furthermore, R11 and R12 may represent an organic residue that is linked to form an aromatic ring (for example, a benzene ring,
naphthalene rings, etc.).

In another preferred embodiment of the present invention, the carboxyl group-generating functional group-containing resin is a resin containing at least one functional group represented by -stratification (TV) (-Co-L2).

In the general formula (IV) (-Co-L2), L2 represents ".".However, R31, R32, R33, R34, R
, i5 each represent a hydrogen atom or an aliphatic group, and R3
t and R33, or R34 and R35 may represent an organic residue that is linked to form a condensed ring.

The aliphatic groups represented by R3+ and R15 preferably have the same content as the aliphatic groups among the hydrocarbon groups represented by R6 to R8.

Further, when R32 and R33 or R34 and R35 represent organic residues that are linked to form a condensed ring, the condensed ring is preferably a 5- to 6-membered monocyclic ring (for example, a cyclopentyl ring, a cyclohexyl ring, etc.). ), 5- to 12-membered aromatic rings (eg, benzene ring, naphthalene ring, thiophene ring, virol ring, pyran ring, quinoline ring, etc.).

Furthermore, as another preferable embodiment of the present invention, the carboxyl group-forming functional group-containing resin is a resin containing at least one oxacylone ring represented by -stratification (V).

In general formula (V), R41 and R4Z may be the same or different from each other, each representing a hydrogen atom or a hydrocarbon group, or R41 and R42 may be linked to form a ring.

Preferably, R41 and R4Z may be the same or different, and each represents a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.). , butyl group, hexyl group, 2
-chloroethyl group, 2-methoxyethyl group, 2-methoxycarbonylethyl group, 3-hydroxypropyl group, etc.)
, optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. evabenzyl group, 4-chlorobenzyl group, 4-acetamidobenzyl group, phenethyl group, 4-methoxybenzyl group, etc.), optionally substituted carbon number 2-12 alkenyl groups (e.g. vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, etc.), optionally substituted 5-7 membered alicyclic groups (e.g. cyclopentyl group, cyclohexyl group, chlorocyclohexyl group, etc.), optionally substituted aromatic groups (e.g. phenyl group, chlorophenyl group, methoxyphenyl group, acetamidophenyl group, methylphenyl group, dichlorophenyl group, nitrophenyl group, naphthyl group, butylphenyl group, dimethylphenyl group) or R'' and R42 may be linked to form a ring (eg, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc.).

General formula (I) (-COO-L1) used in the present invention,
- Resins containing a small number of functional groups (at least one type) selected from the group of functional groups represented by stratification (IV) (-Co-L") have the general formula (1) Or - a method using a so-called polymer reaction to convert into a functional group of stratification (IV); or - stratification (1)
or - polymerization reaction of one or more monomers containing one or more functional groups of stratification (IV) or with other monomers which can be copolymerized therewith. It can be obtained by a method of making a polymer by a polymerization reaction.

These methods are described, for example, in "New Experimental Chemistry Course, Volume 14," edited by the Chemical Society of Japan, "Synthesis and Reactions of Organic Compounds (V) J, Volume 2.
535 pages (published by Maruzen Co., Ltd.), written by Yoshiyu Iwakura and Keisuke Kurita,
It is described in detail in known literature cited in reviews such as "Reactive Polymer", page 170 (published by Kodansha).

General formula (-Coo-L') or (-C
The general formula (
-Coo-L') or (-Co-L'') is preferably produced by a polymerization reaction from monomers containing one or more functional groups. Containing carboxylic acids or their acid halides,
For example, according to the method described in the above-mentioned known documents, etc.
After converting the carboxyl group into a functional group of the general formula [~CO○-L+] or (-Co-L2), it can be produced by performing a polymerization reaction.

Further, the resin containing an oxadurone ring represented by the form (V) can be obtained by polymerization reaction of one or more monomers containing the oxadurone ring, or by the polymerization reaction of the monomer and other monomers that can be copolymerized therewith. It can be obtained by a method of making a polymer by a polymerization reaction with a monomer.

This monomer containing an oxazolone ring can be produced by a dehydration ring closure reaction of N-acyloyl-α-amino acids containing a polymerizable unsaturated bond. Specifically, it can be produced by the method described in the literature cited in the review of "Reactive Polymers", Chapter 3, written by Yoshiyu Iwakura and Keisuke Kurita (published by Kodansha).

Other monomers that can be copolymerized with these monomers include, for example, vinyl acetate, vinyl propionate, vinyl butyrate,
Aliphatic carboxylic acid vinyl or allyl esters such as allyl acetate and allyl propionate; esters or amides of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc.; Examples include styrene derivatives such as styrene, vinyltoluene, and α-methylstyrene; α-olefins; acrylonitrile; methacriconitrile; and vinyl-substituted heterocyclic compounds such as N-vinylpyrrolidone.

As mentioned above, to describe more specifically the copolymer components containing the functional groups of general formulas (1), (IV), and (V) used in the method of producing a desired resin by polymerization reaction, for example, the following - components such as maximum (Vl). However, it is not limited to these copolymer components.

General formula (Vl) (Xll YIG), W In formula (Vl), XIO is -〇-3-CO-1-COO
-1-OCO-1-N-co-1d Z
d3-CON-1-SO2-1-3O2
N-1, -NSO□-1-CH2COO-1 b' or a divalent heterocyclic group. However, dl, d2, d
: I, a4 are each a hydrogen atom, a hydrocarbon group, or a formula (V
b+ and b2 may be the same or different, and represent a hydrogen atom, a hydrocarbon group, or -(Ylo W) in 2 (Vf), and l is 0 to 1
Indicates an integer of 8. a hydrocarbon group represented by b+, b2,
The hydrocarbon groups represented by and dl, , 14 are, respectively,
- has the same meaning as the hydrocarbon group represented by R6-R8 in format (1).

W represents a functional group represented by general formula (1), (R/), or (V).

YlO is typically a divalent connecting group that connects the bonding group X1° and the functional group W, which may be via a heteroatom (heteroatoms include an oxygen atom, a sulfur atom, and a nitrogen atom), for example. , h'1 dゝ? (-CH2COO, -〇-1-S-1-N-1-COO
-1-CON H-1-3O7-1-S O□Nl-i
-, -N HCOO-1-N I CON H-
It is composed of a single or a combination of bonding units of the 1st grade (however, b:l, b4 have the same meanings as the above bl and b2, respectively, and d5 has the same meaning as the above d+ to d4) a I , a 2 may be the same or different, and hydrogen atom, halogen atom (e.g. chlorine atom, bromine atom, etc.)
, a cyano group, a hydrocarbon group (for example, an optionally substituted alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, a butoxycarbonylmethyl group, etc.) groups; aralkyl groups such as Hensyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, xylyl group, chlorophenyl group, etc.), optionally substituted alkoxycarbonyl groups having 1 to 12 carbon atoms (for example, methoxycarbonyl group) , ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, etc.)
, or an alkyl group, alkenyl group, aralkyl group, alicyclic group, or aromatic group having 1 to 18 carbon atoms, which may be substituted with a substituent containing the -W group in formula (VT).

r is 0 or 1.

Specific examples of the functional groups represented by general formulas (1), (IV), and (V) [W group in formula (VT)] of the present invention will be described below. However, the scope of the present invention is not limited to these.

CH.

(8) -COO-3i-C4H.

CI(.

C.IT.

■ (9) Coo Si CJ1tC3H
'r C61(S! (10) -COO-3i-CI.

bHs CI-f 2C6H% (11) Coo Si CH3Cfl2C
, Hs (12) -COOCH2CF3 F3 (13) -COOCR F 3 / N O2 NO□ OCH.

0 Cz Hs CH3 C2H5 C41 (q YOCH, C6H3 (4B) -COOCH20CH3 (50) -COOC(C6H5)3 The polymer component containing a carboxyl group-forming functional group in the resin of the present invention is a polymer component containing a carboxyl group-forming functional group when the resin is a copolymer. In some cases, 20% of the total polymer
It is preferably from 40 to 95% by weight, particularly from 40 to 95% by weight.

In addition, the molecular weight of the resin polymer is 103 to 10 h, especially 5 h.
It is preferable that it is X103-5X10'.

The resin of the present invention is further characterized in that at least a portion thereof is crosslinked in an original plate for electrophotographic planographic printing.

As such a resin, a resin that has been crosslinked in advance during application of the surface layer forming material in the plate-making process may be used, or a resin containing a crosslinkable functional group that causes a curing reaction with heat and/or light may be used. may be used in the surface layer and crosslinked during the manufacturing process of the lithographic printing original plate (for example, during the drying process). Furthermore, these may be used in combination.

When a resin in which a portion of the polymer has been crosslinked in advance (resin having a crosslinked structure in the polymer) is used as the resin for the surface layer, the carboxyl group-forming functional group contained in the resin may be decomposed. When a carboxyl group is generated,
Resins that are sparingly soluble or insoluble in acidic and alkaline aqueous solutions are preferred.

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.

For the method 1- of introducing a crosslinked structure into a polymer, a commonly known method can be used.

That is, in the polymerization reaction of monomers, there are two methods: a method in which polyfunctional monomers are coexisting and polymerization is carried out, and a method in which a functional group that promotes a crosslinking reaction is contained in the polymer and crosslinked by a polymer reaction.

The resin of the present invention does not impair electrophotographic properties, or the manufacturing method is simple (for example, a long reaction is required, the reaction is not quantitative, or impurities are mixed in due to the use of reaction accelerators, etc.) ) etc., a functional group having a self-crosslinking reaction (C0NHCH20R5+ (R'' is a hydrogen atom or an alkyl group) or a crosslinking reaction by polymerization is effective.

In the polymerization-reactive group, preferably the polymerizable functional group is 2
A method in which a monomer having two or more polymerizable functional groups is polymerized together with a monomer containing a functional group that generates a carboxyl group by decomposition according to the present invention, or a monomer having two or more polymerizable functional groups is The resin of the present invention can be produced by polymerizing the monomers contained therein to form a copolymer and then protecting the carboxyl group as described above.

Specifically, the polymerizable functional group is CH2=CH-8CH,
=CH-C1(2-1CH2=CH-C-0-1CH3 CH2=CH-C0NH-1CH2=C-CONH-1
CH,0 CHz=COC-1 CH□-Cll-CH2-O-C-1 CH2=CH-NHCC)-, CH2=CHC)fz NHCO-1CI Z =
CHS Oz-1CH2= CH-CO-1CH2=
Cl-1-0-1CH2=CH-3-3, etc., but monomers having two or more of the above polymerizable functional groups may have these polymerizable functional groups the same or different. Any monomer having two or more of these compounds may be used, and upon polymerization, it forms a polymer that is insoluble in non-aqueous solvents.

Specific examples of monomers having two or more polymerizable functional groups include 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 , esters of methacrylic acid, acrylic acid or crotonic acid, vinyl ethers or allyl ethers of polyhydroxyphenols (e.g. hydroquinone, resorcinol, catechol and their derivatives) - dibasic acids (e.g. malonic acid, succinic acid, glutaric acid,
adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) vinyl esters, allyl esters,
Vinylamide or allylamide; polyamine (e.g. ethylenediamine, 1,3-propylenediamine,
, 4-butylene diamine, etc.) and a vinyl group-containing carboxylic acid (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

In addition, monomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, acryloylpropionic acid, itaconyloyl acetic acid, itaco Vinyl groups of niloylpropionic acid, reactants of carboxylic acid anhydrides and alcohols or amines (e.g. allyloxycarbonylpropionic acid, allyloxycarbonyl M, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.) ester derivatives or amide derivatives containing (e.g. vinyl methacrylate, vinyl acrylate,
Vinyl itaconate, allyl methacrylate, allyl acrylate, vinyl itaconate, vinyl methacryloyl acetate,
Vinyl methacryloylpropionate, allyl methacryloylpropionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonyl ethylene ester acrylate, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide, methacryloylpropionic acid allylamide, etc.) or condensates of amino alcohols (e.g. amine ethanol, 1-amitubanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and carboxylic acids containing vinyl groups. It will be done.

The monomer having two or more polymerizable functional groups used in the present invention is used in an amount of 15% by weight or less, preferably 10% by weight or less of the total monomers, and is polymerized to form a resin.

On the other hand, in the present invention, a resin containing a crosslinkable functional group that causes a curing reaction with heat and/or light together with the carboxyl group-forming functional group is used as a resin for the surface layer, and a crosslinked structure is formed in the subsequent original plate manufacturing process. may be formed.

The functional group may be any functional group as long as it can cause a chemical reaction between molecules and form a chemical bond. That is, it is possible to use a reaction mode in which bonding between molecules by condensation reaction, addition reaction, etc. or crosslinking by polymerization reaction is caused by heat and/or light.

Specifically, a functional group having a dissociable hydrogen atom [(for example, -COOH group, -PO, H group, +1 P R52 (R52 is represented by R6 to RI' in formula (1)) A group having the same content as a hydrogen group or -OR'', 1(R
53 represents the same content as the hydrocarbon group of R52),
-OH group, -3H group, -NH-R'' group (R54 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, butyl group)] and - -CONHCH20
R'' (Rsl represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as hamethyl group, ethyl group, propyl group, butyl group, hexyl group) or a polymerizable double bond group.

Specific examples of the polymerizable double bond group include those mentioned above as specific examples of the polymerizable functional group.

Furthermore, for example, Tsuyoshi Endo, “Refinement of Thermosetting Polymers J.
(C, M, C■, published 1986), Yuji Harasaki, "Latest Binder Technology Handbook" Chapter 1I-1 (General Technology Center, published 1985), Otsu Accompanying "Synthesis of Acrylic Resin"
"Design and New Application Development" (Chubu Business Development Center Publishing Department,
(published in 1985), Eizo Omori “Functional Acrylic Resin”
(Technosystem, 1985), Hideo Inui and Gentabe Nagamatsu, “Photosensitive Polymer” (Kodansha, 1977), Takahiro Tsunoda, “New Photosensitive Resin” (Printing Society Publishing Department, 1988)
1 year), G, E, Green and B,
P., 5tark, J.

Macro, Sci, Revs, Macro,
Chem,, C21(2)+ 187-273(19
81-82), C.G. Roffey, 'Photo
opoly-merization of 5urfa
ce Coatings” (A, WileyInte
It is possible to use functional groups, compounds, etc. cited in reviews such as ``Science Pub, 1982''.

These crosslinkable functional groups may be contained in one copolymer component together with the carboxyl group-generating functional group, or they may be contained in a separate copolymer component from the copolymer component containing the carboxyl group-generating functional group. It may be contained in the ingredients.

Specific monomers corresponding to the copolymer components containing these crosslinkable functional groups include, for example, vinyl-based monomers containing crosslinkable functional groups that can be copolymerized with the above-mentioned type (VT). Any compound may be used.

For example, see the Polymer Data Handbook [Polymer Data Handbook]
Basic Edition] Baifukan (published in 1986), etc.

Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g., α-acetoxy form, α-acetoxymethyl form, α-tetraform, α-bromo form, α-fluoro 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 amide neck, 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, vinyl In the substituents of benzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half-ester derivatives of dicarboxylic acids containing a vinyl group or allyl group, and ester derivatives and amide derivatives of these carboxylic acids or sulfonic acids. Examples include compounds containing the crosslinkable functional group.

The proportion of the "copolymer component containing a crosslinkable functional group" in the resin of the present invention is preferably 0.5 to 50% by weight. More preferably, it is 1 to 30% by weight.

If necessary, a reaction accelerator may be added to such a resin in order to promote the crosslinking reaction. For example, acids (acetic acid, propionic acid, acetic acid, benzenesulfonic acid, P-1
-luenesulfonic acid, etc.), peroxides, azobis compounds, crosslinking agents, aggravating agents, photopolymerizable monomers, and the like.

Specifically, as a crosslinking agent, see Shinzo Yamashita and Tosuke Kaneko,
Compounds described in "Crosslinking Agent Handbook" published by Taiseisha (1981) and the like can be used. For example, commonly used crosslinking agents such as organic silanes, polyurethanes, and polyisocyanates, and curing agents such as epoxy resins and melamine resins can be used.

When containing a photocrosslinking-reactive functional group, an exacerbating agent, a photopolymerizable monomer, etc. can be used, and specifically, the compounds cited in the review on photosensitive resins mentioned above are used. be able to.

When a resin containing a crosslinkable functional group is used, crosslinking in at least a portion of the polymer can be carried out during the process of forming a surface layer or during the process of heating and/or light irradiation before etching treatment. Normally,.

Preferably, a heat curing treatment is performed. This heat curing treatment can be performed by tightening the drying conditions during conventional photoreceptor production. For example, the treatment may be performed at 60''C to 120''C for 5 minutes to 120 minutes. When the above-mentioned reaction accelerator is used in combination, it becomes possible to perform the treatment under milder conditions.

In addition to the resin used in the present invention, conventionally known resins can also be used in combination. Examples include silicone resin, alkyd resin, vinyl acetate resin, polyester resin, styrene-butadiene resin, acrylic resin, etc. Specifically, Ryuji Kurita and Tsugube Ishiwata, "Polymer", Vol. 17,
278 page (1968), Harumi Miyamoto and Hidehiko Takei, "Imaging", 1973 (No. 8), page 9, and other known materials cited in the review.

The resin used in the present invention and known resins can be mixed in any ratio, but the content of the carboxyl group-forming functional group component in the total resin (1) is 20 to 100% by weight, preferably 35 to 99% by weight. Must contain a maximum of % by weight.

The resin of the present invention contains at least one functional group that produces at least one carboxyl group upon decomposition, and is hydrolyzed or hydrolyzed by a desensitizing liquid and dampening solution used during printing to produce at least one carboxyl group. It is a resin that produces groups.

Therefore, in a wood planographic printing original plate containing this resin as a main component in the surface layer (a hydratable layer), the non-image area is made hydrophilic by the carboxyl groups generated in the resin, and the image area becomes lipophilic. It is clearly distinguished from the above, and printing ink does not adhere to non-image areas during printing.

Furthermore, since the resin of the present invention has a crosslinked structure in at least a portion of the polymer in its original plate, the carboxyl group-containing resin produced by the desensitization process becomes water-soluble while retaining its hydrophilicity, resulting in a non-imageable image. It has the effect of preventing the leaching from the part of the body.

Therefore, the hydrophilicity of the non-image area is further enhanced by the carboxyl groups generated in the resin, and the durability is improved.

In terms of more specific effects, even if the amount of carboxyl group-forming functional group-containing resin contained in the surface layer resin is reduced,
Even if the effect of improving hydrophilicity is maintained, or printing conditions become harsher, such as by increasing the size of the printing machine or fluctuating the printing pressure, it is possible to print a large number of prints with clear image quality without background smudges. Become.

In order to improve the strength of the hydrophilic surface layer itself, the adhesion with the electrophotographic photosensitive layer, the electrophotographic properties, etc., resins other than the resins of the present invention described above may be added, or crosslinking agents or plasticizers may be added. May be added.

As the crosslinking agent, commonly used crosslinking agents such as organic peroxides, metal soaps, organic silanes, and polyurethanes, and curing agents such as epoxy resins can be used. Specifically, they are described in "Handbook of Crosslinking Agents" edited by Fuzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981).

Furthermore, the surface layer that can be made hydrophilic has its surface mechanically matted for the purpose of improving development characteristics during toner development, adhesion of toner images, water retention after hydrophilic treatment, etc. A matting agent may be contained in the layer. Examples of matting agents include fillers such as silicon dioxide, zinc oxide, titanium oxide, zirconium oxide, glass particles, alumina, and clay, and polymer particles such as polymethyl methacrylate, polystyrene, and phenolic resin. can.

What is important when forming the surface layer is that the non-image area becomes sufficiently hydrophilic after the fat-unfavoring treatment, as described above.

That is, this wood-philicity can be confirmed, for example, by measuring the contact angle with water.

The contact angle of surface N (hydrophilicizable layer) with water before the desensitizing treatment is about 60° to 120°, but after the desensitizing treatment, it decreases to about 5° to 20°. and become very wet with water. Therefore, the printing plate has an image area made of lipophilic toner and a highly hydrophilic non-image area formed on its surface. Therefore, the contact angle of the surface layer with water after the anti-fat treatment may be 20 degrees or less.

The present invention is particularly superior in that its hydrophilicity is even better than conventional ones.

The electrophotographic photosensitive layer (photoconductive M) used in the present invention includes:
Any photoconductive substance can be used, whether it is an inorganic photoconductive compound or an organic photoconductive compound.

Examples of inorganic photoconductive substances include zinc oxide, titanium oxide, zinc sulfide, selenium, selenium alloys, cadmium sulfide, cadmium selenide, and silicon, which together with the binding resin form the photoconductive layer. You can also
Alternatively, the photoconductive layer may be formed alone by vapor deposition, sputtering, or the like. As an organic photoconductive substance,
For example, as polymers, the following (1) to (5) can be mentioned.

(1) Polyvinylcarbazole and its derivatives described in Japanese Patent Publication No. 34-10966, (2) Japanese Patent Publication No. 43-1
Polyvinylpyrene, polyvinylene helix, polyvinylpyrene, polyvinylpyrene, polyvinylpyrene, and
2=vinyl-4-(4'-dimethylaminophenyl)
-5-phenyl-oxazole, poly-3-vinyl-N
- Vinyl polymers such as ethylcarbazole, (3) Polymers such as polyacenaphthylene, polyindene, copolymers of acenaphthylene and styrene, etc. described in Japanese Patent Publication No. 19193-1983, (4) Japanese Patent Publication No. 13940-1982 Condensation resins such as pyrene-formaldehyde resin, brompyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin described in JP-A-56-90833 and JP-A-56-16155, etc.
Various triphenylmethane polymers described in Publication No. 0.

Examples of low molecular weight compounds include the following (6) to (18).

(6) Triazole derivatives described in US Pat. No. 3,112,197, etc.; (7) Oxadiazole derivatives, described in US Pat. No. 3,189,447, etc.;
Imidazole derivatives described in Publication No. 16096, etc. (9) U.S. Patent No. 3615402, U.S. Patent No. 382098
No. 9, No. 3542544, Special Publication No. 45-555, No. 10983-1983, Japanese Patent Publication No. 93224-1971,
JP-A-55-17105, JP-A-56-4148,
JP-A-55-108667, JP-A-55-15695
No. 3, polyarylalkane derivatives described in JP-A-56-36656, publications, etc. (10) U.S. Pat. No. 3180729, U.S. Pat. No. 42787
No. 46, JP-A-55-88064, JP-A-55-88
No. 065, JP-A-49-105537, JP-A-55-
No. 51086, JP-A-56-80051, JP-A-56
-88141, JP-A-57-45545, JP-A-5
Pyrazoline derivatives and pyrazolone derivatives described in No. 4-112637, JP-A-55-74546, publications, etc., (11) U.S. Pat. -83
No. 435, JP-A-54-110836, JP-A-54-
No. 119925, Special Publication No. 1971-3712, Special Publication No. 1977
Phenyldiamine derivatives described in -28336 specification, gazette, etc.
570-2, West German Patent (DAS) No. 1110518, US Patent No. 3180703, US Patent No. 32405
No. 97, U.S. Patent No. 3,658,520, U.S. Patent No. 42
32103, U.S. Patent No. 4175961, U.S. Patent No. 4012376, JP-A-55-144250, JP-A-56-119132, JP-A-39-27577, JP-A-56-22437 specification 8, publications, etc. (13) Amino-substituted chalcone derivatives described in U.S. Patent No. 3,526,501, (14) N,N-bicalbasil derivatives described in U.S. Pat. No. 3,542,546, etc., (15) Oxazole derivatives described in US Pat. No. 3,257,203, etc.; (16) Styryl anthracene derivatives, described in JP-A-56-46234, etc.; (17) Fluorenone derivatives, described in JP-A-54-10837, etc. , (18) U.S. Patent No. 3717462, Japanese Patent Application Publication No. 1983-5
No. 9143, JP-A-55-52063, JP-A-55-
No. 52064, JP-A-55-46760, JP-A-55
-85495, JP-A-57-11350, JP-A-57-11350
7-148749, each specification 1 publication, and the like.

Two or more of these photoconductive substances may be used in combination depending on the case.

Among these photoconductive materials are poly-N-vinylcarbazole; triarylamines such as tri-p-tolylamine and triphenylamine; 4,4'-bis(diethylamine)-2°2'-dimethyltri polyarylmethane such as phenylmethane; and 3-(4
-dimethylaminophenyl)-1,5-diphenyl-2
-Unsaturated heterocycle-containing compounds represented by pyrazoline derivatives such as pyrazoline are preferably used.

As the binder that can be combined, all conventionally known binders can be used. Typical examples include vinyl chloride-hinyl acetate copolymer, styrene-butadiene copolymer, styrene-butyl methacrylate copolymer, polymethacrylate polyacrylate, polyvinyl acetate, polyvinyl butyral, alkyd resin, silicone resin, epoxy resin,
These include epoxy ester resin and polyester resin. It is also possible to combine it with an aqueous acrylic emulsion or an acrylic ester emulsion.

For examples of specific polymeric materials useful as binders, see
Research Disclosure
Disclosure), Vol. 109, pp. 61-67.
under the title ``Electrophotographic Elements, Materials and Methods''.

Generally, the amount of binder present in the photoconductive compositions used in the present invention can vary. Typically useful amounts of binder range from about 10 to about 90% by weight, based on the total amount of the photoconductive material and binder mixture.

Furthermore, conventionally known compounds can be added as spectral sensitizers. For example, xanthine dyes, triphenylmethane dyes, azine dyes, phthalocyanine dyes (
Examples include metal-containing), polymethine dyes, etc. Specifically, Harumi Miyamoto, Hidehikoshi Takei, "Imaging" 1973 (
No. 8), I.C., J., Young, R.C.A.
Review 15. 469 (1954); Wataru Kiyota, Transactions of the Institute of Electrical Communication Engineers J63-C (No. 2), 9
7 (1980); Yuji Harasaki et al., Industrial Chemistry Magazine, 66.
78 and 188 (1963) i Tadaaki Tani, Journal of the Photographic Society of Japan, 15, 208 (1972); Re5ear
ch Disclosure, 1982 I Kamidan, 1
17-118; Comprehensive technical data collection “Recent development and practical application of photoconductive materials and photoreceptors” Published by Nihon Kagaku Information 0G Publishing Department (19
Examples include publicly known materials cited in reviews such as 1986).

The photoconductive layer may be formed from one layer, or may be formed from two or more layers.

In the case of a multilayer structure, for example, a charge generation layer comprising the above-mentioned inorganic photoconductor or an organic pigment such as a phthalocyanine pigment or an azo pigment, and a binding resin added as necessary;
A so-called functionally separated photoconductive layer may be considered, in which the above-described high molecular compound or low molecular compound and a charge transport layer made of a binding resin are laminated.

The photoconductive layer used in the present invention can be provided on a commonly used and known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably electrically conductive, and examples of the electrically conductive support include metal, paper, etc.
A substrate such as a plastic sheet that has been treated to conductivity by impregnating it with a low-resistance substance, etc. The purpose is to impart conductivity to the back side of the substrate (the side opposite to the side on which the photosensitive layer is provided) and to prevent curling. A1 coated with at least one layer of A1 ．． A material made by laminating a plastic substrate onto paper, etc., can be used.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, “Electronic Photography J 14. (No. 1).

pp. 2-11 (1975); Hiroyuki Moriga, "Introductory Chemistry of Special Papers," Kobunshi Publishing (1975); M, F.

11over, J. Macromol, Sci.
, Chem, , A-4(6), No. 1327-14
17 (1970) etc. can be used.

The coating thickness of the photoconductive composition on a suitable support can vary widely. Usually about 10 microns to about 300 microns
It can be applied within the range of microns (before drying). A preferred range of coating thickness before drying has been found to be within the range of about 50 microns to about 150 microns. However, useful results can be obtained even outside this range. The dry thickness of this coating may range from about 1 micron to about 50 microns.

The thickness of the hydrophilic surface layer of the present invention is 10 μm or less, and is particularly suitable for the Carlson process of 0.1-. 5μ
It is preferable that it is m.

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 make the lithographic printing original plate of the present invention, generally,
First, an electrophotographic photosensitive layer' (
photoconductive layer). Next, on this layer, the resin of the present invention and, if necessary, the above-mentioned additives, etc., are added in a layer with a boiling point of 2.
Dissolved or dispersed in a volatile hydrocarbon solvent below 00°C,
It can be manufactured by coating and drying this. Specifically, preferred organic solvents are halogenated hydrocarbons having 1 to 3 carbon atoms, such as dichloromethane, chloroform, 112-dichloroethane, tetrachloroethane, dichloropropane, and trichloroethane. Others include aromatic hydrocarbons such as chlorohenzene, toluene, xylene or benzene, ketones such as acetone or 2-butanone, ethers such as tetrahydrofuran and methylene chloride, etc.
Various solvents used in coating compositions and mixtures of the above solvents can also be used.

A toner image is formed on the original plate obtained as described above in accordance with a conventional electrophotographic method. A printing plate can be obtained by treating this with a desensitizing treatment liquid (for example, an acidic or alkaline aqueous solution or an aqueous solution containing a reducing agent) to make the non-image area hydrophilic.

In this way, if the hydrophilic layer of the present invention is used,
Any conventionally known electrophotographic photoreceptor can be used as a high-quality lithographic printing original plate.

The hydrophilizable layer is a film that exhibits both high hydrophilicity and water resistance after hydrophilic treatment, and also has extremely good adhesion to the toner image, so the resulting lithographic printing original plate does not cause scumming. It is extremely restrained and has high rigidity resistance.

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 original plate with significantly higher sensitivity than conventional printing original plates for electrophotographic engraving. In addition, conventionally, a single layer must have the properties of photoconductivity and hydrophilicity, so
Previously, only limited materials such as zinc oxide could be used, but in the printing original plate of the present invention, the functions are separated into a photoconductive layer and a hydrophilizable layer, so the range of selection of the photoconductive layer is expanded, and therefore, for example, By selecting a material that is highly sensitive to long wavelength light, it becomes possible to write with a He-Ne laser or a semiconductor laser, which was previously impossible.

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.

(The following is a blank space) (Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

Example I 5 g of 4,4'-bis(diethylamino)-2,2'-dimethyltriphenylmethane as organic photoconductive material
5 g of bisphenol A polycarbonate (manufactured by GE, trade name Lexan 121), 40 mg of a spectral sensitizing dye (A) with the following structural formula, and 0.2 g of an anilide compound (B) with the following structural formula as a chemical sensitizer. Methylene chloride 30
m1 and ethylene chloride 30m! A photosensitive solution was prepared by dissolving it in a mixture of

(Spectral Sensitizing Dye (A)) (Anilide Compound (B)) This photosensitive solution was applied to a conductive transparent support (a 100 μm polyethylene terephthalate support having a vapor-deposited film of indium oxide on it) using a wire round rod. An organic thin film having a photosensitive layer of about 4 μm was obtained by coating on a surface (surface resistance: 10:1Ω).

On the other hand, 20 g of ethyl methacrylate, 8 o g of 11 compounds (1) having the following structure, and 0.0 g of divinylbenzene. A mixed solution of 5 g and 400 g of toluene was heated at a temperature of 70' under a nitrogen stream.
After heating to C, azobisisobutyronitrile (A, T
,B,N,) 1. 0g was added and reacted for 8 hours.

The weight average molecular weight of the obtained copolymer was 543.000. :Resin (i) Monomer CI) H3 CH,=CCH3 Coo Si C=Hq Hx A 5% by weight toluene solution of the obtained copolymer was applied to the surface of the electrophotographic photoreceptor obtained earlier using a doctor blade. A surface layer of about 2 μm was formed. The photosensitive material was desensitized by immersing it in this solution for 3 minutes using a 0.5 mol 1 Efa boric acid aqueous solution as a desensitizing solution.

A droplet of 2 .mu.i 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.degree. The contact angle before the anti-fat treatment was 79°, clearly indicating that the surface layer of the photosensitive material was very well rendered hydrophilic.

The original plate obtained in this way was processed using a fully automatic plate making machine ELP404V (Fuji Photo Film ■) using a negatively charged liquid developer.
(manufactured by Sakurai Seisakusho TM) to form a toner image, which was treated to make it fat-free under the same conditions as above, and used as an offset master to print on high-quality paper using an offset printing machine (Model Oliver 52, manufactured by Sakurai Seisakusho TM).

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

Example 2 5 g of bisazo pigment with the following structural formula, 9 g of tetrahydrofuran
A mixture of 5 g and 30 g of a 5 wt % tetrahydrofuran solution of polyvinyl butyral resin (manufactured by Denki Kagaku Kogyo Co., Ltd.: Denka Butyral 1 #4000-1) was sufficiently ground in a ball mill. Then, this mixture was taken out, and while stirring,
520 g of tetrahydrofuran was added. This dispersion was coated onto the conductive transparent support used in Example 1 using a wire round rod, and the dispersion was coated with a wire round rod to give a coating of approximately 0.00%. A charge generation layer of 7 μm 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) On the other hand, a mixed solution of 15 g of n-probylmeccrylate, 85 g of monomer (II) having the following structure, 1.0 g of diethylene glycol dimethacrylate, and 300 g of l-luene was heated under a nitrogen stream at a temperature of 75°C. After heating to A, 1. B
, N, were added and reacted for 8 hours. The weight average molecular weight of the obtained copolymer was 465.000. :
Resin (II) Monomer (n) H A 5% by weight toluene solution of the obtained copolymer was applied onto the photosensitive layer using a doctor blade to form a surface layer of about 2 μm.

The photosensitive material prepared in this manner was charged to -6 kV with a paper analyzer (manufactured by Kawaguchi Electric, 5P-428), and the initial potential (■.), dark charge retention rate (D, R, R,) and light attenuation exposure were measured. When ffi (E, /, ,) was measured, each was ■. =-530V, D, R, R, = 85% and El/
, O=10. 8 (lux・5ec).

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 toner at 0.04 V, the density of the obtained offset printing master plate was 1.
The image quality was clear when it was 0 or higher.

Furthermore, when etching was performed and printed using a printing press, the printed matter after cane printing had no fog in the non-image area and the image was clear.

Example 3 Ethyl methacrylate Log, monomer (II
I) 75 g, allyl methacrylate 1.5 g and l.
A mixed solution of 300g of toluene was added at a temperature of 60°C under a nitrogen stream.
It was heated to Azobisisovaleronitrile (A, 1.V
, N, ) 0. 8 g was added and reacted for 7 hours. The weight average molecular weight of the obtained copolymer was 78.000. :Resin ([[) Monomer (III) CH30Cl-13 1\OCIf.

Allyl methacrylate 1. Og and A, 1. V.N.

A mixed solution to which 0.01 g was added was applied to the surface of the electrophotographic photoreceptor obtained in Example 1 with a doctor blade, and the temperature was 80
It was dried at 100°C for 2 hours and then at 100°C for 30 minutes to form a surface layer with a thickness of about 2 μm.

The lithographic printing original plate thus prepared was operated and printed under the same conditions as in Example 1. The number of prints that could be printed was 10,000 or more without causing problems with background stains in non-image areas and image quality in image areas.

Example 4 [Methyl methacrylate/ethyl methacrylate/acrylic acid (39/60/1 weight ratio)] copolymer (weight average molecular weight 42,000) 45 g, zinc oxide 200 g, rose bengal 0.03 g, tetrabromophenol blue 0
．． 02g, phthalic anhydride 0. ．． 15g and toluene 30
0g of the mixture was dispersed in a ball mill for 2 hours to prepare a photosensitive layer-forming product, and this was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 25g/rd.
It was dried at 100°C for 1 minute.

On the other hand, after heating a mixed solution of 15 g of ethyl methacrylate, 85 g of monomer (IV) having the following structure, triethylene glycol dimethacrylate H, Og, and 300 g of toluene to a temperature of 70°C under a nitrogen stream, ．． B, N, 1
．． Og was added and the mixture was reacted for 8 hours.

The weight average molecular weight of the obtained copolymer was 430,000. : Resin (IV) Monomer (IV) OCH.

A 5% toluene solution of this copolymer was applied to the upper layer of the above photoreceptor using a doctor blade, and the solution was heated to 100°C for 1 hour.
It was dried for minutes to form a surface layer with a thickness of 2.2 μm.

Then, in the dark under 20'C165%RH conditions for 24 hours.
An electrophotographic light-sensitive material was prepared by allowing the material to stand for a period of time.

This photosensitive material was charged to -6 to ■ using a paper analyzer, the initial potential (■.) was -540V, the dark charge retention rate (D,
R, R, ) 85%, and light attenuation exposure (El/1G)
4. 7 (lux-sec) values were obtained for each.

Furthermore, this was plate-made in the same manner as in Example 2, and the density of the obtained offset printing master plate was 1. The image quality was clear when it was 0 or more.

Furthermore, when etching was performed and printed using a printing press, the printed matter after cane printing had no fog in the non-image area and the image was clear.

Examples 5 to 17 Photosensitive materials were produced in the same manner as in Example 4, except that each resin listed in Table 1 was used instead of resin (IV) used for the surface layer.

Table-1 Table-1 (Quick 1) Table-■ (Quick 2) When this was plate-made using the same device as in Example 1, the density of the obtained offset printing master plate was 1.0 or higher, and the image quality was was clear. When further etched and printed using a printing press, the printed matter after printing 1% of the sheets had clear image quality with no fog.

Further, this photosensitive material was left under conditions of 45° C. and 175% RH, and then subjected to the same treatment as above, but there was no difference at all from before aging.

Example 18 12 g of benzyl methacrylate, 80 g of the above monomer (H)
After heating a mixed solution of 8 g of N-methoxymethylmethacrylamide and 200 g of toluene to a temperature of 75°C under a nitrogen stream, A.1. 2g of B and N were added and reacted for 8 hours. Furthermore, the temperature was raised to 100°C and the reaction was carried out for 2 hours.

The weight average molecular weight of the obtained copolymer was 134°000
Met. : Resin [X■].

A 5% by weight toluene solution of this copolymer was applied to the upper layer of the two-layer separation type photoreceptor prepared in Example 2 using a doctor blade, dried at 100°C for 1 minute, and further heated at 130°C.
Heat treatment for 1 hour and approx. 2. A surface layer of 0 μm was formed. The electrostatic properties of the lithographic printing original plates prepared in this manner were measured using a paper analyzer under the same conditions as in Example 2. =-540V, D, I? ,I? , =
83%, and El/l.

= 10. 8 (Iux-sec).

Next, when the fully automatic plate making machine ELP-404V was operated in the same manner as in Example 2, the density of the obtained Offcera 1 printing master plate was 1.0 or more and the image quality was clear. Furthermore, when etching was performed and printed using a printing press, the printed matter after cane printing had no fog in the non-image area and the image was clear.

Example 19 A mixture of 50 g of a copolymer having the following structure, 1.8 g of 1,6-hexane diisocyanate, and 100 g of toluene was heated to a temperature of 60''C, uniformly dissolved, and stirred for 2 hours. The weight average molecular weight of the copolymer was 284,000. Resin (XIX) copolymer: Weight average molecular weight 40
,000 [wt% composition ratio] A 5 wt% toluene solution of this copolymer was applied to the upper layer of the photoreceptor prepared in Example 1 with a doctor blade, and
It was dried at °C for 1 minute to form a surface layer of about 2.1 μm.

As in Example 1, the fully automatic plate making machine ELP404■
When plate-making was carried out, the density of the obtained offset printing master plate was 1.0 or more and the image quality was clear. Furthermore,
When etching was performed and printed using a printing press, the printed matter after cane printing had no fog in the non-image area and the image was clear.

Example 20 50 g of copolymer with the following structure, 1,4-butanediol 2
A mixture of g and 100 g of toluene was heated to a temperature of 65°C and reacted for 3 hours with stirring. The weight average molecular weight of the obtained copolymer was 326.000. : Resin (XX) Copolymer: Weight average molecular weight 32,000 [wt% composition ratio] Same as Example 1 except that this resin (XX) was used instead of resin (1) in Example 1. An electrophotographic light-sensitive material was prepared.

This plate was made into a plate using the same apparatus as in Example 1, and then etched and printed using a printing press. The density of the master plate for offset printing obtained after plate making was 1.0 or more, and the image quality was clear. In addition, the image quality of the printed matter after printing 1% sheets was a clear image with no ground blur.

(Effects of the Invention) From the above, the electrophotographic lithographic printing original plate having a hydrophilic layer containing the resin of the present invention in its surface layer has both high hydrophilicity and water resistance after the hydrophilic treatment. It is a membrane,
Moreover, the adhesion with the toner image is also very good.
The resulting lithographic printing original plate has a (Z-shaped) crystallinity in terms of both scumming and printing durability.

Furthermore, the resin of the present invention is easy to manufacture.

Procedural amendment August 9, 1999

Claims (3)

[Claims] (1) In a lithographic printing original plate using an electrophotographic photoreceptor in which at least one photoconductive layer is provided on a conductive support and a surface layer is further provided on the uppermost layer, the main component of the surface layer is An original plate for electrophotographic lithographic printing, characterized in that it contains at least one functional group that produces at least one carboxyl group upon decomposition, and at least one resin that is at least partially crosslinked. (2) The resin contains a copolymer component containing at least one functional group that generates at least one carboxyl group upon decomposition, and is sparingly soluble or insoluble in water when the carboxyl group is generated through decomposition. The original plate for electrophotographic lithographic printing according to claim 1, which is a resin that has been crosslinked in advance so as to have the following properties. (3) The resin contains at least one functional group that generates at least one carboxyl group upon decomposition and heat and/or
The original plate for electrophotographic lithographic printing according to claim 1, which is a resin containing at least one functional group that causes a curing reaction with light.