JPH01306856A - Plate for planographic printing - Google Patents

Abstract

PURPOSE:To reproduce the copied image faithful to an original picture and to prevent the generation of scumming by using a resin contg. at least one kind of specific functional group by decomposition as the essential component of a surface layer and allowing a crosslining agent to coexist therein. CONSTITUTION:The surface layer is provided on the uppermost layer of photoconductive layers and the essential component of said surface layer is the resin contg. at least one kind of the functional group forming at least one group among a thiol group, phosphono group, amino group, and sulfo group by decomposition; in addition, the surface layer is so formed that the crosslinking agent coexists therein. The functional group contained in the resin forms at least one hydrophilic group by decomposition and the hydrophilic group formed from one functional group may be 1 or >=2. The copied image faithful to the original picture is reproduced in this way and since the hydrophilic property of the non-image part is good, the generation of the scumming is obviated.

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 section B) Currently, various types of offset original plates for direct plate making have been proposed and put into practical use.Among them, photoconductive particles such as zinc oxide and binders on a conductive support A photoreceptor provided with a photoconductive layer mainly composed of resin 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 treated with an unfavorable etchant called an etchant. A widely used technique is to obtain an offset original plate by selectively making non-image areas hydrophilic by treatment with a liquid.

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 desensitizing treatment liquid, and the non-image area is made sufficiently hydrophilic, while at the same time it is water resistant. 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 fat-proofing properties is a major problem, and in order to improve this problem, various studies have been conducted on the development of zinc oxide binding resins that improve fat-proofing properties. For example, Tokuko Sho 50-3101
No. 1, JP-A-53-54027, JP-A-54-207
:j5, JP-A-57-202544, JP-A-58-
It is disclosed in the specification of No. 68046 and the like. However, even if these resins are said to be effective in improving the anti-grease property, when actually evaluated, they are still unsatisfactory in terms of scumming and stiffness resistance.

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 grained 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 dissolved and removed, which requires a large-scale apparatus, and this takes time, resulting in a slow plate-making speed. Furthermore, since ethylene glycol, glycerin, methanol, ethanol, etc. are used as processing liquids (organic solvents),
This plate-making method still poses problems in terms of cost, safety, pollution, and occupational health.

Furthermore, Japanese Patent Publication No. 5606/1989 discloses a method for creating a water-treated printing plate with a surface roughness in non-image areas that is easy to plate-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 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 a non-image area after toner image formation to make it hydrophilic. In order to maintain the film strength after hydration, 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 a silylating agent, but since it is a polymer reaction, it is difficult to produce it stably. Furthermore, since the chemical structure of the hydrophilic polymer has been determined, it is important to ensure that 1) charging properties, 2) quality of copied images (halftone reproducibility and resolution of image areas, There were problems such as difficulty in preventing the surface layer from affecting 3) exposure problems, etc.) and 3) exposure problems.

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
2-151507), those containing functional groups that generate carboxyl groups upon decomposition (Japanese Patent Application No. 62-28345)
(Japanese Patent Application No. 62-226694), those containing a functional group that generates a thiol group by decomposition (Japanese Patent Application No. 62-226694);
70308), those containing a functional group that generates an amino group upon decomposition (Japanese Patent Application No. 62-42455), and those containing a functional group that generates a sulfo group or phospho group upon decomposition (Japanese Patent Application No. 6242454). 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 stiffness resistance, and even when using resins containing hydrophilic functional groups such as those mentioned above, it is difficult to further improve the hydrophilicity in non-image areas. If the content is increased in order to improve the performance, the hydrophilicity increases due to the hydrophilic groups generated by decomposition, and the surface layer resin becomes water-soluble, which poses a problem, especially in its sustainability. It turns out.

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 purpose of the present invention is to reproduce a copy image that is faithful to the original image, and to provide a lithographic printing method that has excellent desensitization properties and does not cause not only full-scale background smudges but also dotted smudges as an offset original plate. The purpose is to provide the original version.

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

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 main component of the surface layer is a resin containing at least one functional group that generates at least one group among a thiol group, a phospho group, an amino group, and a sulfo group upon decomposition, and a crosslinking agent. It has been found that the problem can be solved by an original plate for electrophotographic planographic printing, which is characterized by the coexistence of the above problems.

The present invention provides at least one of the resins in the surface layer of a lithographic printing original plate.
contains a resin containing at least one functional group that decomposes to produce at least one thiol group, phospho group, amino group and/or sulfo group, and coexists with a cross-linking agent that cross-links the resin. It is characterized by causing As a result, the lithographic printing original plate 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 the ability to maintain hydrophilicity in the non-image area. This has the advantage of excellent printing durability.

Below, the resin containing at least one kind of functional group that decomposes to produce at least one hydrophilic group of thiol group, phospho group, sulfo group and/or amino group (hereinafter simply referred to as "hydrophilic group") used in the present invention will be described. “Resin containing functional groups that generate functional groups”
) will be explained in detail.

The functional group contained in the hydrophilic group-generating functional group-containing resin of the present invention generates at least one hydrophilic group by decomposition, and the number of hydrophilic groups generated from one functional group may be one or two or more.

Hereinafter, a resin containing a functional group that generates at least one thiol group upon decomposition (thiol group-generating functional group-containing resin) will be described in detail. Such a resin has the general formula (1): (-3-LA ) It is a resin containing at least one type of functional group represented by the following.

In general formula (1) (-3-L^), LA is A 1 tube -Si -RA2, CRA4, C
R.A.S.

II II -C-0-RAh, -C-0-R", -3-RA-S However, RAI, RAZ and RAff may be the same or different, and each represents a hydrocarbon group or -0 -R"'(R
AI represents a hydrocarbon group), RA4, RAS,
RAS, RA'T, RAJ, RA9 and RAIO each independently represent a hydrocarbon group.

The functional group of the above -Fukudai (-3-LA) is decomposed,
It produces a thiol group, and will be explained in more detail below.

In the case where A 1 1, A represents 15t-RA, RA l, RAI and RA3 may be the same or different, and each represents a hydrocarbon group or -Q RAI(R
A I I represents a hydrocarbon group). RAI〜R
The hydrocarbon group represented by A3 is preferably a linear or branched alkyl group having 1 to 18 carbon atoms which may be substituted (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group). group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic group (e.g. cyclopentyl group, cyclohexyl group, etc.), number of carbon atoms that may be substituted. 7 to 12 aralkyl groups (e.g. benzyl group, phenethyl group, chlorobenzyl group, fluorobenzyl group, methylbenzyl group, methoxybenzyl group, 3
-phenylpropyl group, etc.) and optionally substituted aromatic groups (eg, phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.). R
The hydrocarbon group represented by AII is preferably the above R^1
It has the same meaning as the hydrocarbon group represented by ~RA3.

RA4, RAS, RA6, RA7, and RA8 each represent a hydrocarbon group. The hydrocarbon group represented by R'' to RA11 is preferably an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (for example, a methyl group, a trichloromethyl group, a trifluoromethyl group, Methoxymethyl group, ethyl group, propyl Ln-7'thyl group,
hexyl group, 3-chloropropyl group, phenoxymethyl group, 2.2.2-trifluoroethyl group, t-butyl group, hexafluoro-1-propyl group, octyl group, decyl group, etc.), even if substituted. Good aralkyl groups having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group, methoxybenzyl group, etc.), optionally substituted aryl groups having 6 to 12 carbon atoms (For example, phenyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group, methoxyphenyl group, butoxyphenyl group, chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.).

In the case where RA9 and RAIO may be the same or different, each represents a hydrocarbon group, and preferably has the same meaning as the hydrocarbon group represented by RA4 to RAII above.

Another preferred thiol group-forming functional group-containing resin of the present invention is a resin containing at least one thiirane ring represented by -Fukudai (I[) or -Fukudai (I[I)].

General formula (II) AI2 General formula (I[[) In formula (n), RAI2 and RA13 may be the same or different from each other and each represents a hydrogen atom or a hydrocarbon group. Preferred hydrocarbon groups have the same meaning as the hydrocarbon groups represented by RA4 to RA7 above.

In 2(I[I), XA represents a hydrogen atom or an aliphatic group. Preferred aliphatic groups include alkyl groups having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group,
butyl group, etc.).

Still another preferable thiol group-forming functional group-containing resin of the present invention is a resin containing at least one sulfur atom-containing heterocyclic group represented by (IV).

General formula (IV) In formula (IV), YA represents an oxygen atom or an -NH- group.

RA14, RAl! + and RA l & may be the same or different and each represents a hydrogen atom or a hydrocarbon group. Preferred hydrocarbon groups have the same meanings as the hydrocarbon groups represented by RA4 to RAff above.

RAIO and RA l 11 may be the same or different and represent a hydrogen atom, a hydrocarbon group, or -ORAI9(RA
IO represents a hydrocarbon group). RAIO and R
The hydrocarbon group represented by AllI is preferably the RA
I, RA It is the same as the hydrocarbon group represented by 3. The hydrocarbon group represented by RAIO has the same meaning as the hydrocarbon group represented by RA11.

According to yet another preferred embodiment of the present invention, the thiol group-generating functional group-containing resin has a functional group having at least two thiol groups that are sterically close to each other and simultaneously protected with one protecting group. It is a resin containing at least one kind of.

Examples of functional groups having at least two thiol groups that are sterically close to each other and simultaneously protected with one protecting group include the following - Futoshiro (V), (Vl) and (
■) can be mentioned.

General formula (V) General formula (Vl) General formula (■) In formula (v) and formula (Vl), ZA directly connects carbon-carbon bonds or C-S bonds, which may be via a heteroatom. Represents a chemical bond (however, the number of atoms between sulfur atoms is 4 or less). Furthermore, one side +ZA...-C
←The bond may represent only a simple bond, for example, as shown below.

In formula (Vl), RA20 and RAll may be the same or different, and each does not represent a hydrogen atom, a hydrocarbon group, or -ORAg6 (RAg6 represents a hydrocarbon group). The hydrocarbon group represented by RA20 and RA21 is preferably an optionally substituted alkyl group having 1 to 12 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-methoxy ethyl group, octyl group, etc.), optionally substituted aralkyl group having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, methylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), Examples include alicyclic groups (for example, cyclopentyl group, cyclohexyl group, etc.) or optionally substituted aryl groups (for example, phenyl group, chlorophenyl group, methoxyphenyl group, methylphenyl group, cyanophenyl group, etc.). The hydrocarbon group represented by RA Z 6 is RA! (Synonymous with the hydrocarbon group represented by 1 and RAll.

In formula (■), RA22, RA21, RA24
, RA2s may be the same or different and each represents a hydrogen atom or a hydrocarbon group. RA22~RA
The hydrocarbon group represented by 2S is preferably RA 20
It has the same meaning as the hydrocarbon group represented by and RAll.

The resin containing at least one type of functional group represented by the general formulas U) to (■) used in the present invention can be obtained by a method in which the thiol group contained in the polymer is protected with a protective group by a polymer reaction. , or a polymerization reaction of a monomer containing one or more thiol groups that has been previously protected with a protecting group, or a polymerization reaction of the monomer and another monomer that can be copolymerized with it. It is produced by a method of polymerization.

Polymers containing thiol groups inhibit radical polymerization, so it is difficult to directly polymerize thiol group-containing monomers. The functional group used in the present invention is produced by polymerizing monomers with protected thiol groups in the form of isothiuronium salts, Bunte salts, etc., and then performing a decomposition reaction to form 1,000-ol groups.

Therefore, it is possible to arbitrarily adjust the functional group that protects the thiol group in the polymer, that it does not contain impurities, or that it will not polymerize unless it is a monomer that protects the thiol group.
Furthermore, since the thiol group in the polymer must ultimately be protected by the protecting group used in the present invention, the polymer contains functional groups of general formulas (1) to (■) in advance. A method of manufacturing by polymerization reaction from monomers is preferred.

As a production method for converting one or at least two thiol groups into a functional group protected by a protecting group, for example,
“Reactive Polymers” by Takao Iwakura and Keisuke Kurita, pages 230-23
7 pages (Kodansha, 1977), Nippon Kagaku Metals "New Experimental Chemistry Course" Volume 14, Synthesis and Reactions of Organic Compounds [■],
Chapter 8, pages 1700-1713, (Maruzen Co., Ltd.
(published in 1978), J., F., W., McOmie,
rProtective Groupsin Or
ganic Chemistry” Chapter 7 (Plenu
m Press,.

(1973), S., Patat, rThe
Chemistry ofThe Th1ol Gro
up Part2 J Chapters 12 and 14 (John
It is possible to apply the methods described in known literature cited in reviews such as Wiley & 5ons+ (published in 1974).

Monomers in which one or more thiol groups are protected with a protecting group, such as monomers containing functional groups represented by formulas (1) to (■), are specifically A compound containing a bond and at least one thiol group, for example, according to the method described in the above-mentioned known literature, etc.
Converting a thiol group to a functional group of the general formula CI) to (■), or reacting a compound containing a functional group of -Fukudai (1) to (■) with a compound containing a polymerizable double bond. It can be manufactured by a method.

- Specific examples of repeating units of polymeric components containing functional groups (1) to (■) are listed below, but the scope of the present invention is not limited thereto. .

(1) -(-CH, -CH-)-S COCH
3 (2) -+CH2-CH← 5COCzHs (3) -(-CH, -CH-)-5COC4H
.

(4) -(-CH2-CH+-5COCRZC
f (5) -(-CH2-CH-)-SC○0CJ
q (8) −+CH2−CH+− S 5i(CHz)3 S−coUjizHs →CH, −C−→− Coo(CH2)2S−COOC2H5(22)
CH.

-(-CH2-C+ Coo(CH2)2S C3OCZH5(23)
CH.

(24) CH3 → CH2-C+ " (25) -(-CH2-CH-)-C00(CH
2) 2S-3i (CH3)3-(-CH2-C+ '5 C3OCzHs (27) -÷CH, -CH-)- □ C00(CH2)2SCOOC,H9 CH.

(2B) -(-CH, -C@- CONH(CH,), 5COOC,H.

(30) -(-CH-CH← S \C/ Convex I S□S S□S S□S CH.

S□5 (42) CH.

-(-CH, -C→- " 0CH2CHCH2SCOCH3 □ C0CH5 -(-CH, -CH-)- -(-CH2-C→- 5COOC2H5 -(-CH, -C-±- C00(CH2)zS-3C,H.

CH.

pole -(-CH, -C→- CH.

-(-CH, -C-±- C00(CH2)Z-3-CONH(CH2)2NI(
CI (3) In the present invention, a resin containing a functional group that decomposes to form a phospho group, for example, a group shown in (■) or (IX) below, will be explained in detail.

- Clothes cost (■) p 1111 RI H General formula (IX) QP+2 -P-Z''-H ZB3 ) (In 2 (■), R1l+ is a hydrocarbon group or 7.12
1'(II2 (here, RI'2 represents a hydrocarbon group, and Zll2 represents an oxygen atom or a sulfur atom).

Q" represents an oxygen atom or a sulfur atom. Zll' represents an oxygen atom or a sulfur atom. In formula (IX),
Qll, Zll3 and ZBl4 each independently represent an oxygen atom or a sulfur atom.

The hydrocarbon group represented by RI I is preferably an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group). , hexyl group, octyl group,
decyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2-ethoxyethyl group, etc.), optionally substituted alicyclic groups (e.g., cyclopentyl group, cyclohexyl group, etc.), optionally substituted Aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, methylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), optionally substituted aromatic groups (e.g., phenyl group, chlorophenyl group, tolyl group, etc.) group, xylyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.). The hydrocarbon group represented by R12 has the same meaning as the hydrocarbon group represented by R81 above.

Examples of the functional group that generates the phosphor group represented by the formula (■) or (IX) upon decomposition include the functional groups represented by the formula (χ) and/or (XI).

General formula (X) 1] R11 Zll Lll General formula (XI) p Zl= II13 □ ZBl l, B2 In formulas (X) and (XI), Qll l, Qll,
Zl, 7, 83, Z84 and R1 represent the contents as defined in formulas (■) and (IX), respectively.

Llll, LIIZ and II3 are each independently CR1111, CR119, COR1+10, II
When representing II II, RI13 and R14 may be the same or different and represent a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.) or a methyl group. X B +
and XI2 represents an electron-withdrawing substituent, preferably a halogen atom (e.g., chlorine atom, bromine atom, fluorine atom, etc.), -CN, -CONH2, N Oa or S O2R
II'' (R13 is a methyl group, an ethyl group, a propyl group,
represents a hydrocarbon group such as butyl group, hexyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, etc.). n represents 1 or 2.

Furthermore, Xl11 may represent a methyl group, and in this case, R113 and R1 are methyl groups and represent n-1.

RIIS L1~L! When l:l represents 13t-R'', R@S, RB& and R1!'7c may be the same or different, and each represents a hydrogen atom, a hydrocarbon group or -0 -R"'(R"' represents a hydrocarbon group). The hydrocarbon group represented by Rss to R1? is preferably a linear or branched chain having 1 to 18 carbon atoms that may be substituted. alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group,
dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic groups (e.g. cyclopentyl group, cyclohexyl group, etc.), optionally substituted carbon atoms having 7 to 12 carbon atoms Aralkyl groups (e.g. benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.), optionally substituted aromatic groups (e.g. phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group) group, dichlorophenyl group, etc.). The hydrocarbon group represented by R1+14 is RBS~R1
It has the same meaning as the hydrocarbon group represented by 17.

1, B 1. Li2 is -C-RB8, -C-R1I9
, s-R1112, where R11! l,
R1'9, RIIIO, RBI+ and R812 each independently represent a hydrocarbon group. The hydrocarbon group represented by R111 to RIII2 is preferably an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms (e.g., methyl group, trichloromethyl group, trifluoromethyl group, methoxy Methyl group, phenoxymethyl L 2,2
．． 2-trifluoroethyl group, ethyl group, propyl group,
hexyl group, t-butyl group, hexafluoro-1-propyl group, etc.), optionally substituted aralkyl groups having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, methylbenzyl group, trimethylbenzyl group, heptamethyl benzyl group, methoxybenzyl group, etc.), an optionally substituted aryl group having 6 to 12 carbon atoms (e.g. phenyl group, tolyl group, xylyl group, nitrophenyl group, cyanophenyl group,
(methanesulfonylphenyl group, methoxyphenyl group, butoxyphenyl group, chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.).

In the case where Yl and Yl2 each independently represent an oxygen atom or a sulfur atom.

The resin containing at least one functional group used in the present invention is the formula (■) or (I) contained in the polymer.
X) A method in which a hydrophilic group (phospho group) is protected with a protecting group by a polymer reaction, or a functional group that is previously protected with a protecting group (for example, a functional group of formula (X) or (XI)) ), or a polymerization reaction between the monomer and another monomer that can be copolymerized with the monomer.

In either method, a similar synthetic reaction can be used to introduce the protecting group. Specifically, J, F, I+1. McOmie, rProt.
activegroups tn Organic C
hemistry J Chapter 6 (Pl, enuIrlPr
ESS, 1973), or Nippon Kagaku Venue, "New Experimental Chemistry Course Volume 14, Synthesis and Reactions of Organic Compounds (■)", page 2497 (Maruzen Co., Ltd., 1978). ), or the same synthetic reaction as the method for introducing a protecting group into a hydroxyl group, as described in the known literature cited in the review, such as S.

Patai, rThe Chemistry of
the Triol Group Part 2” Chapters 13 and 14 (Wiley-1interscience 1
974), T., W., Greene, rP.
protective groups in Organi
Chapter 6 (Wiley-In
It can be produced by a synthetic reaction similar to the method for introducing a protecting group into a thiol group as described in the known literature cited in the review such as Terscience I9B 1st edition).

- The following examples can be given as specific examples of repeating units of the polymeric component containing the functional groups of (X) and/or (XI).

However, the present invention is not limited thereto.

-(-CH2-CH← 0 P O5t(CHz)3 0 5t(CH:+h -(-CH2-CH-)- I CHzOP OS l (CH3)3□ 00-3i(C□),! -(- CH, -CH+- CH2P OS i (C2H5):1OS i (
CzHs)3O5t(OCH3)3 (61) CH.

temporary -(-CH2-C+ 0=P 0COC,, Hs book 0COC6H5 One←CH2-C1(-)- CH.

fCHHz C+ Coo(CHI)20-P-0-COCH3□ 0-COCH5 (64) CH,J □ -(-CHZ-C→- 〇Coo(CH2)20 P O5i(CHa)i0
-3i(CHx'h 0- S i (Clli) zcaHqCOO(CH
2) 20 P OCH3□ O5i (CHx:h S-COCH.

0 COOCt H5 C00(CH2)30-P-S-COOC2H! .

□ 5-COC2H5 0 5i (OCHa) a 0 5t (CH:+:h Q COC2H5 1] Coo (CHz)z〇-P -S CS OCH35
-C3OCH.

OS l (C, +Hs)s 1: Coo(CHz)z○-P-OC,H.

CH.

□ o-cooc, ToI.

1 ÷ CH2-C-deO= POS i (CH3)1 l-13 R0 (CH2)2CN Next, by decomposition, amino groups [e.g. -NH, and/or -NHRC groups (RC is a hydrocarbon group) For example, as a functional group that generates the following
) can be mentioned.

General formula (Xll) -N-COO-RC2 □ C1 General formula (XII[) General formula (XTV) In (XI[) and formula (XIV), PCI each represents a hydrogen atom or a hydrocarbon group. The hydrocarbon group represented by PCI includes an optionally substituted alkyl group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, 2-chloroethyl group, 2-bromoethyl group, 3
-chloropropyl group, 2-cyanoethyl group, methoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-methoxycarbonylethyl group, 3-methoxypropyl group, 6-chlorohexyl group, etc.), number of carbon atoms Alicyclic groups having 5 to 8 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, 1-phenylpropyl group) group, chlorobenzyl group, methoxybenzyl group, bromobenzyl group, methylbenzyl group, etc.), and optionally substituted 7 having 6 to 12 carbon atoms.
1J-l groups (eg, evaphenyl group, chlorophenyl group, dichlorophenyl group, tolyl group, xylyl group, mesityl group, chloromethylphenyl group, chlorophenyl group, methoxyphenyl group, ethoxyphenyl group, chloromethoxyphenyl group, etc.).

When PCI represents a hydrocarbon group, it is preferably a hydrocarbon group having 1 to 8 carbon atoms.

In the functional group represented by formula (XII), RC2 represents an optionally substituted aliphatic group having 2 to 12 carbon atoms, and more specifically, RC2 represents a group represented by the following formula (XV) or an alicyclic group. Represents a formula group.

2(XV) ct □ -(-C-+7 Y C 靜・ In formula (XV), RC7 and RCI+ each independently represent a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, etc.) or a carbon number of 1 to 12 optionally substituted hydrocarbon groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-chloroethyl group, 3-bromopropyl group) , cyclohexyl group, benzyl group, chlorobenzyl group, methoxybenzyl group, methylbenzyl group, phenethyl group, 3-phenylpropyl group, phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl group, methoxyphenyl group, dichlorophenyl group, (tetramethylphenyl group, naphthyl group, etc.), and Yc is a hydrogen atom,
Halogen atoms (e.g. fluorine atoms, chlorine atoms, etc.), cyano groups, alkyl groups having 1 to 4 carbon atoms which may contain substituents (e.g. methyl groups, ethyl groups, propyl groups, butyl groups,
trichloromethyl group, trifluoromethyl group, cyanomethyl group, etc.), alicyclic groups (e.g. cyclopropyl group, bicyclohebutane group, etc.), aromatic groups that may contain substituents (
For example, phenyl, l-IJ group, cyanophenyl group, 2
．． 6-dimethylphenyl i, 2゜4.6-drimethylphenyl group, heptamethylphenyl group, 2.6-simethoxyphenyl group, 2゜4.6-)rimethoxyphenyl group, 2-propylphenyl group , 2-7' tylphenyl group,
2-chloro-6-methylphenyl group, furanyl group, etc.),
or -3O2-RC9 (RC9 represents the same content as the hydrocarbon group of Yc). n represents 1 or 2.

More preferably, when Yc is a hydrogen atom or an alkyl group, RC on the carbon adjacent to the oxygen atom of the urethane bond
7 and RCll represent a substituent other than a hydrogen atom.

When Yc is not a hydrogen atom or an alkyl group, RC7 and RC8 may be any of the groups listed above.

Indicates that preferable examples include cases where a group containing one or more electron-withdrawing groups is formed, or a case where the carbon adjacent to the oxygen atom of the urethane bond forms a sterically bulky group. It is.

The alicyclic group represented by Rew is specifically a monocyclic hydrocarbon group (e.g., cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-methyl-cyclohexyl group, 1-methylcyclo butyl group, etc.)
and crosslinked cyclic hydrocarbon groups (eg, bicyclohebutane group, bicyclooctane group, bicyclooctene group, bicyclononane group, tricyclohebutane group, etc.).

- In Fukudai (XI[I), RC3 and RC4 may be the same or different and each represents a hydrocarbon group having 1 to 12 carbon atoms, specifically, an aliphatic group in Yc of formula (XI or Represents the same content as aromatic groups.

In the general formula (X IV ), XC+ and XC2 may be the same or different and each represents an oxygen atom or a sulfur atom. RC5 and Rcb may be the same or different and each represents a hydrocarbon group having 1 to 8 carbon atoms, and specifically represents the same content as the aliphatic group or aromatic group in YC of formula (XII).

The decomposition used in the present invention results in amino groups (e.g. -NH
2 groups and/or -NHRc groups), for example, the resin containing at least one functional group selected from the group of -Fukudai (XII) to (XIV), for example, Nippon Kashohen. , [New Experimental Chemistry Course Volume 14, Synthesis and Reactions of Organic Compounds (■]), page 2555 (published by Maruzen Co., Ltd.)
, J, F, lda.

McOmie, “Protective group
s in Organic Che+++1s-t, r
y” Chapter 2 (Plenum Press Sl 973), rProtective groups in
Organic 5ynthests, 1 Chapter 7 (Jo
hn Wtley & 5ons, 1981 fl)
It can be produced by the method described in the known literature cited in the review.

For reasons such as being able to arbitrarily adjust the functional groups of general formulas (XII) to (XTV) in the polymer or preventing the inclusion of impurities, the functional groups of general formulas (XII) to (XIV) are prepared in advance. A method of manufacturing by polymerization reaction from the monomers contained is preferred. Specifically, polymerizable double bonds and 1
A monomer containing a primary or secondary amino group is converted into a functional group of general formulas (XI) to (XIV), for example, according to the method described in the above-mentioned known literature, and then a polymerization reaction is carried out. By this, a resin containing at least one kind of functional group of general formulas (Xn) to (XIV) can be produced.

Specific examples of the functional groups of formulas (XII) to (XTV) are shown below, but the present invention is not limited thereto (79)
CH.

□ N HCOOCCH:I CH.

(80) CbH5N HCOOC
CH3C,H% (81) -NHCOOCH2CF: 1 (82)
-NHCOOCH2C (12° (83)
N COOCH2CH2S ○, CH3CH.

(85) CH3N HCOO
CCC13 H3 (94) CH3 (95) CH.

\ vinegar (103)OCH3 □ -N-P-OCR.

CH,0 (104) OCH, CH20CH.

-NH-P-OCH2CH20CH3 (105) OC, H.

□ NHP 0C4H9 Furthermore, examples of the functional group that generates at least one sulfo group upon decomposition include the functional groups represented by the following formula (XVI) or (X■).

General formula (XVI) 13Q, -0-R” General formula (X■) 13Q2-3-R” fI3 In formula (XVI), Rol+ is -(-C)--Y'', D4 -Represents NHCOR"7.

In formula (X), R11g represents an optionally substituted aliphatic group having 1 to 18 carbon atoms, or an aryl group having 6 to 22 carbon atoms, which may have a substituent.

The above-mentioned functional groups (XVI) and (X■) generate sulfo groups upon decomposition, and will be explained in more detail below.

When RD' represents one+C)-rY', D4 Rf13 and Roa may be the same or different, and each independently represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a carbon atom, Number 1 to 6 optionally substituted alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, trifluoromethyl group,
benzyl group) or an aryl group (eg phenyl). YD 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, hexadecyl group, I.lifluoromethyl group) group, methanesulfonylmethyl group, cyanmethyl group, 2-meI・
xyethyl, ethoxymethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-methoxycarbonylethyl, 2-propoxycarbonylethyl, methylthiomethyl, ethylthiomethyl, benzyloxymethyl, etc.), carbon Alkenyl groups that may be substituted with 2 to 18 carbon atoms (e.g., vinyl groups, allyl groups, etc.), aryl groups that may contain substituents of 6 to 12 carbon atoms (e.g., phenyl groups, naphthyl groups, nitrophenyl groups) , dinitrophenyl group, cyanophenyl group, trifluoromethylphenyl group, methoxycarbonylphenyl group, butoxycarbonylphenyl group, methanesulfonylphenyl group,
benzenesulfonylphenyl group, tolyl group, xylyl group, acetoxyphenyl group, nitronaphthyl group, etc.), or (, RD8 (RD8 represents an aliphatic group or an aromatic group, specifically the substituent indicated by YD) (represents the same content as ). n represents O1 or 2. However, when n is 2, the two RD3 and RD4 may be the same or different.

Dff is more preferably a functional group containing at least one electron-withdrawing group in the substituted W:=(-C)goYD. Specifically, when n is 1 or 2 and YD is a hydrocarbon group that does not contain an electron-withdrawing group as a substituent, →ch- has at least one halogen atom. contains. or n is 0.1
or 2, in which Yr' contains at least one electron-withdrawing group. Furthermore, n is Oll or 2 and YD is -CRDII
For example,

The electron-withdrawing group is a substituent having a positive Hammett's substituent constant, such as a halogen atom, -CO2-1
-C-1-SO, -1-CN.

-NO, etc.

Another preferred substituent is -e formula (XVI):
C-3o Examples include cases where a substituent is present at the 6-position.

where Zo represents an organic residue forming a cyclic imide group. Preferably, it represents an organic residue represented by (X) or (XIX) below.

-Fukudai (X■) General formula (XIX) In 2 (X■), RD9 and R11to may be the same or different, and each independently represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a carbon number 1 to 18 optionally substituted alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, doditer group, hexadecyl group, octadecyl group, 2-
chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, 3-chloropropyl L2-(methanesulfonyl)ethyl group, 2-(ethoxyoxycarbonyl)ethyl group, etc.), even if substituted with 7 to 12 carbon atoms Good aralkyl group (for example, hensyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, bromobenzyl Jl'), ff1i number of 3 to 18 substituted It represents a good alkenyl group (eg evaallyl group, 3-methyl-2-propenyl group). m represents an integer of 2 or 3.

Rnq and RDto may be connected to form a ring.

In formula (XIX), R” mouth RDI 2 is each 4 formulas (X■
) has the same meaning as RD9 and RDIO. Also, RD l
l and RIl+2 may be linked to form a ring.

Here, Ro and RDII are each a hydrogen atom, an aliphatic group (specifically, the same content as that of R■ and Rad), or an aryl group (specifically, the same content as that of RI13 and R114) represents. However, both RDS and RDS do not represent a hydrogen atom.

When R111 represents -NHCOR"?, R
D7 represents an aliphatic group or an aryl group, specifically,
R111 and Rad each represent the same content.

In formula (X■), R1 represents an optionally substituted aliphatic group having 1 to 18 carbon atoms or an aryl group having 6 to 22 carbon atoms which may have a substituent. More specifically, the above formula (X
It represents the same content as the aliphatic group and aryl group in YZI in VI).

-Clothing fee (XVI) used in the present invention: [-5O
□−0−R” R or− Clothing cost (X■)=(−3Q2−〇−
The resin containing at least one functional group selected from the group R") can be obtained by converting the sulfo group contained in the polymer into a functional group of general formula (XVI) or (X■) by polymer reaction. or - Polymerization reaction of one or more monomers containing one or more functional groups of (XVI) or (X■), or copolymerization of said monomers and said monomers. It is produced by a method of polymerization by a polymerization reaction with other monomers obtained.

A method of introducing a protecting group into a sulfo group to form a protected functional group (for example, a functional group of formula (XVI) or (X■)) is described in, for example, Nippon Kagaku Kinen "New Experimental Chemistry Course", Vol. 1
Volume 4, Synthesis and Reaction of Organic Compounds [■], Page 1793,
Maruzen ■ (1978); C, O, Meese, “5y
12.1041 (1984)
; V, Konecny, J, Demeck
o, ``Chem, Zvesti,''.

27+ 497 (1973); G, Berner
+ R, Kirchwayr, G.

R15t, W, Rutsch, ”J, Rad,
Curing" + 1986+No., 10.10, etc. can be mentioned.

The method for converting into the functional group by polymer reaction can be carried out in the same manner as the synthesis method for monomers.

For reasons such as being able to arbitrarily adjust the functional groups of general formula (XVI) and/or (X Preferred is the method (2) in which the polymer is produced by a polymerization reaction from a monomer containing a functional group. Specifically, a sulfonic acid containing a polymerizable double bond is converted into a sulfo group by the general formula (
After converting the functional group into the functional group of formula (XVI) and/or (X■), a polymerization reaction can be carried out to produce a resin containing the functional group of general formula (XVI) and/or (X■).

Specific examples of the functional groups of the general formulas (χ■) and (X■) are shown below, but the present invention is not limited thereto.

(10B) -3O,OCH,CF3(110)
-3○zOcHz(CHF)zcHzF(111)
-3O20CH2CCQ3(113) -3o□0(
CH2)2SO2C,H.

DoH3 C, H3 (122) -3o□0-CH-COC,H.

(123) -3O20(CH2)ZSO2C2H5
(124) -3o□SC,H7 (125) ~5O7SC6H13 (126) -3O□5(CH2)20C,H.

(128) -3O20CH2CHFCH2F As mentioned above, general formulas (1) to (■), (X) to (XrV) used in the method of producing a desired resin by polymerization reaction
, (XVI) and (X■) are more specifically described, examples include components such as the following (A). However, the copolymer components are not limited to these examples.

General formula (A) a I a 2 →-CH-C+ X'-Y=W In formula (■), X' is -〇-2-CO-1d' 1000-1-OCO-1- N-CO-1d”
(1'-CON-2S O2-5-
3O2N-1-NSO7-1-CH,COO-1 b+ □ -CH,0CO-1-(-C←, indicates a divalent aromatic group or a divalent heterocyclic group. However, dl, dZ ,dl,d
4 is each a hydrogen atom, a hydrocarbon group, or - in formula (A)
←y'-W), bl and b2 may be the same or different, and represent a hydrogen atom, a hydrocarbon group, or → in formula (A)
Y'-W), and ni represents an integer from 0 to 18. I)
', I: a hydrocarbon group represented by l'', and dl,
The hydrocarbon groups represented by dZ, d3, and d4 have the same meanings as the hydrocarbon groups represented by RA l, , R, and A 3 in 2 (1), respectively.

W represents the general formula (I) to (■), (X) to (XIV), (X
It represents a functional group represented by VI) and (X■).

Y' is a divalent linking group that may connect the bonding group X' and the functional group W, and may be via a heteroatom (heteroatoms include an oxygen atom, a sulfur atom, and a nitrogen atom),
For example, □ (-CH=CH-)-3-〇-1-S-1-N-1-C
OO-1-CONH-2-SO2-1-8O□NH-1
-NHCOO-1 -NHCONH-1 and other bonding units singly or in combination (however, b3 and bJ are each the above-mentioned b
ds has the same meaning as dl and d4. ) a l and a 2 may be the same or different, and are hydrogen atoms, halogen atoms (e.g. chlorine atoms, bromine atoms, 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.) aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, xylyl group, and chlorophenyl group), optionally substituted alkoxycarbonyl groups having 1 to 12 carbon atoms (e.g. 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 (A).

In addition, the [XI Yl ) bonding residue in formula (A) is -C
A portion of -C+ and -W may be directly connected.

In the case where the resin of the present invention is a copolymer, the polymer component containing a functional group that decomposes to produce at least one hydrophilic group of thiol group, phospho group, sulfo group and/or amino group is It is preferably 30 to 100% by weight, particularly 40 to 95% by weight of the total polymer. In addition, the molecular weight of the resin polymer is 103 to 106, especially 5X
10'' to 5X10S, preferably.

In addition, in order to enhance the crosslinking effect between the resin of the present invention and the crosslinking agent, -OH groups, -3H
group, -N HRl group (R' is an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.) or an aryl group (e.g., phenyl group, tolyl group, methoxy group) A component containing a substituent having at least one type of dissociable hydrogen atom such as phenyl group, butylphenyl group, etc.) or a component containing an epoxy group, thioepoxy group, etc. may be present. The proportion of the copolymer component containing these polar groups in the resin of the present invention is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight.

The copolymer component containing the polar group is, for example,
Any vinyl compound containing the polar group that can be copolymerized with A) may be used. Specifically, derivatives containing the polar group in the substituent of the same compound as described in the general formula (A) above may be mentioned.

Furthermore, the resin of the present invention contains a monomer containing the general formula (1) (% formula %) (X) and any of the above polar group-containing monomers as well as other monomers other than these may be contained as a copolymerization component.

For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylnitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls (e.g. vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene) , vinylimidacilline, vinylpyrazole, vinyl-dioxane, vinylquinoline, vinylthiazole, vinyl-oxazine, etc.). In particular, vinyl acetate, allyl acetate, acrylonitrile, methacrylonitrile, styrenes, and the like are preferred components from the viewpoint of improving film strength.

In the present invention, as the crosslinking agent used, compounds commonly used as crosslinking agents can be used. Specifically, Shinzo Yamashita and Azusuke Kaneko, "Crosslinking Agent Handbook" published by Taiseisha (19B'1), Polymer Data [Polymer Data Handbook [Basic Edition]] Baifukan (1986)
Compounds described in et al. can be used.

For example, silane coupling agents such as organic silane compounds (e.g., vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane) etc.), polyisocyanate compounds (e.g. toluylene diisocyanate, O-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, isocyanate, polymeric polyisocyanate, etc.), polyol compounds (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1.■).

1-trimethylolpropane, etc.), polyamine compounds (e.g., ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds, and Epoxy resins (for example, "New Epoxy Resin" edited by Hiroshi Kakiuchi, published by Shokodo (1985), "Epoxy Resin" edited by Kuniyuki Hashimoto
Compounds described in Nikkan Kogyo Shimbunsha (1969), etc.), melamine resins (for example, "Uria Melamine Resin" edited by Kazube Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbunsha (19'69)
Poly(meth)acrylate compounds (e.g., "Oligomer" edited by Makoto Okawara, Takeo Saegusa, and Toshinobu Higashimura, published by Kodansha (1976), Eizo Omori "Functional Acrylic Resin") Technosystem (published in 1985), etc., and specific examples include polyethylene glycol diacrylate, neopentyl glycol cyacrylate, 1,6-hexanesiol diacrylate, and trimethylolpropane triacrylate. , pentaerythritol polyacrylate, bisthraenol A-diglycidyl ether diacrylate, oligoester acrylate: methacrylates thereof, etc.).

The surface layer resin according to the present invention is crosslinked with the above-mentioned crosslinking agent after the surface layer forming product is applied.

In order to effect crosslinking, it is preferable, for example, to set the drying conditions to high temperature and/or for a long time, or to perform further heat treatment after drying the coating solvent. For example 60°C-120°C
Process for 5 to 120 minutes.

If necessary, a reaction accelerator may be added to the surface layer resin 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, sensitizers, photopolymerizable monomers, and the like. When these reaction accelerators are used in combination with the above-mentioned crosslinking agent, it becomes possible to perform the treatment under milder conditions.

Further, although crosslinking should be carried out at least between the resins of the present invention, it may also be carried out between other resins.

When the hydrophilic group-generating functional group of the present invention generates a hydrophilic group by decomposition, it is preferable that the resin becomes a resin that is sparingly soluble or insoluble in acidic and alkaline aqueous solutions.

The amount of crosslinking agent present in the resin is 0.1 to 30% by weight.
, particularly preferably 0.5 to 20% by weight.

Conventionally known resins can also be used together with the resins used in the present invention. Examples include silicone resins, alkyd resins, vinyl acetate resins, polyester resins, styrene-butadiene resins, acrylic resins, etc. Specifically, Ryuji Kurita and Tsugube Ishiwata, "Polymers", Vol. 17, No. 278 (1968); Harumi Miyagi and Hidehiko Takei, "Imaging", 1973 (Nα8), 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 proportion, but the content of the hydrophilic group-forming functional group-containing resin in the total amount of resin is 30% or more, preferably 4%.
It is 0% by weight or more.

The resin containing at least one type of hydrophilic group-forming functional group of the present invention is hydrolyzed or hydrolyzed by a fat-proofing liquid or a dampening solution used during printing to generate a hydrophilic group. Therefore, in the present lithographic printing original plate containing the resin in the surface rfI ('a hydratable layer), the non-image area is made hydrophilic by the hydrophilic groups generated in the resin, and the image area becomes lipophilic. It is clearly distinguished and prevents printing ink from adhering to non-image areas during printing. As a result, it becomes possible to print a larger number of prints with clear image quality and no background smearing than with conventional lithographic original plates using resin.

Furthermore, the resin of the present invention contains a crosslinking agent that causes a crosslinking reaction, and the crosslinking reaction occurs during the process of forming the surface layer or the process of heating and/or light irradiation before etching treatment, and the crosslinking reaction occurs between the polymers. A bridge is formed. The hydrophilic group-containing resin that is decomposed and generated by etching treatment and dampening water during printing on the printing press becomes hydrophilic, and when the content thereof is large, it becomes water-soluble. However, since the resin of the present invention has a crosslinked structure, its solubility in water is significantly reduced while maintaining hydrophilicity, and the resin becomes poorly soluble or insoluble. That is, the crosslinking agent has the effect of preventing the resin from becoming water-soluble and eluting from the non-image area.

More specifically, it is possible to print a large number of prints with clear image quality without background smudges even when printing conditions become severe, such as when the printing machine becomes larger or printing pressure fluctuates.

In order to improve the strength of the hydrophilic surface layer itself, adhesion with the electrophotographic window light layer, electrophotographic properties, etc., resins other than the resin of the present invention described above or plasticizers etc. may be added. You may.

Furthermore, the surface layer that can be made hydrophilic may have its surface mechanically matted or layered for the purpose of improving development characteristics during toner development, adhesion of toner images, or water retention after hydrophilic treatment. may contain a matting agent. Examples of the matting agent 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 phenol resin.

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

That is, this hydrophilicity can be determined, for example, by measuring the contact angle with water.

The contact angle of the surface of the surface layer (hydrophilizable N) with water before the desensitization process is about 60' to 120°, but after the desensitization process, it decreases to about 56 to 20°. , becomes 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 window optical layer (photoconductive N) 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, polyvinylanthracene, poly-2 described in JP-A No. 8674 and Japanese Patent Publication No. 43-19192
-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, prombylene-formaldehyde resin, and ethylcarbazole-formaldehyde resin described in publications, etc. (5) JP-A-56-90833, JP-A-56-16155
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 U.S. Patent No. 3112197, etc., (7) Oxadiazole derivatives described in U.S. Patent No. 3189447, specifications, etc., (8) Japanese Patent Publication No. 37
Imidazole derivatives described in -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, polyaryl alkane derivatives described in JP-A-56-36656, publications, etc. (10) U.S. Pat. No. 3,180,729, U.S. Pat.
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
Phenyl diamine derivatives described in -28336 specification, gazette, etc.
No. 5702, West German Patent (DAS) No. 1110518,
U.S. Patent No. 3180703, U.S. Patent No. 324059
No. 7, U.S. Patent No. 3,658,520, U.S. Patent No. 423
No. 2103, U.S. Patent No. 4175961, U.S. Patent No. 4012376, JP 55-144250, JP 56-119132, JP 39-27577,
Arylamine derivatives described in JP-A-56-22437 and publications, (13) Amine-substituted chalcone derivatives described in US Pat. No. 3,526,501, (14) US Pat. No. 3,542,546! (15) Oxazole derivatives described in U.S. Pat. 17) Fluorenone derivatives described in JP-A-54-110837, etc., (18) U.S. Pat. No. 3,717,462, JP-A-54-5
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'-dimethyltriphenyl; polyarylmethane such as methane; 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-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-butyl methacrylate copolymer, polymethacrylate, polyacrylate, polyvinyl acetate, polyvinyl butyral, alkyd resin, silicone resin, and epoxy resin. , epoxy ester resin, polyester resin, etc.

It is also possible to combine it with aqueous acrylic emulsion or acrylic ester emulsion.

For examples of specific polymeric materials useful as binders, see
Research Disclosure
Disclosure), Volume 109, Pages 61-6'7, 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, examples include "Imaging J1973" edited by Harumi Miyamoto and Hidehiko Takei.
Nα8), 2iC, J, Young, R, C, A
Revie-Ko 5, 469 (1954); Wataru Kiyota,
IEICE Transactions J63-C (No. 2), 97 (
1980): Yuji Harasaki et al., Industrial Chemistry Journal, Dandan, 78 and 188 (1963); Tadaaki Tani, Journal of the Photographic Society of Japan, 20B (1972); Re5earch D
isclosure, 1982 Presentation Day, 117-1
18; Comprehensive technical data collection ``Recent Development and Practical Application of Photoconductive Materials and Photoreceptors'' published by Nihon Kagaku Information Publishing Department (1986), etc. Publicly known materials cited in the review.

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-mentioned beak molecule 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. to those coated with at least one layer or more, those with a water-resistant adhesive layer provided on the surface of the support, and those with at least one pre-coated layer provided on the surface layer of the support as necessary. A material made by laminating a plastic substrate onto which grade 2 is vapor-deposited onto paper can be used.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, “Electronic photography, 114. (Nα1).

pp. 2-11 (197!5), Hiroyuki Moriga, "Introductory Special Paper Chemistry J Polymer Publishing Association (1975) 1. F.

Hoover, J., Macromol, Sct.
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, particularly 0.1 to 5 μm for Carlson process.
It is preferable that

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 window light material and an increase in residual potential.

In order to actually make the lithographic printing original plate of the present invention, - between the shells,
First, an electrophotographic photosensitive layer (photoconductive layer) is formed on a conductive support according to a conventional method. Next, on this layer, the resin of the present invention and, if necessary, the above-mentioned additives, etc., are added to a boiling point of 20.
It can be produced by dissolving or dispersing it in a volatile hydrocarbon solvent at 0°C or lower, coating it, and drying it. The organic solvent used is specifically preferably a halogenated hydrocarbon having 1 to 3 carbon atoms, such as dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, dichloropropane, or 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 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 fat-free 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 hydrophilic layer is a film that exhibits both high hydrophilicity and water resistance after parent wood treatment, and also has extremely good adhesion to plate making and toner images. In addition to greatly suppressing the occurrence of , it 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 having significantly higher sensitivity than conventional printing 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.

(Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

Example 1 5 g of 4,4'-bis(diethylamino)-2,2'-dimethyltriphenylmethane as an organic photoconductive substance
5 g of 1-bisphenol A polycarbonate (manufactured by GE, trade name Lexan 121), 40+ng of a spectral sensitizing dye (A) with the following structural formula, and 0.2 g of an anilide compound CB) with the following structural formula as a chemical aggravating agent, were mixed with methylene chloride. It was dissolved in a mixture of 30 d of chloride and 30 ml of ethylene chloride to prepare a photosensitive liquid.

(Spectral Sensitizing Dye (A)) (Anilide Compound (B)) This photosensitive solution was applied to a conductive transparent support (a 100 μm polyethylene terephthalate support) with a vapor-deposited film of indium oxide using a wire round iron. An organic thin film having a photosensitive layer of about 4 μm was obtained by coating on a surface (surface resistance: 10 3 Ω).

On the other hand, after heating a mixed solution of 40 g of benzyl methacrylate, 12 g of 2-hydroxyethyl methacrylate, 48 g of monomer (A) corresponding to the copolymer component of the present invention, and 300 g of toluene to a temperature of 75°C under a nitrogen stream, Azobisisobutyronitrile (^, 1.B, N,) 1. ,
Og was added and reacted for 8 hours. The weight average molecular weight of the obtained copolymer was 48.000. ;Resin CI
) Monomer (A) CH3 CH,=C C00 (CHz) 45OzOCHtCHC1 □ 5% by weight of the obtained copolymer was applied to the surface of the electrophotographic photoreceptor obtained earlier.
A toluene solution containing 0.5% by weight of hexamethylene diisocyanate and hexamethylene diisocyanate was applied with a doctor blade.
It was dried at 0°C for 2 hours to form a surface layer of about 2 μm. The photosensitive material is desensitized using a processing solution [Fuji Photo Film ■]
ELP-EX (manufactured by ELP-EX) was used to desensitize the sample by passing it through an etching processor twice.

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 106 or less. The contact angle before the desensitization treatment was 84°, clearly indicating that the surface layer of the photosensitive material was made very well 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, Ltd.) to form a toner image, which was desensitized under the same conditions as above, used as an offset master, and printed on offset printing a (manufactured by Sakurai Seisakusho ■, model 52) on high-quality paper.

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 of polyvinyl butyral resin (Edenki Butyral #4000-1 manufactured by Denki Kagaku Kogyo Co., Ltd.) and 30 g of a 5% by weight tetrahydrofuran solution was sufficiently ground in a ball mill.Then, this mixture was taken out and 520 g of tetrahydrofuran was added under stirring. Ta. This dispersion was coated onto the conductive transparent support used in Example 1 using a wire round rod to form a charge generation layer of about 0.7 μm.

(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 g and 0 g of tetrahydrofuranthro was applied onto the charge generation layer using a wire round rod to form a charge transport layer of about 18 μm to obtain an electrophotographic photoreceptor having a photosensitive layer consisting of two layers. .

(Hydrazone compound) Next, a 5% by weight toluene solution of the hexamethylene diisocyanate-containing copolymer used in Example 1 was applied onto the photosensitive layer using a doctor blade, and the mixture was heated at 100°C for 2 hours.
After drying for hours, a surface layer of about 2 μm was formed.

The photosensitive material prepared in this way was charged to -6 to ■ using a paper analyzer (Kawaguchi Denki model, 5P-428), and the initial potential (VO), dark charge retention rate (D, R, R,) and optical attenuation were measured. When the exposure amount (El, '+.) was measured, each was ■. −
-550V, D, R, R, = 88% and E+z+o1
0. 8 (1ux・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.

The above electrostatic property evaluation items were measured as follows.

In a dark room at a temperature of 20'C and 165% RH, each photosensitive material was subjected to corona discharge for 20 seconds at -6 and ■ using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Denki 0 Kiku), and then left for 10 seconds. And the surface potential at this time is V. was measured. Next, the potential ■7° was measured after being left to stand still for 60 seconds in a dark room, and the retention of the potential after dark decay for 60 seconds, that is, the dark decay retention rate (D, R, R, (
%)] was calculated as (V70/V+.)X100(%).

After the surface of the photoconductive layer was charged to -400 μ by corona discharge, the surface of the photoconductive layer was irradiated with visible light at an illuminance of 2.0 lux until the surface potential (V+) attenuated to 1/10. Find the time of exposure and from this, exposure IE, /I. Calculate (looks/seconds).

Example 3 [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 0.05g and toluene 30
0g of the mixture was dispersed in a ball mill for 2 hours to prepare a photosensitive layer-forming product, which was coated on electrically conductive treated paper with a wire bar so that the dry adhesion amount was 25g/rrT.
00°C'''?! Dry for 1 minute.

On the other hand, a mixed solution of 5 g of glycidyl methacrylate, 45 g of monomer (B) according to the present invention described below, and 150 g of toluene was brought to a temperature of 75°C under a nitrogen stream, and 1. B, N
, 1. 0g was added and reacted for 8 hours.

The weight average molecular weight of the obtained copolymer was 37.000. : Resin [■] Monomer (B) CH.

CH,=C C00CR1CI(2NHCOOC(CH,,)+0.0% hexamethylene diisocyanate on the above photoreceptor.
A toluene solution containing 4% by weight and 5% by weight of the above copolymer was applied with a doctor blade and heated at 100°C for 1 hour.
．． It was dried and heated for 5 hours to form a surface layer of about 2 μm.

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. =-530V, D, R, R.

-83% and El/109. 6 (lux-sec)
Met.

Next, the same operation as in Example 2 was carried out using a fully automatic plate making machine ELP-404V, and 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.

Examples 4 to 19 Example 1 except that the copolymer shown in Table 1 below was used instead of the resin (1) of the present invention.
Each electrophotographic light-sensitive material was produced in the same manner as described above.

Table-1 C) 13 CI+3-←CHz
C-6-moC11,-C-to1-H-X-to1-C
OOC-H9C00 (C) 12) aOII [wt% composition ratio] Table-1 (Continued 1) Table-1 (Continued 2) Table-1 (Continued 3) This was carried out using the fully automatic plate making machine ELP404V as in Example 1. When the plate was made, the density of the obtained master plate for offset printing was 1.2 or more, and the image quality was clear. Furthermore, when the image was etched and printed using a printing press, the printed matter after printing 10,000 sheets had no capri in the non-image area and had a clear image quality.

Further, this photosensitive material was left under conditions of (45°C, 175% RH) for two weeks, and then treated in exactly the same manner as above, but there was no change at all from before aging.Example 20 The following chemical structural formula Example 1 except that the copolymer of the present invention shown by (weight average molecular weight 32,000): PA resin (XIX) copolymer: resin (XIX) was used instead of resin CI) of Example 1. A similar operation was carried out to obtain an electrophotographic material.

When this was plate-made using the same apparatus as in Example 1, the density of the obtained offset printing master plate was 1.0 or more and the image quality was clear. Further, when etching was performed and printed on a printing press, the printed matter after printing 10,000 sheets had clear image quality with no fogging.

Further, this photosensitive material was left under conditions of (45° C., 175% RH) for two weeks and then subjected to the same treatment as above, but there was no change at all compared to before aging.

Examples 21 to 25 Photosensitive materials were produced in the same manner as in Example 1, except that the compounds shown in Table 2 below were used instead of hexamethylene diisocyanate used in Example 1.

Table 2 This was plate-made using the same device as in Example 1, 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 in January was a clear image without any blurring.

(Effects of the Invention) From the above, the electrophotographic lithographic printing original plate having a hydrophilic layer containing the resin and crosslinking agent of the present invention in its surface layer has high hydrophilicity and water resistance after hydrophilic treatment. Since the film is compatible with both of the following and also has extremely good adhesion to the toner image, the resulting lithographic printing original plate has excellent quality in both scumming resistance and rigidity resistance.

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

Representative Patent Attorney (8107) Kiyotaka Sasaki 1.゛・、
Procedural amendment September 1, 1999

Claims (1)

[Claims] 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 electrophotographic resin containing at least one functional group that generates at least one of a thiol group, a phospho group, an amino group, and a sulfo group upon decomposition, and in which a crosslinking agent coexists. Original plate for lithographic printing.