JP2001175001A - Original plate for planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an original plate for planographic printing plate suitable for exposure by laser beam and having both high adhesion and excellent fouling property. SOLUTION: The original plate for planographic printing plate is formed by providing an intermediate layer containing a polymer having a cationic group and a radical reactive group and a photopolymerizable photosensitive layer containing a photopolymerization initiator, a compound having an addition polymerizable ethylenic unsaturated bond and a high polymer binder on an aluminum supporting body treated for hydrophilicity impartation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate precursor, and more particularly to a lithographic printing plate precursor suitable for drawing with a laser beam.

[0002]

2. Description of the Related Art Heretofore, as a lithographic printing plate precursor, a PS plate having a structure in which a lipophilic photosensitive resin layer is provided on a hydrophilic support has been widely used.
After exposure with a mask (surface exposure) through a lith film, the non-image portion was dissolved and removed to obtain a desired printing plate.
In recent years, electronically processing image information using a computer,
Digitization technology for storing and outputting is becoming widespread. Then, various new image output systems corresponding to such digitizing technology have come to be practically used. As a result, computer-to-plate (CTP) technology that scans highly directional light such as laser light in accordance with digitized image information and directly manufactures a printing plate without passing through a lithographic film has been desired. It is an important technical problem to obtain a printing plate precursor adapted to this.

As one method for obtaining such a lithographic printing plate precursor capable of being scanned and exposed, a lipophilic photosensitive resin layer (hereinafter, also referred to as a photosensitive layer) provided on a hydrophilic support has conventionally been used.
As an example, there has been proposed a configuration in which a layer containing a photopolymerizable composition having excellent photosensitivity is provided, and a protective layer having an oxygen-blocking property is further provided. The lithographic printing plate precursor having the above configuration can be a printing plate having a desirable printing performance such that the developing process is simple and the resolution, the inking property and the printing durability are excellent. However, lithographic printing plates prepared from such conventional high-sensitivity photopolymerization type lithographic printing plate precursors do not have sufficient adhesion between the image area and the support. When printing, there was a problem that the image portion was missing or thinned.

Heretofore, as a method for improving the adhesion between a support of a lithographic printing plate precursor and a photopolymerizable photosensitive layer, a method of providing an intermediate layer containing an organic phosphoric acid compound has been widely known. However, it is not yet sufficient in terms of printing durability.
JP-A-7-159983 discloses a sol-gel intermediate layer containing a polymerizable group, and JP-A-9-269593 discloses a sol-gel intermediate layer further added with a phenolic compound or a phosphoric acid compound. These certainly give good adhesion, but there is a problem that the non-image area is still stained depending on the development conditions and the like. As described above, the photopolymerization type lithographic printing plate precursor for laser exposure has a problem that it is difficult to achieve sufficient adhesion of the image area, that is, printing durability, and contamination of the non-image area.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a lithographic printing plate precursor having both high adhesion and excellent stainability, particularly suitable for drawing by laser light. To provide a lithographic printing plate precursor.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a cationic group was formed between the support of the lithographic printing plate precursor and the photopolymerizable photosensitive layer. The inventors have found that the above object can be achieved by providing an intermediate layer containing a polymer having a radical reactive group, and have accomplished the present invention. That is, the present invention provides an intermediate layer containing a polymer having a cationic group and a radical reactive group, a photopolymerization initiator, and an addition-polymerizable ethylenically unsaturated bond on an aluminum support subjected to a hydrophilic treatment. It is a lithographic printing plate precursor provided with a photopolymerizable photosensitive layer containing a compound having a polymer binder.

One of the features of the lithographic printing plate precursor according to the present invention is as a method for improving the adhesion between the photosensitive layer and the support.
An object of the present invention is to provide an intermediate layer containing a polymer having a cationic group and a radical reactive group. The printing plate obtained from the lithographic printing plate precursor according to the invention is compared with a printing plate using an intermediate layer containing a conventional organic phosphoric acid compound or the like,
An excellent printing plate having both printing durability and stain resistance can be obtained. Although the effect of the polymer having a cationic group and a radical reactive group is not yet clear, the following may be considered as the reason. That is, since the polymer used for the intermediate layer has a cationic group, the polymer interacts with the anionic inorganic substance on the surface of the substrate, and exhibits strong adhesion to the substrate. However, cationic groups are themselves hydrophilic,
Since it is essentially removable with an aqueous developer, it is completely removed in the unexposed areas and does not cause stains. On the other hand, in the exposed area, the radical-reactive group forms a bond between the photopolymerizable photosensitive layer and / or itself and the molecule due to the action of radicals generated by the exposure, and gels, so that it is not removed by the developer. And sufficient printing durability is provided by the high adhesion of the cationic group. In the present invention, from the viewpoint of imparting sufficient adhesion and printing durability, it is important to use a compound having a cationic group and a radical reactive group as a polymer, not as a low molecular or oligomer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION <Intermediate Layer> First, an intermediate layer which is a characteristic part of the lithographic printing plate precursor according to the present invention will be described. The intermediate layer of the lithographic printing plate precursor according to the invention contains at least one polymer having a cationic group and a radical reactive group. The polymer of the present invention preferably has an acrylic resin, a styrene resin, or a copolymer thereof, a urethane resin, a polyester resin, or a polyamide resin. An acrylic resin, a styrene resin, or a copolymer thereof is preferable from the viewpoints of printing durability and synthesis suitability. The molecular weight can be arbitrarily set according to the performance design of the lithographic printing plate precursor. If the weight average molecular weight is low, favorable results are obtained in terms of stain resistance, and if the weight average molecular weight is high, printing durability is improved. Preferred weight average molecular weight is 2,000 to 1,000,000,
More preferably, it is 5,000 to 100,000.

Examples of the cationic group include a cationic group comprising an atom belonging to Group V or Group VI of the periodic table.
It is preferably a cationic group consisting of a nitrogen atom, a phosphorus atom or a sulfur atom, and more preferably a cationic group consisting of a nitrogen atom. Examples of the radical reactive group include an unsaturated bond capable of addition polymerization (for example, a (meth) acryloyl group, a (meth) acrylamide group, a (meth) acrylonitrile group, an allyl group, a styrene structure, a vinyl ether structure, and an acetylene structure), SH, -PH, SiH,-
GeH, a disulfide structure and the like. Preferably, it is an unsaturated bond capable of addition polymerization from the viewpoint of printing durability. Here, the (meth) acryl group represents an acryl group or a methacryl group.

A specific method for synthesizing a polymer having a cationic group and a radical reactive group according to the present invention in the present invention is shown below, but the present invention is not limited thereto. Acrylic resin, styrene resin, or copolymer thereof Acrylic resin, styrene resin, or a method for introducing a cationic group and a radical reactive group into a copolymer thereof include the following -1) to- 5) and the like.

-1) An acrylic or styrene monomer having a cationic group and an acrylic or styrene monomer having at least one reactive functional group are copolymerized to form a polymer having the reactive group in a side chain. The obtained polymer is subjected to a polymer reaction with a compound having a group reactive with the reactive functional group and a radical reactive group at the same time,
A method of introducing a radical reactive group. Examples of the acrylic or styrene-based monomer having a cationic group include compounds represented by the following general formulas (1) to (3).

[0012]

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Wherein R ¹ is a hydrogen atom or a methyl group, R ²
Represents a substituent. R ³ represents an alkyl group which may have a substituent having 1 to 20 carbon atoms, or an aralkyl group. A represents an oxygen atom or NR ^4,. (R ⁴ represents a hydrogen atom or a hydrocarbon group which may have a substituent having 1 to 10 carbon atoms.) J represents a single bond or a divalent linking group, and D represents a cationic group. Represents a group. Z ^- is a halogen _{^{ion, ClO 4 -, BF 4 -}} , PF 6 -, SbF 6 -, AsF 6 -, S
O ₃ ⁻ represents a monovalent anion selected from the group consisting of alkylsulfonate ions and arylsulfonate ions. p represents an integer from 0 to 4, and when p is 2 to 4, R ² may be the same or different.

As R ² , any substituent consisting of a nonmetallic atom can be mentioned. More preferred substituents are a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and a carbon atom number. Is an alkyl group or an alkoxyl group which may have 1 to 5 substituents.

R ³ represents an alkyl group which may have a substituent having 1 to 20 carbon atoms, or an aralkyl group. Preferred examples thereof include a methyl group, an ethyl group and an n-pentyl group. I-pentyl group, neopentyl group, n-hexyl group, cyclohexyl group, methoxyethyl group, 2-hydroxypropyl group, carboxymethyl group, 1,2-epoxypropyl group, 2-methylthioethyl group, 2- (methoxy Carbonyl) ethyl group, 4-chlorohexyl group, 2-methyl-2-pentenyl group, perfluorohexyl group, -CH ₂ CH ₂ SO ₃ ^- group (in this case, Z ^- is unnecessary), tetrahydrofurfuryl group, benzyl Group, 4-
(T-butyl) benzyl group, 3,5-bis (trifluoromethyl) benzyl group, naphth-2-yl-methyl group,
And a phenethyl group.

J is a single bond or a divalent linking group,
As the divalent linking group, any linking group consisting of a non-metallic atom can be exemplified. More preferred linking groups include
-O -, - S -, - NR 4 -, - CO -, - SO 2 -, -
^{NR 4 CO -, - NR 4} COO-, or -NR ⁴ CON
R ⁴ - (. R ⁴ has the same meaning as in general formula (1) where, if R ⁴ is present in plurality, they may be the same or different.) Consisting of It may be interrupted one or more times by a group selected from the group, and may be a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. More preferably, it is an uninterrupted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.

D represents a cationic group, specifically, a cationic group represented by the following general formulas (4) to (6).

[0018]

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In the formula, R ^{5 to} R ⁷ each independently represent a hydrogen atom, or an alkyl group, an aryl group, or an aralkyl group which may have a substituent having 1 to 20 carbon atoms, and R ⁸ represents Represents an alkylidene group which may have a substituent having 1 to 20 carbon atoms. R ^{4 to} R ⁸ may be linked to each other or to a part of J to form a ring. Y ¹ represents a nitrogen atom or a phosphorus atom, and Y ² represents a sulfur atom. Z ^- has the same meaning as in formula (3).
Among the cationic groups represented by the general formulas (4) to (6), the cationic group represented by the general formula (4) or (5), furthermore, Y ¹ is a nitrogen atom because of easy synthesis. Groups are particularly preferred.

Specific examples of the acrylic and styrene monomers having a cationic group are shown below, but the present invention is not limited to these. (Specific examples of monomers having a cationic group)

[0021]

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[0022]

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[0023]

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[0024]

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The acrylic or styrenic monomer having at least one reactive functional group includes acrylate, methacrylate, acrylamide, methacrylamide or styrene represented by the following general formula (7) or (8). Derivatives can be mentioned.

[0026]

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In the formula, E is a hydroxyl group, a carbonyl halide group, a carboxyl group or a salt thereof, an amino group,
It represents a reactive functional group selected from the group consisting of an epoxy group and a haloalkyl group. A, R ¹ , R ² , J and p have the same meanings as in formulas (1) and (2).

Specific examples of such an acrylic or styrene-based monomer having at least one reactive functional group include hydroxyl groups described in "Polymer Data Handbook-Basic Edition-(Polymer Society, Baifukan, 1986)". Group, a carbonyl halide group, a carboxyl group or a salt thereof, an amino group, an epoxy group, and an acrylic acid having a reactive functional group selected from the group consisting of a haloalkyl group, a methacrylic acid derivative, an acrylate derivative,
Examples include methacrylic acid ester derivatives, acrylamide, and methacrylamide derivatives.

When an acrylic or styrene monomer having at least one reactive functional group and an acrylic or styrene monomer having a cationic group are copolymerized to form a polymer having the reactive functional group in a side chain, Alternatively, an acrylic or styrene monomer having at least one reactive functional group may be used alone, or two or more kinds may be used in combination. Further, an acrylic or styrene monomer having a cationic group may be used alone or in combination of two or more.

If necessary, one or more other monomers may be further combined and copolymerized to obtain a tertiary or higher copolymer. Such monomers include:
From the viewpoint of imparting alkali developability to the intermediate layer, it is preferable to use a monomer having an acid group. Preferred as acid groups, an acid dissociation constant (pKa) of 7 or less of the acid groups, more preferably, -COOH, -SO ₃ H, -
_{OSO 3 H, -PO 3 H 2} , -OPO 3 H 2, -CONHS
O ₂ — or —SO ₂ NHSO ₂ —. Specific examples of such a monomer include those described in JP-A-11-84674. As the copolymerization method, a conventionally known polymerization method can be used, and the form of the polymer is preferably a random copolymer, a block copolymer, or a graft copolymer.

A compound having a group reactive with the reactive functional group and a radical reactive group at the same time is added to the polymer having a reactive functional group in the side chain obtained by the above method by a method selected from the following reactions. The polymer having a cationic group and a radical-reactive group in the present invention can be obtained by polymer reaction and introducing a radical-reactive group.

A) a urethanization reaction using a hydroxyl group in the polymer side chain and an isocyanate having a radical reactive group; b) a carboxylic acid or carboxylic acid halide having a hydroxyl group in the polymer side chain and a radical reactive group; Esterification reaction using sulfonic acid halide or carboxylic acid anhydride c) Esterification reaction using carboxyl group or its salt of polymer side chain and isocyanate having radically reactive group d) Halogenation of polymer side chain Esterification reaction using carbonyl group, carboxyl group or its salt and alcohol having radical reactive group

E) Amidation reaction using a carbonyl group, a carboxyl group or a salt thereof on the polymer side chain and an amine having a radical reactive group. F) The amino group on the polymer side chain and the radical reactive group G) Amidation reaction using a carboxylic acid, a carboxylic acid halide, a sulfonic acid halide or a carboxylic anhydride having a radical-reactive group and an amino group in a polymer side chain. ) Ring-opening reaction between epoxy group in polymer side chain and various nucleophilic compounds having radical reactive group i) Etherification reaction between haloalkyl group in polymer side chain and alcohols having radical reactive group

-2) After polymerizing monomers represented by the following general formulas (9) to (11) to form a polymer, a compound having a haloalkyl group and a radical-reactive group at the same time is reacted to form a radical reaction with a cationic group. A method of simultaneously introducing a functional group.

[0035]

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In the formula, R ¹ , R ² , A, J and p have the same meanings as in formulas (1) and (2). G represents a group represented by the following general formula (12) or (13).

[0037]

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In the formula, R ⁵ , R ⁶ , Y ¹ and Y ² have the same meanings as in formulas (4) to (6). R ⁵ and R ⁶ may be linked to each other or to a part of J to form a ring.

Among the groups represented by the general formulas (12) and (13), a group in which Y ¹ is a nitrogen atom is particularly preferable because of easy synthesis.

Specific examples of the monomers represented by the general formulas (9) to (11) include 7-amino-3,7-dimethyloctyl methacrylate, 2- (5-ethyl-2-pyridyl) ethyl acrylate, (Dimethylamino) ethyl acrylate, 3- (dimethylamino) phenyl acrylate, 2- (dimethylamino) -2-methylpropyl acrylate, 2-hydroxy-3-piperidinopropyl acrylate, (2-diethylamino) ethyl methacrylate, Dicyclohexylamino) ethyl methacrylate, N- (2-dimethylaminoethyl) acrylamide, N-2- (morpholinoethyl) acrylamide, N- (3-diethylaminopropyl) acrylamide, N- (1,1-dimethyl-3-dimethylamino) Propyl) acrylamide N- (1,3-dimethylmorpholinobutyl) acrylamide, N- (1,3-dimethylpyrrolidinobutyl) acrylamide, N- [4- (phenylamino) phenyl] acrylamide, N- (2-dimethylaminoethyl) methacryl Amide, N- (2,2-
Dimethyl-3-dimethylaminopropyl) methacrylamide, aminostyrene, N, N-dimethylaminostyrene, 4-amino-3-nitrostyrene, (aminomethyl) styrene, vinylbenzyldiallylamine, N-
(Vinylbenzyl) piperidine, N- (vinylbenzyl) morpholine, (2-aminoethyl) styrene, (diethylaminoethyl) styrene, (vinylphenyl) methylsulfide, (vinylphenyl) methylsulfide, vinylpyridine, 2-vinyl-5 -Methylpyridine, 5-ethyl-2-vinylpyridine, 5-bromo-3
-Vinyl pyridine and the like.

The monomers represented by formula (8) or (9) may be used alone or in combination of two or more. If necessary, one or more other monomers may be further combined and copolymerized to form a binary or more copolymer. As such a monomer, the aforementioned monomer having an acid group is preferable.

By reacting the polymer obtained by polymerizing the monomers represented by the general formulas (9) to (11) with a compound having both a haloalkyl group and a radical reactive group, the cationic A group and a radical-reactive group can be introduced simultaneously, and a polymer having a cationic group and a radical-reactive group in the present invention can be obtained. At this time, the compound having a haloalkyl group and a radical reactive group simultaneously may be used alone or in combination of two or more.

Specific examples of the compound having a haloalkyl group and a radical-reactive group at the same time include 3-bromo-1-propyne, 1-bromo-2-butyne, 6-bromo-1-hexyne, 2-bromoethyl vinyl ether, 3-Iodopropyl vinyl ether, 6-iodohexyl vinyl ether, 2-bromoethyl acrylate, cinnamyl bromide, chloromethylstyrene, vinylbenzyl bromide, allyl bromide, allyl iodide and the like.

-3) The following general formula (14) or (1)
Polymerizing the monomer represented by 5) to form -CH _TwoX group to side chain
After having a polymer having, the following general formulas (16) to (1)
Reacting the compound represented by 8) with the cationic group
A method of simultaneously introducing a cal-reactive group.

[0045]

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Wherein R ¹ , R ² , R ⁵ , R ⁶ , A, J,
Y ¹ , Y ² and p have the same meanings as in formulas (1) to (6). X represents an atom selected from the group consisting of chlorine, bromine and iodine. M represents a radical reactive group.

Specific examples of the compound represented by the general formula (14) or (15) include 2-bromoethyl acrylate, chloromethylstyrene, bromomethylstyrene and the like. The monomers represented by the general formula (14) or (15) may be used alone or in combination of two or more. If necessary, one or more other monomers may be further combined and copolymerized to form a binary or more copolymer. As such a monomer, the aforementioned monomer having an acid group is preferable.

The polymer having a —CH ₂ X group in a side chain obtained by polymerizing a monomer represented by the general formula (14) or (15) reacts with the —CH ₂ X group to form a cationic group. Is reacted with the compounds represented by the general formulas (16) to (18) having both a group that expresses a group and a radical-reactive group, whereby a cationic group and a radical-reactive group are simultaneously introduced into the polymer, A polymer having a cationic group and a radical reactive group in the above is obtained.

Specific examples of the compounds represented by the general formulas (16) to (18) include, in addition to the compounds shown as specific examples of the monomers represented by the general formulas (9) to (11), 1-diethylamino -1-hexyne, 2-dimethylaminoethyl vinyl ether, diethanolamine monovinyl ether, 2-phenylaminoethyl vinyl ether, 2-pyrrolidylethyl monovinyl ether, 2-methylthioethyl vinyl ether, 2-allylthioethyl vinyl ether, 3-neopentylthiopropyl Vinyl ether,
3-benzylthiopropyl vinyl ether, 2-phenylthioethyl vinyl ether, triallylamine, 3-
(4-dimethylaminophenyl) -2- (4-methoxyphenyl) acrylonitrile, diallyl sulfide, pyridylacetylene and the like.

Among the compounds represented by the general formulas (16) to (18), the compounds represented by the general formula (1)
A compound represented by formula (6) or (17), wherein Y ¹ is a nitrogen atom, or a compound represented by formula (18) is particularly preferred. The general formula (16) or (17)
May be used alone or in combination of two or more.

-4) A method of copolymerizing a monomer having a cationic group and an acrylic or styrene monomer having a radically reactive group having a relatively slow reaction rate. Examples of the monomer having a cationic group include those represented by the aforementioned general formulas (1) to (3).
An acrylic or styrene monomer having a radically reactive group having a relatively slow reaction rate includes an acrylic or styrene structure that forms a main chain skeleton by polymerization, and an unsaturated bond having a lower addition polymerization property (for example, an allyl group). ,
Monomer having an acetylene structure).

The monomer has at least two radical reactive groups having different reactivities in the molecule. However, in the copolymerization with a monomer having a cationic group, the radical reactivity of an acrylic or styrene structure is high. A radically reactive group having a relatively slow reaction rate does not affect the polymerization.
Therefore, a radical reactive group can be introduced into a side chain without causing gelation, and a polymer having a cationic group and radical reactivity in the present invention can be obtained.

Preferred specific examples of the acrylic or styrenic monomer having a radically reactive group having a relatively slow reaction rate include allyl acrylate, allyl methacrylate, allyloxymethyl methacrylate, acetylmethyl methacrylate, 2-propynyl acrylate,
-Methyl-2-propynyl acrylate, 3-butynyl acrylate, N-allylacrylamide, N-allylmethacrylamide, allylstyrene, (vinylphenyl) allyl ether, (vinylphenyl) acetylene and the like.

The monomer having a cationic group and the monomer having a radically reactive group having a relatively slow reaction rate are
Each may be used alone, or two or more kinds may be used in combination. If necessary, one or more other monomers may be further combined and copolymerized to form a tertiary or higher copolymer. As such a monomer, it is preferable to use the above-described monomer having an acid group from the viewpoint of imparting alkali developability to the intermediate layer.

-5) A method of polymerizing a monomer having a radically reactive group and a cationic group having a relatively low reaction rate at the same time. Examples of the monomer having a radically reactive group and a cationic group having a relatively low reaction rate at the same time include compounds represented by formulas (19) to (21).

[0056]

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Wherein R ¹ , R ² , A, J, Z ⁻ , and p
Has the same meaning as in formulas (1) to (3). R ² represents an alkyl group or an aralkyl group having a radical polymerizable group having lower reactivity than the styrene structure forming the main chain skeleton. D ′ represents a cationic group represented by the following general formulas (22) to (24).

[0058]

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In the formula, Y ¹ , Y ² , and Z ⁻ have the same meanings as in formulas (4) to (6). R ^{11 to} R ¹² each independently represent a hydrogen atom, or an alkyl group or an aryl group which may have a substituent having 1 to 20 carbon atoms,
R ¹³ represents an aralkyl group, and R ¹³ represents an alkylidene group which may have a substituent having 1 to 20 carbon atoms. However, in the general formula (22), R ^{10 to} R ¹² and the general formula (2)
R ¹⁰ or R ¹³ in 3), in the general formula (24) has a low radical polymerizable group reactive than acrylic or styrene structure forms a main chain skeleton to at least one of R ¹⁰ or R ¹¹ ing. If possible, R ^{10 to} R ¹³ may be bonded to each other or to any part of J to form a ring.

Among the cationic groups represented by the general formulas (22) to (24), the compound is represented by the general formula (22) or (23) because of easy synthesis, and Y ¹ is a nitrogen atom. Certain groups are particularly preferred. Specific examples of the monomer having a radically reactive group and a cationic group having a relatively low reaction rate at the same time are shown below, but the present invention is not limited thereto.

[0061]

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The intermediate layer in the lithographic printing plate precursor according to the present invention can be provided by the following method. That is,
A solution obtained by dissolving a polymer having the above-mentioned cationic group and radical-reactive group in water or an organic solvent such as methanol or ethanol or a mixed solvent thereof is coated on a hydrophilized aluminum support, and dried. A method of providing an intermediate layer, and an aluminum support obtained by subjecting a solution obtained by dissolving a polymer having a cationic group and a radical reactive group to water or an organic solvent such as methanol or ethanol or a mixed solvent thereof to a hydrophilic treatment. By dipping the polymer having the cationic group and the radical-reactive group, followed by washing and drying with water or the like to form an intermediate layer. In the former method, the cationic group and the radical reactive group are added in an amount of 0.005 to 1
The coating solution dissolved at a concentration of 0% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the method of washing with water or the like after immersion in a solution in which the compound of the present invention is dissolved, the concentration of the solution is 0.01 to 20.
%, Preferably 0.05 to 5% by weight, the immersion temperature is 20 ° C. to 90 ° C., preferably 25 ° C. to 50 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds. ~
One minute.

The coating amount of the intermediate layer after drying is 2 mg / m ² to
200 mg / m ² is suitable, preferably 5 mg / m ^{2 to} 100 mg / m ^2.
mg / m ^2, more preferably from ^{5mg / m 2 ~50mg / m 2} .
If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. Also, if the amount is more than 200 mg / m ² , sufficient printing durability cannot be obtained. The solution used when providing the intermediate layer in the lithographic printing plate precursor of the present invention is ammonia,
Basic substances such as triethylamine and potassium hydroxide,
The pH can be adjusted with an acidic substance such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, and carboxylic acid, and the pH can be used in the range of 1 to 12. JP-A-7-314937 and JP-A-5-314937
The adhesion can be further enhanced by applying the intermediate layer described in -278362 under acidic conditions or by previously treating the silicate with an acid. In order to improve the tone reproducibility of the lithographic printing plate precursor, a yellow dye may be added.

In the intermediate layer of the lithographic printing plate precursor according to the present invention, there may be used a known phosphonic acid having an amino group such as carboxymethylcellulose, dextrin, gum arabic, 2-aminoethylphosphonic acid, glycine or β-alanine. And a hydrochloride of an amine having a hydroxyl group such as a hydrochloride of triethanolamine. The intermediate layer of the present invention desirably contains at least 20% by weight or more of the above-mentioned polymer having a cationic group and a radical reactive group, more preferably 50% by weight or more, and most preferably 80% by weight or more. The intermediate layer may be a mixture with other components (binder polymer, photopolymerizable compound, photoinitiator) as described in JP-A-9-34104 and JP-A-10-260536.

Next, portions of the lithographic printing plate precursor according to the present invention other than the intermediate layer will be described. <Photopolymerizable photosensitive layer> In the lithographic printing plate precursor according to the present invention, a photopolymerizable photosensitive layer (hereinafter, also simply referred to as a photosensitive layer) provided on the intermediate layer includes a photopolymerization initiator, A compound having an ethylenically unsaturated bond and a polymer binder as essential components, if necessary, a co-sensitizer,
It contains various additives such as coloring agents, plasticizers, and thermal polymerization inhibitors.

[(1) Addition-Polymerizable Compound] The addition-polymerizable compound having at least one ethylenically unsaturated double bond, which is used in the photosensitive layer of the lithographic printing plate precursor according to the invention, has a terminal ethylenically unsaturated compound. It is selected from compounds having at least one, preferably two or more, saturated bonds. Such compounds are widely known in the industrial field, and they can be used in the invention without any particular limitation. These have chemical forms such as, for example, monomers, prepolymers, ie, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of the monomer and its copolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, and are preferred. As the ester, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound are used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional A dehydration-condensation reaction product with a functional carboxylic acid is also preferably used. Further, an isocyanate group, or an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group and a monofunctional or polyfunctional alcohol, amine, or thiol, and further, a halogen group or Also, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is preferable. As another example, it is also possible to use a group of compounds in which unsaturated phosphonic acid, styrene, vinyl ether or the like is substituted for the above unsaturated carboxylic acid.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate , So Bi penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like. Crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, and JP-A-57-196231, and JP-A-59-5240 and JP-A-59-5240. 59-524
1, those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Further, the above-mentioned ester monomers can be used as a mixture.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

A urethane-based addition-polymerizable compound produced by an addition reaction between an isocyanate and a hydroxyl group is also suitable.
JP-A-8-41708 discloses a polyisocyanate compound having two or more isocyanate groups per molecule, to which a hydroxyl-containing vinyl monomer represented by the following general formula (I) is added. Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups.

CH ₂ CC (R ¹⁴ ) COOCH ₂ CH (R ¹⁵ ) OH Formula (I) (where R ¹⁴ and R ¹⁵ represent H or CH ₃ )

Further, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and
No. 49860, No. 56-17654, No. 62
Urethane compounds having an ethylene oxide skeleton described in JP-B-39417 and JP-B-62-39418 are also suitable. Further, Japanese Patent Application Laid-Open No. 63-277653,
-260909 and JP-A-1-105238, by using an addition polymerizable compound having an amino structure or a sulfide structure in a molecule, a photopolymerizable composition having a very high photosensitive speed can be obtained. be able to.

As another example, see JP-A-48-641.
No. 83, JP-B-49-43191, JP-B-52-30
No. 490, and polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in each publication. Also,
JP-B-46-43946, JP-B-1-40337,
Specific unsaturated compounds described in JP-B-1-40336,
Vinyl phosphonic acid compounds described in JP-A-2-25493 can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Japan Adhesion Association Journal vol. 20, No. 7, pages 300-308 (198
(4 years) as photocurable monomers and oligomers can also be used.

Details of the method of using these addition-polymerizable compounds, such as what kind of structure is used, whether they are used alone or in combination, and how much is added, are based on the performance of the final lithographic printing plate precursor. Can be set arbitrarily according to the design. For example, it is selected from the following viewpoints. From the viewpoint of the photosensitive speed, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or more functional structure is preferable. Also,
In order to increase the strength of the image area, that is, the cured film, those having three or more functional groups are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylates, methacrylates, styrene compounds, vinyl ether compounds). It is also effective to adjust both the photosensitivity and the intensity by using these in combination. A compound having a large molecular weight or a compound having high hydrophobicity is excellent in photosensitive speed and film strength, but may not be preferable in terms of developing speed and precipitation in a developing solution. Also, the selection and use of the addition polymerization compound is an important factor for compatibility and dispersibility with other components (for example, a binder polymer, an initiator, and a colorant) in the photosensitive layer. The compatibility may be improved by using a low-purity compound or by using two or more compounds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion of the above-mentioned intermediate layer, an overcoat layer described below, and the like. Regarding the compounding ratio of the addition polymerizable compound in the photosensitive layer, the larger the proportion, the more advantageous in sensitivity. However, if the ratio is too large, undesired phase separation occurs or a problem in the production process due to the stickiness of the photosensitive layer. (Eg, poor production resulting from transfer of the photosensitive layer components and adhesion) and problems such as precipitation from the developer. From these viewpoints, the preferred compounding ratio is, in many cases, from 5 to 80% by weight, and preferably from 25 to 75% by weight, based on all components of the photosensitive layer composition. These may be used alone or in combination of two or more. In addition, the use of the addition-polymerizable compound depends on the degree of
From the viewpoints of resolution, fogging property, change in refractive index, surface tackiness, etc., an appropriate structure, blending and addition amount can be arbitrarily selected, and in some cases, a layer structure and a coating method such as undercoating and overcoating may be performed.

[(2) Photopolymerization initiator] As the photopolymerization initiator, various photopolymerization initiators known in patents and literatures, or two or more photopolymerization initiators may be used depending on the wavelength of the light source used. Can be used by appropriately selecting a combination system (photopolymerization initiation system). When a visible light, an Ar laser, a second harmonic of a semiconductor laser, or an SHG-YAG laser is used as a light source, various photopolymerization initiators (systems) have been proposed. For example, US Pat. No. 2,850,445. Certain photoreducing dyes described in (1), for example, Rose Bengal, Eosin, Erythrosine and the like, or a system using a combination of a dye and an initiator, for example, a complex initiation system of a dye and an amine (Japanese Patent Publication No. 44-20189), A combination system of hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No. 45-
37377), hexaarylbiimidazole and p-
Dialkylaminobenzylidene ketone system
No. 2528, JP-A-54-155292), and a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-155292).
84183), a system of a cyclic triazine and a merocyanine dye (Japanese Patent Application Laid-Open No. 54-151024), a system of a 3-ketocoumarin and an activator (Japanese Patent Application Laid-Open Nos. 52-112681 and 5).
8-155503), a system of biimidazole, a styrene derivative, and a thiol (JP-A-59-140203), and a system of an organic peroxide and a dye (JP-A-59-1504, JP-A-59-140203). JP-A-59-189340
No., JP-A-62-174203, JP-B-62-164
No. 1, U.S. Pat. No. 4,766,055), a system of a dye and an active halogen compound (JP-A-63-1718105, JP-A-63-258903, Japanese Patent Application No. 2-63054), a system of a dye and a borate compound (Japanese Unexamined Patent Publication No. Sho 62-143)
No. 044, JP-A-62-150242, JP-A-64-142.
No. 13140, JP-A-64-13141, JP-A-64
-13142, JP-A-64-13143, JP-A-6-142
4-1144, JP-A-64-17048, JP-A-1-229003, JP-A-1-298348, JP-A-1-138204, etc., and a system comprising a dye having a rhodanine ring and a radical generator (JP-A-Hei. No. 2-196443,
JP-A-2-244050), a system of titanocene and 3-ketocoumarin dye (JP-A-63-221110), a combination of titanocene and a xanthene dye, and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group. System (JP-A-4-221958, JP-A-4-221958)
No. 219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061), a system of titanocene and a dye having a benzopyran ring (JP-A-8-33489).
No. 7).

In the photosensitive layer of the lithographic printing plate precursor according to the invention, at least one photopolymerization initiator (system) is preferably used.
Contains the species titanocene. The titanocene compound used as the photopolymerizable initiator (system) in the present invention may be any titanocene compound that can generate an active radical when irradiated with light in the presence of another sensitizing dye. For example, JP-A-59-152396, JP-A-61-151197, JP-A-63-41483,
JP-A-63-41484, JP-A-2-249, JP-A-2-291, JP-A-3-27393, JP-A-3-27
Known compounds described in JP-A-12403 and JP-A-6-41170 can be appropriately selected and used.

More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,3 4,5,6-pentafluorophenyl-1-yl (hereinafter also referred to as “T-1”), di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1- Yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl
1-yl, di-cyclopentadienyl-Ti-bis-
2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-difluorophenyl
1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-
Yl, di-methylcyclopentadienyl-Ti-bis-
2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-
Difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-
Yl) phenyl) titanium (hereinafter also referred to as “T-2”).

These titanocene compounds can be further subjected to various chemical modifications to improve the properties of the photosensitive layer. For example, binding with sensitizing dyes, addition-polymerizable unsaturated compounds and other radical-generating parts, introduction of hydrophilic sites, improvement of compatibility, introduction of substituents for suppressing crystal precipitation, introduction of substituents for improving adhesion And methods such as polymerization. The method of using these titanocene compounds can be appropriately set as appropriate according to the performance design of the lithographic printing plate precursor, similarly to the above-mentioned addition polymerizable compound. For example, by using two or more kinds, the compatibility with the photosensitive layer can be enhanced. The larger the amount of the titanocene compound used, the more advantageous in terms of photosensitivity, and it is sufficient to use 0.5 to 80 parts by weight, preferably 1 to 50 parts by weight, per 100 parts by weight of the photosensitive layer component. High photosensitivity is obtained. on the other hand,
The main object of the present invention is to use a small amount of titanocene from the viewpoint of fogging due to light near 500 nm when used in white lighting such as yellow light, but in combination with other sensitizing dyes. , The amount of titanocene used is 6 parts by weight or less, further 1.9 parts by weight or less, more preferably 1.
Even if it is reduced to 4 parts by weight or less, sufficient photosensitivity can be obtained.

[(3) Polymer Binder] As the polymer binder (also referred to as a binder polymer) used in the photosensitive layer of the lithographic printing plate precursor according to the invention, a linear organic polymer is preferable. Any of such “linear organic high molecular polymers” may be used. Preferably, a water- or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic high molecular polymer is selected and used not only as a film forming agent of the composition but also as a water, weakly alkaline water or organic solvent developing agent. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such a linear organic high molecular polymer include addition polymers having a carboxylic acid group in a side chain, for example, JP-A-59-44615 and JP-B-54-34327.
No., JP-B-58-12577, JP-B-54-2595
7, JP-A-54-92723, JP-A-59-538.
No. 36, JP-A-59-71048, namely, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, There are esterified maleic acid copolymers and the like. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / Other addition-polymerizable vinyl monomers as needed) copolymer,
It is suitable because it has an excellent balance of film strength, sensitivity and developability. In addition, Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-12
No. 0041, No. 7-120042, No. 8-1
No. 2424, JP-A-63-287944, JP-A-63-287944
Urethane-based binder polymers containing an acid group described in JP-A-287947, JP-A-1-271741, Japanese Patent Application No. 10-116232 and the like have extremely high strength, and therefore have high printing durability and low printing durability. This is advantageous in terms of exposure suitability.
Further, the binder having an amide group described in Japanese Patent Application No. 9-363195 is preferable because it has both excellent developability and film strength.

Further, as the water-soluble linear organic polymer, polyvinyl pyrrolidone, polyethylene oxide and the like are useful. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

In the present invention, the most preferred binder polymer is itself a crosslinkable group (also referred to as an unsaturated group).
And a carboxyl group in the side chain, and a crosslinkable group (also referred to as an unsaturated group) having the following general formula [II]

[0085]

Embedded image

Wherein R ^{16 to} R ²⁰ are hydrogen, halogeno,
A group selected from carboxyl, sulfo, nitro, cyano, amide, amino and optionally substituted alkyl, aryl, alkoxy, aryloxy, alkylamino, arylamino, cyclic alkyl, alkylsulfonyl, arylsulfonyl And L is selected from oxygen, sulfur, NH or NR ²¹ (R ²¹ is an alkyl group)].

In the above general formula [II], R ^{16 to} R ^{16
The 20} alkyl groups may be linear, branched or cyclic, and preferably have 1 to 7 carbon atoms. These alkyl groups further include an alkoxy group having 1 to 2 carbon atoms and 1 to 3 carbon atoms.
May have a substituent such as an alkoxycarbonyl group, a phenyl group, or a hydroxy group. As the aryl group of R ^{16 to} R ^20, a phenyl group or a furyl group is preferable. ), A hydroxy group, an alkyl group having 1 to 7 carbon atoms, an aryl group (for example, phenyl, methoxyphenyl, etc.), an alkoxy group having 1 to 7 carbon atoms, a nitro group, an amino group, an N, N-dialkylamino group, and the like. May have a substituent. R ^{16 to} R
The alkoxy group having ²⁰ is preferably a group having 1 to 7 carbon atoms, and the aryloxy group is preferably a phenyloxy group, which may have a substituent such as an alkyl or alkoxy group having 1 to 7 carbon atoms. Good. As the alkylamino group for R ^{16 to} R ²⁰ , those having 1 to 15 carbon atoms are preferable, and as the arylamino group, a phenylamino group,
A naphthylamino group is preferred. As the alkylsulfonyl group for R ^{16 to} R ²⁰ , those having 1 to 15 carbon atoms are preferable,
As the arylsulfonyl group, a phenylsulfonyl group and the like are preferable, and these include an alkyl group having 1 to 15 carbon atoms,
It may have a substituent such as an alkoxy group or an amino group having 1 to 5 carbon atoms.

Further, the polymer having a crosslinkable group in the side chain, which is used as a binder for the photosensitive layer of the lithographic printing plate precursor according to the present invention, is disclosed in US Pat.
Nos. 556,792 and 3,556,793, each of which is disclosed in the specification. As for the disclosed polymer, the polymer itself is used as a photocrosslinkable resist,
There is a clear difference from the method of using the photosensitive layer composition of the lithographic printing plate precursor according to the invention as a binder.

The methods for synthesizing the above polymers are roughly classified into the following two methods. (Method A): For a backbone polymer having a carboxylic acid, a carboxylic acid halide, or a carboxylic anhydride group as a side chain, the following general formula [II-a]

[0090]

Embedded image

Wherein R ^{16 to} R ²⁰ have the same meanings as in formula [II], and M is OH, —SH, —NH ₂ , —NHR
²¹ (R ²¹ is an alkyl group) or a halogen atom. ]
The polymer represented by the following general formula [II
-B]

[0092]

Embedded image

(Wherein R ^{16 to} R ²⁰ have the same meanings as in the case of the general formula [II]).
-, - CONH-, or -CONR ²¹ - method (R ²¹ is an alkyl group) is introduced through each linking group. (Method B): A monomer having a crosslinkable group represented by the general formula [II] and an ethylenically unsaturated group having a higher addition polymerization reactivity than the crosslinkable group is copolymerized with an unsaturated carboxylic acid. To obtain a polymer.

When the method A is described in more detail, examples of the trunk polymer include a copolymer of acrylic acid or methacrylic acid and a copolymer in which the copolymer is an acid halide by a polymer reaction. Also, maleic anhydride,
And copolymers such as itaconic anhydride. Examples of the comonomer to be copolymerized include styrene or an alkyl-substituted derivative thereof, an alkyl acrylate, an aryl acrylate, an alkyl methacrylate, an aryl methacrylate, or an aliphatic vinyl ester. Preferred are copolymers of acrylic acid or methacrylic acid with methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and benzyl methacrylate. In order to introduce a crosslinkable group into these copolymers, a crosslinkable alcohol, amine, thiol, or halide represented by the general formula [II-a] is mixed with the above-described copolymer in a reaction solvent under predetermined reaction conditions. It is obtained by mixing and dissolving, adding a reaction catalyst and a polymerization inhibitor, and heating. Specifically, a copolymer of methacrylic acid and benzyl methacrylate is shown below as an example.

Poly (methacrylic acid / benzyl methacrylate = 27/73) was placed in a 300 ml three-necked flask equipped with a stirring rod and stirring blades, a reflux condenser and a thermometer.
19.8 g), 40.2 g of ethylene glycol monomethyl ether acetate as a reaction solvent, 6.0 g of allyl bromide as a reagent containing a crosslinkable group, and 10.4 g of trimethylbenzylammonium hydroxide as a catalyst.
g of paramethoxyphenol and 0.1 g of paramethoxyphenol as a polymerization inhibitor.
And mixed and dissolved at 70 ° C. in a nitrogen atmosphere.
Heating and stirring were performed for hours. After cooling, methyl ethyl ketone is added to remove free quaternary salts. Further, the mixture is diluted with methanol and poured into dilute hydrochloric acid to precipitate. After washing with water, suction filtration and vacuum drying, the yield of the polymer obtained is 1
It was 3.6 g. Allyl groups were introduced at 35% relative to the carboxylic acid of the backbone polymer. At this time, the viscosity was [η] = 0.161 for methyl ethyl ketone at 30 ° C.

A synthesis example in which the crosslinkable group is introduced into a copolymer of maleic anhydride can be carried out by the method described in US Pat. No. 2,047,398, whereby the maleic anhydride moiety is formed. A ring-opened unsaturated ester, amide, thioester or the like is introduced. As a method for introducing a crosslinkable group into a maleic anhydride copolymer, JP-A-48-82
No. 902, there is a similar example, but the crosslinkable group by this method is bonded to the nitrogen atom of maleic imide, and is clearly a compound different from the above-mentioned polymer, and is used in the present invention. Polymer having a crosslinkable group in the side chain.

On the other hand, the method B is described in more detail. The monomer containing at least two carbon-carbon double bonds having a crosslinkable group can be prepared by a known synthesis method using an alcohol, amine, thiol or the like having the crosslinkable group. And unsaturated carboxylic acids,
Preferably, it is synthesized by a condensation reaction with acrylic acid or methacrylic acid. By copolymerizing the monomer containing at least two or more unsaturated groups with an unsaturated carboxylic acid, preferably acrylic acid or methacrylic acid, a copolymer having the crosslinkable group is obtained. The monomer to be copolymerized may be further copolymerized with another monomer in addition to the unsaturated carboxylic acid, for example, alkyl acrylate, alkyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, acrylonitrile, and the like. No.

Hereinafter, examples of copolymerization of allyl methacrylate and methacrylic acid will be described. A similar synthetic method includes the method described in U.S. Pat. No. 2,047,398. 1.68 l of 1,2-dichloroethane as a reaction solvent was placed in a 3-liter 4-neck flask equipped with a stirring rod and a stirring blade, a reflux condenser, a dropping funnel and a thermometer, and heated to 70 ° C while purging with nitrogen. In a dropping funnel, 100.8 g of allyl methacrylate, 7.6 g of methacrylic acid, and 1.68 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were added to 0.44 liter of 1,2-dichloroethane. The mixed solution was dropped into the flask over 2 hours with stirring. After completion of the dropwise addition, the mixture was further stirred at a reaction temperature of 70 ° C. for 5 hours to complete the reaction. After completion of the heating, 0.04 g of paramethoxyphenol was added as a polymerization inhibitor, and 500 ml of the reaction solution was added.
The concentrated liquid was added to 4 liters of hexane to precipitate, and dried under vacuum to obtain 61 g (yield 56%) of a copolymer. At this time, the viscosity was [η] = 0.068 in methyl ethyl ketone at 30 ° C.

Representative compounds represented by the general formula [II-a] include allyl alcohol, 2-methylallyl alcohol, crotyl alcohol, 3-chloro-2-propen-1-ol, and 3-phenyl-2. -Propen-1-ol, 3- (hydroxyphenyl) -2-propen-1-
All, 3- (2-hydroxyphenyl) -2-propen-1-ol, 3- (3,4-dihydroxyphenyl) -2-propen-1-ol, 3- (2,4-dihydroxyphenyl-2 -Propen-1-ol, 3-
(3,4,5-trihydroxyphenyl) -2-propen-1-ol, 3- (3-methoxy-4-hydroxyphenyl) -2-propen-1-ol, 3- (3,4
-Dihydroxy-5-methoxyphenyl) -2-propen-1-ol, 3- (3,5-dimethoxy-4-hydroxyphenyl) -2-propen-1-ol, 3-
(2-hydroxy-4-methylphenyl) -2-propen-1-ol, 3- (4-methoxyphenyl) -2-
Propen-1-ol, 3- (4-ethoxyphenyl)
-2-propen-1-ol, 3- (2-methoxyphenyl) -2-propen-1-ol, 3- (3,4-dimethoxyphenyl) -2-propen-1-ol, 3-
(3-methoxy-4-propoxyphenyl) -2-propen-1-ol,

3- (2,4,6-trimethoxyphenyl) -2-propen-1-ol, 3- (3-methoxy-4-benzyloxyphenyl) -2-propen-1-
All, 3-1- (3′-methoxyphenyl) -4-benzyloxyphenyl) -2-propen-1-ol,
3-phenoxy-3-phenyl-2-propen-1-ol, 3- (3,4,5-trimethoxyphenyl) -2
-Propen-1-ol, 3- (4-methylphenyl)
-2-propen-1-ol, 3-phenyl-3-
(2,4,6-trimethylphenyl) -2-propene-
1-ol, 3,3- {di- (2,4,6-trimethylphenyl)}-2-propen-1-ol, 3-phenyl-3- (4-methylphenyl) -2-propen-1-
All, 3,3-diphenyl-2-propen-1-ol, 3- (2-chlorophenyl) -2-propen-1-
All, 3- (3-chlorophenyl) -2-propene-
1-ol, 3- (4-chlorophenyl) -2-propen-1-ol, 3- (2,4-dichlorophenyl)-
2-propen-1-ol, 3- (2-bromophenyl) -2-propen-1-ol, 3-bromo-3-phenyl-2-propen-1-ol, 3-chloro-3-
Phenyl-2-propen-1-ol, 3- (4-nitrophenyl) -2-propen-1-ol,

3- (2-nitrophenyl) -2-propen-1-ol, 3- (3-nitrophenyl) -2-propen-1-ol, 2-methyl-3-phenyl-2-ol
Propen-1-ol, 2-methyl-3- (4-chlorophenyl) -2-propen-1-ol, 2-methyl-
3- (4-nitrophenyl) -2-propen-1-ol, 2-methyl-3- (4-aminophenyl) -2-propen-1-ol, 2-methyl-3,3-diphenyl-2- Propen-1-ol, 2-ethyl-1,3-diphenyl-2-propen-1-ol, 2-ethoxymethylene-3-phenyl-2-propen-1-ol, 2
-Phenoxy-3-phenyl-2-propen-1-ol, 2-methyl-3- (4-methoxyphenyl) -2-
Propen-1-ol, 2,3-diphenyl-2-propen-1-ol, 1,2,3-triphenyl-2-propen-1-ol, 2,3,3-triphenyl-2-
Propen-1-ol, 2-ethoxy-3-phenyl-
2-propen-1-ol, 1,3-diphenyl-2-
Propen-1-ol, 1- (4-methylphenyl)-
3-phenyl-2-propen-1-ol, 1-phenyl-3- (4-methylphenyl) -2-propen-1-
All, 1-phenyl-3- (4-methoxyphenyl)
-2-propen-1-ol, 1- (4-methoxyphenyl) -3-phenyl-2-propen-1-ol,

1,3-di (4-chlorophenyl) -2-
Propen-1-ol, 1- (4-bromophenyl)-
3-phenyl-2-propen-1-ol, 1-phenyl-3- (4-nitrophenyl) -2-propen-1-
All, 1,3-di (2-nitrophenyl) -2-propen-1-ol, 1- (4-dimethylaminophenyl) -3-phenyl-2-propen-1-ol, 1-
Phenyl-3- (4-dimethylaminophenyl) -2-
Propen-1-ol, 1,1-di (4-dimethylaminophenyl) -3-phenyl-2-propen-1-ol, 1,1,3-triphenyl-2-propen-1-ol, 1, 1,3,3-tetraphenyl-2-propen-1-ol, 1- (4-methylphenyl) -3-phenyl-2-propen-1-ol, 1- (dodecylsulfonyl) -3-phenyl-2 -Propen-1-ol,
1-phenyl-2-propen-1-ol, 1,2-diphenyl-2-propen-1-ol, 1-phenyl-
2-methyl-2-propen-1-ol, 1-cyclohexyl-2-propen-1-ol, 1-phenoxy-
2-propen-1-ol, 2-benzyl-2-propen-1-ol, 1,1-di (4-chlorophenyl)-
2-propen-1-ol, 1-carboxy-2-propen-1-ol,

1-carboxamido-2-propene-1
-Ol, 1-cyano-2-propen-1-ol, 1
-Sulfo-2-propen-1-ol, 2-ethoxy-
2-propen-1-ol, 2-amino-2-propen-1-ol, 3- (3-amino-4-methoxyphenylsulfonyl) -2-propen-1-ol, 3- (4
-Methylphenylsulfonyl) -2-propen-1-ol, 3-phenylsulfonyl-2-propen-1-ol, 3-benzylsulfonyl-2-propen-1-ol, 3-anilinosulfonyl-2-propene- 1-ol, 3- (4-methoxyanilinosulfonyl) -2-
Propen-1-ol, 3-anilino-2-propene-
1-ol, 3-naphthylamino-2-propene-1-
All, 3-phenoxy-2-propen-1-ol,
3- (2-methylphenyl) -2-propen-1-ol, 3- (3-methylphenoxy) -2-propen-1
-Ol, 3- (2,4-dimethylphenyl) -2-propen-1-ol, 1-methyl-3-carboxy-2
-Propen-1-ol, 3-carboxy-2-propen-1-ol, 3-bromo-3-carboxy-2-propen-1-ol, 1-carboxy-3-chloro-3
-Methyl-2-propen-1-ol, 1-carboxy-3-methyl-2-propen-1-ol,

1- (2-carbethoxyisopropyl)-
3-methyl-2-propen-1-ol, 1- (1-carbethoxypropyl) -2-propen-1-ol,
-(1-carbethoxyethyl) -3-methyl-2-propen-1-ol, 1-carbethoxy-3-chloro-3
-Methyl-2-propen-1-ol, 1-carbethoxymethylene-3-methyl-2-propen-1-ol,
1-amido-2,3-dimethyl-2-propen-1-ol, 1-cyano-3-methyl-2-propen-1-ol, 3-sulfo-2-propen-1-ol, 3-butoxy- 2-propen-1-ol, 1-cyclohexyl-3- (2-hydroxycyclohexyl) -2-propen-1-ol, 3-cyclobenzyl-2-propen-1-ol, 3-furyl- 2-propen-1-ol, 3-chrom-2-propen-1-ol, 3-bromo-2-propen-1-ol, 2-methyl-3-chloro-2-propen-1-ol, 2- Methyl-3-bromo-2-propen-1-ol, 1-carboisobutoxy-3-chloro-3-methyl-2-propen-1-ol, 2-chloro-3-phenyl-2-propen-1- Oar (2-chlorosi Cinnamyl alcohol), 2-bromo-3-phenyl-2-propen-1-ol (2-bromo cinnamyl alcohol),

2-bromo-3- (4-nitrophenyl)
-2-propen-1-ol, 2-fluoro-3-phenyl-2-propen-1-ol (2-fluorocinnamyl alcohol), 2-fluoro-3- (4-methoxyphenyl) -2-propene- 1-ol, 2-nitro-
3-chloro-3-phenyl-2-propen-1-ol, 2-nitro-3-phenyl-2-propen-1-ol (2-nitrocinnamyl alcohol), 2-cyano-3-phenyl-2-ol Propen-1-ol (2-cyanocinnamyl alcohol), 2-chloro-2-propen-1-ol (2-chloroallyl alcohol), 2-bromo-2-propen-1-ol (2-bromoallyl alcohol) ), 2-carboxy-2-propen-1-ol (2-carboxyallyl alcohol), 2-carbethoxy-2-propen-1-ol (2-carbethoxyallyl alcohol), 2-sulfonic acid-2-propene- 1
2-ol (allyl alcohol 2-sulfonate), 2-nitro-2-propen-1-ol (2-nitroallyl alcohol), 2-bromo-3,3-difluoro-2-propen-1-ol, 2- Chlor-3,3-difluoro-2-propen-1-ol, 2-fluoro-3-chloro-2-propen-1-ol, 2,3-dibromo-3
-Carboxy-2-propen-1-ol,

2,3-diiodo-3-carboxy-2-
Examples include propen-1-ol, 2,3-dibromo-2-propen-1-ol, and 2-chloro-3-methyl-2-propen-1-ol. In the above specific examples, a compound in which the alcohol at the 1-position is replaced with a thioalcohol, an amine or a halogen can of course be used. The preferable range of the crosslinkable group content in the polymer is 10 to 90 mol% and 5 to 60 mol%, respectively, and the more preferable range is 20 to 70 mol% and 10 to 40 mol% in copolymerization molar ratio.

These organic high-molecular polymers can be mixed in an arbitrary amount in the total composition of the photosensitive layer components. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably 10-90%,
More preferably, it is 30 to 80%. The weight ratio of the photopolymerizable ethylenically unsaturated compound and the organic high molecular weight polymer is preferably in the range of 1/9 to 9/1. A more preferred range is 2/8 to 8/2, and still more preferably 3/8.
7 to 7/3. Although the acid value / molecular weight of the binder polymer has a large effect on image strength and developability, a preferred region in the present invention has an acid value of 0.4 to 1.6 meq /.
g, the molecular weight is in the range of 10,000 to 300,000, the acid value is 0.6 to 1.3 meq / g, and the molecular weight is in the range of 20,000 to 200,000.

In the photosensitive layer of the lithographic printing plate precursor according to the invention,
In addition to the above basic components, other components suitable for the use, the production method, and the like can be added as appropriate. Hereinafter, preferred additives will be exemplified. [(4) Co-sensitizer] By using a co-sensitizer in the photosensitive layer of the lithographic printing plate precursor according to the invention, the sensitivity of the photosensitive layer can be further improved. Although their mechanism of action is not clear, most are thought to be based on the following chemical processes. That is, various intermediate active species (radicals, peroxides, oxidizing agents, reducing agents, etc.) generated during the photoreaction initiated by the above-mentioned photopolymerization initiator (system) and the subsequent addition polymerization reaction. And the co-sensitizer reacts to generate a new active radical. These are largely (a) those that can be reduced to form active radicals, (b) those that can be oxidized to form active radicals, and (c) those that react with less active radicals and are more active radicals. Or acting as a chain transfer agent, but there is often no myth as to which of these compounds each belongs to.

(A) Compound that generates an active radical upon being reduced Compound having a carbon-halogen bond: It is considered that the carbon-halogen bond is reductively cleaved to generate an active radical. Specifically, for example, trihalomethyl-s-triazines and trihalomethyloxadiazoles can be suitably used. Compound having a nitrogen-nitrogen bond: It is considered that the nitrogen-nitrogen bond is cleaved reductively to generate an active radical. Specifically, hexaarylbiimidazoles and the like are preferably used. Compound having an oxygen-oxygen bond: It is considered that an oxygen-oxygen bond is cleaved reductively to generate an active radical. Specifically, for example, organic peroxides and the like are preferably used. Onium compounds: carbon-hetero bond or oxygen-
It is thought that the nitrogen bond is cleaved to generate an active radical. Specifically, for example, diaryliodonium salts,
Triarylsulfonium salts, N-alkoxypyridinium (azinium) salts and the like are preferably used. Ferrocene, iron arene complexes: Active radicals can be generated reductively.

(B) Compound which is oxidized to generate an active radical Alkyl ate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to generate an active radical. Specifically, for example, triarylalkyl borates are preferably used. Alkylamine compound: It is considered that the CX bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical. X is preferably a hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group, or the like.
Specifically, for example, ethanolamines, N-phenylglycine, N-trimethylsilylmethylaniline, and the like can be mentioned. Sulfur-containing and tin-containing compounds: The above-mentioned amines in which the nitrogen atom is replaced with a sulfur atom or a tin atom can generate an active radical by the same action. Compounds having an SS bond are also known to be sensitized by SS cleavage.

Α-Substituted methylcarbonyl compound: An active radical can be generated by the cleavage of carbonyl-α carbon bond by oxidation. In addition, those obtained by converting carbonyl to oxime ether also show the same action. In particular,
2-alkyl-1- [4- (alkylthio) phenyl]
Examples thereof include -2-morpholinopronones-1 and oxime ethers obtained by reacting these with hydroxyamines and then etherifying N-OH. Sulfinates: Active radicals can be generated reductively. Specific examples include sodium arylsulfinate and the like.

(C) Compounds that react with radicals to convert them to highly active radicals or act as chain transfer agents: For example, compounds having SH, PH, SiH, and GeH in the molecule are used. These can generate a radical by donating hydrogen to a low-activity radical species, or can generate a radical by being oxidized and then deprotonated. Specific examples include 2-mercaptobenzimidazoles. More specific examples of these co-sensitizers are described in, for example, JP-A-9-236913 as additives for the purpose of improving sensitivity. The following are some examples, but the materials used for the photosensitive layer of the lithographic printing plate precursor according to the invention are not limited thereto.

[0113]

Embedded image

These co-sensitizers can be further subjected to various chemical modifications for improving the characteristics of the photosensitive layer. For example, binding with sensitizing dyes, titanocene, addition-polymerizable unsaturated compounds and other radical-generating parts, introduction of hydrophilic sites, improvement of compatibility, introduction of substituents for suppressing crystal precipitation, and substituents for improving adhesion Methods such as introduction and polymerization can be used. These co-sensitizers can be used alone or in combination of two or more. The amount used is 0.05 to 100 parts by weight, preferably 1 to 80 parts by weight, per 100 parts by weight of the compound having an ethylenically unsaturated double bond.
A suitable range is 3 parts by weight, more preferably 3 to 50 parts by weight.

[(5) Polymerization Inhibitor] In the photosensitive layer of the lithographic printing plate precursor according to the invention, a polymerizable ethylenically unsaturated double bond is added during the production or storage of the photosensitive composition. It is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the compound having the compound. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone,
4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-
Butylphenol), N-nitrosophenylhydroxyamine cerium salt and the like. The addition amount of the thermal polymerization inhibitor is about 0.01% by weight to the weight of the total composition.
About 5% by weight is preferred. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The added amount of the higher fatty acid derivative is preferably about 0.5% by weight to about 10% by weight of the whole composition.

[(6) Colorant] Further, a dye or pigment may be added to the photosensitive layer of the lithographic printing plate precursor according to the invention for the purpose of coloring the same. As a result, it is possible to improve the so-called plate inspection, such as the visibility of the printing plate after plate making and the suitability for an image density measuring device. As a coloring agent, a pigment is particularly preferable because many dyes lower the sensitivity of the photopolymerizable photosensitive layer. Specific examples include, for example, phthalocyanine pigments, azo pigments, carbon black, pigments such as titanium oxide, ethyl violet, crystal violet, azo dyes,
There are dyes such as anthraquinone dyes and cyanine dyes. The amount of dyes and pigments added is preferably from about 0.5% to about 5% by weight of the total composition.

[(7) Other Additives] Further, inorganic fillers and other plasticizers for improving the physical properties of the cured film, oil-sensitizing agents capable of improving the ink adhesion of the photosensitive layer surface, and the like. Known additives may be added. Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like.When a binder is used, ethylene is used. It can be added in an amount of 10% by weight or less based on the total weight of the compound having an unsaturated double bond and the binder. Further, a UV initiator, a thermal crosslinking agent, and the like can be added to enhance the effect of heating and exposure after development for the purpose of improving the film strength (printing durability) described later.

When the above-mentioned photosensitive layer is provided on the intermediate layer, the photopolymerizable composition of the photosensitive layer component is dissolved in various organic solvents, and the mixture is applied so as to be coated on the intermediate layer. . As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, methyl lactic acid Ethyl and the like. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 2 to 50% by weight.

The coating amount of the photosensitive layer mainly affects the sensitivity, developability of the photosensitive layer, and the strength and printing durability of the exposed film, and is desirably appropriately selected according to the application. If the coating amount is too small, the printing durability will be insufficient. On the other hand, if the amount is too large, the sensitivity is lowered, and it takes a long time for exposure, and a longer time is required for the developing process, which is not preferable. The main object of the present invention, as a lithographic printing plate precursor for scanning exposure, the coating amount is about 0.1 g / dry weight.
range of m ² ~ about 10 g / m ² are suitable. More preferably, it is 0.5 to 5 g / m ² .

<Support> As the support of the lithographic printing plate precursor of the present invention, a conventionally known aluminum support subjected to a hydrophilic treatment and used for a lithographic printing plate precursor can be used without limitation. Can be. The aluminum support used is preferably a dimensionally stable plate-like material, and a suitable aluminum plate is a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element. Aluminum may be a laminated or vapor-deposited plastic film. The foreign elements contained in aluminum alloys include silicon, iron, manganese, copper, magnesium,
There are chromium, zinc, bismuth, nickel, titanium and the like.
The content of the foreign element in the alloy is at most 10% by weight or less.
Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 m.
m to 0.4 mm, particularly preferably 0.2 mm to 0.3 m
m.

The aluminum support in the present invention is preferably subjected to surface treatment such as surface roughening (graining) or anodic oxidation. The surface roughening treatment of the aluminum plate is performed by various methods.
For example, it is performed by a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically selectively dissolving the surface. Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in an electrolytic solution such as hydrochloric acid or nitric acid. As disclosed in JP-A-54-63902, a method in which both are combined can also be used. Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove rolling oil on the surface. Anodizing treatment, for example, phosphoric acid, chromic acid, sulfuric acid, inorganic acids such as boric acid, or oxalic acid,
It is carried out by passing a current in an electrolytic solution of an organic acid such as sulfamic acid or a salt thereof or an aqueous solution or a non-aqueous solution alone or in combination of two or more with an aluminum plate as an anode. Furthermore, Japanese Patent Publication No. 46-27481
JP-A-52-58602, JP-A-52-3050
No. 3, a surface treatment obtained by combining a support provided with electrolytic grains and the above-described anodic oxidation treatment is also useful. Further, those subjected to mechanical roughening, chemical etching, electrolytic graining, and anodizing treatment in this order as disclosed in JP-A-56-28893 are also suitable.

As the treatment for hydrophilizing the surface of the support, widely known methods can be applied. As a particularly preferred treatment, a hydrophilic treatment with a silicate or polyvinyl phosphonic acid is performed. The coating is formed at a Si or P element content of ^{2 to} 40 mg / m ² , more preferably 4 to 30 mg / m ² . The coating amount can be measured by fluorescent X-ray analysis.
In the above-mentioned hydrophilization treatment, alkali metal silicate or polyvinylphosphonic acid is contained in an amount of 1 to 30% by weight, preferably 2 to 30% by weight.
This is carried out by immersing the aluminum substrate on which the anodized film is formed in an aqueous solution having a pH of 10 to 13 at 25 ° C. at a temperature of 15 to 80 ° C. for 0.5 to 120 seconds.

As the alkali metal silicate used in the hydrophilization treatment, sodium silicate, potassium silicate, lithium silicate and the like are used. Hydroxides used to raise the pH of the alkali metal silicate aqueous solution include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. In addition, an alkaline earth metal salt or a Group IVB metal salt may be added to the above-mentioned processing solution.
Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, and water-soluble salts such as sulfate, hydrochloride, phosphate, acetate, oxalate and borate. Salts. IV
Examples of the group B metal salt include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, and the like. be able to.

The alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. The preferred range of these metal salts is 0.01 to 10
% By weight, and a more preferred range is 0.05 to 5.0.
% By weight. Further, silicate electrodeposition as described in U.S. Pat. No. 3,658,662 is also effective. JP-B-46-27481, JP-A-52-586
No. 02, Japanese Patent Application Laid-Open No. 52-30503, and a surface treatment obtained by combining an anodizing treatment and a hydrophilizing treatment with a support provided with electrolytic grains are also useful.

<Protective Layer> As a desirable mode of the lithographic printing plate precursor according to the invention, usually, exposure is performed in the air.
It is preferable to further provide a protective layer on the above-mentioned photosensitive layer. The protective layer prevents exposure of the photosensitive layer to low-molecular compounds such as oxygen and basic substances present in the atmosphere that inhibit the image forming reaction caused by exposure in the photosensitive layer. I do. Therefore, a desired property of such a protective layer is that the permeability of low molecular compounds such as oxygen is low, and further, the transmission of light used for exposure is not substantially inhibited, and the adhesion to the photosensitive layer is excellent. In addition, it is desirable that it can be easily removed in a developing step after exposure. Such a device for the protective layer has been conventionally devised, and US Pat.
No. 311 and JP-A-55-49729. As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used, and specifically, polyvinyl alcohol, polyvinylpyrrolidone, acidic celluloses, gelatin, gum arabic, and polystyrene. Water-soluble polymers such as acrylic acid are known. Of these, use of polyvinyl alcohol as a main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether or an acetal as long as it contains an unsubstituted vinyl alcohol unit for obtaining necessary oxygen barrier properties and water solubility. Similarly, a part thereof may have another copolymer component. Specific examples of polyvinyl alcohol include those having a hydrolysis of 71 to 100% and a molecular weight of 300 to 2,400.
Specifically, Kuraray's PVA-105, PV
A-110, PVA-117, PVA-117H, PV
A-120, PVA-124, PVA-124H, PV
A-CS, PVA-CST, PVA-HC, PVA-2
03, PVA-204, PVA-205, PVA-21
0, PVA-217, PVA-220, PVA-22
4, PVA-217EE, PVA-217E, PVA-
220E, PVA-224E, PVA-405, PVA
-420, PVA-613, L-8 and the like.

The components of the protective layer (selection of PVA, use of additives), coating amount, etc. are selected in consideration of fogging properties, adhesion, and scratch resistance in addition to oxygen blocking properties and development removal properties. Generally, the higher the hydrolysis rate of the PVA used (the higher the content of unsubstituted vinyl alcohol units in the protective layer) and the thicker the film thickness, the higher the oxygen barrier properties, which is advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, there arises a problem that an unnecessary polymerization reaction occurs at the time of production or raw storage, and that unnecessary fogging and thickening of an image occur at the time of image exposure. Further, the adhesion to the image area and the scratch resistance are also extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on a lipophilic photosensitive layer, film peeling due to insufficient adhesive force tends to occur, and the peeled portion causes defects such as poor film curing due to inhibition of polymerization of oxygen. On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, U.S. Pat. No. 292,501 and U.S. Pat. No. 44,563 disclose an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer or the like in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesiveness can be obtained by mixing by weight% and laminating on a photosensitive layer. Any of these known techniques can be applied to the protective layer in the present invention. The method of applying such a protective layer is described in detail in, for example, U.S. Pat. No. 3,458,311 and JP-A-55-49729.

In addition, as a plate making process for making a lithographic printing plate from the lithographic printing plate precursor of the present invention, if necessary, the entire surface may be heated before exposure, during exposure, or between exposure and development. Is also good. By such heating, an image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity can be obtained. Further, for the purpose of improving image strength and printing durability, it is also effective to post-heat or expose the entire surface of the developed image. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. If the temperature is too high, there arises a problem that the non-image portion is covered. Very strong conditions are used for heating after development. Usually, it is in the range of 200 to 500 ° C. If the temperature is too low, a sufficient image strengthening effect cannot be obtained.

The method of exposing a lithographic printing plate precursor according to the present invention comprises:
Known methods can be used without limitation. Desirable wavelength of the light source is 350 nm to 650 nm, and specifically, various laser light sources are suitable. The exposure mechanism may be any of an internal drum type, an external drum type, a flat bed type, and the like. The photosensitive layer component of the lithographic printing plate precursor according to the invention can be made soluble in neutral water or weakly alkaline water by using a highly water-soluble one. After the lithographic printing plate precursor is loaded on a printing press, a system such as exposure-development can be performed on the printing press.

Other exposure light rays for the lithographic printing plate precursor according to the present invention include ultrahigh-pressure, high-pressure, medium-pressure and low-pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible and ultraviolet lamps. Various laser lamps, fluorescent lamps, tungsten lamps, sunlight and the like can also be used.

The lithographic printing plate precursor according to the invention is exposed and then developed. As a developer used for such a development treatment, an aqueous alkali solution having a pH of 14 or less is particularly preferred, and an alkaline aqueous solution having a pH of 8 to 12 containing an anionic surfactant is more preferably used. For example,
Tribasic sodium, potassium, ammonium,
Dibasic sodium, potassium, ammonium,
Inorganic alkali agents such as sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine,
Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used. These alkaline agents are used alone or in combination of two or more.

In the development of the lithographic printing plate precursor according to the present invention, anionic surfactants 1 to 20 w
Although t% is added, it is more preferably used at 3 to 10% by weight. If the amount is too small, the developability deteriorates. If the amount is too large, adverse effects such as deterioration of the image, such as abrasion resistance, occur. As the anionic surfactant, for example, sodium salt of lauryl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, for example, sodium salt of isopropylnaphthalenesulfonic acid, sodium salt of isobutylnaphthalenesulfonic acid, polyoxyethylene glycol Alkyl aryl sulfonates such as sodium salt of mononaphthyl ether sulfate, sodium salt of dodecylbenzenesulfonic acid, sodium salt of metanitrobenzenesulfonic acid, higher alcohol sulfuric acid having 8 to 22 carbon atoms such as secondary sodium alkyl sulfate Esters, aliphatic alcohol phosphates such as sodium salt of cetyl alcohol phosphate,
For example, C ₁₇ H ₃₃ CON (CH ₃ ) CH ₂ CH ₂ SO ₃ Na
And sulfonates of dibasic aliphatic esters such as dioctyl sodium sulfosuccinate and dihexyl sodium sulfosuccinate.

If necessary, an organic solvent such as benzyl alcohol which is mixed with water may be added to the developer. As the organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and preferably selected from those having a solubility of 5% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol, 1,4
-Phenylbutanol, 2,2-phenylbutanol,
1,2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-
Methylcyclohexanol, 4-methylcyclohexanol, 3-methylcyclohexanol and the like can be mentioned. The content of the organic solvent is preferably from 1 to 5% by weight based on the total weight of the developer at the time of use. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the anionic surfactant as the amount of the organic solvent increases. This is because if the amount of the organic solvent is large when the amount of the anionic surfactant is small, the organic solvent does not dissolve, so that it is impossible to expect good developability.

Further, if necessary, an antifoaming agent and hard water
Additives such as softeners can also be included. hard water
As the softener, for example, Na_TwoP_TwoO₇, Na_FiveP_ThreeO_Three, N
a_ThreeP _ThreeO₉, Na_TwoO_FourP (NaO_ThreeP) PO_ThreeNa_Two, Calgon
Polyphosphates such as (sodium polymetaphosphate), eg
For example, ethylenediaminetetraacetic acid, its potassium salt,
Sodium salt of diethylenetriaminepentaacetic acid;
Potassium and sodium salts of triethylenetetramine
Hexaacetic acid, its potassium salt, its sodium salt;
Roxyethylethylenediaminetriacetic acid, potassium
Salt, its sodium salt; nitrilotriacetic acid, its potassium
Salt, sodium salt thereof; 1,2-diaminocyclohexene
Suntetraacetic acid, its potassium salt, its sodium salt;
1,3-diamino-2-propanoltetraacetic acid, the
Aminopoly such as potassium salt, its sodium salt, etc.
Other than carboxylic acids 2-phosphonobutanetricarboxylic acid-
1, 2, 4, its potassium salt, its sodium salt;
Phosphonobtanone tricarboxylic acid-2,3,4,
Lithium salt, its sodium salt; 1-phosphonoethanetri
Carboxylic acid-1,2,2, its potassium salt, its sodium
Salt; 1-hydroxyethane-1,1-diphosphone
Acid, its potassium salt, its sodium salt;
(Methylene phosphonic acid), its potassium salt, its sodium
Organic phosphonic acids such as um salts
Wear. The optimal amount of such a water softener depends on the hard water used.
Varies depending on the hardness of
Is 0.01 to 5% by weight in the developer at the time of use, more preferably
Or 0.01 to 0.5% by weight.
You.

Further, when the lithographic printing plate precursor is developed using an automatic developing machine, the developer becomes fatigued according to the processing amount. Therefore, the processing is performed using a replenisher or a fresh developer. You may restore your abilities. In this case, U.S. Pat.
Replenishment is preferably carried out by the method described in U.S. Pat. Also, JP-A-50-26601 and JP-A-58-26601.
No. 54341, JP-B-56-39464, No. 56-4
The developing solutions described in JP-A Nos. 2860 and 57-7427 are also preferable.

The lithographic printing plate precursor thus developed is described in JP-A-54-8002 and JP-A-55-1150.
As described in JP-A Nos. 45 and 59-58431 and the like, post-treatment is carried out with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. . In the post-treatment of the lithographic printing plate precursor according to the invention, these treatments can be used in various combinations. The lithographic printing plate obtained by such a process is set on an offset printing machine and used for printing a large number of sheets. As a plate cleaner used for removing stains on the plate at the time of printing, a conventionally known plate cleaner for PS plate is used. For example, CL-1, CL-2, C
P, CN-4, CN, CG-1, PC-1, SR, IC
(Manufactured by Fuji Photo Film Co., Ltd.).

[0136]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. (Synthesis Example 1, Method -1) 70 g of 2-methoxyethanol was used as a reaction solvent in a 200 ml three-necked flask equipped with a stirring rod and a stirring blade, a reflux condenser, and a thermometer.
21.3 g of (4-vinylbenzyl) triethylammonium chloride and 8.3 g of 4-vinylbenzoic acid were added, and the mixture was stirred at 50 ° C. for 30 minutes under a nitrogen stream to obtain a homogeneous solution. There, 2,2'-azobis (2,2
1.04 g of 4-dimethylvaleronitrile) was added, and 80
The mixture was stirred at 7 ° C. for 7 hours to carry out polymerization. This solution was poured into 500 ml of ethyl acetate, and the obtained precipitate was dried in vacuo to obtain 29.5 g of a polymer having a cationic group and a reactive group. The acid value of this polymer was 1.85 meq / g.

In a 300 ml three-necked flask equipped with a stirring rod and a stirring blade, a reflux condenser and a thermometer, 150 ml of methanol as a reaction solvent and 9.5 g of the obtained polymer having a cationic group and a reactive group were placed. Added and dissolved.
1.3 g of glycidyl methacrylate was added thereto, and the mixture was heated under reflux for 5 hours. This solution was poured into 1,000 ml of ethyl acetate, and the obtained precipitate was dried in vacuo to obtain 10.1 g of a polymer (P-1) having a cationic group and a radical reactive group in the present invention. The acid value of this polymer was 0.79 meq / g.

(Synthesis Example 2, Method -1) In a 300 ml three-necked flask equipped with a stirring rod and a stirring blade, a reflux condenser, and a thermometer, 150 ml of dimethyl sulfoxide as a reaction solvent was obtained in Synthesis Example 1. 9.5 g of a polymer having a cationic group and a reactive group was added and dissolved. There 2
-(Methacryloyloxy) ethyl isocyanate 1.4
g and 3 drops of di-n-butyltin dilaurate.
The mixture was heated and stirred at 5 ° C. for 5 hours. This solution is diluted with ethyl acetate 100
The resulting precipitate was dried under vacuum to obtain 10.3 g of a polymer (P-2) having a cationic group and a radical reactive group in the present invention. The acid value of this polymer was 0.84 meq / g.

(Synthesis Example 3, Method 2) A 200 ml three-necked flask equipped with a stirring rod and stirring blade, a reflux condenser, and a thermometer was charged with 50 g of methanol as a reaction solvent.
Poly (4-vinylpyridine) (weight average molecular weight 20,000
0) 10.5 g was added and dissolved. Thereto was added 6.1 g of 4- (chloromethyl) styrene, and the mixture was refluxed for 8 hours. This solution was poured into 8000 ml of ethyl acetate, and the resulting precipitate was dried under vacuum to obtain a polymer (P-3) having a cationic group and a radical reactive group in the present invention.
Was obtained in an amount of 15.4 g.

(Synthesis Example 4, Method -2) In a 200 ml three-necked flask equipped with a stirring rod and a stirring blade, a reflux condenser, and a thermometer, 50 g of methanol was used as a reaction solvent.
15.7 g of poly [(dimethylamino) ethyl methacrylate] (weight average molecular weight 78,000) was added and dissolved. Thereto was added 12.0 g of propargyl bromide, and the mixture was heated under reflux for 8 hours. This solution was poured into 800 ml of ethyl acetate, and the resulting precipitate was dried under vacuum to obtain 21.3 g of a polymer (P-4) having a cationic group and a radical reactive group in the present invention.

(Synthesis Example 5, Method -3) In a 200 ml three-necked flask equipped with a stirring rod and a stirring blade, a reflux condenser and a thermometer, 80 ml of methanol, 20 ml of acetone and poly (chloromethyl) were used as reaction solvents. styrene)
7.6 g (weight average molecular weight 24,000) was added and dissolved.
1.6 g of 2- (dimethylamino) ethyl methacrylate was added and heated at 40 ° C. for 3 hours. 6.6 g of Nn-butylamine was added thereto, and the mixture was further heated at 40 ° C. for 3 hours.
This solution was poured into 500 ml of ethyl acetate, and the obtained precipitate was dried under vacuum to obtain a polymer having a cationic group and a radical reactive group (P-
5) was obtained in an amount of 12.4 g.

(Synthesis Example 6, Method -4) In a 200 ml three-necked flask equipped with a stirring rod and stirring blades, a reflux condenser, and a thermometer, 90 g of 2-methoxyethanol as a reaction solvent and [2- (methacrylic acid) were used. Loyloxy) ethyl] trimethylammonium methyl sulfate (80% by weight
17.7 g of a mat solution, 3.8 g of allyl methacrylate, and 1.7 g of methacrylic acid were added, and the mixture was stirred at 50 ° C. for 30 minutes under a nitrogen stream to obtain a uniform solution. Thereto was added 1.24 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and the mixture was stirred at 80 ° C. for 8 hours to perform polymerization. This solution was poured into 1,000 ml of ethyl acetate, and the obtained precipitate was dried in vacuo to obtain 19.6 g of a polymer (P-6) having a cationic group and a radical reactive group in the present invention. The acid value of this polymer is 0.9
It was 6 meq / g.

(Synthesis Example 7, Method -5) 50 g of N, N-dimethylacetamide as a reaction medium, and 200 g of a three-necked flask equipped with a stirring rod and a stirring blade, a reflux condenser, and a thermometer, and (4) -Vinylbenzyl) triallylammonium hexafluorophosphate 12.0
g was stirred at 50 ° C. for 30 minutes to obtain a homogeneous solution. Thereto was added 0.15 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and the mixture was stirred at 80 ° C for 7 hours to carry out polymerization. This solution is poured into 1000 ml of water,
The obtained precipitate was dried under vacuum to obtain 10.3 g of a polymer (P-7) having a cationic group and a radical reactive group in the present invention.

(Examples 1 to 6, Comparative Examples 1 to 3) A lithographic printing plate precursor was prepared by the following procedure, and the printing performance was evaluated.
Table 2 shows the results. <Pretreatment of Support> A surface of a 1S aluminum plate having a thickness of 0.3 mm was grained with a No. 8 nylon brush and an 800 mesh aqueous suspension of pamistone, and then washed thoroughly with water. After being immersed in 10% by weight of sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water for 20 minutes.
It was neutralized and washed with weight% nitric acid and then washed with water. This is V _A
Under the condition of = 12.7 V, an electrolytic surface roughening treatment was carried out in a 1% by weight nitric acid aqueous solution at an anode electricity of 300 coulomb / dm ² using a sinusoidal alternating current. When the surface roughness was measured, it was 0.45 μm (Ra display according to JIS B0601).

<Hydrophilic Treatment of Support Surface> The above support was treated with No. 3 sodium silicate (SiO ₂ = 28 to 30%, Na ₂
O = 9-10%, Fe = 0.02% or less) 2.5% by weight, pH = 11.2, immersed in 70 ° C. aqueous solution for 13 seconds,
Subsequently, it was washed with water. Si determined by X-ray fluorescence analysis of the surface
From the amount of elements, the amount of surface silicate was 10 mg / m ² .

<Coating of Intermediate Layer> On the surface of the above-mentioned hydrophilized support, the applied amount of the non-volatile component was 10 mg to 35 mg / m 2.
A coating solution having the following composition (A) or (B) was prepared so as to be ² , applied by a wheeler at 180 rpm, and dried at 80 ° C. for 30 seconds.

(Intermediate Layer Coating Solution A) The polymer having a cationic group and a radical reactive group of the present invention synthesized in Synthesis Examples 1 to 7 (compounds described in Table 1 below) 0.07 to 1.4 g Additives (compounds listed in Table 1 below) (based on polymer having cationic group and radical reactive group) 2 to 100% by weight methanol 200 g

(Intermediate Layer Coating Solution B) The polymer having the cationic group and the radical reactive group of the present invention synthesized in Synthesis Examples 1 to 7 (the compound described in Table 1) was added in an amount of 0.07 to 1.4 g. Agent (compound described in Table 1 below) (20 to 100% by weight based on polymer having cationic group and radical reactive group) 100 g of methanol 100 g of water

<Coating of photosensitive layer> A photosensitive solution having the following composition was prepared on a support provided with the above-mentioned intermediate layer, and the coating amount of the non-volatile component was adjusted to 1.0 to 2.0 g / m ^2. Was applied with a wheeler and dried at 100 ° C. for 1 minute.

(Photosensitive solution) Addition polymerizable compound (compound described in Table 1) 1.5 g Binder polymer (compound described in Table 1) 2.0 g Sensitizing dye (compound described in Table 1) 0.2 g Photopolymerization initiator (compound described in Table 1) 0.4 g Co-sensitizer (compound described in Table 1) 0.4 g Color pigment dispersion (the following composition) 2.0 g Thermal polymerization inhibitor (N-nitrosophenyl hydroxylamine aluminum salt) 0.01 g Surfactant (Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.02 g Methyl ethyl ketone 20.0 g Propylene glycol monomethyl ether 20.0 g

Composition of the Color Pigment Dispersion Pigment Blue 15: 6 15 parts by weight Allyl methacrylate / methacrylic acid copolymer 10 parts by weight (copolymerization molar ratio 83/17) Thermal polymerization Cyclohexanone 15 parts by weight Methoxypropyl acetate 20 parts by weight propylene Glycol monomethyl ether 40 parts by weight

<Coating of Protective Layer> A 3% by weight aqueous solution of polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 550) was coated on the above photosensitive layer so that the dry coating weight was 2 g / m ^2. And dried at 100 ° C. for 2 minutes.

<Exposure of Lithographic Printing Plate Precursor> The lithographic printing plate precursor thus obtained was subjected to FD-YAG (532
nm) using a laser exposure machine (Heidelberg plate setter: Gutenberg), adjusting the exposure power so that the plate surface exposure energy density becomes 200 μJ / cm ² ;
Solid image exposure and halftone image exposure at 2540 dpi, 175 lines / inch, 1% to 99% in 1% increments were performed.

<Development / Plate Making> A predetermined developing solution and a finisher FP-2W manufactured by Fuji Photo Film Co., Ltd. were charged into an automatic developing machine LP-850 manufactured by Fuji Photo Film Co., Ltd., respectively. The plate that had been exposed under the conditions of seconds was developed / plate-making to obtain a lithographic printing plate.

<Printing durability test> R201 manufactured by Roland was used as a printing machine, and G was manufactured by Dainippon Ink Co., Ltd. as an ink.
EOS-G (N) was used. The printed matter in the solid image area was observed, and the printing durability was examined based on the number of sheets at which the image began to fade. The higher the number, the better the printing durability.

<Dot Printing Durability Compulsory Test> R201 manufactured by Roland was used as a printing machine, and GEOS-G (N) manufactured by Dainippon Ink was used as an ink. 5 from the start of printing
On the 000 th sheet, PS plate cleaner CL-2 manufactured by Fuji Photo Film Co., Ltd. was soaked into a printing sponge, halftone dots were wiped off, and the ink on the plate surface was washed. Then, 10,0
The printing of 00 sheets was performed, and the presence or absence of halftone dot skipping in the printed matter was visually observed.

<Stain test> R201 manufactured by Roland was used as a printing machine, and G was manufactured by Dainippon Ink Co., Ltd.
EOS-G (S) was used. The non-image portion of the printed matter was observed, and the stain property was evaluated.

[0158]

[Table 1]

[0159]

[Table 2]

(Examples 7 to 15, Comparative Examples 4 to 6) The performance of the lithographic printing plate precursors shown in Table 3 was evaluated in the same manner as in Examples 1 to 6.

[0161]

[Table 3]

[0162]

[Table 4]

As is clear from Tables 2 and 4, a lithographic printing plate precursor provided with an intermediate layer containing a polymer having a cationic group and a radical-reactive group has extremely excellent press life and stain resistance. Gave.

The compounds shown in Tables 1 and 3 are shown below.

[0165]

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[Addition polymerizable compounds in Tables 1 and 3] (M-1) Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; NK ester A-TMM)
T) (M-2) Glycerin dimethacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd .; UA101H) [Materials for photopolymerization initiator in Tables 1 and 3]

[0167]

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[Binder Polymers in Tables 1 and 3] (B-1) Allyl methacrylate / methacrylic acid / N-isopropylacrylamide (copolymerization molar ratio: 67/13/20) Actually measured acid value determined by NaOH titration. Weight average molecular weight 130,000 determined by 15 meq / g GPC measurement (B-2) Allyl methacrylate / methacrylic acid copolymer (copolymer molar ratio 83/17) Actual measured acid value 1.55 meq / g GPC measurement determined by NaOH titration Weight average molecular weight of 125,000

(B-3) Polyurethane resin 4,4'-diphenylmethane diisoisonate (MD) which is a condensation polymer of the following diisocyanate and diol
I) Hexamethylene diisocyanate (HMDI) polypropylene glycol, weight average molecular weight 1000
(PPG1000) 2,2-bis (hydroxymethyl) propionic acid (DMPA) copolymer molar ratio (MDI / HMDI / PPG1000 / D
MPA) 40/10/15/35 Acid value measured by NaOH titration 1.05 meq / g Weight average molecular weight determined by GPC measurement 45,000

[Developers in Tables 1 and 3] (D-1) Aqueous solution having the following composition and having a pH of 10: 0.1 parts by weight of monoethanolamine 1.5 parts by weight of triethanolamine Compound of the following formula 1 4.0 Parts by weight Compound of the following formula 2 2.5 parts by weight Compound of the following formula 3 0.2 parts by weight Water 91.7 parts by weight

[0171]

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In the above (formula 1), R ²¹ represents a hydrogen atom or a butyl group.

(D-2) Aqueous solution having the following composition 1 K potassium silicate 3.0 parts by weight Potassium hydroxide 1.5 parts by weight 0.2 part by weight of compound of formula 3 0.2 parts by weight 95.3 parts by weight of water

[0174]

As described above, the lithographic printing plate precursor according to the present invention has an intermediate layer containing a polymer having a cationic group and a radical reactive group between a support and a photosensitive layer. The printing durability and stain resistance were extremely excellent. The lithographic printing plate precursor according to the present invention has sufficient practical sensitivity for scanning exposure with laser light.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 2H025 AA01 AA02 AA12 AA14 AB03 AC08 AD01 BC13 BC31 CB00 CB48 DA35 DA36 DA40 FA10 2H096 AA06 BA05 CA03 CA05 EA03 EA05 EA23

Claims (1)

[Claims] 1. An intermediate layer containing a polymer having a cationic group and a radical reactive group, a photopolymerization initiator, and an addition-polymerizable ethylenically unsaturated bond are formed on an aluminum support subjected to a hydrophilic treatment. A lithographic printing plate precursor comprising a photopolymerizable photosensitive layer containing a compound having a polymer binder.