JPH05273799A - Planographic printing original plate - Google Patents

Abstract

PURPOSE:To prevent the generation of similar stains on the entire surface and spot like stains by incorporating specific polymer components into a binding resin on the surface layer, thereby stabilizing the resin even if the printing conditions are varied and even if a color printing is excecuted. CONSTITUTION:An electrophotographic sensitive body provided with at least one photoconductive layer on a conductive supporting body and further provided with a surface layer on the uppermost layer thereof is utilized. In such a case, at least one kind of specific binding resin is incorporated into the binding resin of the surface layer. A polymer component incorporating at least one kind of functional group generating -COOH group by a chemical reaction treatment, a polymer component incorporating at least one kind of functional group selected from functional groups generating -SO3 H group, -SO2 H group and -PO3 H2 group by the treatment, a polymer component incorporating at least one kind of thermosetting and/or photosetting group and a copolymer incorporating at least these components are used as the binding resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic lithographic printing plate precursor prepared by electrophotography, and more particularly to a lithographic plate provided with a surface layer having specific properties on a photoconductive layer. Regarding the original plate for printing.

[0002]

2. Description of the Related Art At present, various types of offset original plates for direct plate making have been proposed and put into practical use. Above all, photoconductive particles such as zinc oxide and a binder resin are mainly used on a conductive support. The photoconductor provided with the photoconductive layer as a component is subjected to a normal electrophotographic process to form a highly lipophilic toner image on the photoconductor surface, and then the surface is treated with a desensitizing solution called an etchant. However, a technique for obtaining an offset original plate by selectively making the non-image portion hydrophilic is widely used.

In order to obtain a good printed matter, first, the original image is faithfully copied to the offset original plate, the surface of the photoconductor is easily compatible with the desensitizing solution, and the non-image area is sufficiently hydrophilized. It has water resistance, and in printing, the photoconductive layer with the image does not come off, it is well compatible with fountain solution, and it is sufficiently non-image area so that stains do not occur even when the number of printed sheets increases. It is necessary to have such properties as maintaining the hydrophilicity of.

In recent years, a method of preparing a printing plate of a hydrophilic treatment type on the surface of a non-image area which is easy to make by providing a specific resin layer on an ordinary electrophotographic photosensitive member is disclosed in JP-B-45-560.
No. 6 publication. That is, a printing plate is disclosed in which a surface layer comprising a vinyl ether, a maleic anhydride copolymer, and a hydrophobic resin compatible with the vinyl ether is provided on the electrophotographic photosensitive layer. This layer is a layer that can be made hydrophilic by hydrolyzing the acid anhydride ring portion by treating the non-image portion with an alkali after forming a toner image (hydrophilizable layer).

The vinyl ether-maleic anhydride copolymer used therein becomes water-soluble in the state of being ring-opened and hydrophilized, so that even if it is miscible with other hydrophobic resin, the layer is formed. The water resistance is extremely poor, and the printing durability is 500 at most.
The limit was ~ 600 sheets.

Further, Japanese Patent Laid-Open Nos. 60-90343 and 60-
159756, 61-217292, etc.,
A method of providing a surface layer (hydrophilizable layer) containing a silylated polyvinyl alcohol as a main component and a crosslinking agent together is disclosed. That is, this layer is for hydrolyzing the silylated polyvinyl alcohol by hydrolyzing it in the non-image area after toner image formation. Further, in order to maintain the film strength after hydrophilization, the degree of silylation of polyvinyl alcohol is adjusted and the residual image hydroxyl groups are crosslinked with a crosslinking agent. And, it is described that, by these, the background stain property of the printed matter is improved and the number of printed sheets is improved.

However, when actually evaluated, it is still unsatisfactory, especially in the background stain. Also,
Silylated polyvinyl alcohol is produced by silylating polyvinyl alcohol with a silylating agent to a desired ratio, but it is difficult to produce it stably because it is a polymer reaction. Furthermore, since the chemical structure of the hydrophilic polymer is limited, 1) chargeability and 2) quality of copied image (halftone dot reproducibility / resolution of image area, Fog in the image area, etc.), 3)
There is a problem that it is difficult to prevent the surface layer from affecting the exposure sensitivity and the like.

In order to improve the problems of the above electrophotographic lithographic printing plate precursor, the present inventors have
An electrophotographic lithographic printing plate precursor using a resin containing a functional group capable of generating a carboxyl group as a main component of the surface layer by decomposition has been proposed (JP-A-62-28345). Further, as the surface layer resin, a resin containing a functional group capable of generating a hydrophilic group upon decomposition and a compound capable of cross-linking the resin in the photosensitive layer are examined in combination, and for example, a functional group capable of generating a hydroxyl group upon decomposition. A group containing a group (JP-A-1-245970, JP-A-1-262556) and a group containing a functional group capable of generating a carboxyl group by decomposition (JP-A-1-28357, 1-2848).
No. 60), and those containing functional groups that generate a thiol group, an amino group, a phosphono group, a sulfo group and the like by decomposition (JP-A-1-304465 and 1-306855).

Further, it has been studied to use a small amount of fine particles having a functional group capable of generating a hydrophilic group by decomposition in the surface layer and forming a higher-order network structure. For example, those containing a functional group capable of generating a carboxyl group by decomposition (JP-A-2-13965), those containing a functional group capable of generating a hydroxyl group by decomposition (JP-A-2-13966), and sulfo by decomposition. A group containing a functional group that generates a group, a phosphono group, etc. (JP-A-2-13967) is disclosed.

These binder resins or resin particles form a hydrophilic group by being hydrolyzed, hydrolyzed or photolyzed by a desensitizing solution or immersion water used for printing. When these are used as the surface layer resin of the lithographic printing plate precursor, in any case, deterioration of electrophotographic properties (dark charge retention amount and photosensitivity) caused when the hydrophilic group itself is contained from the beginning can be avoided. The hydrophilicity of the non-image area which is hydrophilized by the desensitizing liquid is more expressed by the hydrophilic group produced by decomposition in the binder resin or resin particles in the surface layer, thereby improving the hydrophilicity of the image area. The oiliness and hydrophilicity of the non-image area become clear, the printing ink is prevented from adhering to the non-image area at the time of printing, and the surface layer has a crosslinked structure, so that the resin hydrophilized Further, it becomes water-insoluble, and due to the cross-linking effect, the hydrophilic cross-linking resin contains water and swells, water retention is created, and the hydrophilicity of the surface layer is sufficiently maintained. As a result, it becomes possible to print a large number of printed matter with clear image quality without scumming.

[0011]

The resin of the type which produces a hydrophilic group by the above decomposition reaction is decomposed by a treatment liquid to decompose a carboxyl group or a hydroxyl group masked with a protective group in advance, and the protected group is protected. It releases the group, and therefore, this type of resin is stable under the influence of atmospheric humidity (moisture) without being hydrolyzed during storage, and is rapidly deprotected during hydrophilization. An important characteristic is that the group reaction proceeds to generate a hydrophilic group and the hydrophilicity of the non-image area can be improved.

However, if a hydrophilic group-forming functional group (protecting group) is present which does not decompose even under severe conditions such as storage in a hot and humid environment for a long period of time and is stable, a rapid decomposition by the treatment liquid and a hydrophilic group It has been found that difficulties arise in rapid onset.

Further, when the lithographic printing plate precursor using the above-mentioned resin which produces a hydrophilic group is evaluated in more detail, variations in printing conditions on an offset printing machine (for example, dampening during printing). Depending on the amount of water supply) or the type of printing machine (Synflow method or Molton method), the number of prints increases from the occurrence of scumming during printing / printing to the production of a scum-free printed matter: There is a problem that the latitude for obtaining stable and high printing durability during printing is narrow, such as a reduction in the number of printed sheets that does not cause stains.

On the other hand, in the lithographic printing plate precursor using photoconductive zinc oxide, the surface of the lithographic printing plate is made hydrophilic by chemically treating zinc oxide with a desensitizing solution under acidic conditions, as is known.
The treatment liquid showing a good desensitizing ability is limited to those containing yellow blood salt as a main ingredient.

Due to these restrictions, it is necessary to limit the waste liquid treatment method of the desensitizing treatment liquid containing yellow blood salt as the main ingredient, and it is necessary to maintain the acidic conditions for printing. , When using neutral paper printing paper, the number of printable sheets decreases sharply (that is, printing durability deteriorates),
Alternatively, since the principle of desensitization is the formation of a hydrophilized product by a chelation reaction, it easily interacts with polyvalent metal ions contained in the color ink during printing, which causes abnormal emulsification of the ink. As a result, there are various problems and restrictions such as a decrease in the number of printable sheets especially when performing color printing.

The present invention improves the above-mentioned problems of the conventional lithographic printing plate precursor. That is,
One of the objects of the present invention is to provide an offset original plate which is stable even when the printing conditions in the printing process are varied and color printing is performed, and causes not only uniform ground stains but also spot stains. It is an object of the present invention to provide a lithographic printing plate precursor that is excellent in desensitizing property and is not caused.

A second object of the present invention is to provide a lithographic printing plate precursor having a high printing durability and having very little loss of paper at the time of printing to any offset printing machine having a different printing system. .. An object 3 of the present invention is to provide a lithographic printing plate precursor having high printing durability, which can use a combination of a desensitizing solution and a fountain solution with a processing solution having no environmental hygiene problems. ..

An object 4 of the present invention is to provide a lithographic printing plate precursor capable of high printing durability even when neutral paper is used as the printing paper without causing problems in the printing process as in the acid paper. That is.

[0019]

SUMMARY OF THE INVENTION The present invention has been made for the above object by utilizing an electrophotographic photosensitive member comprising a conductive support and at least one photoconductive layer on the conductive support, and a surface layer on the uppermost layer. In the lithographic printing plate precursor, the binder resin of the surface layer is
This is achieved by a lithographic printing plate precursor that contains at least one of the following binder resins [A]. As the binder resin [A], a polymer component (a) containing at least one functional group that produces a —COOH group by a chemical reaction treatment, a —SO ₃ H group, a —SO ₂ H group, and —PO by the treatment.
Polymer component (b) containing at least one functional group selected from functional groups that generate ₃ H ₂ groups and polymer component (c) containing at least one heat and / or photocurable group.
A copolymer containing at least is used.

Preferably, in the copolymer component (a) contained in the binder resin [A], at least one functional group which produces a --COOH group is a main chain of a polymer chain of the copolymer. Is directly bound to. More preferably, in the photoconductive layer of the present invention, together with the binder resin [A], heat and / or
Alternatively, it is characterized by containing a photocurable compound.

Further, the photoconductive compound used in the photoconductive layer of the present invention may be any one as long as it is used by being dispersed in the binder resin, but it is particularly low cost and pollution-free. Therefore, a system using at least a combination of photoconductive zinc oxide and / or photoconductive titanium oxide and a spectral sensitizing dye is preferable.

[0022]

The lithographic printing plate precursor of the present invention is different from the conventional system in which zinc oxide is chemically treated to develop hydrophilicity and utilizes the desensitizing property to the printing ink, and thus it is oxidized by hydrophilicity. The binder resin used for the surface layer is designed to be water-insoluble and hydrophilic without using zinc at all. Therefore, as the photoconductor, any one can be used as long as it is used in the resin dispersion type, in consideration of the cost and pollution-free as the lithographic printing plate precursor, as described above, Conductive zinc oxide and / or titanium oxide are preferred.

The conventional lithographic printing plate precursor using zinc oxide has a printing durability of about 10,000 sheets under specific conditions. To reduce or solve this specific condition, It is a difficult problem in principle as I did. Therefore, the present inventors have further studied earnestly, including the contents of the technology disclosed previously, in order to eliminate various restrictions at the time of printing and to maintain high printing durability of 10,000 sheets or more. .. As a result, it was found that the original plate of the present invention exhibits extremely excellent performance by using the binder resin [A] of the present invention and further by forming the film with a higher order structure.

That is, in order to show the excellent performance of the printing original plate after the chemical treatment using only the binder resin, the wettability of the desensitized film (non-image area) with water. Is extremely good (specifically, the contact angle value with distilled water is 0 °)
At the same time, it is extremely important that the entire photoconductive layer after the desensitizing treatment has an appropriate amount of water absorption.
Controls whether the difference in printing method or the change in the amount of dampening water supplied during printing (that is, the balance between dampening water and printing ink on the printing press) has a large effect or is stable. Has become clear. Further, it was also clarified that whether or not this state can be maintained when printing is continued affects high printing durability.

In order to achieve and maintain such a film structure of the lithographic original plate, as shown in the binder resin [A] of the present invention,
As a hydrophilic group generated by the desensitizing treatment, a carboxyl group and at least one hydrophilic group selected from a sulfo group, a sulfino group and a phosphono group are contained in the same polymer chain, and more preferably It is important that the carboxyl group is directly linked to the polymer main chain, and the binder resin [A] further contains a photo- and / or thermosetting group, It is important that the photoconductive layer forms a high-order crosslinked structure, and that the photoconductive layer and / or the thermosetting compound are used in combination in order to sufficiently form the high-order crosslinked structure.

That is, the polymer chain having a hydrophilic group expressed by the desensitizing treatment of the present invention exhibits sufficient desensitizing property and has a high-order cross-linking structure so that the polymer chain is highly hydrophilized. The molecule is made water-insoluble to maintain the strength of the membrane, and the membrane absorbs water to maintain a certain amount of water absorption. At this time, it is considered that the swelling property of the film is different depending on the degree of cross-linking of the high-order cross-linking structure of the film and affects the water absorption of the film.

In a lithographic plate using a conventionally known resin that produces a carboxyl group, swelling of the film is suppressed, and although the film strength is high to some extent, a high-order crosslinked structure is formed to the extent that it does not break. The surface wettability and the amount of water absorption of the film were insufficient, and scumming occurred on the printed matter after printing depending on the printing conditions as described above. This is presumed to be because even if the film strength is good, the state of the film cannot maintain sufficient wettability and water absorption because the hydrophilicity is insufficient with only the carboxyl group.

On the other hand, when a conventionally known resin which produces a sulfone group or a phosphono group is used, the crosslinking necessary for suppressing the swelling property of the film and sufficiently crosslinking until the high printing durability can be maintained. When the components are introduced, these cross-linking components are lipophilic, and as a result, the surface wettability of the resin is deteriorated, and scumming occurs from printing. On the other hand, when the introduction of the lipophilic cross-linking component is suppressed by using the resin that produces the sulfone group or the phosphono group, the produced sulfo group or phosphono group is very hydrophilic as compared with the carboxyl group, and The high-order structure film was able to retain a sufficient amount of water absorption, and it was possible to obtain a printed matter with no background stain after printing. However, when the printing durability was examined on a large-sized printing press where the printing pressure during printing was severe, the printing durability was reduced. It is considered that this is because it is difficult to satisfy both the strength of the film, the surface wettability of the film and the water absorption amount of the film.

Therefore, as a means for satisfying both the expansion of latitude during printing and high printing durability, an original plate in which the above-mentioned resin for forming a carboxyl group and a resin for forming a sulfo group and / or a phosphono group are mixed was examined. However, no improvement in performance was seen. However, it was confirmed that by using the binder resin [A] of the present invention, the state of the film as the original plate as described above can be controlled, and a high-performance original plate was found.

Further, the chemical structure of the polymer component in which at least one of the produced carboxyl groups is directly linked to the main chain of the polymer, the surface wettability is further improved and the latitude of printing conditions is further expanded. Found. The functional group used in the present invention for decomposing to produce at least one carboxyl group (hereinafter sometimes simply referred to as a carboxyl group-forming functional group) will be described in detail.

The carboxyl group-producing functional group of the present invention produces a carboxyl group by decomposition, but the number of carboxyl groups produced from one functional group may be one or two or more. According to one preferred embodiment of the present invention, the carboxyl group-forming functional group-containing resin has the general formula (I) [-COO-
L ₁ ] is a resin containing at least one functional group.

In the general formula (I) [-COO-L ₁ ], L ₁ is

[0033]

[Chemical 1]

Represents However, R ₁ and R ₂ may be the same or different and each represents a hydrogen atom or an aliphatic group, X represents an aromatic group, Z represents a hydrogen atom, a halogen atom, a trihalomethyl group, an alkyl group, CN, -N
_{O 2, -SO 2 R 1 '} , -COOR 2', -O-R 3 '
Or —CO—R ₄ ′ (provided that R ₁ ′, R ₂ ′, R ₃ ′,
R ₄ ′ each represents a hydrocarbon group), n, m
Represents 0, 1 or 2.

A ₁ and A ₂ may be the same or different and Ha
It represents an electron-withdrawing group having a positive substituent constant σ value of mmett. R ₃ represents a hydrogen atom or a hydrocarbon group. R ₄ , R ₅ and R ₆ may be the same or different from each other and represent a hydrocarbon group or —O—R ₅ ′ (provided that R ₅ ′ represents a hydrocarbon group).

Y ₁ represents an oxygen atom or a sulfur atom,
R ₇ , R ₈ and R ₉ may be the same or different and each represents a hydrogen atom or an aliphatic group, and p represents an integer of 5 or 6. Y ₂ represents an organic residue forming a cyclic imide group.
Functional groups of the general formula [-COO-L _1], which generates a carboxyl group by decomposition is described hereinafter in more detail.

L ₁ is

[0038]

[Chemical 2]

In the case of representing R₁, R₂Are each other
May be the same or different, preferably a hydrogen atom,
Or, a straight chain or branched chain having 1 to 12 carbon atoms which may be substituted.
Alkyl groups (eg methyl, ethyl, propyl)
Group, chloromethyl group, dichloromethyl group, trichloromethyl group
Cyl group, trifluoromethyl group, butyl group, hexyl
Group, octyl group, decyl group, hydroxyethyl group, 3-
Chloropropyl group) and X is preferably substituted.
Optionally a phenyl or naphthyl group (eg phenyl
Group, methylphenyl group, chlorophenyl group, dimethyl group
Phenyl group, chloromethylphenyl group, naphthyl group, etc.)
And Z is preferably a hydrogen atom or a halogen atom (eg,
For example, chlorine atom, fluorine atom, etc., trihalomethyl group (eg,
For example, trichloromethyl group, trifluoromethyl group, etc.), charcoal
A linear or branched alkyl having a prime number of 1 to 12 which may be substituted.
Kill group (eg methyl group, chloromethyl group, dichloromethyl group
Cyl, ethyl, propyl, butyl, hexyl
Group, tetrafluoroethyl group, octyl group, cyanoethyl
Group, chloroethyl group, etc.), -CN, -NO₂, -SO
₂R ₁'[R₁′ Is an aliphatic group (for example, having 1 to 12 carbon atoms)
Optionally substituted alkyl group: specifically, a methyl group, an ether group
Cyl group, propyl group, butyl group, chloroethyl group, pen
Even if it is substituted with a carbon number of 7 to 12, such as a tyl group or an octyl group.
Good aralkyl group: benzyl group, phenethyl group
Group, chlorobenzyl group, methoxybenzyl group, chlorophenyl group
Phenethyl group, methylphenethyl group, etc.) or aromatic group (eg
For example, a phenyl group or naphthyl which may contain a substituent
Group: Specifically, a phenyl group, a chlorophenyl group, a di group
Lolophenyl group, methylphenyl group, methoxyphenyl
Group, acetylphenyl group, acetamidophenyl group,
(Toxycarbonylphenyl group, naphthyl group, etc.)
], -COOR₂′ (R₂′ Is the above R₁Is synonymous with
), -OR₃′ (R₃′ Is the above R₁Is synonymous with
Or -CO-R_Four′ (R_Four′ Is the above R₁Synonymous with '
There is). n and m represent 0, 1 or 2.

L ₁ is

[0041]

[Chemical 3]

In the case of representing_Four, R_Five, R₆
May be the same or different from each other, preferably carbon
An optionally substituted aliphatic group of the formulas 1 to 18 [an aliphatic group is
Alkyl group, alkenyl group, aralkyl group or alicyclic group
As the substituent, for example, a halogen atom, a -CN group,
-OH group, -O-Q '(Q' is an alkyl group, aralkyl
Group, alicyclic group, aryl group) and the like],
An optionally substituted aromatic group having 6 to 18 carbon atoms (for example, fluorine group)
Phenyl group, tolyl group, chlorophenyl group, methoxyphen
Nyl group, acetamidophenyl group, naphthyl group, etc.) or
-OR_Four'[R _Four′ Is an optionally substituted carbon number 1 to 1
2 alkyl groups, optionally substituted C 2-12
Lucenyl group, optionally substituted aralkyl having 7 to 12 carbon atoms
A kill group, an alicyclic group having 5 to 18 carbon atoms which may be substituted,
A C6-18 optionally substituted aryl group is shown]
Represent.

L ₁ is

[0044]

[Chemical 4]

In the case of representing, A ₁ and A ₂ may be the same or different from each other, at least one of which is an electron-withdrawing group, and the sum of the Hammett σ _p values of -A ₁ and -A ₂ is the same. It may be 0.45 or more. Examples of the electron-withdrawing group here include, for example, an acyl group, an aroyl group,
Formyl group, alkoxycarbonyl group, phenoxycarbonyl group, alkylsulfonyl group, aroylsulfonyl group, nitro group, cyano group, halogen atom, halogenated alkyl group, carbamoyl group and the like can be mentioned.

The Hammett's σ _p value is usually used as an index for estimating the degree of electron withdrawing / donating of a substituent, and the larger it is on the + side, the more it is treated as a strong electron withdrawing group. Specific numerical values for each substituent are described in Naoki Inamoto, "Hammett's Rule-Structure and Reactivity," Maruzen (1984) and the like. In addition, Ham in this system
The σ _p value of mett is considered to be additive, and −A
_1, both -A ₂ need not be an electron withdrawing group. Therefore, for example, when -A ₁ is an electron-withdrawing group, the other substituent of -A ₂ has a sum of σ _p values of -A ₁ and -A ₂ of 0.
Any material may be used as long as it is 45 or more, and there is no particular limitation.

L ₁ is

[0048]

[Chemical 5]

In the case of representing, Y ₁ represents an oxygen atom or a sulfur atom. R ₇ , R ₈ and R ₉ may be the same or different from each other, preferably a hydrogen atom, and an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group,
Octadecyl group, chloroethyl group, methoxyethyl group,
Methoxypropyl group, etc.), optionally substituted alicyclic group (eg, cyclopentyl group, cyclohexyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group, chlorobenzyl group, Methoxybenzyl group, etc.), optionally substituted aromatic group (eg, phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.) or —O—R ₆ ′ ( R ₆ ′
Represents a hydrocarbon group, specifically, R ₇ , R ₈ and R
_The same substituents as the hydrocarbon group ₉ are shown).

P represents an integer of 5 or 6. L ₁ is

[0051]

[Chemical 6]

In the case of representing, Y ₂ represents an organic residue forming a cyclic imide group. Preferably, it represents an organic residue represented by the general formula (II) or (III).

[0053]

[Chemical 7]

In the formula (II), R ₁₂ and R ₁₃ may be the same or different, and each may be substituted with a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom, etc.) or a C 1-18 substituent. Alkyl group (for example, 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.] ,
Aralkyl group having 7 to 12 carbon atoms which may be substituted (eg, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, bromobenzyl group), carbon An alkenyl group which may be substituted and has a number of 3 to 18 (eg allyl group, 3-methyl-2-propenyl group, 2
-Hexenyl group, 4-propyl-2-pentenyl group,
12-octadecenyl group, etc.), —S—R ₇ ′ [R ₇ ′ is a substituent having the same meaning as the alkyl group, aralkyl group, or alkenyl group of R ₁₂ or R ₁₃ or an aryl group which may be substituted. (For example, phenyl group, tolyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group,
Ethoxyphenyl group, ethoxycarbonylphenyl group, etc.)] or —NHR ₈ ′ (R ₈ ′ has the same meaning as R ₇ ′). In addition, R ₁₂ and R ₁₃ may represent a residue forming a ring [eg, a 5- or 6-membered monocyclic ring (eg, cyclopentyl ring, cyclohexyl ring), or a 5- or 6-membered bicyclo ring (eg, bicyclo ring). Heptane ring,
Bicycloheptane ring, bicyclooctane ring, bicyclooctene ring, etc.), and these rings may not be substituted, and the substituents include the same as those described above for R ₁₂ and R ₁₃ .

Q represents an integer of 2 or 3. Formula (II
In I), R ₁₄ and R ₁₅ may be the same or different, and
₁₂ and have the same contents as R ₁₃ . Furthermore, R ₁₄ and R ₁₅ may represent an organic residue that continuously forms an aromatic ring (eg, benzene ring, naphthalene ring, etc.). 6-membered monocyclic ring (for example, cyclopentyl ring, cyclohexyl ring, etc.), 5-membered to 12-membered aromatic ring (for example, benzene ring,
Naphthalene ring, thiophene ring, pyrrole ring, pyran ring,
Quinoline ring, etc.) and the like.

L ₁ is

[0057]

[Chemical 8]

In the case of representing, R ₁₀ and R ₁₁ have the same meanings as R ₆ . Furthermore, another preferable embodiment of the present invention is a resin containing at least one oxazolone ring represented by the following general formula (IV).

[0059]

[Chemical 9]

In the general formula (IV), R ₁₆ and R ₁₇ may be the same or different and each represents a hydrogen atom or a hydrocarbon group, or R ₁₆ and R ₁₇ together form a ring. May be. Preferably, R ₁₆ and R ₁₇ may be the same or different from each other, and each is a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (eg, methyl group, ethyl group, propyl group). Group, butyl group, hexyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-
Methoxycarbonylethyl group, 3-hydroxypropyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, 4-chlorobenzyl group, 4
-Acetamidobenzyl group, phenethyl group, 4-methoxybenzyl group, etc.), optionally substituted carbon number 2 to 1
2 alkenyl groups (eg ethylene group, allyl group, isopropenyl group, butenyl group, hexenyl group, etc.), optionally substituted 5- to 7-membered alicyclic groups (eg cyclopentyl group, cyclohexyl group, chlorocyclohexyl group) Groups, etc.), optionally substituted aromatic groups (eg phenyl groups,
Chlorophenyl group, methoxyphenyl group, acetamidophenyl group, methylphenyl group, dichlorophenyl group,
Nitrophenyl group, naphthyl group, butylphenyl group, dimethylphenyl group, etc.) or R ₁₆ and R ₁₇ together form a ring (eg, tetramethylene group, pentamethylene group, hexamethylene group, etc.) May be.

As the functional group which produces at least one sulfo group by a chemical reaction, for example, a functional group represented by the general formula (V) or (VI) can be mentioned. Formula _{(V) -SO 2 -O-L} 2 formula _{(VI) -SO 2 -S-L} 2 formula in L ₂ is,

[0062]

[Chemical 10]

Represents Specifically, the general formula (I) -C
It has the same meaning as the corresponding protecting group for OO-L ₁ .
In addition, examples of the functional group that produces at least one sulfinic acid group by a chemical reaction include a functional group represented by the general formula (VII).

[0064]

[Chemical 11]

Further, as the functional group which forms a —PO ₃ H ₂ group, for example, the general formula (VIII) can be mentioned.

[0066]

[Chemical 12]

In the formula, L ₃ and L ₄ may be the same or different, and specifically, the protective group L of the general formula (I) -COO-L ₁
Indicates the same content as ₁ . The above-mentioned general formula (I)
Specific examples of the contents of (VIII) to (VIII) will be illustrated. However, the content of the present invention is not limited to these. In the following specific examples, each symbol represents the following content.

[0068]

[Chemical 13]

[0069]

[Chemical 14]

[0070]

[Chemical 15]

[0071]

[Chemical 16]

[0072]

[Chemical 17]

Copolymers used in the present invention containing a functional group capable of forming a hydrophilic group of --COOH, --SO ₃ H, --SO ₂ H or --PO ₃ H ₂ by the chemical reaction as described above. The components are not particularly limited. Preferred are those represented by the following general formula (IX).

[0074]

[Chemical 18]

[In the above formula (IX), Z'is -COO-,
-OCO -, - O -, - CO -, - CON (r 1) -,
_{-SO 2 N (r 1) -} (r 1 represents a hydrogen atom or a hydrocarbon group), - CONHCOO -, - CONHCONH
_{-, - CH 2 COO -,} - CH 2 OCO-,

[0076]

[Chemical 19]

Represents Y 'represents an organic residue bonded to or directly connected to -Z'- and -W _0. further

[0078]

[Chemical 20]

[0079]

[Chemical 21]

Alternatively, -W ₀ may be directly connected. —W ₀ represents a functional group represented by any one of formulas (I) to (VIII).
b ₁ and b ₂ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group or an aryl group. The general formula (IX) will be described in more detail.

Preferably Z'is

[0082]

[Chemical formula 22]

Represents However, r ₁ is a hydrogen atom and has 1 carbon atom
To 8 optionally substituted alkyl groups (eg, methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxyethyl group,
2-hydroxyethyl group, 3-bromopropyl group, etc.),
An optionally substituted aralkyl group having 7 to 9 carbon atoms (eg, benzyl group, phenethyl group, 3-phenylpropyl group,
Chlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group, dibromobenzyl group, etc.), an optionally substituted aryl group (for example, phenyl group, tolyl group, xylyl group, mesityl group, Methoxyphenyl group, chlorophenyl group, bromophenyl group, chloro-methyl-phenyl group, etc.) and the like.

Y'is a direct bond for connecting, or -Z'- and-
Represents an organic residue connecting W ₀ . When Y'represents an organic residue to be linked, this linking group represents a carbon-carbon bond which may be through a hetero atom (as a hetero atom, an oxygen atom, a sulfur atom or a nitrogen atom is shown), for example,

[0085]

[Chemical formula 23]

The bonding units such as the above are constituted either alone or in combination. (However, r ₂ , r ₃ , r ₄ , r ₅ , r
₆ represents the same content as r ₁ above). b ₁ , b
₂ may be the same or different, and is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group, a hydrocarbon group (eg, methyl group, ethyl group, propyl group, butyl group, methoxycarbonyl group, ethoxycarbonyl). Group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, methoxycarbonylmethyl group,
An optionally substituted alkyl group having 1 to 12 carbon atoms such as an ethoxycarbonylmethyl group and a butoxycarbonylmethyl group, an aralkyl group such as a benzyl group and a phenethyl group, an aryl group such as a phenyl group, a tolyl group, a xylyl group and a chlorophenyl group. Etc.).

Further, in the general formula (IX)

[0088]

[Chemical formula 24]

[0089]

[Chemical 25]

It is also possible to directly connect -W ₀ . Specific examples of the polymer component containing the functional groups represented by the general formulas (I) to (VIII) of the present invention are shown below. However, the scope of the present invention is not limited to these. Also, for example (b
During -1) ~ (b-36) , b represents -H or -CH _3. n represents 2-8. m represents 0 or an integer of 1 to 8.

[0091]

[Chemical formula 26]

[0092]

[Chemical 27]

The above-mentioned --COO used in the present invention
H, -SO ₃ H, a functional group expressed by the chemical reaction of -PO ₃ H ₂ and -SO ₂ H is a functional group with a protected hydrophilic group, chemically bonded to the hydrophilic these protecting groups The method of introduction according to J. et al. Can be easily performed by a conventionally known method. F. W. McOmie "Protectiv
e groups in Organic Chemi
story ”(Plenum Press. 1973), F.I. W. Greene, "Protective
groups Organic Syntheses
is ”(Wiley-linterscience, 19
1981), Chemical Society of Japan, "New Experimental Chemistry Course, No. 14"
Volume, Synthesis and Reaction of Organic Compounds "[Maruzen Co., Ltd., 1978] Yoshio Iwakura, Keisuke Kurita," Reactive Polymer "(Kodansha)
Each unit reaction described in the above is used.

As a method for introducing these functional groups to be used in the present invention into the resin [A], --COOH and --SO ₃ H, --PO ₃ H ₂ , --SO, which are important for the present invention, are used.
A method by a so-called polymer reaction in which a polymer each containing at least one hydrophilic group selected from ₂ H is converted into a functional group in which each hydrophilic group is protected by a reaction, or by the above-mentioned general formula By synthesizing one or more monomers containing one or more of the functional groups shown, and then polymerizing with any other monomer copolymerizable therewith to form a polymer. can get.

For the reason that the functional group necessary for the present invention can be arbitrarily adjusted in the polymer or that impurities (catalyst or by-product used in the case of polymer reaction) are not mixed, It is preferably produced by a method (preliminarily obtaining a desired monomer and carrying out a post-polymerization reaction). For example −
In the case of introducing a functional group that produces COOH, specifically, a carboxylic acid containing a polymerizable double bond or an acid halide thereof, for example, the carboxyl group is generally converted according to the method described in the above-mentioned publicly known documents. Formula (I) [-C
[OO-L ₁ ] is converted into a functional group, and then a polymerization reaction is carried out for production.

Further, the resin containing an oxazolone ring represented by the general formula (IV) as a functional group for forming a carboxylic acid in the reaction is a resin containing one or more monomers containing the oxazolone ring, or It can be obtained by a method of forming a polymer by a polymerization reaction of the monomer and another monomer copolymerizable therewith. The oxazolone ring-containing monomer can be produced by a dehydration ring-closing reaction of N-acylloyl-α-amino acids having a polymerizable unsaturated bond. Specifically, it can be produced by the method described in the literature cited in the review article in Yoshio Iwakura: Keisuke Kurita, "Reactive Polymer", Chapter 3 (published by Kodansha).

Next, contained in the resin [A] of the present invention,
The copolymer component containing a heat and / or photocurable group will be described. The "heat and / or photo-curable functional group" refers to a functional group that cures the resin by at least one of heat and light. Specific examples of the photocurable functional group include Hideo Inui, Mototaro Nagamatsu, "Photosensitive Polymer" (Kodansha, published in 1977), Takahiro Tsunoda, "New Photosensitive Resin" (published by The Printing Society of Japan, published in 1981), G ． E. Green
and B. P. Strak, J .; Macro. Sc
i. Reas. Macro. Chem. , C21
(2), 187-273 (1981-82), C.I. G.
Rattee, "Photopolymirizati
on of Surface Coatings "
(A. WileyInter Science Pu
b. The functional group used in the conventionally known photosensitive resin or the like is used as the photocurable resin cited in the review article such as 1982).

Further, the "thermosetting functional group" in the present invention
For example, Takeshi Endo, “Refining thermosetting polymer” (CMC Co., Ltd., published in 1986), Yuji Harazaki “Latest Binder Technology Handbook” Chapter II-I (Comprehensive Technical Center). , 1985), Takayuki Otsu "Synthesis and design of acrylic resin and new application development" (Chubu Business Development Center Publishing Department, 1985), Eizo Omori "Functional Acrylic Resin" (Technosystem, 1985), etc. The functional groups cited in the reviews can be used.

For example, --COOH group, --PO ₃ H ₂ group,-
SO ₂ H group, -OH group, -SH group, -NH ₂ group, -NH
R _A group [ _RA represents a hydrocarbon group having, for example, 1 to 1 carbon atoms.
8 alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, etc.). ], Cyclic acid anhydride-containing group [The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and as the cyclic acid anhydride to be contained, aliphatic dicarboxylic acid anhydride, aromatic Group dicarboxylic acid anhydrides may be mentioned.

Examples of the aliphatic dicarboxylic acid anhydride include:
Succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic acid anhydride ring, cyclohexane-1,2-dicarboxylic acid anhydride ring, cyclohexene-1,2-dicarboxylic acid ring Acid anhydride ring,
2,3-bicyclo [2,2,2] octanedicarboxylic acid anhydride ring and the like, and these rings include, for example, halogen atoms such as chlorine atom and bromine atom, methyl group, ethyl group,
An alkyl group such as a butyl group and a hexyl group may be substituted.

As an example of the aromatic dicarboxylic acid anhydride,
Is a phthalic anhydride ring, naphthalene-dicarboxylic acid anhydride
Ring, pyridine-dicarboxylic anhydride ring, thiophene-
Examples include dicarboxylic acid anhydride rings, and these rings are examples.
For example, halogen atom such as chlorine atom and bromine atom, methyl
Alkyl groups such as groups, ethyl groups, propyl groups, butyl groups,
Hydroxyl group, cyano group, nitro group, alkoxycal
Bonyl group (eg, as an alkoxy group, for example, methoxy
Group, etc.) and the like may be substituted. ],-
N = C = O group, blocked isocyanate group [isocyanate
Decomposed by heat with an adduct of nato group and active hydrogen compound
A functional group that produces an isocyanate group. Active hydrogen
As the compound, 2,2,2-trifluoroethanol,
2,2,2,2 ', 2', 2'-hexafluoroisopro
Pill alcohol Phenols (phenol, chlorophene
Nole, cyanophenol, cresol, methoxyphen
), Active methylene compounds (acetylacetone,
Acetoacetic acid esters, malonic acid diesters, malon
Dinitrile etc.), compounds containing cyclic N atom (eg imida
Sol, piperazine, morpholine, etc.) and the like.
], -CONHCH₂OR _B[R_BIs hydrogen atom or charcoal
Alkyl group having a prime number of 1 to 8 (specifically, R_AAlkyl group of
(Same content as). ], At least one -OR group
Containing silane coupling group [for example, -Si (OR)
₃, -Si (OR)₂(R), -Si (OR) (R)₂
And -OR or -R represents a hydrocarbon group,
Physically, the above general formula (I) -COOL₁R shown by₁When
Represent the same content. ], Containing at least one —OR group
A titanate coupling group having

[0102]

[Chemical 28]

A heteroatom-containing cyclic functional group having high stericity, such as Cd ₁ ═CH, which facilitates the ring-opening reaction.
d ₂ group (d ₁ and d ₂ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, etc.), etc. be able to. Further, as the polymerizable double bond group,
In particular

[0104]

[Chemical 29]

Examples thereof include: The copolymer component containing heat and / or photocurability as described above can be copolymerized with a monomer corresponding to the above-mentioned copolymer component containing a functional group expressing a hydrophilic group. Any monomer can be used. For example, as the copolymer component, the general formula (X)
Is shown.

[0106]

[Chemical 30]

W ₁ represents a heat and / or photocurable group described above. Further, the resin [A] of the present invention comprises a functional group-containing polymer component expressing a hydrophilic group as described above, light and / or
Alternatively, a polymer component other than these may be contained together with the thermosetting group-containing polymer component. Any other polymer component may be used as long as it copolymerizes with the monomer corresponding to the above polymer component. For example, "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science, Baifukan (1986
Annual), J. Brandrup. E. H. Image
ut. "Polymer Handbook" (Jo
hn Wileyd Sons, published in 1989) and the like.

Specifically, acrylic acid, α and / or β
Substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form Body, β-chloro form, β-bromo form,
α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg 2-pentenoic acid) , 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-
Hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids In addition to half-ester derivatives of vinyl or allyl groups, methacrylic acid esters, acrylic acid esters, crotonic acid esters, α-olefins, vinyl carboxylates or acrylic acid esters (for example, acetic acid, propionic acid as carboxylic acid) , Butyric acid, valeric acid, benzoic acid,
Naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (eg, dimethyl ester, diethyl ester, etc.),
Acrylamides, methacrylamides, styrenes (eg styrene, vinyltoluene, chlorostyrene,
Hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compound, vinylketone-containing compound, heterocyclic vinyls (eg vinylpyrrolidone, vinylpyridine, vinylimidazole, Vinyl thiophene, vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine and the like).

The abundance ratio of each polymer component of the resin [A] of the present invention is such that the total amount of the functional group-containing components expressing the hydrophilic group [that is, the polymer component (a) and the polymer is 100 parts by weight of the total polymer]. The total amount of component (b)] is 60 to 55% by weight, preferably 60
Is about 90% by weight. Moreover, the ratio of the polymer component (a) and the polymer component (b) is such that the total amount of the component (a) and the component (b) is 1
The amount of component (a) / component (b) is 5 to 90 as 100 parts by weight.
% / 95 to 10% by weight, preferably 10 to 80% by weight / 80 to 20% by weight.

The proportion of the photo- and / or thermosetting group-containing component (c) present is 5-40% by weight, preferably 1%.
It is 0 to 30% by weight. Further, the content of other copolymerization components other than these is 35% by weight or less at most.

If the content of each polymer component is out of the above range, the effect of the present invention as a printing original plate will be reduced. That is, the reduction in the background stain suppression from the printing at the time of printing,
The number of printed sheets decreases. Next, the light and / or thermosetting compound used together with the resin [A] of the present invention will be described.

The light and / or thermosetting compound may be any of a low molecular weight compound, an oligomer and a polymer containing at least one kind of the curable group. The light and / or thermosetting group refers to a functional group that cures the resin by at least one of heat and light. Specific examples of the “photo-curable functional group” and “thermo-curable functional group” include those having the same content as the functional group of the polymer component (c) contained in the resin [A].

Examples of these curable compounds include compounds usually used as a crosslinking agent. Specifically, compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taisei (1981), "Polymer Data Handbook Basic Edition", Baifukan (1986), edited by The Society of Polymer Science, Japan, etc. Can be used. For example, an organic silane-based compound (for example, a silane coupling agent such as vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidokichipropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane). Etc.), polyisocyanate compounds (eg, toluylene diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate). Isocyanates, high molecular weight polyisocyanates, etc.), polyblocked isocyanate compounds (blocking agents include those having the same contents as those described for the polymer (c) component), polycarbocarbonate Acid compounds and their carboxylic acid anhydrides (such as phthalic acid, maleic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, benzene 1,2,4,5
Tetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, etc. and their anhydrides, etc.),
Polyol compounds (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, Phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), titanate coupling compounds (eg, tetrabutoxytitanate, tetrapropoxytitanate, isopropyltristearoyl titanate, etc.), aluminum coupling compounds [ For example, aluminum butyrate,
Aluminum acetyl acetate, aluminum oxide octoate, aluminum tris (acetyl acetate), etc.], polyepoxy group-containing compounds and epoxy resins (for example, "New Epoxy Resins" edited by Hiroshi Kakiuchi, Shokoido (19
1985), "Epoxy Resins" edited by Kuniyuki Hashimoto, compounds described in Nikkan Kogyo Shimbun (Published in 1969), melamine resins (e.g., Ichiro Miwa, Hideo Matsunaga, "Uria.
"Melamine resin", compounds described in Nikkan Kogyo Shimbun (1969), poly (meth) acrylate compounds (for example, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura "Oligomer" Kodansha (1976), Omori The compounds described in Eizo "Functional Acrylic Resin" Techno System (published in 1985) and the like can be mentioned. Specifically, styrene derivatives such as divinylbenzene and trivinylbenzene: polyhydric alcohol (for example, 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 Methacrylic acid, esters of acrylic acid or crotonic acid, vinyl ethers or allyl ethers of rehydroxyphenols (eg hydroquinone, resorcin, catechol and their derivatives): dibasic acids (eg malonic acid, succinic acid, glutaric acid, Adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) vinyl esters, allyl esters, vinyl amides or allyl amides: polyamines (eg ethylenediamine, 1,3-propylenediamine, 1,4-
Butylenediamine, etc.) with a vinyl group-containing carboxylic acid (eg, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.), vinyl group-containing carboxylic acid (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid) , Acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl acetic acid,
Itaconiloylpropionic acid, carboxylic acid anhydride, etc.) and a reaction product of alcohol or amine (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid,
Ester derivatives or amide derivatives containing vinyl groups such as 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc. (eg vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, itacone) Allyl acid, vinyl methacryloyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyl oxycarbonyl methyl ester methacrylic acid, vinyloxy carbonyl methyl oxycarbonyl ethylene acrylate, N-allyl acrylamide, N-allyl methacrylamide, N-allyl Itaconic acid amide, methacryloyl propionic acid allylamide, etc.) or amino alcohols (eg aminoethanol, 1-aminopropanol, 1-amido) Butanol, 1-amino hexanol, 2-amino butanol) and the like condensates of carboxylic acids containing vinyl groups.

Further, a polymer containing the same photo- and / or thermosetting group-containing polymer component as that contained in the resin [A] can be mentioned. The light and / or thermosetting resin has a weight average molecular weight of 1 × 10 ³ to 1 × 10 ⁶ , preferably 3 × 1.
It is in the range of 0 ³ to 1 × 10 ⁵ . As described above, the binder resin for the surface layer of the present invention is preferably used in a combination in which a chemical bond between polymer chains is easily promoted in a crosslinking reaction in the presence of a curable compound. For example, as a polymer reaction by a combination of functional groups, a well-known method is usually mentioned, and a combination of a functional group of group A and a functional group of group B as shown in Table 1 below is exemplified. However, it is not limited to these.

[0115]

[Table 1]

[0116] In Table 1, represents a R ₁ ^0, R ₂ ⁰ alkyl group. Represents R ₃ ⁰ ~R ₅ ⁰ alkyl group or an alkoxy group,
And at least one of the substituents represents an alkoxy group. In the present invention, in order to promote the crosslinking reaction in the surface layer film, a reaction accelerator may be added to the resin as the main component, if necessary. When the crosslinking reaction is a reaction mode in which a chemical bond between functional groups is formed, for example, an organic acid (acetic acid, propionic acid,
Butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc., phenols (phenol, chlorophenol,
Nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc.), organometallic compounds (acetylacetonate zirconium salt, acetylacetone zirconium salt, acetylacetocobalt salt, etc., dibutoxytin dilaurate, etc.), dithiocarbamic acid compound (diethyldithiocarbamate) Etc.), thiuram disulfide compounds (tetramethyl thiuram disulfide, etc.), carboxylic acid anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butylsuccinic anhydride, etc.),
3,3 ′, 4,4′-tetracarboxylic acid benzophenone dianhydride, trimellitic acid anhydride, etc.) and the like.

When the crosslinking reaction is in a polymerizable reaction mode, a polymerization initiator (such as a peroxide or an azobis compound) can be used. The resin, which is the main component of the surface layer of the present invention, is light-cured and / or heat-cured after applying the photosensitive layer forming material. In order to carry out the heat curing, for example, the drying conditions are made more severe than the conventional drying conditions at the time of producing the photoreceptor.
For example, the drying conditions are high temperature and / or long time. Alternatively, it is preferable to further heat-treat after drying the coating solvent. For example, the treatment is performed at 60 ° C to 150 ° C for 5 to 120 ° C. When the above reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As a method for curing the specific functional group in the resin which is the main component of the surface layer of the present invention by irradiation with light, a step of irradiation with "chemically active light" may be included. As the “chemically actinic rays” used in the present invention,
Visible rays, ultraviolet rays, far ultraviolet rays, electron rays, X rays, γ rays, α
Any of lines and the like may be used, but ultraviolet rays are preferable. More preferably, the wavelength is 310 nm to 500 n
It can emit light rays in the range of m, and generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp or the like is used. The light irradiation process is usually 5 cm to 50 c
Irradiation for 10 seconds to 10 minutes from the distance m can be sufficiently performed.

As the resin used in the surface layer of the present invention, another binder resin may be used in combination. Examples of resins that can be used include conventionally known binder resins for electrophotographic photosensitive layers. For example, Ryuji Shibata and Jiro Ishiwatari, Kogaku, Vol. 17, p. 278 (1968) Harumi Miyamoto. , Hidehiko Takei, Imaging, 1973 (No.8), Koichi Nakamura, "Practical Technology of Binder for Recording Material", Chapter 10, C.I.
H. C. Published (1985) edited by The Institute of Electrophotography, "Present Symposium on Organic Photoconductors for Electrophotography" Proceedings (1985
), Hiroshi Komon, “Recent development of photoconductive materials and photoconductors
Practical application ”, Japan Science Information Co., Ltd. (1986), edited by The Institute of Electrophotography,“ Basics and Applications of Electrophotographic Technology ”Chapter 5, Corona Publishing Co., Ltd. (1988), D.I. Tatt, S.M. C. Hei
decker, Tappi, 49 (No. 10), 43
9 (1966), E.I. S. Baltazzi, R.A. G.
Blanclotte et al, Photo. Sc
i. Eng. 16 (No. 5), 354 (1972),
Nguyen Chang Kae, Isamu Shimizu, Eiichi Inoue, Electrophotographic Society Journal 18 (No. 2), 22 (1980) and the like.

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

These other binder resins which may be contained are
After the desensitizing treatment with the light-sensitive material of the present invention, it is used within a range that does not impair the function of expressing water retention. Specifically, the content is at most 30% by weight, preferably 20% by weight or less, in 100 parts by weight of the total binder resin. In order to improve the strength of the hydrophilizable surface layer itself, the adhesion to the electrophotographic photosensitive layer or the electrophotographic characteristics, a resin other than the resin of the present invention described above is added, or a crosslinking agent or a plasticizer is added. You may add.

As the crosslinking agent, a commonly used organic peroxide, metal soap, organic silane, a crosslinking agent such as polyurethane, a curing agent such as an epoxy resin and the like can be used. Specifically, it is described in "Crosslinking Agent Handbook" edited by Fuzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981). Furthermore, the surface layer which can be made hydrophilic is the development characteristics during toner development,
The surface of the toner image may be mechanically matted or a layer may contain a matting agent for the purpose of improving the adhesiveness of the toner image or the water retention after the hydrophilic treatment. As the matting agent, fillers such as silicon dioxide, zinc oxide, titanium oxide, zirconium oxide, glass particles, alumina and clay, polymethylmethacrylate, polystyrene,
Examples thereof include polymer particles such as phenol resin.

What is important in constructing the surface layer is that the non-image area becomes sufficiently hydrophilic after the desensitizing treatment, as described above. That is, this hydrophilicity can be confirmed, for example, by measuring the contact angle with water. The contact angle of water on the surface of the surface layer (hydrophilizable layer) before the desensitizing treatment is about 60 ° to 120 °, but it decreases to about 0 ° to 5 ° after the desensitizing treatment. However, it becomes very wet with water. Therefore, the printing plate has an image portion made of lipophilic toner and a highly hydrophilic non-image portion formed on its surface. Therefore,
The surface layer after desensitizing treatment may have a contact angle with water of 5 degrees or less.

The present invention is particularly excellent in that it is more hydrophilic than the conventional ones. For the electrophotographic photosensitive layer (photoconductive layer) used in the present invention, any photoconductive substance can be used regardless of whether it is an inorganic photoconductive compound or an organic photoconductive compound. Examples of the inorganic photoconductive substance include zinc oxide, titanium oxide, zinc sulfide, selenium, selenium alloy, cadmium sulfide, cadmium selenide, and silicon, which form a photoconductive layer together with a binder resin. Alternatively, the photoconductive layer may be formed solely by vapor deposition, sputtering, or the like. As the organic photoconductive substance, for example, in the case of polymer, the following (1) to (5) can be mentioned. (1) Polyvinylcarbazole and its derivatives described in JP-B-34-10966, (2) Polyvinylpyrene, polyvinylanthracene, and poly-2-vinyl- described in JP-B-43-18674 and JP-B-43-19192 4- (4 '
-Dimethylaminophenyl) -5-phenyl-oxazole, vinyl polymers such as poly-3-vinyl-N-ethylcarbazole, (3) Polyacenaphthylene, polyindene, acenaphthylene and styrene described in JP-B-43-19193. Polymers such as the copolymers of (4), condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin and ethylcarbazole-formaldehyde resin described in JP-B-56-13940.
(5) Various triphenylmethane polymers described in JP-A-56-90833 and JP-A-56-161550.

For low molecular weight compounds, for example, the following (6)
(18) can be mentioned. (6) Triazole derivatives described in U.S. Pat. No. 3,112,197, etc., (7) U.S. Pat. No. 3,189,447.
Oxadiazole derivatives described in JP-B No. 3754062, (8) Imidazole derivatives described in JP-B-37-16096, and (9) US Pat. No. 3615402.
No. 3820989, 3542544, Japanese Patent Publication No. 45-555,
JP-B-51-10983, JP-A-51-93224, JP-A-55-17105
JP-A-56-4148, JP-A-55-108667, JP-A-55-
No. 156953, JP-A-56-36656, and the like, polyarylalkane derivatives described in (10) US Pat. No. 31.
80729, 4278746, JP-A-55-88064, JP-A
55-88065, JP-A-49-105537, JP-A-55-51086,
JP-A-56-80051, JP-A-56-88141, JP-A-57-45545
Nos. 54-112637, 55-74546, and the like, and pyrazoline derivatives and pyrazolone derivatives described in the gazette, (11) U.S. Pat. No. 3,615,404, Japanese Patent Publication No. 51-10105. , JP-A-54-83435, JP-A-54-110836
No. 4, JP-A-54-119925, JP-B-46-3712, JP-B-47
-28336 specification, publications, and the like, (12) U.S. Pat. No. 3,567,450, Japanese Patent Publication No. 49-35702, West German Patent (DAS) 1110518, U.S. Pat. No. 3,180,703, U.S. Pat. No. 3240597, U.S. Patent No.
3658520, U.S. Pat.No. 4,232,103, U.S. Patent No. 4175
961, U.S. Pat.No. 4012376, JP-A-55-144250,
JP-A-56-119132, JP-B-39-27577, JP-A-56-224
Nos. 37, 37, and the like, (13) amino-substituted chalcone derivatives described in US Pat. No. 3,526,501, (14) US Pat. No. 354254.
N, N-bicarbazyl derivatives described in No. 6, etc.,
(15) Oxazole derivatives described in US Pat. No. 3,257,203 and the like, (16) Styrylanthracene derivatives described in JP-A-56-46234, and (17) JP-A-54.
-110837 and other fluorenone derivatives, (18) U.S. Pat. No. 3717462, JP-A-54-59143
No. 5, JP-A-55-52063, JP-A-55-52064, JP-A-55-4
6760, JP-A-55-85495, JP-A-57-11350, JP-A-SHO
No. 57-148749 Hydrazone derivatives disclosed in their respective specifications and publications.

Two or more kinds of these photoconductive materials 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'-
Polyarylmethanes such as dimethyltriphenylmethane; and 3- (4-dimethylaminophenyl) -1,
Unsaturated heterocycle-containing compounds represented by pyrazoline derivatives such as 5-diphenyl-2-pyrazoline are preferably used.

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

For examples of specific polymeric materials useful as binders, see Research Disclosure (Research
Disclosure), 109, pages 61-67, under the title "Electrophotographic Elements, Materials and Methods". Generally, the amount of binder present in the photoconductive composition used in the present invention can be varied. Typically, a useful amount of binder is based on the total amount of mixture of photoconductive material and binder,
It is in the range of about 10 to about 90% by weight.

Further, a conventionally known compound can be added as a spectral sensitizer. For example, xanthene dye,
Examples thereof include triphenylmethane-based dyes, azine-based dyes, phthalocyanine-based dyes (metal-containing), polymethine-based dyes, and the like. Specifically, Harumi Miyamoto, Hidehiko Takei, “Imaging” 1973 (No. 8), 2 ; CJYou-ng, RCA Review 1
5, 469 (1954); Kyohei Kiyota, Transactions of the Institute of Electrical Communication J63
-C (No. 2), 97 (1980); Yuji Harasaki et al., Journal of Industrial Chemistry, 6
6, 78 and 188 (1963); Tadaaki Tani, Journal of the Photographic Society of Japan, 35, 208.
(1972); Rese-arch Disclosure, 1982 216, 117-118
The publicly known materials and the like, which are referred to in general reviews, such as "Development and practical use of recent photoconductive materials and photoconductors" published by Nippon Kagaku Kagaku Co., Ltd. (1986), are listed.

The photoconductive layer may be formed of one layer, or may be formed of two or more layers. In the case of a multi-layer, for example, the inorganic photoconductor or a phthalocyanine pigment, a charge generation layer consisting of an organic pigment such as an azo pigment and a binder resin optionally added, and the above-mentioned polymer compound or low-molecular compound And a charge-transporting layer made of a binding resin, which is a so-called function-separated type photoconductive layer.

The photoconductive layer used in the present invention can be provided on a commonly used known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, the substrate such as metal, paper or plastic sheet is impregnated with a low resistance substance as in the conventional case. Those which have been subjected to a conductive treatment by, for example, those which are coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided), and further for preventing curling, the support Having a water-resistant adhesive layer on its surface, having at least one precoat layer provided on the surface layer of the support as required, and having a substrate plastic laminated with Al or the like laminated on paper Etc. can be used.

Specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto, “Electrophotography” 14, (No. 1),
2-11 (1975); Hiroyuki Moriga "Introduction to Special Paper Chemistry" Polymer Publishing (1975); MF Hoover, J. Mac-romol. Sci. Ch
Those described in em., A-4 (6), pages 1327 to 1417 (1970) and the like can be used. The coating thickness of the photoconductive composition on a suitable support can vary widely.
Generally, it can be applied in the range of about 10 microns to about 300 microns, but before drying. It has been found that the preferred range of coating thickness before drying is in the range of about 50 microns to about 150 microns. However, it is possible to obtain useful results outside this range. The dried thickness of this coating may be in the range of about 1 micron to about 50 microns.

The thickness of the hydrophilizable surface layer of the present invention is 10 μm.
m or less, especially 0.1 for the Carlson process
It is preferably ˜5 μm. If it is thicker than 5 μm, there may occur inconveniences such as a decrease in sensitivity of the lithographic printing plate precursor as an electrophotographic photoreceptor and an increase in residual potential. To actually make the lithographic printing plate precursor of the invention, generally, an electrophotographic photosensitive layer (photoconductive layer) is first 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 and the like have a boiling point of 200 ° C.
It can be produced by dissolving or dispersing in the following volatile hydrocarbon solvent, coating and drying it. As the organic solvent used, specifically, a halogenated hydrocarbon having 1 to 3 carbon atoms such as dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, dichloropropane or trichloroethane is particularly preferable. Other aromatic hydrocarbons such as chlorobenzene, toluene, xylene or benzene, acetone or 2
It is also possible to use various solvents used in the coating composition and mixtures of the above solvents, such as ketones such as butanone, ethers such as tetrahydrofuran and methylene chloride.

A toner image is formed on the original plate obtained as described above according to a usual 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 in which a reducing agent is dissolved) to change the non-image area to hydrophilic. As described above, by using the hydrophilizable layer in the invention, any conventionally known electrophotographic photoreceptor can be used as a high quality lithographic printing plate precursor. The hydrophilizable layer is a film that has both high hydrophilicity and water resistance after hydrophilic treatment, and also has very good adhesion to a toner image,
Therefore, the obtained lithographic printing plate precursor has extremely suppressed generation of background stain and has high printing durability.

Further, since the printing plate of the present invention can maintain the original sensitivity of the electrophotographic photosensitive layer almost as it is, it is possible to obtain a printing plate plate having significantly higher sensitivity than the conventional printing plate for electrophotographic plate making. .. Further, in the past, since one layer had to have the property of being photoconductive and capable of being made hydrophilic, only a limited material such as zinc oxide could be used. Since the functions are separated in the hydrophilizable layer, the range of selection of the photoconductive layer is widened. Therefore, for example, if a material having high sensitivity in the long wavelength light region is selected, it has been impossible to achieve the He-Ne laser. It becomes possible to write with a semiconductor laser.

In the present invention, various dyes can be used together as a spectral sensitizer depending on the kind of light source such as visible light exposure or semiconductor laser light exposure. For example, Miyamoto Harumi, Takei Hidehiko: Imaging 1973 (N
o. 8) Page 12, C.I. J. Young et al .: RCA R
view 15, 469 (1954), Kouhei Kiyota et al .: Transactions of the Institute of Electrical Communication, J63-C (No. 2), 9
7 pages (1980), Yuji Harasaki et al., Journal of Industrial Chemistry, 6
6,78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan, 35, 208 (1972), and other general references, carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes. , Polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain a metal), and the like.

More specifically, those mainly containing carbonium type dyes, triphenylmethane type dyes, xanthene type dyes and phthalein type dyes are disclosed in Japanese Examined Patent Publication No. 51-4.
52, JP-A-50-90334, 50-11422.
7, JP-A-53-39130, JP-A-53-82353, US Pat. Nos. 3,052,540 and 4,054,450, and JP-A-57-16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Harmmer "The Cyanin
eDyes and Related Compound
The dyes described in "ds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,110,591,
3121008, 3125447 and 312817
9, No. 3132942, No. 3622317,
British Patent Nos. 12268892, 1309274, 14
No. 05898, Japanese Patent Publications No. 48-7814, 55
The dyes described in each publication of 18892 are listed.

Furthermore, the near infrared light having a long wavelength of 700 nm or more can be used.
As polymethine dyes for spectrally sensitizing infrared light, JP-A-47-840, JP-A-47-44180 and JP-B-51-41 are known.
061, ibid 49-5034, ibid 49-45122, ibid 5
7-46245, 56-351141, 57-157.
254, 61-26044, 61-27551, U.S. Pat. Nos. 3,619,154 and 4,175,956, and "Research Disclosure".
e ”, 1982, 216, pp. 117-118.

The photoconductor of the present invention is also excellent in that its performance does not easily change depending on the sensitizing dye even when various sensitizing dyes are used in combination. Furthermore, various conventionally known additives for electrophotographic photoreceptors can be used in combination, if necessary. These additives include chemical sensitizers for improving electrophotographic sensitivity, various plasticizers for improving film properties, surfactants and the like.

Examples of the chemical sensitizer include halogen, benzoquinone, chloranil, fluoranyl, bromanil,
Electron-withdrawing compounds such as dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, 2,3-dichloro-5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone and tetracyanoethylene , Hiroshi Komon et al. "Recent Development and Practical Use of Photoconductive Materials and Photoconductors" No. 4
Chapter-Chapter 6: Japan Science Information Publishing Co., Ltd. (1986)
The polyarylalkane compound, the hindered phenol compound, the p-phenylenediamine compound, etc. Moreover, JP-A-58-65439 and 58-
102239, 58-129439, 62-719.
The compounds described in each of the 65 publications and the like can also be mentioned.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methylphthalylethyl glycolate and dimethyl. Glycol phthalate or the like can be added to improve the flexibility of the photoconductive layer. These plasticizers can be contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer.

A known method can be applied to prepare a printing plate using the lithographic printing plate precursor of the present invention obtained as described above, and a copy image is formed on the electrophotographic plate having the above-mentioned structure by a conventional method. After formation, it is created by desensitizing the non-image area. That is, it is charged substantially uniformly in a dark place, and an electrostatic latent image is formed by imagewise exposure. Examples of the exposure method include scanning exposure using a semiconductor laser, a He-Ne laser, or the like, reflection image exposure using a xenon lamp, a Tigsten lamp, a fluorescent lamp, or the like as a light source, contact exposure through a transparent positive film, and the like. Next, the electrostatic latent image is developed with toner. As the developing method, conventionally known methods, for example, various methods such as cascade development, porcelain brush development, powder cloud development and liquid development can be used. Among them, liquid development is capable of forming a fine image and is suitable for making a printing plate. The formed toner image can be fixed by a known fixing method such as heat fixing, pressure fixing, solvent fixing and the like.

With respect to the lithographic printing original plate having the toner image thus formed, the non-image area is then desensitized to produce a printing plate. In the desensitizing treatment used in the present invention, the above-mentioned protected hydrophilic group chemically reacts with the treatment liquid to express the hydrophilic group. Specifically, a basic treatment liquid is used, preferably pH 8
Any of the water-soluble treatment liquids Nos. 14 to 14 may be used.

The compound that makes the treatment liquid basic may be any of conventionally known inorganic compounds and organic compounds, for example, carbonates, sodium hydroxide, potassium hydroxide, potassium silicate, sodium silicate, organic amine compounds. Any of these may be used alone or in combination. Furthermore, as a compound used in combination to accelerate the hydrophilization reaction, the nucleophilic constant n [R. G. Pearson, H .; Sobel, J .;
Songstad, J.M. Amer. Chem. So
c. , 90, 319 (1968)] contains a substituent having a value of 5.5 or more, and in 100 parts by weight of distilled water,
A hydrophilic compound that dissolves in an amount of 1 part by weight or more is included.

Specific compounds include, for example, hydrazine, hydroxylamine, sulfite (ammonium salt,
Sodium salt, potassium salt, zinc salt, etc.), thiosulfate, etc., and at least one polar group selected from a hydroxyl group, a carboxyl group, a sulfo group, a phosphono group, and an amino group in the molecule. Mercapto compounds,
Examples thereof include hydrazide compounds, sulfinic acid compounds, primary amine compounds, secondary amine compounds, and the like.

For example, as a mercapto compound, 2-mercaptoethanol, 2-mercaptoethylamine, N-
Methyl-2-mercaptoethylamine, N- (2-hydroxyethyl) 2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenecarboxylic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethylphosphonic acid, mercapto Benzenesulfonic acid, 2-mercaptopropionylaminoacetic acid, 2-mercapto-1-aminoacetic acid, 1-mercaptopropionylaminoacetic acid, 1,2-dimercaptopropionylaminoacetic acid, 2,3-dihydroxypropylmercaptan, 2-methyl-2 -Mercapto-1-aminoacetic acid and the like, as a sulfinic acid compound, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid, Carboxybenzenesulfinic acid and the like, 2-hydrazinoethanolsulfonic acid, 4-hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid and the like as hydrazide compounds, Examples of the primary or secondary amine compound include N- (2-hydroxyethyl) amine, N,
N-di (2-hydroxyethyl) amine, N, N-di (2-hydroxyethyl) ethylenediamine, tri (2
-Hydroxyethyl) ethylenediamine, N- (2,3
-Dihydroxypropyl) amine, N, N-di (2,3
-Dihydroxypropyl) amine, 2-aminopropionic acid, aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2-hydroxyethylmorpholine, 2
-Carboxyethyl morpholine, 3-carboxy piperazine etc. can be mentioned.

The amount of the nucleophilic compound present in these treatment solutions is 0.05 mol / liter to 10 mol / liter, preferably 0.1 mol / liter to 5 mol / liter. Further, the pH of the treatment liquid is preferably 4 or more. The treatment conditions are preferably a temperature of 15 ° C. to 60 ° C. and an immersion time of 10 seconds to 5 minutes. The treatment liquid comprises the above-mentioned nucleophilic compound and p
Other compounds may be contained in addition to the H regulator. For example, an organic solvent soluble in water is added to 1 to 50 parts by weight in 100 parts by weight of water.
You may contain a weight part. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propanol alcohol, benzyl alcohol, phenethyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, Trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.) amides (dimethylformamide, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, etc.), etc. These may be used alone or in admixture of two or more.

Further, the surfactant may be contained in 100 parts by weight of water in an amount of 0.1 to 20 parts by weight. Examples of the surfactant include conventionally known anionic, cationic or nonionic surfactants. For example, compounds described in Hiroshi Horiguchi "New Surfactants" Sankyo Publishing Co., Ltd. (1975), Ryohei Oda, Kazuhiro Teramura "Synthesis of Surfactants and Their Applications" Maki Shoten (1980), etc. Can be used.

The treatment conditions are preferably a temperature of 15 ° C. to 60 ° C. and an immersion time of 10 seconds to 5 minutes. Furthermore, the hydrophilic treatment containing the nucleophilic compound can obtain the same effect even when the immersing water at the time of printing is used by containing the nucleophilic compound.

[0151]

【Example】

Example 1 and Comparative Examples A to C Example 1 40 g of a binder resin [B-1] having the following structure, 200 g of photoconductive zinc oxide, 0.02 g of uranine, and rose bengal 0.1.
A mixture of 04 g, bromphenol blue 0.03 g, chilylic acid 0.15 g and toluene 300 g was placed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 1 × 10 ⁴ r.p.
p. m. Was dispersed for 10 minutes at the rotation speed of. To this, 0.1 g of phthalic anhydride and 0.02 g of o-chlorophenol were added, and the rotation speed was 1 × 10 ³ r. p. m. Dispersed for 1 minute. The dispersion for forming a photosensitive layer was coated on a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ² , dried at 100 ° C. for 30 seconds, and further heated at 140 ° C. for 1 hour.

[0152]

[Chemical 31]

A solution having the following contents was applied on the surface of the photoreceptor by a wire bar, dried by touch with a finger, and further heated at a temperature of 140 ° C. for 1 hour to form a surface layer having a thickness of 2.3 μm. Then, the mixture was left in the dark at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material. Resin [A-1] having the following structure 8 g Resin [P-1] having the following structure 2 g Phthalic anhydride 0.1 g O-chlorophenol 0.02 g Tetrahydrofuran 90 g

[0154]

[Chemical 32]

Comparative Example A An electrophotographic light-sensitive material was prepared in the same manner as in Example 1 except that 8 g of resin [R-1] having the following structure was used instead of 8 g of resin [A-1]. Was produced.

[0156]

[Chemical 33]

Comparative Example B An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 8 g of the resin [R-2] having the following structure was used instead of 8 g of the resin [A-1] in Example 1. It was made.

[0158]

[Chemical 34]

Comparative Example C In Example 1, 5.8 g of resin [R-1] and 2.2 g of resin [R-2] (resin [R-1] / resin [R-1] instead of 8 g of resin [A-1]] were used. R-2] = 72/28 (weight ratio)]
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that was used.

The imaging properties and printability of these light-sensitive materials were examined. As for printability, a fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) was used to expose and develop an image to form an image, and a desensitizing solution E-
It was examined by using a lithographic printing plate obtained by desensitizing treatment using No. 1. The printability was evaluated using each of the Symflow system printer and the Molton system printer in order to investigate the influence of the difference between the dampening water and the printing ink supply system of the printer. Furthermore, by using a large-sized printing machine that prints a Kikuzen size (1003 × 800 mm), the durability of the printing plate when the printing pressure on the offset printing machine becomes strong is determined by how many clear prints can be obtained. The printing durability was evaluated.

[0161]

[Table 2]

Embodiments of the evaluation items shown in Table 2 are as follows. Note 1) Imaging: Each photosensitive material and fully automatic plate-making machine ELP4
04V (manufactured by Fuji Photo Film Co., Ltd.) is left at room temperature and normal humidity (20 ° C, 65%) for one day and then plate-formed to form a copy image, and the obtained copy original image (fog, image Visually observe the image quality). Note 2) Water retention after printing: Each light-sensitive material itself was immersed for 3 minutes in E-1 (desensitizing treatment solution having the following formulation) at a temperature of 40 ° C. (original plate not made into a plate: abbreviated as raw plate). These plates were printed using F-1 shown below as dampening water, and the presence or absence of background stains on the 50th printed sheet after printing was visually evaluated. Desensitizing treatment liquid: E-1 Monoethanolamine 60 g Neosoap (manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) 8 g Benzyl alcohol 100 g was diluted with distilled water to make a total amount of 1.0 liter and then adjusted to pH 13.5 with potassium hydroxide. It was adjusted.

Damping water: F-1 Damping water for PS plate Alky A (manufactured by Toyo Ink Co., Ltd.) was diluted 200 times with distilled water (pH 9.5) Imprint water retention I: Molton A Ryobi 3200CD type (manufactured by Ryobi Co., Ltd.) was used as a type printing machine. Imprinted water retention II: Ryobi 3200MCD type was used as a synflow type printing machine. Note 3) Printing durability After sensitizing each light-sensitive material in the same manner as in Note 3) above, immersing it in the processing solution of E-1 used in Note 4) for 3 minutes, ), The neutralizing paper was used as the printing paper, and the Oliver 94 was used as the printing machine.
Using a mold [Sakurai Mfg. Co., Ltd.], the number of printed sheets from which a clear image free of background stain was obtained was examined. The surface smoothness of each photographic material was good. The electrostatic characteristics were good, and the actual picked-up image was good for all copied images.

Next, each of these photoconductors is subjected to a desensitizing treatment to determine the degree of presence or absence of ink adhesion (water retention) in the non-image area on the actual printing machine, from the print start to the 50th print. The degree of scumming was visually evaluated. The original plate of the present invention showed extremely good water retention without any ink adhesion, regardless of the printing machine.

On the other hand, Comparative Example A, which is a plate producing a carboxyl group, caused a large difference in the occurrence of background stains on the printed matter due to the difference in the fountain solution and the ink supply system. That is, when the printing is started, the supply of dampening water is insufficient as compared with the Molton system, and in the insufficient synflow system, ink adheres to the non-image portion of the printed matter, causing scumming. This means that in the original plate of Comparative Example A, the surface of the hydrophilized photoconductive layer has sufficiently good wettability with water, but the amount of water retained by the entire photoconductive layer (particularly in the film). If the supply of dampening water is unbalanced due to insufficient water retention), an extremely thin water layer (Vienna Reversi d'Adery layer: WBL) is formed on the surface of the plate at the start of printing. It is presumed that it cannot be retained.

Further, Comparative Example B which is a plate producing a sulfo group
In comparison with Comparative Example A, the ink adhesion was improved even in the case of the synflow system. However, since the water retention capacity of the membrane increases in this case, W. B. L. It is presumed that the formation of the is still insufficient. Further, Comparative Example C, which was used by blending both resins used in Comparative Examples A and B, could not fill the defects of both, and as a result, the same results as Comparative Example A were obtained.

Next, when the printing durability was examined using a large-sized printing machine, the image quality of the printed matter of the present invention was clear even after printing 5,000 sheets. On the other hand, Comparative Examples A, B and C are 5
It became about 600 or 1,000. The reason why the printing durability of Comparative Example A was deteriorated was that, when a large number of sheets were imprinted, the water retention amount of the film caused the W. B. L.
It is also considered that the amount of water retention is no longer sufficient. In Comparative Examples B and C, it is presumed that the resin having a sulfo group-containing crosslinked structure has a large amount of water retention, resulting in insufficient strength of the film and deterioration of printing durability due to film breakage. It was

From these things, it is
Even if you can print many good prints
Was only the material of the present invention. Example 2 and Comparative Examples DF 40 g of a binder resin [B-2] having the following structure, and the above resin [P
-1] 8 g, photoconductive zinc oxide 200 g, uranine 0.
02 g, dye [I] having the following structure: 0.015 g, the following structure
Dye [II] 0.012 g, N-hydroxyphthalic acid
A mixture of 0.18 g of imide and 300 g of toluene was added to
7 × 10 in a modifier (manufactured by Nippon Seiki Co., Ltd.)
³r. p. m. Was dispersed for 8 minutes at the rotation speed of. Anhydrous to this
Phthalic acid 0.1 g, acetylacetone zirconium salt
Rotation speed 1 × 10 by adding 0.002g ³r. p. m.
Dispersed for 1 minute. Conductive treatment of this photosensitive layer forming dispersion
25 g / m on dry paper²To be a wire
Bar and dry at 100 ° C for 30 seconds, then
Heated at 0 ° C. for 1 hour.

[0169]

[Chemical 35]

[0170]

[Chemical 36]

On the photosensitive layer, a coating solution having the following content was applied by a wire bar, dried by touch with a finger, and then heated at a temperature of 140 ° C. for 1 hour to form a surface layer having a film thickness of 2.5 μm. Then, the mixture was left in the dark at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material. Resin [A-2] having the following structure 8.5 g Resin [P-2] having the following structure 1.5 g Phthalic anhydride 0.05 g Acetylacetone zirconium salt 0.001 g O-chlorophenol 0.001 g Toluene 90 g

[0172]

[Chemical 37]

Comparative Example D An electron was produced in the same manner as in Example 2 except that 8.5 g of the resin [R-3] having the following structure was used instead of 8.5 g of the resin [A-2] in Example 2. A photographic light-sensitive material was produced.

[0174]

[Chemical 38]

Comparative Example E In Example 2, except that 8.5 g of the resin [R-3] having the following structure was used instead of 8.5 g of the resin [A-2],
An electrophotographic photosensitive material was prepared in the same manner as in Example 2.

[0176]

[Chemical Formula 39]

Comparative Example F In Example 2, 5.0 g of resin [R-3] and 3.5 [R-4] were used instead of 8.5 g of resin [A-2].
g (Resin [R-3] / Resin [R-4] = 58.8 / 4
1.2 (weight ratio)] was used and an electrophotographic photosensitive material was produced in the same manner as in Example 2.

The image pick-up property and the water retention after printing of each light-sensitive material were examined in the same manner as in Example 1. In addition, the fountain solution used in printing has a different pH (that is, pH 4.5, pH
7.0, pH 9.5) was used to examine the degree of influence on the printed matter. The above results are shown in Table 3.

[0179]

[Table 3]

Note 6) Dependence on fountain solution Printing was carried out in the same manner as in Note 5) above. However, as the dampening water used for printing, three kinds of the following contents were used. I: dampening water for pS plate EU-3 (manufactured by Fuji Photo Film Co., Ltd.) diluted 100 times with distilled water (pH 4.5) II: dampening water for pS plate SG-23 (Tokyo Ink Co., Ltd.
Made by diluting 130 times with distilled water (pH)
7.0) III: Damping water for pS plate Alky A (Toyo Ink Co., Ltd.)
Made by diluting 200 times with distilled water (pH)
9.5) In both Example 2 and Comparative Examples D to F, the image pickup property was good.

Next, when the water retention after printing was examined, the water retention of the present invention was good, but the water retention of the comparative examples D to F in the synflow type printing machine decreased. In the case of Comparative Example E, in Shinfuro manner, why it does not reach the good water retention, the resin [R-4], the -PO ₃ H ₂ group expressed in the desensitizing, water capacity of the film Although sufficient, the hydrophilic group is bonded to the polymer main chain through a hydrophobic linking group, so that the wettability with water on the surface of the film is not sufficient during printing. It is estimated that

Further, evaluation of printing durability was carried out by changing the kind of dampening water. With the present invention, 5,000 good prints were obtained regardless of the type of fountain solution. On the other hand, Comparative Examples D to F are good only in the case of dampening water (III),
With other dampening waters, the background stains caused by ink adhesion occurred more or less to the extent of imprinting, and did not improve even after imprinting.

These are greatly affected by the pH of the dampening water,
It is considered to be related to the dissociation constant of the hydrophilized hydrophilic group. That is, since the influence is dominant in Comparative Example D, the —COOH group of the resin [R-3] is
Although it exists in a state of being dissociated into a —COOH ⁻ group, the affinity with water is remarkably improved. It is considered that when the pH becomes low, the amount of dissociated groups decreases and the affinity with water decreases.

That is, the dissociation constant (: p
It was found that unless the water having a small Ka) is used in combination, the water retention greatly varies depending on the type of dampening water. From the above, the material of the present invention can be printed even with the dampening water of the PS plate printed by a large-sized printing press, so that it can be easily printed on another printing original plate without cleaning and inspecting the printing press. It became possible to use it in common with. Examples 3 to 13 Each electrophotographic photosensitive material was operated in the same manner as in Example 1 except that each resin [A] shown in Table 4 below was used instead of the resin [A-1]. Was produced.

[0185]

[Table 4]

[0186]

[Table 5]

[0187]

[Table 6]

Various performances of each light-sensitive material were evaluated in the same manner as in Example 1. All showed the same electrostatic characteristics and image pick-up property as the photosensitive material of Example 1. As for the performance as a printing plate, good water retention was exhibited from the start of printing on both the Morton type and the Synflow type printing machines, and the printing durability was more than 5,000 sheets. Examples 14 to 25 In Example 1, instead of the resin [A-1], the resin [P-1] and the crosslinking compound [phthalic anhydride and o-chlorophenol], the compounds shown in Table 5 below were used. Others were operated in the same manner as in Example 1 to prepare each light-sensitive material.

[0189]

[Table 7]

[0190]

[Table 8]

[0191]

[Table 9]

[0192]

[Table 10]

[0193]

[Table 11]

Various performances of each light-sensitive material were evaluated in the same manner as in Example 1. All showed the same electrostatic characteristics and image pick-up property as the photosensitive material of Example 1. As for the performance as a printing plate, good water retention was exhibited from the start of printing on both the Morton type and the Synflow type printing machines, and the printing durability was more than 5,000 sheets. Example 26 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 1
g, resin [B-3] 10 g having the following structure, resin [P-1]
500 g of a mixture of 0.3 g and 80 g of tetrahydrofuran
Put the glass beads together with the glass beads in a ml glass container, disperse for 60 minutes with a paint shaker (manufactured by Toyo Seiki Seisakusho), add 0.3 g of ethylene glycol diglycidyl ether, disperse for 2 minutes, filter the glass beads and disperse the photosensitive layer. And

Then, this dispersion was applied on a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, with a wire bar, and was dried by touch with a finger, and then in a 110 ° C. circulating oven. It was dried for 20 seconds. 1 at 140 ℃
Heated for hours. The film thickness of the obtained photosensitive layer was 8 μm.

[0196]

[Chemical 40]

On this photosensitive member, a coating solution having the following content was applied.
Apply with a wire bar, dry to the touch, and heat at 140 ° C for 1
It was heated for an hour to form a surface layer having a film thickness of 2.0 μm. Resin [A-25] having the following structure: 8.0 g Resin [P-1] having the following structure: 2 g Phthalic anhydride 0.1 g o-Cresol 0.02 g Toluene 90 g

[0198]

[Chemical 41]

This light-sensitive material was left under a condition of (20 ° C., 65% RH) for one day and night, and then the light-sensitive material was charged with −6 kV, and a 2.8 mW output gallium-aluminum-arsenic semiconductor laser was used as a light source. Oscillation wavelength of 780 nm) and a dose of 64 erg / cm ² on the surface of the photosensitive material at a pitch of 25 μm and a scanning speed of 300 m / s.
ELP-T as a liquid developer after ec speed exposure
A copy image (fog, image quality) obtained by developing using (Fuji Photo Film Co., Ltd.), washing with a rinse solution of isoparaffin Isopar G (Esso Chemical Co., Ltd.) solvent, and fixing. When visually evaluated, a clear image free of background fog was obtained.

Next, the plate prepared by the above method was desensitized and printed under the same conditions as in Example 1. As a result, both the water retention after printing (I) and (II) were good. When the printing durability was examined, more than 5,000 clear prints were obtained. Example 27 In Example 26, 8 g of resin [A-25], resin [P
-1] 2 g and, instead of 0.3 g of ethylene glycol diglycidyl ether, a resin [A-26] having the following structure
A light-sensitive material was prepared in the same manner as in Example 26 except that only 10 g was used. However, the cross-linking of the membrane is not performed by heating (140
Instead of the method of (1 ° C., 1 hour), light irradiation was performed for 3 minutes at a distance of 80 cm using a lamp using a high pressure mercury lamp as a light source.

[0201]

[Chemical 42]

When the electrostatic characteristics and printing characteristics of the light-sensitive material of the present invention were evaluated by the same method as in Example 26, all showed good results as in the case of the light-sensitive material of Example 26. Examples 28 to 30 Each photosensitive material was prepared in the same manner as in Example 1 except that 8 g of each resin [A] shown in Table 6 below was used instead of 8 g of the resin [A-1]. It was made.

[0203]

[Table 12]

When each of the light-sensitive materials was evaluated for electrostatic characteristics and printability in the same manner as in Example 1, all showed good results equivalent to those of the light-sensitive material in Example 1. Examples 31 to 42 Using each of the light-sensitive materials prepared in Examples 1 to 30, desensitizing treatment was performed as follows to prepare an offset printing original plate.

Distilled water was added to 0.2 g of the nucleophilic compound shown in Table 7 below, 100 g of an organic solvent and 2 g of Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) to make 1 liter, and then
The pH of each mixture was adjusted to 13.5. Each photosensitive material,
A desensitizing treatment was carried out by immersing in the treatment liquid at a temperature of 35 ° C. for 3 minutes. The obtained plate was printed under the same printing conditions as in Example 1. Each of the light-sensitive materials exhibited good performance equivalent to that in the case of Example 1.

[0206]

[Table 13]

[0207]

According to the present invention, it is possible to provide a lithographic printing plate precursor that is free from background stains, is excellent in desensitization and has high printing durability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03G 5/147 502 6956-2H

Claims (4)

[Claims] 1. A lithographic printing plate precursor using an electrophotographic photosensitive member comprising a conductive support and at least one photoconductive layer provided on the conductive support, and a surface layer provided on the uppermost layer of the photoconductive layer. The binder resin contains at least one of the following binder resins [A].
A lithographic printing plate precursor containing a seed. Binder resin [A]: a polymer component (a) containing at least one functional group that produces a —COOH group by a chemical reaction treatment,
The polymer component (b) containing at least one functional group selected from the functional groups that form a —SO ₃ H group, a —SO ₂ H group, and a —PO ₃ H ₂ group in the treatment, and heat and / or light. A copolymer containing at least a polymer component (c) containing at least one curable group. 2. In the binder resin [A], in the copolymer component (a), at least one functional group that produces a —COOH group is directly bonded to the main chain of the polymer chain of the copolymer. The lithographic printing plate precursor as claimed in claim 1, wherein 3. Along with the binder resin [A], heat and / or
Alternatively, it contains a photocurable compound.
Or the lithographic printing plate precursor as described in 2. 4. The photoconductive layer comprises photoconductive zinc oxide and / or
Alternatively, the lithographic printing plate precursor according to any one of claims 1 to 3, which contains at least a photoconductive compound made of photoconductive titanium oxide and a spectral sensitizing dye.