JP2010059371A - Manufacturing method for curable polymer compound, composition, and lithographic printing original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a curable polymer compound being excellent in reactivity and in stability in a reaction solution of the obtained curable polymer compound, a composition containing the curable polymer compound obtained by the manufacturing method, and a lithographic printing original plate. <P>SOLUTION: In the manufacturing method for the curable polymer compound, an epoxy compound having an ethylenically unsaturated group is added to an acid group existing in the polymer compound. The manufacturing method is characterized in that a salt of carboxylic acid having pKa of 3.0 or lower is used as a catalyst. The composition and the lithographic printing original plate contain the curable polymer compound obtained by the manufacturing method. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a curable polymer compound and a composition of the curable polymer compound. Further, the present invention relates to a lithographic printing plate precursor capable of image recording with a laser and capable of making a plate by development processing or on-press development.

  In recent years, with the development of various printing plates and electronics applications, materials that can provide excellent resolution are required to obtain fine patterns. Significant progress has been made in the polymer industry driven by these market needs, and a wide variety of polymer materials have been developed and used extensively. In response to such market needs, reactive oligomers or polymers having a plurality of double bonds in the side chain are thermosetting, photocurable, electron beam curable polymer compounds, and the like. As functional polymer compounds, they are studied and developed from various fields for a wide range of industrial applications.

  Among them, in particular, the curable polymer compound having a carbon-carbon double bond in the side chain is a curable polymer compound such as an unsaturated polyester polymer compound having a carbon-carbon double bond and an ester bond in the main chain. In order to have superior performance in terms of physical properties, its use is expanding in various fields, and in particular, it is attracting attention in the field of lithographic printing plates.

In general, a lithographic printing plate comprises an oleophilic image area that receives ink in the printing process and a hydrophilic non-image area that receives dampening water. Lithographic printing utilizes the property that water and oil-based inks repel each other, so that the oleophilic image area of the lithographic printing plate is the ink receiving area and the hydrophilic non-image area is dampened with the water receiving area (ink non-receiving area). As described above, a difference in ink adhesion is caused on the surface of a lithographic printing plate, and after ink is applied only to an image portion, the ink is transferred to a printing medium such as paper and printed.
In order to produce this lithographic printing plate, a lithographic printing plate precursor (PS plate) in which an oleophilic photosensitive layer (image recording layer) is provided on a hydrophilic support has been widely used. Usually, after exposing a lithographic printing plate precursor through an original image such as a lithographic film, the photosensitive layer corresponding to the image portion is left, and the unnecessary photosensitive layer corresponding to the non-image portion is removed with an alkaline developer or an organic developer. A lithographic printing plate is obtained by dissolving and removing with a solvent-containing developer and exposing the surface of the hydrophilic support to form a non-image area.

  In the conventional plate making process of a lithographic printing plate precursor, a step of dissolving and removing unnecessary photosensitive layers with a developer or the like is necessary after exposure. However, such additional wet processing is unnecessary or simplified. Is one of the issues. In particular, in recent years, disposal of waste liquids discharged with wet processing has become a major concern for the entire industry due to consideration for the global environment, and therefore, the demand for solving the above-mentioned problems has become stronger.

As one of the simple plate making methods, a photosensitive layer that can remove unnecessary portions of the photosensitive layer in a normal printing process is used, and after exposure, the unnecessary portions of the photosensitive layer are removed on a printing press to perform lithographic printing. A method called on-press development for obtaining a plate has been proposed.
As a specific method of on-press development, for example, a method of using a lithographic printing plate precursor having a photosensitive layer that can be dissolved or dispersed in a fountain solution, an ink solvent, or an emulsion of a fountain solution and an ink, The method of mechanically removing the photosensitive layer by contact with the rollers and blankets of the printing press, the cohesive force of the photosensitive layer or the adhesive force between the photosensitive layer and the support was weakened by penetration of dampening water, ink solvent, etc. Thereafter, there is a method in which the photosensitive layer is mechanically removed by contact with rollers or a blanket.

  For example, as an on-press development type lithographic printing plate precursor for image recording with an infrared laser, which does not require wet development treatment with an alkali developer, an infrared absorber, a radical polymerization initiator, and a polymerizable compound on a support There is known a lithographic printing plate precursor provided with a photosensitive layer containing: (for example, see Patent Document 1).

  In order to improve the on-press developability, a method of adding a polymer compound having at least one of an ether group, an ester group and an amide group in the molecule to such a polymerizable composition has been proposed (for example, , See Patent Document 2). However, since improvement in on-press developability, that is, increasing hydrophilicity tends to reduce printing durability, it is difficult to achieve both on-press developability and printing durability. Further technical improvements were desired.

  In order to improve printing durability, it is known that a photosensitive layer containing a polymer compound having at least one ethylenically unsaturated bond in the side chain is effective (see, for example, Patent Document 3). . This document also states that a lithographic printing plate precursor having this photosensitive layer can be developed on the machine.

  As a method for synthesizing such a polymer compound having an ethylenically unsaturated bond in the side chain, there is a method in which a monomer containing two or more unsaturated bonds in the molecule is used alone or by copolymerizing with various monomers. Usually, in the polymerization of a monomer having a plurality of highly reactive acrylic groups or methacrylic groups (hereinafter, sometimes referred to as (meth) acrylic groups in order to indicate acrylic groups or methacrylic groups), in a dilute solution, However, a plurality of functional groups are involved in the reaction during the polymerization, causing a problem of gelation due to three-dimensional cross-linking between molecules.

  In order to solve this problem, it is known that a (meth) acrylate monomer having a long-chain substituent is copolymerized and the cross-linking reaction between molecules is suppressed by utilizing the steric effect of the substituent. (See Patent Document 4). However, the cross-linking reaction has partially progressed, and the molecular weight distribution becomes wider than that of a normal polymer. Further, it is not suitable for polymerization at a high reaction rate and a high solid content concentration. In addition, there is an example of polymerization of monomers having unsaturated groups having different reactivity such as allyl methacrylate. In this case, under the condition where the solid content concentration exceeds 10% by mass, there arises a problem that gelation occurs due to three-dimensional cross-linking between molecules as in the above example. For this reason, the reaction is usually carried out under dilute conditions, but even under dilute conditions, some gelation is observed when the reaction rate is 90% or more.

  The above-mentioned various production methods are difficult to produce at a high solid content concentration, and gelation occurs when the reaction rate is increased, so that a large amount of monomer remains, which is not a sufficient production method from the viewpoint of productivity.

In the case of a polymer compound having a carbon-carbon double bond in the side chain, a compound having a double bond is added to the functional group of the polymer compound having no carbon-carbon double bond in the side chain. Is also manufactured by. Among them, a polymer compound having a carbon-carbon double bond in the side chain adds a compound having both an ethylenically unsaturated group and an epoxy group in the molecule to the polymer compound having a carboxy group in the side chain. Is known to be synthesized (for example, see Patent Documents 5 to 7). In addition, use of a polymer compound obtained by adding a carboxy group to an ethylenically unsaturated compound having an epoxy group for a lithographic printing plate precursor is also known (see, for example, Patent Document 8).
In these prior arts, a tertiary amine catalyst, a phosphine catalyst, and a quaternary ammonium-halide ion catalyst are used as an addition reaction catalyst. However, when an epoxy compound having an unsaturated group is added to all carboxy groups of a polymer compound having a carboxy group in the side chain using a tertiary amine catalyst or a phosphine catalyst, However, the stability of the added ethylenically unsaturated site was poor. Further, when a phosphine catalyst is used, there is a problem that the reaction solution after the reaction is colored brown. In addition, when an ammonium-halide ion catalyst is used, when an ethylenically unsaturated compound having an epoxy group is added to all carboxy groups of a polymer compound having a carboxy group in the side chain, the polymer is reacted during the reaction. There was a problem that ethylenically unsaturated groups in the compound were cross-linked to increase the molecular weight or gelled. Further, when a polymer compound synthesized using the catalyst is applied to a lithographic printing plate precursor, there is a problem that dot-like stains due to halide ions occur over time in the printed image non-image area. Therefore, when a polymer compound having an ethylenically unsaturated group in the side chain is produced using these described methods, it is necessary to go through a reprecipitation step after production, which is sufficient in terms of performance and productivity. It was not a method.

JP 2002-287334 A JP 2006-116941 A JP 2006-111860 A JP-A-4-252213 JP-A-1-289820 JP-A-6-138659 JP 2005-163033 A JP-A-9-134011

  The object of the present invention was obtained when an epoxy compound having an ethylenically unsaturated group was added to a polymer compound having an acid group, which did not contain halide ions and had excellent reactivity. A method for producing a curable polymer compound in which the curable polymer compound has excellent stability in a reaction solution, and a composition and a lithographic printing plate precursor comprising the curable polymer compound obtained by the production method It is to provide.

  As a result of intensive studies to solve such problems, the present inventors have found that the above problems can be solved by using, as a reaction catalyst, a salt of a carboxylic acid having a pKa of 3.0 or less, The present invention has been completed. The present invention is as follows.

1. A method for producing a curable polymer compound in which an epoxy compound having an ethylenically unsaturated group is added to an acid group present in a polymer compound, wherein a carboxylic acid salt having a pKa of 3.0 or less is used as a catalyst. A method for producing a curable polymer compound, which is characterized by being used.
2. 2. The method for producing a curable polymer compound according to 1 above, wherein the carboxylic acid salt is an onium salt of a carboxylic acid.
3. 3. The method for producing a curable polymer compound according to 1 or 2 above, wherein the carboxylic acid has at least one fluorine atom.
4). The above-mentioned 1-3, wherein the epoxy compound having an ethylenically unsaturated group is at least one selected from a compound represented by the following general formula (A) and a compound represented by the following general formula (B) The manufacturing method of the curable high molecular compound in any one of.

[In General Formula (A), R ^{1 to} R ⁸ each independently represents a hydrogen atom, a carbonyl group, an alkyloxy group, an alkyl group, an aryl group, a heterocyclic group, or a hydroxy group. Y ¹ represents a single bond or a divalent linking group. In General Formula (B), R ^{9 to} R ¹⁸ each independently represent a hydrogen atom, a carbonyl group, an alkyloxy group, an alkyl group, an aryl group, a heterocyclic group, or a hydroxy group. Y ² represents a single bond or a divalent linking group. ]

  5. The curable polymer compound is a polymer compound having at least one selected from the group represented by the following general formula (1) and the group represented by the following general formula (2) in the side chain. The manufacturing method of the curable high molecular compound in any one of said 1-4.

[In General Formula (1), R ^{1 to} R ⁸ each independently represents a hydrogen atom, a carbonyl group, an alkyloxy group, an alkyl group, an aryl group, a heterocyclic group, or a hydroxy group. Y ¹ represents a single bond or a divalent linking group. In General Formula (2), R ^{9 to} R ¹⁸ each independently represent a hydrogen atom, a carbonyl group, an alkyloxy group, an alkyl group, an aryl group, a heterocyclic group, or a hydroxy group. Y ² represents a single bond or a divalent linking group. ]

6). 6. The method for producing a curable polymer compound according to any one of 1 to 5 above, wherein the acid value of the curable polymer compound is less than 3.0 mgKOH / g.
7). A curable polymer compound composition comprising the curable polymer compound obtained by the production method according to any one of 1 to 6 above.
8). A lithographic printing plate precursor comprising a curable polymer compound obtained by the production method according to any one of 1 to 6 above.
9. The lithographic printing plate precursor as described in 8 above has a photosensitive layer on the support that can form an image by supplying printing ink and fountain solution on a printing machine after exposure to remove unexposed portions. Feature lithographic printing plate precursor.

  According to the present invention, in the production of a curable polymer compound, there is no cross-linking between polymers, and there is excellent reactivity, and the storage stability of the polymer solution after the reaction can be improved. Since the polymer produced by this method is excellent in curability, a good curable polymer composition is possible. When used in a lithographic printing plate precursor, it is excellent in developability and printing durability, and a halide as a catalyst. Since it does not contain ions, a lithographic printing plate precursor having improved dot-like stains can be provided.

1. Method for Producing Curable Polymer Compound The method for producing a curable polymer compound of the present invention is characterized in that, when an epoxy compound having an ethylenically unsaturated group is added to an acid group present in the polymer compound, pKa is used as a catalyst. It is characterized by using a salt of a carboxylic acid having an A of 3.0 or less. The present invention includes adding an epoxy compound having an ethylenically unsaturated group to some or all of the acid groups of a polymer compound having an acid group.

[High molecular compound having an acid group]
The polymer compound having an acid group of the present invention means a polymer compound having at least one acid group. Here, the acid group includes a carboxy group, a phenolic hydroxy group, a sulfonylamino group, and a phenolic mercapto group, and from the viewpoint of availability of raw materials, more preferably a carboxy group and a phenolic hydroxy group, A carboxy group is preferable.
The polymer compound having an acid group has a method of copolymerizing a radically polymerizable compound having at least one acid group, a method of copolymerizing maleic anhydride and then ring-opening an acid anhydride group, and having a hydroxy group It can be synthesized by a known method such as a method of adding an acid anhydride to a polymer compound or a method of performing a polyaddition reaction between a diol compound having an acid group and a diisocyanate compound.

  Among these, a method of copolymerizing a radically polymerizable compound having at least one acid group is preferable. Examples of the radically polymerizable compound having at least one acid group include acrylic acid, methacrylic acid, vinylphenol, and vinylthiophenol. N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide, a modified unsaturated monocarboxylic acid chain-extended between an unsaturated group and a carboxylic acid, such as β-carboxyethyl ( (Meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acid having an ester bond such as lactone modification, modified unsaturated having an ether bond Monocarboxylic acid like Thing, and the like.

Specifically, as the modified unsaturated monocarboxylic acid, a compound represented by the following formula (3) as a compound obtained by modifying lactone with (meth) acrylic acid is a lactone-modified product obtained by acid-modifying a terminal hydroxy group with an acid anhydride. As examples thereof, compounds represented by the following formula (4) may be mentioned.
^{_{CH 2 = C (-R 1)}} CO- [O (CR 2 R 3) l CO] m -OH (3)
CH ₂ ═C (—R ¹ ) COO—CH ₂ CH ₂ O [CO (CR ² R ³ ) ₁ O] _n COR ⁴ COOH (4)
[In the formulas (3) and (4), R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ each represent a hydrogen atom, a methyl group or an ethyl group, and may be different from each other. R ⁴ is a divalent aliphatic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, a p-xylylene group, a phenylene group, etc. Represents. l represents an integer of 4 to 8, m represents an integer of 1 to 10, and n represents an integer of 0 to 10. ]

As a modified unsaturated monocarboxylic acid having an ether bond, an epoxy compound such as ethylene oxide is added to (meth) acrylic acid, and the molecular terminal hydroxy group of the adduct is converted to an acid-modified product with an acid anhydride (5) ).
CH ₂ = C (—R ¹ ) COO — [(CR ² R ³ ) _m O] _n COR ⁴ COOH (5)
[In formula (5), ^{R 1} represents a hydrogen atom or a methyl group. R ² and R ³ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group, and may be different from each other. R ⁴ represents a divalent aliphatic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, p-xylylene, a phenylene group, or the like. To express. m and n represent the integer of 1-10. ]

  Further, the radically polymerizable compound having at least one acid group may be a compound containing two or more carboxy groups such as maleic acid in the molecule.

  The radically polymerizable compound having at least one acid group may be used alone or in combination of two or more.

The polymer compound having at least one acid group of the present invention may contain another copolymer component.
Examples of radically polymerizable compounds that can form other copolymerization components include acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrenes, Examples include radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.

  Specifically, for example, acrylic esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms), (for example, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid) Butyl, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol Monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (for example, phenyl acrylate) Methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl) such as alkyl methacrylate (the alkyl group preferably has 1 to 20 carbon atoms). Methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, Glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl meta Relates, etc.), aryl methacrylates (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.), styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl) Styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (for example, methoxy styrene, 4-methoxy-3-methyl styrene, Dimethoxystyrene), halogenated styrene (eg, chlorostyrene, dichlorostyrene, trichlorostyrene) ), Tetrachlorostyrene, pentachlorostyrene, promstyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.) And acrylonitrile.

[Epoxy compound having an ethylenically unsaturated group]
The epoxy compound having an ethylenically unsaturated group of the present invention is a compound having at least one unsaturated group having radical polymerizability and an epoxy group in one molecule. Specific examples include aliphatic epoxy group-containing unsaturated compounds and alicyclic epoxy group-containing unsaturated compounds.

  Examples of the aliphatic epoxy group-containing unsaturated compound include glycidyl ethers such as aryl glycidyl ether, glycidyl vinyl ether, and 2-methylallyl glycidyl ether, and compounds represented by the following general formula (A). Especially, the compound represented by general formula (A) is preferable.

In general formula (A), R ^{1 to} R ⁸ each independently represents a hydrogen atom, a carbonyl group, an alkyloxy group, an alkyl group, an aryl group, a heterocyclic group, or a hydroxy group. Y ¹ represents a single bond or a divalent linking group. At least two of R ^{1 to} R ⁸ may be bonded to each other to have a ring structure.

In general formula (A), examples of the alkyl group represented by R ^{1 to} R ⁸ include a linear, branched, or cyclic alkyl group. Among these, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , And 2-norbornyl groups.

Examples of the aryl group represented by R ^{1 to} R ⁸ include phenyl group, naphthyl group, tolyl group, xylyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, ethoxyphenyl group, dimethoxyphenyl group, methoxy Preferred examples include a carbonylphenyl group and a dimethylaminophenyl group.

Examples of the heterocyclic group represented by R ^{1 to} R ⁸ include a pyridyl group, a quinolyl group, a pyrimidinyl group, a thienyl group, and a furyl group.

R ^{1 to} R ⁸ are preferably an alkyl group or a hydrogen atom, and most preferably a hydrogen atom.

Examples of the linking group represented by Y ¹ include the following divalent groups or groups constituted by appropriately combining them.

Among these, Y ¹ is preferably a single bond or an alkylene group having 1 to 6 carbon atoms which may have a substituent, and is preferably a single bond from the viewpoint of addition reactivity.

  Specific examples of the compound represented by the general formula (A) include glycidyl methacrylate, β-methyl glycidyl methacrylate, glycidyl crotonate, 4,5-epoxypentyl methacrylate, glycidyl-α-ethyl acrylate, glycidyl acrylate, and the like. . Of these, glycidyl methacrylate is preferable.

Examples of the alicyclic epoxy group-containing unsaturated compound which is an epoxy compound having an ethylenically unsaturated group of the present invention include compounds represented by the following structural formula and compounds represented by the general formula (B). In the following structural formulas, R ⁰⁶ represents a hydrogen atom or a methyl group, R ⁰⁷ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ⁰⁸ represents a divalent carbon atom having 1 to 10 carbon atoms. Indicates a hydrogen group.

In General Formula (B), R ^{9 to} R ¹⁸ each independently represent a hydrogen atom, a hydrogen atom, a carbonyl group, an alkyloxy group, an alkyl group, an aryl group, a heterocyclic group, or a hydroxy group. Y ² represents a single bond or a divalent linking group. At least two of R ^{9 to} R ¹⁸ may be bonded to each other to have a ring structure.

In the general formula (B), specific examples of the alkyl group, aryl group and heterocyclic group represented by R ^{9 to} R ¹⁸ include an alkyl group represented by R ^{1 to} R ⁸ in the general formula (A), The same thing as the specific example of an aryl group and a heterocyclic group is mentioned. The divalent linking group represented by Y ² has the same meaning as Y ¹ in the general formula (A).

R ^{9 to} R ¹⁸ are preferably an alkyl group or a hydrogen atom, and most preferably a hydrogen atom. The Y ^2, a single bond is most preferred.

  The alicyclic epoxy group-containing unsaturated compound is preferably a compound represented by the general formula (B), and among the compounds represented by the general formula (B), 3,4-epoxycyclohexylmethyl (meth) Acrylate is preferred.

  Among the above, glycidyl methacrylate is most preferable as the epoxy compound having an ethylenically unsaturated group used in the present invention.

  These epoxy compounds having an ethylenically unsaturated group may be used alone or in combination of two or more.

  The addition amount of the epoxy compound having an ethylenically unsaturated group is desirably in the range of 2 to 70% by mass with respect to the obtained curable polymer compound. Good curability can be obtained within this range. The addition amount of 2% by mass or more is preferable because the curability is improved and the physical properties of the cured film are improved. When the content is 70% by mass or less, the storage stability of the polymer compound is improved, which is preferable.

[Salt of carboxylic acid having pKa of 3.0 or less]
In the present invention, when an ethylenically unsaturated group-containing epoxy compound is added to a part or all of the acid groups of the polymer compound having at least one acid group, a carboxylic acid having a pKa of 3.0 or less is used as a catalyst. Use the salt. The pKa of the carboxylic acid is 3.0 or less and more preferably −1 or more.
Carboxylic acids having a pKa of 3.0 or less include fluoroacetic acid (pKa = 2.7), difluoroacetic acid (pKa = 1.2), trifluoroacetic acid (pKa = 0.2), bromoacetic acid (pKa = 2.9), dibromoacetic acid (pKa = 1.5), tribromoacetic acid (pKa = 0.7), chloroacetic acid (pKa = 2.9), dichloroacetic acid (pKa = 1.3), trichloroacetic acid (pKa = 0.7), dihydroxyfumaric acid (pKa = 1.1), maleic acid (pKa = 1.9), pyruvic acid (pKa = 2.5), nitroacetic acid (pKa = 1.7), malonic acid (pKa = 2.8), o-bromobenzoic acid (pKa = 2.9), o-chlorobenzoic acid (pKa = 2.9), etc. However, it is not limited to these.

  Among carboxylic acids having a pKa of 3.0 or less, carboxylic acids having at least one fluorine atom in the molecule are preferable. Such carboxylic acid salts include fluoroacetic acid (pKa = 2.7), difluoroacetic acid (pKa = 1.2), trifluoroacetic acid (pKa = 0.2), pentafluoropropionic acid (pKa = 0.2), heptafluorobutanoic acid ( pKa = 0.2), nonafluoropentanoic acid (pKa = 0.2), tridecafluoroheptanoic acid (pKa = 0.3), pentadecafluorooctanoic acid (pKa = 0.4), heptadecafluorononanoic acid (pKa = 0.4), nonadeca Fluorodecanoic acid (pKa = 0.4), perfluorododecanoic acid (pKa = 0.4), bromodifluoroacetic acid (pKa = 0.4), chlorodifluoroacetic acid (pKa = 0.5), hexafluoroglutaric acid (pKa = 0.8), α-fluoro Phenylacetic acid (pKa = 2.0), α-fluorocinnamic acid (pKa = 2.2), 2,2-difluorosuccinic acid (pKa = 0.3), tetrafluorosuccinic acid (pKa = -0.9), tetrafluoropyropionic acid ( pKa = 0.5), 7H-dodecafluoroheptanoic acid (pKa = 0.4), 9H-hexadecafluoro Nanic acid (pKa = 0.4), 3-bromo-4-chloropentafluorobutanoic acid (pKa = 0.3), 3-chlorotetrafluoropropionic acid (pKa = 0.3), 4- (trifluoromethyl) hexafluoro-2-pentene Acid (pKa = 0.9), α, α-difluorophenylacetic acid (pKa = 1.2), chlorofluoroacetic acid (pKa = 1.5), perfluorocyclohexanecarboxylic acid (pKa = -4.7), 2,2-difluoropropionic acid (pKa = 1.6), 2,2-difluorobutanoic acid (pKa = 1.5), 2-fluoropropionic acid (pKa = 2.7), bromofluoroacetic acid (pKa = 1.7), fluoroiodoacetic acid (pKa = 2.0), 2,2- Difluoro-4-pentenoic acid (pKa = 1.5), pentafluorobenzoic acid (pKa = 1.5), trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutanoic acid, nonafluoropentanoic acid, tridecafluoroheptanoic acid , Pentadecafluoroo Tantanic acid, heptadecafluorononanoic acid, nonadecafluorodecanoic acid and perfluorododecanoic acid are more preferred, and trifluoroacetic acid is most preferred.

  Examples of the counter cation of the carboxylic acid salt include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as calcium and barium, onium groups such as ammonium, pyridinium, phosphonium, sulfonium and iodonium, and reactions. From the viewpoint of safety, onium groups such as ammonium, pyridinium, phosphonium, sulfonium and iodonium are preferred, and from the viewpoint of reactivity, ammonium groups and phosphonium groups are preferred, and ammonium groups are most preferred. As the ammonium group, a quaternary ammonium group represented by the following general formula (6) is preferable.

In general formula (6), R ¹ , R ² , R ³ and R ⁴ each independently represents an alkyl group, an aryl group or an aralkyl group. Examples of the alkyl group represented by R ¹ , R ² , R ³ and R ⁴ include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , And 2-norbornyl groups.

Examples of the aralkyl group represented by R ¹ , R ² , R ³ and R ⁴ include those having 7 to 12 carbon atoms such as benzyl group, phenethyl group and naphthylmethyl group.
Examples of the aryl group represented by R ¹ , R ² , R ³ and R ⁴ include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethyl Phenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl Group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group Phosphono phenyl group, phosphonium Hona preparative phenyl group, and the like.

  The ammonium group represented by the general formula (6) is preferably a quaternary ammonium group having 48 or less carbon atoms, and specifically, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentyl. Ammonium, tetrahexylammonium, tetraoctylammonium, tetradecylammonium, tetradodecylammonium and benzyltrimethylammonium are preferred.

  As the catalyst used for the production of the curable polymer compound, a salt of a carboxylic acid composed of a combination of the above-described carboxylic acid having a pKa of 3 or less and preferred embodiments of a counter cation can be preferably used. Specifically, tetramethylammonium trifluoroacetate, tetraethylammonium trifluoroacetate, tetrapropylammonium trifluoroacetate, tetrabutylammonium trifluoroacetate, tetrapentylammonium trifluoroacetate, tetrahexylammonium trifluoroacetate, tetratetrafluoroacetate Octylammonium, tetradecylammonium trifluoroacetate, tetradodecylammonium trifluoroacetate, benzyltrimethylammonium trifluoroacetate, tetramethylammonium nonafluoropentanoate, tetraethylammonium nonafluoropentanoate, tetrapropylammonium nonafluoropentanoate, nonafluoropentane Tetrabutylammonium acid, nonafluoropentanoic acid Lapentylammonium, tetrahexylammonium nonafluoropentanoate, tetraoctylammonium nonafluoropentanoate, tetradecylammonium nonafluoropentanoate, tetradodecylammonium nonafluoropentanoate, benzyltrimethylammonium nonafluoropentanoate, tetraheptadecafluorononanoate Methylammonium, tetraethylammonium heptadecafluorononanoate, tetrapropylammonium hepadecafluorononanoate, tetrabutylammonium hepadecafluorononanoate, tetrapentylammonium hepadecafluorononanoate, tetrahexylammonium hepadecafluorononanoate, heptadecafluoro Tetraoctylammonium nonanoate, heptadecafluo Preferred are tetradecylammonium nonanoate, tetradodecylammonium heptadecafluorononanoate, and benzyltrimethylammonium hepadecafluorononanoate, tetramethylammonium trifluoroacetate, tetraethylammonium trifluoroacetate, tetrabutylammonium trifluoroacetate, tetrafluoroacetate acetic acid Most preferred are hexyl ammonium, tetraoctyl ammonium trifluoroacetate, and tetradecyl ammonium trifluoroacetate.

  The addition amount of the carboxylic acid salt as the catalyst of the present invention is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the polymer compound having an acid group. Within this range, good catalytic effects and physical properties of the cured film can be obtained.

[Other manufacturing conditions and products]
The solvent that can be used for the synthesis of the curable polymer is not particularly limited as long as it dissolves the monomer and the polymer. Specifically, for example, aromatic hydrocarbons such as benzene, toluene, xylene, alcohols such as methanol, ethanol, 2-propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol , Glycols such as ethylene glycol, propylene glycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethers such as diethyl ether, dibutyl ether, dioxane, methyl propylene glycol, methyl dipropylene glycol, ethyl acetate, Isobutyl acetate, methyl lactate, ethyl lactate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoalkyl Esters such as acetate, dipropylene glycol monoalkyl acetate, methyl propylene glycol acetate, 2-methoxyethyl acetate, amides such as propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, carbon tetrachloride, chloroform, ethylene dichloride, etc. Sulfoxides such as dimethyl sulfoxide and the like are used. These solvents may be used alone or in combination. In particular, those having a boiling point higher than the reaction temperature and dissolving the raw materials and products are preferred.

  The polymer compound concentration in the reaction solvent is preferably 20% by mass to 60% by mass. When the polymer compound concentration is 20% by mass or more, a sufficient reaction rate can be obtained, and when the polymer compound concentration is 60% by mass or less, a gelled product is not likely to be produced during the reaction.

  The reaction temperature is preferably 60 ° C. or higher and 130 ° C. or lower, and particularly preferably 80 ° C. to 120 ° C. A reaction temperature of 60 ° C. or higher is preferable because a practically sufficient reaction rate can be obtained, and a temperature of 130 ° C. or lower is preferable because there is no fear that a double bond portion is cross-linked by radical polymerization due to heat and a gelled product is formed.

In order to prevent the formation of a gelled product during the reaction, the ring-opening addition is preferably performed in the presence of a polymerization inhibitor. Polymerization inhibitors include hindered phenols such as hydroquinone, methylhydroquinone, t-butylmethoxyphenol, tris- (2-methyl-4-hydroxy-5-tertiarybutylphenyl) butane (trade name Topanol), phenothiazine, N -Nitrosophenylhydroxylamine ammonium salt (trade name Cuperon), piperidine-1-oxyl free radical compounds, pyrrolidine-1-oxyl free radical compounds, and the like.
The amount of these polymerization inhibitors is 1 to 10000 ppm, preferably 50 to 5000 ppm, based on the entire reaction solution. When the amount of the polymerization inhibitor is 1 ppm or more with respect to the whole reaction solution, a sufficient polymerization inhibition effect is obtained, and when it is 10000 ppm or less, there is no fear of adversely affecting the physical properties of the produced polymer compound.

[Curable polymer compound]
The curable polymer compound of the present invention is obtained by adding an epoxy compound having an ethylenically unsaturated group to an acid group in a polymer compound having an acid group as described above. Among them, the curable polymer compound of the present invention is preferably a polymer compound having the following structure.

^R 1 to R ⁸ and ^{Y 1} in the general formula (1), respectively, it has the same meaning as ^R 1 to R ⁸ and ^{Y 1} in formula (A), and their preferred embodiments are also the same. R < ⁹ > -R < ¹⁸ > and Y < ² > of General formula (2) are synonymous with R < ⁹ > -R < ¹⁸ > and Y < ² > of General formula (B) respectively, A preferable aspect is also the same.

  Although the preferable specific example of group represented by General formula (1) or (2) is shown next, it is not limited to these.

  In this production method, the acid value of the curable polymer compound is 0 to 150 mgKOH / g, more preferably 0 to 20 mgKOH / g, most preferably from the point of having excellent reactivity without cross-linking between polymers. It is suitably used for the production of a curable polymer compound that is less than 3 mg KOH / g. In addition, a curable polymer compound of less than 3 mg KOH / g can be preferably used in the on-press development type lithographic printing plate described later from the on-press developability.

  The curable polymer compound produced by the method of the present invention has a mass average molar mass (Mw), preferably 2,000 or more, and from the viewpoint of the physical properties of the curable film, 40,000 to 300,000. The range is preferable, and the range of 40,000 to 90,000 is most preferable from the viewpoint of stability during the reaction. The curable polymer compound according to the present invention may contain an unreacted monomer. In this case, the proportion of the monomer in the polymer compound is desirably 15% by mass or less.

  The curable polymer compound produced by the method of the present invention is cured by visible light, ultraviolet light, infrared light or heat, X-ray or electron beam, or a combination thereof.

2. Curable polymer compound composition The curable polymer compound composition of the present invention is characterized by including at least one of the curable polymer compounds of the present invention as an essential component.

In the curable polymer compound composition of the present invention, various polymerizable compounds, radical polymerization initiators, sensitizing dyes, chain transfer agents, solvents and the like are mixed with the curable polymer compound of the present invention as necessary. can do. Specific examples of the components to be mixed include the same components as those described as the components used in the photosensitive layer of the lithographic printing plate precursor described later.
The content of the curable polymer compound contained in the curable polymer compound composition of the present invention is preferably about 5 to 95% by mass, more preferably based on the solid content of the curable polymer compound composition. About 10-85% by mass. Within this range, good image area strength and image formability can be obtained.

3. Lithographic printing plate precursor The lithographic printing plate precursor according to the invention contains the curable polymer compound. More specifically, the lithographic printing plate precursor according to the invention has a photosensitive layer on a support, and the photosensitive layer contains the curable polymer compound. Further, the lithographic printing plate precursor according to the invention may have a layer other than the photosensitive layer, a protective layer, an undercoat layer, and the like, if necessary.

(Photosensitive layer)
The photosensitive layer of the present invention contains the curable polymer compound. The content of the curable polymer compound contained in the photosensitive layer is preferably about 5 to 95% by mass, more preferably about 10 to 85% by mass, based on the solid content of the photosensitive layer. Within this range, good image area strength and image formability can be obtained.
Furthermore, the photosensitive layer of the present invention comprises (A) a sensitizing dye, (B) a radical polymerization initiator, and ( C) It is preferable to contain a polymerizable compound. It is also preferable to contain (D) a hydrophobized precursor. Furthermore, the photosensitive layer of the present invention can contain various additives as required.
Below, each component which can be contained in a photosensitive layer is demonstrated one by one.

<(A) Sensitizing dye>
The sensitizing dye used in the present invention is preferably a sensitizing dye having an absorption peak at 350 to 850 nm when an image is formed by a visible light or ultraviolet laser light source, and a laser emitting infrared light at 760 to 1200 nm. When forming an image with a light source, it is preferable to use an infrared absorber (A2).
When the sensitizing dye used in the present invention is a cationic compound, it is preferable to use a counter ion that does not contain a halide ion.

(A1) Sensitizing dye having an absorption peak at 350 to 850 nm The sensitizing dye preferably has an absorption peak at 300 to 850 nm, and more preferably has an absorption peak at 300 to 600 nm. Examples of such sensitizing dyes include spectral sensitizing dyes and the following dyes or pigments that absorb light from a light source and interact with a photopolymerization initiator.
Preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrolan, rhodamine B, rose bengal), cyanines (eg, thianes). Carbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thioene, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), phthalocyanines (For example, phthalocyanine, metal phthalocyanine), porphyrins (for example, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (for example, chlorophyll, chlorophyllin, center) Genus substituted chlorophyll), metal complexes, anthraquinones (e.g., anthraquinone), Sutaariumu compound (such as Sutaariumu), and the like.

  Examples of more preferable spectral sensitizing dyes or dyes include styryl dyes described in JP-B-37-13034, cationic dyes described in JP-A-62-143044, and quinoxalinium described in JP-B-59-24147. Salts, new methylene blue compounds described in JP-A No. 64-33104, anthraquinones described in JP-A No. 64-56767, benzoxanthene dyes described in JP-A No. 2-1714, JP-A No. 2-226148 and Acridines described in JP-A-2-226149, pyrylium salts described in JP-B-40-28499, cyanines described in JP-B-46-42363, benzofuran dyes described in JP-A-2-63053, Conjugated ketone dyes described in Kaihei 2-85858 and JP-A-2-216154 Dyes described in Japanese Utility Model Laid-Open No. 57-10605, azocinnamilidene derivatives described in Japanese Patent Publication No. 2-30321, cyanine dyes described in Japanese Patent Application Laid-Open No. 1-287105, Japanese Patent Application Laid-Open No. 62-31844, Japanese Patent Application 62-31848, xanthene dyes described in JP-A-62-143043, aminostyryl ketones described in JP-B-59-28325, merocyanine dyes described in JP-B-61-9621, and JP-A-2-179634 Dyes described in JP-A-2-244050, merocyanine dyes described in JP-A-2-244050, merocyanine dyes described in JP-B-59-28326, merocyanine dyes described in JP-A-59-89803, and JP-A-8-129257 Merocyanine dyes, benzopyran dyes described in JP-A-8-334897, and the like Door can be.

  The sensitizing dye used in the present invention is more preferably one represented by the following general formula (7).

In the general formula (7), A represents an aromatic ring or a heterocyclic ring which may have a substituent, X represents an oxygen atom or a sulfur atom or —N (R ¹ ) —, and Y represents an oxygen atom or — N (R ¹ ) — is represented. R ¹ , R ² and R ³ each independently represents a hydrogen atom or a monovalent non-metallic atomic group, and A and R ¹ , R ² and R ³ are bonded to each other to form an aliphatic group. Alternatively, an aromatic ring can be formed.

Here, when R ¹ , R ² and R ³ represent a monovalent nonmetallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or aryl group.
Next, preferred examples of R ¹ , R ² and R ³ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxy groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N ′ An arylureido group, an N ′, N′-diarylureido group, an N′-alkyl-N′-arylureido group, an N-alkylureido group, an N-arylureido group, an N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group Group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxy group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group , Alkylsulfinyl group, ali Sulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfina Moyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfato group Famoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), Zia Kiruhosuhono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (- PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group) ), Phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO _3). (aryl) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), Monoarukiruho Honookishi group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter And cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups, which may further have a substituent.

  Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group. , Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl Group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonopheny Group, and a phosphate Hona preparative phenyl group.

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and as a particularly preferred example of the heteroaryl ring in the heteroaryl group, Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, cinolin, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, fura Emissions, and the like. These further may be benzo-fused or may have a substituent.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfa Yl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ¹ , R ² , or R ³ obtained by combining the above substituents with an alkylene group include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonyl Bonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl- N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolyl Sulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group , Methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatobutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenyl Ethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3- A butynyl group, and the like.

Specific examples of preferred aryl groups as R ¹ , R ² , or R ³ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. preferable.

Specific examples of the preferred substituted aryl group as R ¹ , R ² , or R ³ include a monovalent nonmetallic atomic group (other than a hydrogen atom) as a substituent on the ring-forming carbon atom of the aryl group. What has is used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophene Group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatephenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group Group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

In addition, more preferable examples of R ² and R ³ include a substituted or unsubstituted alkyl group. A more preferable example of R ¹ includes a substituted or unsubstituted aryl group. The reason for this is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, generating radicals, acids or bases of the initiator compound. It is estimated that the efficiency is improved.

Next, A in the general formula (7) will be described. A represents an aromatic ring or a heterocyclic ring which may have a substituent. Specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R ¹ and R ² in the general formula (7). Or the same as those exemplified in the above description of R ³ .
Among these, preferable A includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and particularly preferable A includes an aryl group having an amino group.

  Next, Y in the general formula (7) will be described. Y represents a nonmetallic atomic group necessary for forming a heterocyclic ring in cooperation with the above-mentioned A and adjacent carbon atoms. Examples of such a heterocyclic ring include 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocyclic rings that may have a condensed ring, and preferably 5- or 6-membered heterocyclic rings.

Examples of nitrogen-containing heterocycles include, for example, LG Brooker et al., Journal of American Chemical Society, Vol. 73 (1951), p. Any of those known to constitute a basic nucleus in merocyanine dyes described in 5326-5358 and references can be suitably used.
Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, 4,5-di (2-furyl) thiazole, etc.), benzothiazoles (eg, benzothiazole, 4-chlorobenzothiazole, 5-chloro Benzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole 4-methoxybenzo Azole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2 ] Thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [ , 2] thiazole, etc.), thianaphtheno-7 ′, 6 ′, 4,5-thiazole (for example, 4′-methoxythianaphtheno-7 ′, 6 ′, 4,5-thiazole, etc.), oxazole ( For example, 4-methyl oxazole, 5-methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole, 4,5-dimethyl oxazole, 5-phenyl oxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzo Oxazole, 4-ethoxybe Nzooxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.),

Naphthoxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (eg, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles ( For example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazoles (for example, naphtho [1,2] selenazole, Naphtho [2,1] selenazole, etc.], thiazolines (for example, thiazoline, 4-methylthiazoline, 4,5-dimethylthiazoline, 4-phenylthiazoline, 4,5-di (2-furyl) thiazoline, 4,5 -Diphenylthiazoline, 4,5-di (p-methoxyphenyl) thi Zoline, etc.), 2-quinolines (for example, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6- Ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), 4-quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, Isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (eg, isoquinoline, etc.), benzimidazoles (eg, 1,3-dimethylbenzimidazole, 1,3-diethylbenzimidazole, 1-ethyl-3) -Phenylbenzimidazole, etc.), 3,3-dialkylin Renins (for example, 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.), 2-pyridines (for example, pyridine, 5-methylpyridine, Etc.), 4-pyridine (for example, pyridine etc.) and the like. Moreover, the substituents of these rings may combine to form a ring.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.
Specific examples include benzodithiols (for example, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (for example, naphtho [1,2] dithiol, naphtho [2,1 Dithiols, etc.), dithiols (for example, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonyldithiols, 4,5-diethoxycarbonyldithiols) 4,5-ditrifluoromethyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyldithiol, etc.).

  Among the examples of the nitrogen-containing or sulfur-containing heterocyclic ring formed by Y in cooperation with the above-described A and the adjacent carbon atom in the general formula (7) described above, the partial structural formula of the following general formula (8) The dye having the structure represented is particularly preferable because it gives a photosensitive composition having high sensitizing ability and extremely excellent storage stability.

In General Formula (8), A represents an aromatic ring or a heterocyclic ring which may have a substituent, and X represents an oxygen atom, a sulfur atom, or —N (R ¹ ) —. R ¹ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and A and R ¹ , R ⁴ , R ⁵ and R ⁶ are bonded to each other. Can form an aliphatic or aromatic ring.
In the general formula (8), A and R ¹ are the same as in the general formula (7), R ⁴ and R ² in the general formula (7), and R ³ R ⁵ in the general formula (7), R ⁶ has the same meaning as R ¹ in formula (7).

  The compound represented by the general formula (7) is more preferably a compound represented by the following general formula (9).

In General Formula (9), A represents an aromatic ring or a heterocyclic ring which may have a substituent, and X represents an oxygen atom, a sulfur atom, or —N (R ¹ ) —. R ¹ , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ¹ , R ⁴ and R ⁵ are each aliphatic or aromatic. Can be linked to form a ring. Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the substituent on the Ar skeleton needs to have a sum of Hammett values greater than zero. Here, the sum of the Hammett values is greater than 0 means that the substituent has one substituent, and the Hammett value of the substituent may be greater than 0, and has a plurality of substituents. The sum of Hammett values at may be greater than zero.

In the general formula (9), A and R ¹ have the same meanings as those in formula (7), R ⁴ is formula and R ² in (7), R ⁵ is the same meaning as R ³ in the general formula (7) It is. Ar represents an aromatic ring or a heterocyclic ring having a substituent, and specific examples thereof include an aromatic ring or a heterocyclic ring having a substituent among those previously described in the description of A in the general formula (7). The specific example which concerns is mentioned similarly. However, as a substituent that can be introduced into Ar in the general formula (9), it is essential that the sum of Hammett values is 0 or more. Examples of such a substituent include a trifluoromethyl group and a carbonyl group. , Ester groups, halogen atoms, nitro groups, cyano groups, sulfoxide groups, amide groups, carboxy groups, and the like. The Hammett values of these substituents are shown below. Trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), carbonyl group (eg, —COH, m: 0.36, p: 0.43), ester group (—COOCH ₃ , m : 0.37, p: 0.45), halogen atom (for example, Cl, m: 0.37, p: 0.23), cyano group (-CN, m: 0.56, p: 0.66), A sulfoxide group (for example, —SOCH ₃ , m: 0.52, p: 0.45), an amide group (for example, —NHCOCH ₃ , m: 0.21, p: 0.00), a carboxy group (—COOH, m: 0.37, p: 0.45) and the like. The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is. Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

  Although the preferable specific example (Exemplary compound D1-Exemplary compound D57) of the sensitizing dye represented by General formula (7) below is shown, this invention is not limited to these. Of these, compounds corresponding to the compound represented by the general formula (8) are exemplified compounds D2, D6, D10, D18, D21, D28, D31, D33, D35, D38, D41 and D45 to D57. is there.

A method for synthesizing the compound represented by the general formula (7) will be described.
The compound represented by the general formula (7) is usually obtained by a condensation reaction between an acidic nucleus having an active methylene group and a substituted or unsubstituted aromatic ring or heterocyclic ring. These compounds are described in JP-B-59-28329. And can be synthesized. For example, as shown in the following reaction formula (I), a synthesis method using a condensation reaction of an acidic nucleus compound and a basic nucleus material having an aldehyde group or a carbonyl group on the heterocyclic ring can be mentioned. The condensation reaction is carried out in the presence of a base (Base) as necessary. As the base, generally used ones such as amines, pyridines (trialkylamine, dimethylaminopyridine, diazabicycloundecene DBU, etc.), metal amides (lithium diisopropylamide, etc.), metal alkoxides ( Sodium methoxide, potassium-t-butoxide, etc.) and metal hydrides (sodium hydride, potassium hydride, etc.) can be used without limitation.

Further, as another desirable synthesis method, a method according to the following reaction formula (II) may be mentioned. That is, as an acidic nucleus compound in the reaction formula (I), an acid nucleus compound in which Y is a sulfur atom is used as a starting material, and a dye precursor is obtained by a condensation reaction of a basic nucleus material having an aldehyde group or a carbonyl group on a heterocyclic ring. The process up to the step of synthesizing the product is carried out in the same manner as in the above reaction formula (I), and then the dye precursor is further reacted with a sulfur atom to form a metal sulfide and a metal salt and water. This is a reaction in which a secondary amine compound (R—NH _2, where R represents a monovalent nonmetallic atomic group) is allowed to act.
Among these, the reaction represented by the reaction formula (II) has a high yield of each reaction and is particularly preferable in terms of synthesis efficiency. In particular, this reaction is used when synthesizing the compound represented by the general formula (8). The reaction represented by formula (II) is useful.

In the reaction formula (II), M ^{n +} X _n represents a metal salt that can form a metal sulfide by chemically interacting with the sulfur atom of the thiocarbonyl group. As specific compounds, for example, M is Al, Au, Ag, Hg, Cu, Zn, Fe, Cd, Cr, Co, Ce, Bi, Mn, Mo, Ga, Ni, Pd, Pt, Ru, Rh. , Sc, Sb, Sr, Mg, Ti, etc., and X is F, Cl, Br, I, NO ₃ , SO ₄ , NO ₂ , PO ₄ , CH ₃ CO _2, etc., AgBr, AgI, AgF, AgO, AgCl, Ag ₂ O, Ag (NO ₃ ), AgSO ₄ , AgNO ₂ , Ag ₂ CrO ₄ , Ag ₃ PO ₄ , Hg ₂ (NO ₃ ) ₂ , HgBr ₂ , Hg ₂ Br ₂ , HgO, HgI ₂ , Hg (NO ₃ ) ₂ , Hg (NO ₂ ) ₂ , HgBr ₂ , HgSO ₄ , Hg ₂ I ₂ , Hg ₂ SO ₄ , Hg (CH ₃ CO ₂ ) ₂ , AuBr, AuBr ₃ , AuI, AuI ₃ , _{auF 3, Au 2 O 3,} AuCl, AuC1 3, CuCl, C _{I, CuI 2, CuF 2,} CuO, CuO 2, Cu (NO 3) 2, CuSO 4, Cu 3 (PO 4) 2 of such compounds. Among these, a silver salt can be used as the most preferable metal salt in that it easily interacts with a sulfur atom.

The sensitizing dye represented by the general formula (7) used in the present invention can be further subjected to various chemical modifications for improving the characteristics of the photosensitive layer. For example, sensitizing dye and addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) are bonded by a method such as covalent bond, ionic bond, hydrogen bond, etc. Unnecessary precipitation suppression of the dye from the subsequent film can be performed.
Further, a partial structure having a radical generating ability in a sensitizing dye and a radical polymerization initiator described later (for example, reductive decomposable sites such as alkyl halide, onium, peroxide, biimidazole, borate, amine, trimethylsilylmethyl, The photosensitivity can be remarkably enhanced particularly in a state where the concentration of the starting system is low due to the coupling with oxidatively cleavable sites such as carboxymethyl, carbonyl, imine and the like.

Furthermore, when the photosensitive composition of the present invention is used as a photosensitive layer of a lithographic printing plate precursor which is a preferred mode of use, it is hydrophilic for the purpose of enhancing the suitability for processing in an alkaline or aqueous developer. It is effective to introduce a functional moiety (carboxy group and its ester, sulfo group and its ester, ethylene oxide group or other acid group or polar group). In particular, ester-type hydrophilic groups have a relatively hydrophobic structure in the photosensitive layer, so that they have excellent compatibility, and in the developer, acid groups are generated by hydrolysis, resulting in increased hydrophilicity. Have.
In addition, for example, a substituent can be appropriately introduced in order to improve compatibility in the photosensitive layer and to suppress crystal precipitation. For example, in certain types of photosensitive systems, unsaturated bonds such as aryl groups and allyl groups may be very effective in improving compatibility. By introducing an obstacle, crystal precipitation can be remarkably suppressed. In addition, by introducing a phosphonic acid group, an epoxy group, a trialkoxysilyl group, or the like, adhesion to an inorganic substance such as a metal or a metal oxide can be improved. In addition, a method such as polymerization of a sensitizing dye can be used depending on the purpose.

As the sensitizing dye used in the present invention, it is preferable to use at least one sensitizing dye represented by the general formula (7). As long as it is represented by the general formula (7), for example, the modification described above The details of the usage, such as what kind of structure is used, such as those that have been used, whether they are used alone or in combination of two or more, and how much is added, match the performance design of the final photosensitive material Can be set as appropriate. For example, the compatibility with the photosensitive layer can be increased by using two or more sensitizing dyes in combination.
In selecting the sensitizing dye, in addition to the photosensitivity, the molar extinction coefficient at the emission wavelength of the light source used is an important factor. By using a dye having a large molar extinction coefficient, the amount of the dye added can be made relatively small, which is economical and advantageous from the viewpoint of film properties of the photosensitive layer.
In the present invention, not only the sensitizing dye represented by the general formula (7) but also other general-purpose sensitizing dyes can be used as long as the effects of the present invention are not impaired.

Since the photosensitivity and resolution of the photosensitive layer and the physical properties of the exposure film are greatly affected by the absorbance at the light source wavelength, the addition amount of the sensitizing dye is appropriately selected in consideration of these. For example, the sensitivity decreases in a low region where the absorbance is 0.1 or less. Also, the resolution becomes low due to the influence of halation. However, for the purpose of curing a thick film of, for example, 5 μm or more, there is a case where such a low absorbance can be increased instead. In the region where the absorbance is 3 or more, most of the light is absorbed on the surface of the photosensitive layer, and the internal curing is inhibited. For example, when used as a printing plate, the film strength and the substrate adhesion are poor. It will be insufficient.
For example, when the composition of the present invention is used in the photosensitive layer of a lithographic printing plate precursor using a relatively thin film thickness, the addition amount of the sensitizing dye is such that the absorbance of the photosensitive layer is 0.1 to 1.5. Is preferably set to be in the range of 0.25 to 1. Since the absorbance is determined by the addition amount of the sensitizing dye and the thickness of the photosensitive layer, the predetermined absorbance can be obtained by controlling both conditions. The absorbance of the photosensitive layer can be measured by a conventional method. As a measuring method, for example, on a transparent or white support, a photosensitive layer having a thickness appropriately determined in a range where the coating amount after drying is necessary for a lithographic printing plate is formed, and a transmission type optical densitometer is used. Examples thereof include a method of measuring, a method of forming a photosensitive layer on a reflective support such as aluminum, and measuring a reflection density.
When the composition of the present invention is used as a photosensitive layer of a lithographic printing plate precursor, the addition amount of the sensitizing dye is usually 0.05 to 30 mass with respect to 100 parts by mass of all solid components constituting the photosensitive layer. Parts, preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass.

(A2) Infrared absorber In the present invention, an infrared absorber is usually used when exposure using a laser emitting infrared rays of 760 to 1,200 nm as a light source is performed. The infrared absorber has a function of converting the absorbed infrared light into heat and a function of being excited by the infrared light and transferring electrons and / or energy to a radical polymerization initiator described later. The infrared absorber used in the present invention is a dye or pigment having an absorption maximum at a wavelength of 760 to 1200 nm.

As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.
Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-60-78787, JP-A-58-173696, 58-181690, JP-A-58-194595, etc., methine dyes, JP-A-58-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59- No. 73996, JP-A-60-52940, JP-A-60-63744 and the like, Naphthoquinone dyes described in JP-A-58-112792, etc., British Patent 434,875 And cyanine dyes.

Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. . Moreover, as another example preferable as a dye, the near-infrared absorptive dye described as the formula (I) and (II) in US Patent 4,756,993 can be mentioned.
Other preferable examples of the infrared absorbing dye of the present invention include specific indolenine cyanine dyes described in JP-A-2002-278057 as exemplified below.

  Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and particularly preferred examples include cyanine dyes represented by the following general formulas (a) to (e).

In formula (a), X ¹ represents a hydrogen atom, a halogen atom, -NPh ^_2, -X ₂ -L ¹ or a group shown below. Here, X ² represents an oxygen atom, a nitrogen atom, or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or 1 to 1 carbon atom containing a hetero atom. 12 hydrocarbon groups are shown. In addition, a hetero atom here shows N, S, O, a halogen atom, and Se. Xa ^- the Za described later ^- is defined as for, R ^a represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom.

R ¹ and R ² each independently represents a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the photosensitive layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxy groups, and sulfo groups. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred. Za ⁻ represents a counter anion. However, when the cyanine dye represented by formula (a) has an anionic substituent in its structure and does not require charge neutralization, Za ^- is not necessary. Preferred Za ⁻ is a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, from the viewpoint of storage stability of the photosensitive layer coating solution. Hexafluorophosphate ion and aryl sulfonate ion.

  Specific examples of the cyanine dye represented by formula (a) that can be preferably used in the present invention include those exemplified below, and paragraph numbers [0017] to [0019] of JP-A No. 2001-133969. And those described in paragraph numbers [0012] to [0038] of JP-A No. 2002-023360 and paragraph numbers [0012] to [0023] of JP-A No. 2002-040638.

In the general formula (b), L represents a methine chain having 7 or more conjugated carbon atoms, the methine chain may have a substituent, and the substituents may be bonded to each other to form a ring structure. Good. Zb ⁺ represents a counter cation. Preferred counter cations include ammonium, iodonium, sulfonium, phosphonium, pyridinium, alkali metal cations (Na ⁺ , K ⁺ , Li ⁺ ) and the like. R ⁹ to R ¹⁴ and R ¹⁵ to R ²⁰ are each independently a hydrogen atom or a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, thio group, sulfonyl group, sulfinyl group, oxy group Or a substituent selected from amino groups, or a combination of two or three of these, and may be bonded to each other to form a ring structure. Here, in general formula (b), L represents a methine chain having 7 conjugated carbon atoms, and R ^{9 to} R ¹⁴ and R ^{15 to} R ²⁰ all represent hydrogen atoms are easily available. It is preferable from the viewpoint of effect.

  Specific examples of the dye represented by formula (b) that can be suitably used in the present invention include those exemplified below.

In the general formula (c), Y ³ and Y ⁴ each represent an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom. M represents a methine chain having 5 or more conjugated carbon atoms. R ^{21 to} R ²⁴ and R ^{25 to} R ²⁸ may be the same or different, and are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thiol group, Represents a group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group. Further, wherein Za ^- include a counter anion, Za in the general formula (a) ^- it is synonymous.

  In the present invention, specific examples of the dye represented by formula (c) that can be suitably used include those exemplified below.

In the general formula (d), R ²⁹ to R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ³³ and R ³⁴ each independently represents an alkyl group, a substituted oxy group, or a halogen atom. n and m each independently represents an integer of 0 to 4. R ²⁹ and R ³⁰ , or R ³¹ and R ³² may be combined to form a ring, and R ²⁹ and / or R ³⁰ is R ³³ and R ³¹ and / or R ³² is R ³⁴ taken together, may form a ring, further, when R ³³ or R ³⁴ there are a plurality, R ³³ or between R ³⁴ each other may be bonded to each other to form a ring. X ² and X ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of X ² and X ³ represents a hydrogen atom or an alkyl group. Q is a trimethine group or a pentamethine group which may have a substituent, and may form a ring structure together with a divalent organic group. Zc ⁻ represents a counter anion and has the same meaning as Za ⁻ in the general formula (a).

  In the present invention, specific examples of the dye represented by the general formula (d) that can be suitably used include those exemplified below.

In the general formula (e), R ³⁵ ~R ⁵⁰ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a hydroxy group, a carbonyl group, a thio group, a sulfonyl group, When a sulfinyl group, an oxy group, an amino group, or an onium salt structure is shown and a substituent can be introduced into these groups, it may have a substituent. M represents two hydrogen atoms or metal atoms, a halometal group, and an oxymetal group, and the metal atoms contained therein include IA, IIA, IIIB, IVB group atoms of the periodic table, first, second, second Examples include three-period transition metals and lanthanoid elements, among which copper, magnesium, iron, zinc, cobalt, aluminum, titanium, and vanadium are preferable.

  In the present invention, specific examples of the dye represented by formula (e) that can be suitably used include those exemplified below.

  Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Yokoshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm. When the particle diameter of the pigment is 0.01 μm or more, the stability of the dispersion in the photosensitive layer coating solution is increased, and when it is 10 μm or less, the uniformity of the photosensitive layer is improved.

  As a method for dispersing the pigment, a known dispersion technique used for ink production, toner production or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

These sensitizing dyes (A) such as infrared absorbers added to accelerate the curing of the composition are used when the composition of the present invention is applied as a photosensitive layer of a negative lithographic printing plate precursor. Alternatively, another layer such as an overcoat layer or an undercoat layer may be provided and added thereto. In particular, when the composition of the present invention is applied to the photosensitive layer of a negative photosensitive lithographic printing plate, these (A) sensitizing dyes have a wavelength of 760 nm to 1200 nm of the photosensitive layer from the viewpoint of sensitivity. The optical density at the absorption maximum in the range is preferably between 0.1 and 3.0. Since the optical density is determined by the amount of the infrared absorber added and the thickness of the photosensitive layer, the predetermined optical density can be obtained by controlling both conditions.
The optical density of the photosensitive layer can be measured by a conventional method. As a measuring method, for example, on a transparent or white support, a photosensitive layer having a thickness appropriately determined in a range where the coating amount after drying is necessary for a lithographic printing plate is formed, and a transmission type optical densitometer is used. Examples thereof include a method of measuring, a method of forming a photosensitive layer on a reflective support such as aluminum, and measuring a reflection density.

<(B) Radical polymerization initiator>
The (B) radical polymerization initiator used in the present invention is a compound that generates radicals by light, heat, or both, and initiates and accelerates polymerization of the polymerizable compound (C). As the radical polymerization initiator that can be used in the present invention, a known thermal polymerization initiator, a compound having a bond with a small bond dissociation energy, a photopolymerization initiator, and the like can be used.
Examples of the radical polymerization initiator in the present invention include (a) an organic halide, (b) a carbonyl compound, (c) an azo polymerization initiator, (d) an organic peroxide, (e) a metallocene compound, (f ) Azide compound, (g) hexaarylbiimidazole compound, (h) organic borate compound, (i) disulfone compound, (j) oxime ester compound, (k) onium salt compound.

  (A) Specific examples of organic halides include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A 48-36281, JP-A 55-32070, JP-A 60-239736, JP-A 61-169835, JP-A 61-169837, JP-A 62-58241, JP Sho 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and particularly preferable examples include oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  More preferred are s-triazine derivatives and oxadiazole derivatives to which at least one mono, di, or trihalogen-substituted methyl group is bonded. Specifically, for example, 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6- (Trichloromethyl) -s-triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-fluorophenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2,6-difluorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-biphenylyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-chloro-4-biphenylyl) -4,6 Bis (trichloromethyl) -s-triazine, 2- (p-cyanophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-acetylphenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-ethoxycarbonylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-phenoxycarbonylphenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-methylsulfonylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-dimethylsulfoniumphenyl) -4,6-bis (trichloromethyl) -s- Triazine tetrafluoroborate, 2- (2,4-difluorophenyl) -4,6-bis (trichloromethyl) -s-tria Gin, 2- (p-diethoxyphosphorylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [4- (4-hydroxyphenylcarbonylamino) phenyl] -4,6-bis (trichloro) Methyl) -s-triazine, 2- [4- (p-methoxyphenyl) -1,3-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis ( Trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4, 6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bi (Trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6 -Tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy -4,6-bis (tribromomethyl) -s-triazine, 2- (o-methoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 2- (3,4-epoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 2- [1-phenyl-2- (4-methoxyphenyl) vinyl] -5-trichloromethyl-1,3 4-oxadiazole, 2- (p-hydroxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 2- (3,4-dihydroxystyryl) -5-trichloromethyl-1,3 4-oxadiazole, 2- (pt-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole and the like.

  (B) Examples of the carbonyl compound include benzophenone, Michler ketone, 4,4′-bis (N, N-diethylamino) benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromo. Benzophenone derivatives such as benzophenone and 2-carboxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1- Hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-pro N-one, acetophenone derivatives such as 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone Thioxanthone derivatives such as 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  (C) As the azo compound, for example, an azo compound described in JP-A-8-108621 can be used.

  (D) Examples of the organic peroxide include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert -Butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5- Dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) Hexane, 2,5-oxanoyl Peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropylperoxide Oxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxyneodecanoate, tert-butylperoxyocta Noate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- ( t- Xylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogendiphthalate), carbonyldi (t-hexyl) Peroxydihydrogen diphthalate) and the like.

  (E) As metallocene compounds, JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705 Various titanocene compounds described in JP-A-5-83588, for example, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1- , Di-cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl , Di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pen Fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoro Phen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluoro-3- (pyrrol-1-yl) phen-1-yl, Examples thereof include iron-arene complexes described in 304453 and JP-A-1-152109.

(F) Examples of the azide compound include 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
(G) Examples of hexaarylbiimidazole compounds include JP-B-6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Various compounds described in the specification, specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o- Bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetrakis (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5 , 5'-tetraphenylbiimidazole, 2 , 2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′- Examples include tetraphenylbiimidazole and 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole.

  (H) Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, JP-A-9-188710, JP 2000-131837, JP 2002-107916, JP 2764769, JP 2002-116539, and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, and organic boron oxosulfonium complexes described in JP-A-6-157563, JP-A-175554, JP-A-6-1755 No. 3, an organoboron iodonium complex, an organoboron phosphonium complex described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, Specific examples include organoboron transition metal coordination complexes such as JP-A-7-306527 and JP-A-7-292014.

  (I) Examples of the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2003-328465.

  (J) Examples of the oxime ester compound include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, and JP-A 2000-80068. Specific examples thereof include compounds represented by the following structural formula.

  (K) Examples of the onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium salts described in Bal et al, Polymer, 21, 423 (1980), ammonium salts described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055 and 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, 2-150848, JP-A-2-296514, iodonium salts, European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297,442 U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,73 No. 4,444, 2,833,827, German Patent Nos. 2,904,626, 3,604,580, and 3,604,581 . V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

In particular, the above oxime ester compounds, diazonium salts, iodonium salts, and sulfonium salts are preferable in terms of reactivity and stability. In the present invention, these onium salts function not as acid generators but as ionic radical polymerization initiators.
Preferred onium salts for the present invention are onium salts represented by the following general formulas (RI-I) to (RI-III).

Formula (RI-I) in, Ar ¹¹ represents a 1-6 having unprotected aryl group having 20 or less carbon atoms is also a substituent, preferred examples of the substituent include an alkyl group having 1 to 12 carbon atoms, 1 to 4 carbon atoms -12 alkenyl group, C1-C12 alkynyl group, C1-C12 aryl group, C1-C12 alkoxy group, C1-C12 aryloxy group, halogen atom, C1-C12 An alkylamino group, a C1-C12 dialkylamino group, a C1-C12 alkylamide group or arylamide group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a C1-C12 thioalkyl group, A C1-C12 thioaryl group is mentioned. Z ^11- represents a monovalent anion, a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability From the viewpoint of the visibility of the printout image, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, and sulfinate ions are preferable.

In the formula (RI-II), Ar ²¹ and Ar ²² each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms. An alkyl group, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom , An alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, 1 carbon atom -12 thioalkyl group and C1-C12 thioaryl group are mentioned. Z ^21- represents a monovalent anion, a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability From the viewpoint of the visibility of the printout image, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferable.

In the formula (RI-III), R ³¹ , R ³² and R ³³ each independently represents an aryl group having 20 or less carbon atoms, an alkyl group, an alkenyl group or an alkynyl group which may have 1 to 6 substituents. In view of reactivity and stability, an aryl group is desirable. Preferred substituents are alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, C1-C12 aryloxy group, halogen atom, C1-C12 alkylamino group, C1-C12 dialkylamino group, C1-C12 alkylamide group or arylamide group, carbonyl group, carboxy group Group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ^31- represents a monovalent anion, which is a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, and is stable. From the viewpoint of visibility of the printout image, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferable, and more preferable are JP-A-2001-343742. And the carboxylate ions described in JP-A No. 2002-148790 are particularly preferable.

  Examples of onium salts that can be suitably used as radical polymerization initiators in the present invention will be given below, but the present invention is not limited thereto.

(B) The radical polymerization initiator is not limited to the above, but particularly from the viewpoint of reactivity and stability, (a) an organic halide, particularly, a triazine-based initiator included therein, (j) oxime Diazonium salts, iodonium salts, and sulfonium salts included in the ester compounds and (k) onium salt compounds are more preferable. From the viewpoint of spot-like stains, when an ionic compound is used, it is preferable to use a compound that does not contain halide ions. Among these radical polymerization initiators, from the viewpoint of improving the visibility of the printout image in combination with an infrared absorber, it is an onium salt and an inorganic anion such as PF ₆ ⁻ , BF as a counter ion. ₄ ^- such as those having preferred. Furthermore, diaryliodonium is preferred as the onium salt because of its excellent color development.

These (B) radical polymerization initiators may be used alone or in combination of two or more.
(B) The radical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 0.8 to 20% by mass with respect to the total solid content constituting the photosensitive layer. Can be added at a ratio of Within this range, good sensitivity and good stain resistance of the non-image area during printing can be obtained.
Moreover, these (B) radical polymerization initiators may be added to the same layer as other components, or another layer may be provided in the photosensitive layer or adjacent thereto and added thereto.

<(C) Polymerizable compound>
The polymerizable compound (C) that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably two or more. It is chosen from the compound which has. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.

  Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group with monofunctional or polyfunctional alcohols, amines or thiols. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and 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, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 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-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxy group are also suitable. Specific examples of such compounds are described in, for example, Japanese Patent Publication No. 48-41708. Containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxy group represented by the following general formula (m1) to a polyisocyanate compound having two or more isocyanate groups in the molecule A vinyl urethane compound etc. are mentioned.

CH ₂ = C (R ¹⁹ ) COOCH ₂ CH (R ²⁰ ) OH General formula (m1)
(However, R ¹⁹ and R ²⁰ each represent H or CH _3. )

  Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 And urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the case, it is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and acrylic acid or methacrylic acid described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. In addition, JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, specific unsaturated compounds described in each publication, vinylphosphonic acid compounds described in JP-A-2-25493, and the like are also included. Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984) as photocurable monomers and oligomers can also be used.

About these addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final planographic printing plate precursor. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image portion, that is, the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether). It is also effective to adjust both sensitivity and strength by using a compound of the type).
In addition, the selection and use of the addition polymerization compound is also an important factor for compatibility and dispersibility with other components in the photosensitive layer (for example, binder polymer, radical polymerization initiator, colorant, etc.). For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion of the support or the protective layer described later.

In the present invention, the polymerizable compound (C) is preferably used in the range of 5 to 80% by mass, more preferably 25 to 75% by mass with respect to the non-volatile component in the photosensitive layer.
In addition, the use method of the addition polymerizable compound can arbitrarily select an appropriate structure, blending, and addition amount from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration / coating method such as undercoating or overcoating can be carried out.

  The photosensitive layer of the present invention can contain the following components as required.

<(D) Hydrophobized precursor>
The hydrophobizing precursor in the present invention means fine particles capable of converting the photosensitive layer to hydrophobic when heat is applied. The fine particles are preferably at least one particle selected from hydrophobic thermoplastic polymer fine particles, heat-reactive polymer fine particles, microcapsules enclosing a hydrophobic compound, and microgel.

Hydrophobic thermoplastic polymer fine particles include Research Disclosure No. 1 of January 1992. 33303, hydrophobic thermoplastic polymer fine particles described in JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250 and European Patent No. 931647 are suitable. Can be cited as
Specific examples of the polymer constituting such polymer fine particles include homopolymers of monomers such as ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, and vinylcarbazole. Mention may be made of polymers or copolymers or mixtures thereof. Among them, more preferred are polystyrene and polymethyl methacrylate.

The average particle diameter of the hydrophobic thermoplastic polymer fine particles used in the present invention is preferably 0.01 to 2.0 μm.
Examples of the method for synthesizing hydrophobic thermoplastic polymer fine particles having the above-mentioned particle size that can be used as a hydrophobizing precursor include an emulsion polymerization method and a suspension polymerization method. In addition, these compounds are dissolved in a water-insoluble organic solvent. There is a method (solution-dispersion method) in which this is mixed and emulsified with an aqueous solution containing a dispersant, and further heated to solidify into fine particles while flying off the organic solvent.

  Examples of the heat-reactive polymer fine particles used in the present invention include polymer fine particles having a heat-reactive group, and these form a hydrophobized region by cross-linking by a heat reaction and a functional group change at that time.

  The thermally reactive group in the polymer fine particle having a thermally reactive group used in the present invention may be any functional group that performs a reaction as long as a chemical bond is formed, but is an ethylenically unsaturated group that performs a radical polymerization reaction. Group (for example, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.), cationically polymerizable group (for example, vinyl group, vinyloxy group, etc.), isocyanate group that performs addition reaction or its block, epoxy group, vinyloxy group And a functional group having an active hydrogen atom as a reaction partner thereof (for example, an amino group, a hydroxy group, a carboxy group, etc.), a carboxy group for performing a condensation reaction, a hydroxy group or an amino group as a reaction partner, a ring-opening addition reaction Examples of preferred acid anhydrides and reaction partners are amino groups or hydroxy groups. It is possible.

Introduction of these functional groups into the polymer fine particles may be performed at the time of polymerization, or may be performed using a polymer reaction after the polymerization.
When introduced at the time of polymerization, the monomer having the above functional group is preferably subjected to emulsion polymerization or suspension polymerization. Specific examples of the monomer having the above functional group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, 2- (vinyloxy) ethyl methacrylate, p-vinyloxystyrene, p- {2- (vinyloxy) ethyl} styrene, Block isocyanate with glycidyl methacrylate, glycidyl acrylate, 2-isocyanatoethyl methacrylate or alcohol thereof, block isocyanate with 2-isocyanatoethyl acrylate or alcohol, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 2- Hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, maleic anhydride, bifunctional acrylate, Such as functional methacrylates include, but are not limited to.

  In the present invention, a copolymer of these monomers and a monomer that is copolymerizable with these monomers and does not have a thermally reactive group can also be used. Examples of the copolymer monomer having no heat-reactive group include styrene, alkyl acrylate, alkyl methacrylate, acrylonitrile, vinyl acetate, and the like. It is not limited to.

  Examples of the polymer reaction used when the introduction of the thermally reactive group is carried out after polymerization include the polymer reaction described in International Publication No. 96/34316 pamphlet.

  Among the polymer fine particles having a heat-reactive group, those in which the polymer fine particles are coalesced by heat are preferable, and those having a hydrophilic surface and being dispersed in water are particularly preferable. The coating contact angle (water droplets) produced by applying only polymer fine particles and drying at a temperature lower than the solidification temperature is higher than the contact angle (water droplets) produced by drying at a temperature higher than the solidification temperature. It is preferable to lower. In order to make the surface of the polymer fine particles hydrophilic in this manner, a hydrophilic polymer or oligomer such as polyvinyl alcohol or polyethylene glycol or a hydrophilic low molecular weight compound may be adsorbed on the surface of the polymer fine particles. However, the surface hydrophilization method is not limited to this.

  The solidification temperature of the polymer fine particles having these thermoreactive groups is preferably 70 ° C. or higher, but more preferably 100 ° C. or higher in view of the stability over time. The average particle size of the polymer fine particles is preferably 0.01 to 2.0 μm, more preferably 0.05 to 2.0 μm, and most preferably 0.1 to 1.0 μm. Within this range, good resolution and stability over time can be obtained.

  As the microcapsules used in the present invention, for example, as described in JP-A Nos. 2001-277740 and 2001-277742, the constituent components of the photosensitive layer (the components (A) to (C) described above) are used. All or part of them are encapsulated in microcapsules. The constituent components of the photosensitive layer can also be contained outside the microcapsules. Furthermore, it is preferable that the photosensitive layer containing the microcapsule includes a hydrophobic constituent component in the microcapsule and a hydrophilic constituent component outside the microcapsule.

  In this invention, the aspect containing a crosslinked resin particle, ie, a microgel, may be sufficient. This microgel can contain a part of the above-mentioned (A) to (C) in and / or on the surface thereof. In particular, the microgel has (C) a polymerizable compound on the surface thereof to form a reactive microgel. This aspect is particularly preferable from the viewpoints of image formation sensitivity and printing durability.

  As a method for microencapsulating or microgelling the constituent components of the photosensitive layer, known methods can be applied.

  For example, as a method for producing a microcapsule, US Pat. No. 2,800,547, US Pat. No. 2,800,498, a method using coacervation, US Pat. No. 3,287,154, Japanese Patent Publication No. 38-19574, 42-446 by the interfacial polymerization method, U.S. Pat. Nos. 3,418,250 and 3,660,304, by precipitation of polymers, and U.S. Pat. No. 3,796,669. Urea-formaldehyde found in US Pat. No. 3,914,511, US Pat. No. 3,914,511, US Pat. No. 3,914,511, US Pat. No. 4,087,376 and US Pat. No. 4,089,802. System or urea formaldehyde-resorcino A method using a wall-based wall forming material, a method using a wall material such as melamine-formaldehyde resin and hydroxycellulose, as described in US Pat. No. 4,025,445, and Japanese Patent Publication Nos. 36-9163 and 51-9079. In situ method by monomer polymerization, spraying method found in British Patent No. 930422, US Pat. No. 3,111,407, electrolytic dispersion cooling method seen in British Patent Nos. 952807 and 967074 However, it is not limited to these.

  A preferable microcapsule wall used in the present invention has a three-dimensional cross-linking and has a property of swelling with a solvent. From such a viewpoint, the wall material of the microcapsule is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, and a mixture thereof, and particularly preferably polyurea and polyurethane. Moreover, you may introduce | transduce into the microcapsule wall the compound which has crosslinkable functional groups, such as an ethylenically unsaturated bond which can be introduce | transduced into the above-mentioned curable polymer compound.

On the other hand, as a method for preparing the microgel, granulation by interfacial polymerization described in JP-B-38-19574 and JP-A-42-446, as described in JP-A-5-61214, etc. It is possible to utilize granulation by non-aqueous dispersion polymerization. However, it is not limited to these methods.
As the method using the interfacial polymerization, the above-described known microcapsule production method can be applied.

  Preferred microgels used in the present invention are those granulated by interfacial polymerization and having three-dimensional crosslinking. From such a viewpoint, the material to be used is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, and a mixture thereof, and polyurea and polyurethane are particularly preferable.

  The average particle size of the microcapsules or microgel is preferably 0.01 to 3.0 μm. 0.05-2.0 micrometers is further more preferable, and 0.10-1.0 micrometer is especially preferable. Within this range, good resolution and stability over time can be obtained.

  The content of the hydrophobized precursor is preferably in the range of 5 to 90% by mass in terms of solid content.

<Other ingredients>
The photosensitive layer in the present invention may further contain other components as required. When the component used is a cationic compound, it is preferable to use a compound that does not contain a halide ion as a counter ion.
Hereinafter, other components used in the photosensitive layer of the present invention will be described.

(1) Surfactant A surfactant can be used for the photosensitive layer in the invention in order to improve the coated surface state.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants. Among these, fluorosurfactants are preferable.

  Examples of the fluorosurfactant include a fluorosurfactant containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. Moreover, the fluorine-type surfactant described in each gazette of Unexamined-Japanese-Patent No. 62-170950, 62-226143, and 60-168144 is also mentioned suitably.

Surfactant can be used individually or in combination of 2 or more types.
When halide ions are contained as impurities or counter ions in the surfactant, it is preferable to remove or exchange with other anions by a method such as desalting or ion exchange.
The content of the surfactant is preferably 0.001 to 10% by mass and more preferably 0.01 to 5% by mass with respect to the total solid content of the photosensitive layer.

(2) Colorant In the photosensitive layer according to the invention, a dye having a large absorption in the visible light region can be used as an image colorant. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientated chemistry) Kogyo Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI522015), etc. And dyes described in No. 293247. Also, pigments such as phthalocyanine pigments, azo pigments, carbon black, titanium oxide, etc. can be suitably used.
When these colorants are used, it is easy to distinguish between an image area after image formation and a non-image area, so it is preferable to add them.
The amount added is 0.01 to 10% by mass with respect to the total solid content of the photosensitive layer.

(3) Print-out agent To the photosensitive layer in the invention, a compound that changes color by an acid or a radical can be added in order to produce a print-out image.
As such a compound, for example, various dyes such as diphenylmethane, triphenylmethane, thiazine, oxazine, xanthene, anthraquinone, iminoquinone, azo, and azomethine are effectively used.

  Specific examples include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo Fred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue BOH [manufactured by Hodogaya Chemical Co., Ltd.], Oil Blue # 603 [Orient Chemical Industry Co., Ltd.], Oil Pink # 312 [Orient Chemical Co., Ltd.], Oil Red 5B [Orient Chemical Co., Ltd.], Oil Scarlet # 308 [Orient Gaku Kogyo Co., Ltd.], Oil Red OG [Orient Chemical Co., Ltd.], Oil Red RR [Orient Chemical Co., Ltd.], Oil Green # 502 [Orient Chemical Co., Ltd.], Spiron Red BEH Special [made by Hodogaya Chemical Co., Ltd.], m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p- Diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4- - dyes and p of diethylamino phenyl imino-5-pyrazolone, p ', p "- hexamethyl triamnotriphenylmethane (leuco crystal violet), and a leuco dye such as Pergascript Blue SRB (manufactured by Ciba-Geigy).

  In addition to the above, a leuco dye known as a material for thermal paper or pressure-sensitive paper is also suitable. Specific examples include crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2- (N-phenyl-N-methylamino) -6- (Np-tolyl-N-ethyl) amino-fluorane, 2-anilino. -3-methyl-6- (N-ethyl-p-toluidino) fluorane, 3,6-dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) ) -Fluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane, 3 -(N, N-diethylamino) -6-methyl-7-xylidinofluorane, 3- (N, N-diethylamino) -6-methyl-7-chloro Fluorane, 3- (N, N-diethylamino) -6-methoxy-7-aminofluorane, 3- (N, N-diethylamino) -7- (4-chloroanilino) fluorane, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-diethylamino) -7,8-benzofluorane, 3- (N, N-dibutyl) Amino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-n-butyl- -Methylindol-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl- 2-methylindol-3-yl) -4-zaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, and the like.

  A suitable addition amount of the dye that changes color by an acid or a radical is preferably 0.01 to 10% by mass with respect to the solid content of the photosensitive layer.

(4) Polymerization inhibitor A small amount of a thermal polymerization inhibitor is added to the photosensitive layer in the invention in order to prevent unnecessary thermal polymerization of the polymerizable compound (C) during the production or storage of the photosensitive layer. Is preferred.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- (Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and N-nitroso-N-phenylhydroxylamine aluminum salt are preferred.
The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the photosensitive layer.

(5) Higher fatty acid derivative, etc. In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the photosensitive layer in the present invention, and in the drying process after coating. It may be unevenly distributed on the surface of the photosensitive layer.
The amount of the higher fatty acid derivative added is preferably from about 0.1 to about 10% by weight based on the total solid content of the photosensitive layer.

(6) Plasticizer The photosensitive layer in the invention may contain a plasticizer in order to improve the on-press developability.
Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diallyl phthalate; Glycol esters such as glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicaprylate; Phosphate esters such as tricresyl phosphate and triphenyl phosphate Diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioct Ruazereto, aliphatic dibasic acid esters such as dibutyl maleate; polyglycidyl methacrylate, triethyl citrate, glycerin triacetyl ester, butyl laurate in.
The plasticizer content is preferably about 30% by mass or less based on the total solid content of the photosensitive layer.

(7) Inorganic fine particles The photosensitive layer according to the invention may contain inorganic fine particles in order to improve the cured film strength and the on-press developability.
Suitable inorganic fine particles include, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof. These can be used for strengthening the film, enhancing interfacial adhesion by surface roughening, and the like.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 μm to 3 μm. Within the above range, it is possible to form a non-image portion excellent in hydrophilicity that is stably dispersed in the photosensitive layer, sufficiently retains the film strength of the photosensitive layer, and does not easily cause stains during printing.
The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 40% by mass or less, and more preferably 30% by mass or less, based on the total solid content of the photosensitive layer.

(8) Low molecular weight hydrophilic compound The photosensitive layer in the invention may contain a low molecular weight hydrophilic compound because it improves the on-press developability without decreasing the printing durability.
Examples of the low molecular weight hydrophilic compound include water-soluble organic compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like, and ether or ester derivatives thereof, glycerin, Polyhydroxys such as pentaerythritol and tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine and diethanolamine monoethanolamine and salts thereof, organic sulfones such as alkylsulfonic acid, toluenesulfonic acid and benzenesulfonic acid Acids and salts thereof, organic sulfamic acids such as alkylsulfamic acid and salts thereof, organic sulfates such as alkylsulfuric acid and alkylethersulfuric acid and salts thereof, Organic phosphonic acids and their salts such as Ruhosuhon acid, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, organic carboxylic acids and salts thereof such as amino acids, betaine compounds, and the like.
Among these, organic sulfonic acids, organic sulfamic acids, organic sulfates such as sodium salts and lithium salts of organic sulfates, and betaine compounds are preferably used.

  Specific examples of organic sulfonates include sodium normal butyl sulfonate, sodium isobutyl sulfonate, sodium sec-butyl sulfonate, sodium tert-butyl sulfonate, sodium normal pentyl sulfonate, and sodium 1-ethylpropyl sulfonate. , Sodium normal hexyl sulfonate, sodium 1,2-dimethylpropyl sulfonate, sodium 2-ethylbutyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium cyclohexyl sulfonate, sodium normal heptyl sulfonate, sodium normal octyl sulfonate, tert -Sodium octyl sulfonate, sodium normal nonyl sulfonate, sodium allyl sulfonate, 2-methylallyl sulfonic acid Thorium, sodium 4- [2- (2-butyloxy-ethoxy) -ethoxy] -butane-1-sulfonate, sodium 4- [2- (2-hexyloxy-ethoxy) -ethoxy] -butane-1-sulfonate 4- {2- [2- (2-ethyl) hexyloxy-ethoxy] -ethoxy} -butane-1-sulfonic acid sodium, 4- [2- (2-decyloxy-ethoxy) -ethoxy] -butane-1 Sodium sulfonate, 4- {2- [2- (2-butyloxy-ethoxy) -ethoxy] -ethoxy} -butane-1-sulfonic acid sodium, 4- [2- {2- [2- (2-ethyl) ) Hexyloxy-ethoxy] -ethoxy} -ethoxy] -butane-1-sulfonate, sodium benzenesulfonate, sodium p-toluenesulfonate , Sodium p-hydroxybenzenesulfonate, sodium p-styrenesulfonate, sodium dimethyl-5-sulfonate isophthalate, disodium 1,3-benzenedisulfonate, trisodium 1,3,5-benzenetrisulfonate, Sodium p-chlorobenzenesulfonate, sodium 3,4-dichlorobenzenesulfonate, sodium 1-naphthylsulfonate, sodium 2-naphthylsulfonate, sodium 4-hydroxynaphthylsulfonate, disodium 1,5-naphthalenedisulfonate, 2 , 6-Naphthalenedisulfonic acid disodium, 1,3,6-naphthalene trisulfonic acid trisodium, and lithium salt exchangers thereof.

  Specific examples of the organic sulfamate include sodium normal butyl sulfamate, sodium isobutyl sulfamate, sodium tert-butyl sulfamate, sodium normal pentyl sulfamate, sodium 1-ethylpropyl sulfamate, sodium normal hexyl sulfamate, Examples include sodium 1,2-dimethylpropylsulfamate, sodium 2-ethylbutylsulfamate, sodium cyclohexylsulfamate, and lithium salt exchangers thereof.

  These compounds have a small hydrophobic part structure and almost no surface-active action, and are clearly distinguished from the above-mentioned surfactants in which long-chain alkyl sulfonates and long-chain alkyl benzene sulfonates are used favorably. .

  As the organic sulfate, a compound represented by the following general formula (10) is particularly preferably used.

  In the general formula (10), R represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, m represents an integer of 1 to 4, and X represents sodium, potassium, or lithium. .

  R is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, or an aryl group having 20 or less carbon atoms. Can be mentioned. These groups may further have a substituent. In that case, examples of the substituent that can be introduced include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, and those having 1 to 12 carbon atoms. Examples include an alkenyl group, an alkynyl group having 1 to 12 carbon atoms, a halogen atom, and an aryl group having 20 or less carbon atoms.

  Preferred examples of the compound represented by the general formula (10) include sodium oxyethylene-2-ethylhexyl ether sulfate, sodium dioxyethylene-2-ethylhexyl ether sulfate, potassium dioxyethylene-2-ethylhexyl ether sulfate, dioxy Ethylene-2-ethylhexyl ether lithium sulfate, sodium trioxyethylene-2-ethylhexyl ether sulfate, sodium tetraoxyethylene-2-ethylhexyl ether sulfate, sodium dioxyethylene hexyl ether sulfate, sodium dioxyethylene octyl ether sulfate, dioxyethylene Examples include sodium lauryl ether sulfate. Of these, the most preferred compounds include sodium dioxyethylene-2-ethylhexyl ether sulfate, potassium dioxyethylene-2-ethylhexyl ether sulfate, and lithium dioxyethylene-2-ethylhexyl ether sulfate.

  The amount of the low molecular weight hydrophilic compound added to the photosensitive layer is preferably 0.5% by mass or more and 20% by mass or less of the total solid content of the photosensitive layer. More preferably, they are 1 mass% or more and 10 mass% or less, More preferably, they are 2 mass% or more and 8 mass% or less. In this range, good on-press developability and printing durability can be obtained.

  As the betaine compound, compounds represented by general formula (11) and general formula (12) are preferably used.

R ^{1 to} R ³ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group or an aryl group, and may be substituted with a hydroxy group or an amino group. Z represents an alkylene group having 1 to 4 carbon atoms, and may be substituted with a hydroxy group. At least two of R ^{1 to} R ³ and Z may be bonded to form a heterocyclic ring.

By containing these compounds in the photosensitive layer, it is possible to improve the on-press developability without reducing the printing durability. Among them, it is desirable R ¹ to R ³ is a heterocyclic 5-6 membered ring two are bonded alkyl group having 1 to 3 carbon atoms, or R ¹ to R ³ and Z,, in particular, R ¹ ~ quaternary ammonium skeleton R ³ is a methyl or ethyl group, or R ¹ to R ³ and two of pyrrolidine skeleton bonded to form a ring of Z,, piperidine skeleton, a pyridine skeleton, those having a imidazoline skeleton desirable.

Although the specific compound of the said General formula (11) is illustrated below, this invention is not limited to the following.

  Although the specific compound of the said General formula (12) is illustrated below, this invention is not limited to the following.

  Since these organic sulfonic acids, organic sulfamic acids, organic sulfates and betaine compounds have a small hydrophobic portion structure and almost no surface-active action, the fountain solution penetrates into the photosensitive layer exposed area (image area). The ink receptivity and printing durability of the photosensitive layer can be satisfactorily maintained without lowering the hydrophobicity and film strength of the image area.

The amount of the compound represented by formula (11) or (12) added to the photosensitive layer is preferably 0.1% by mass or more and 10% by mass or less of the total solid content of the photosensitive layer. More preferably, it is 0.2 mass% or more and 5 mass% or less, More preferably, it is 0.4 mass% or more and 2 mass% or less. Within these ranges, good on-press developability and printing durability can be obtained.
These low molecular weight hydrophilic compounds may be used alone or in combination of two or more.

(9) Grease-sensitizing agent When an inorganic layered compound is contained in the protective layer, which will be described later, in order to improve the inking property, the photosensitive layer is sensitive to phosphonium compounds, nitrogen-containing low molecular weight compounds, ammonium group-containing polymers, etc. An oiling agent can be used. Further, different types of sensitizers may be used in combination.
These compounds function as a surface coating agent (greasy sensitizer) for the inorganic layered compound, and prevent a decrease in the inking property during printing by the inorganic layered compound.

  Suitable phosphonium compounds include compounds represented by the following general formula (K1) described in JP-A-2006-297907 or the following general formula (K2) described in JP-A-2007-50660.

In Formula (K1), R ₁ ~R ₄ are each independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio Represents a group, a heterocyclic group or a hydrogen atom. At least two of R _{1 to} R ₄ may be bonded to form a ring. X ⁻ represents a counter anion.

In General Formula (K2), Ar _{1 to} Ar ₆ each independently represents an aryl group or a heterocyclic group, L represents a divalent linking group, X ⁿ⁻ represents an n-valent counter anion, and n Represents an integer of 1 to 3, and m represents a number satisfying n × m = 2. Here, as the aryl group, phenyl group, naphthyl group, tolyl group, xylyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, ethoxyphenyl group, dimethoxyphenyl group, methoxycarbonylphenyl group, dimethylaminophenyl A group and the like are preferable. Examples of the heterocyclic group include a pyridyl group, a quinolyl group, a pyrimidinyl group, a thienyl group, and a furyl group. L represents a divalent linking group. 6-15 are preferable and, as for carbon number in a coupling group, More preferably, it is a C6-C12 coupling group. Preferred examples of X ⁿ⁻ include halide anions such as Cl ⁻ , Br ⁻ and I ⁻ , toluenesulfonate, naphthalene-1,7-disulfonate, naphthalene-1,3,6-trisulfonate, and 5-benzoyl. Examples include sulfonate anions such as -4-hydroxy-2-methoxybenzene-4-sulfonate, carboxylate anions, sulfate anions, sulfate anions, PF ₆ ⁻ , BF ₄ ⁻ , and perchlorate anions. Of these, a sulfonate anion is particularly preferable.

  Specific examples of the phosphonium compound represented by the general formula (K1) or (K2) are shown below.

  In addition to the above-mentioned phosphonium compound, the following nitrogen-containing low molecular weight compounds can be mentioned as the sensitizers preferably used in the present invention. Preferred nitrogen-containing low molecular weight compounds include compounds having the structure of the following general formula (K3).

In the formula, R ^{1 to} R ⁴ each independently represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aryl group, aralkyl group, heterocyclic group or hydrogen atom. At least two of R ^{1 to} R ⁴ may be bonded to form a ring. X ⁻ is an anion, PF ₆ ⁻ , BF ₄ ⁻ , or an organic sulfone having a substituent selected from an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group, and a heterocyclic group Indicates an acid anion.

That the nitrogen-containing low molecular weight compound for use in the present invention include quaternary ammonium salts wherein at least one amine salt is a hydrogen atom R ¹ to R ^4, and R ¹ to R ⁴ is not any hydrogen atom . In addition, imidazolinium salts represented by the following general formula (K4), benzimidazolinium salts represented by the following general formula (K5), pyridinium salts represented by the following general formula (K6), and the following general formula (K7) The quinolinium salt structure may be used.

In the above formula, R ⁵ and R ^{6 each} represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aryl group, aralkyl group, heterocyclic group or hydrogen atom. X < ^- > is an anion and is synonymous with X < ^- > of the said general formula (K3).

  Among these, quaternary ammonium salts and pyridinium salts are preferably used. Specific examples thereof are shown below.

  The amount of the phosphonium compound or nitrogen-containing low molecular weight compound added to the photosensitive layer is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass based on the solid content of the photosensitive layer. % Is most preferred. Within these ranges, good ink fillability during printing can be obtained.

  As the sensitizer used in the present invention, the following ammonium group-containing polymers are also preferred. The ammonium group-containing polymer may be any polymer as long as it has an ammonium group in its structure, but is preferably a polymer containing structures of the following general formulas (K8) and (K9) as repeating units.

(Wherein R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group. R ² represents an alkylene group which may have a substituent, an alkyleneoxy group which may have a substituent, etc. R ³¹ , R ³² and R ³³ each independently represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group, X ⁻ represents F ⁻ , Cl ⁻ , Br ⁻ , I ^−. Benzenesulfonic acid anion, methyl sulfate anion, ethyl sulfate anion, propyl sulfate anion, butyl sulfate anion that may be branched, amyl sulfate anion that may be branched, PF ₆ ⁻ , BF _{4 ^{-, B (C 6 F 5}} ) 4 - is .R ⁴ represents an organic or inorganic anion such as an alkyl group having 1 to 21 carbon atoms, an aralkyl group, an aryl _{group, - (C 2 H 4 O} ) n - R ⁵ _{or, - (C 3 H 6 O} ) n -R 5 The stands, R ⁵ is .n represents a hydrogen atom, a methyl group or an ethyl group is 1 or 2.)

  The ammonium salt-containing polymer contains at least one structural unit represented by general formula (K8) and general formula (K9), but either one may be two or more, and both are 2 There may be more than species. Although the ratio of both structural units is not limited, The molar ratio is particularly preferably 5:95 to 80:20. Moreover, this polymer may contain another copolymerization component within the range which can ensure the effect of this invention.

  The ammonium salt-containing polymer has a reduced specific viscosity (unit: cSt / g / ml) determined by the following measurement method, preferably in the range of 5 to 120, more preferably in the range of 10 to 110. The range of 15-100 is especially preferable.

<Measurement method of reduced specific viscosity>
Weigh 3.33 g of 30% polymer solution (1 g as solid content) into a 20 ml volumetric flask and make up with N-methylpyrrolidone. This solution is put into an Ubbelohde reduced viscosity tube (viscosity constant = 0.010 cSt / s), and the time for flowing at 30 ° C. is measured. Time to pass (second) ") is calculated by the usual method.

The content of the ammonium salt-containing polymer is preferably 0.0005% by mass to 30.0% by mass, more preferably 0.001% by mass to 20.0% by mass with respect to the total solid content of the photosensitive layer, and 0.002 A mass% to 15.0 mass% is most preferred. Within this range, good inking properties can be obtained. The ammonium salt-containing polymer may be further contained in the protective layer.
Specific examples of the ammonium salt-containing polymer are shown below.

(10) Chain transfer agent The photosensitive layer according to the invention may contain a chain transfer agent. In particular, when the exposure light source is ultraviolet light or visible light and a sensitizing dye having an absorption peak at a wavelength of 350 to 850 nm is used, a chain transfer agent is preferably used.
Chain transfer agents contribute to sensitivity and storage stability. As the compound that acts as a chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals.

In the photosensitive layer of the present invention, in particular, a thiol compound (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) Can be preferably used as a chain transfer agent.
Moreover, the polyfunctional thiol compound which has a 2 or more mercapto group in 1 molecule can be used. Specific examples of the polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4-butanediol bis (3-mercaptopropionate), 1,4-butanediol bis (mercaptoacetate), ethylene glycol bis (mercaptoacetate). ), Ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoisobutyrate), penta Examples include erythritol tetrakis (mercaptoacetate) and pentaerythritol tetrakis (3-mercaptopropionate).

  Especially as a chain transfer agent, the thiol compound represented by following General formula (13) of Unexamined-Japanese-Patent No. 2006-091479 is used especially suitably. By using this thiol compound as a chain transfer agent, the problem of odor and sensitivity reduction due to evaporation from the photosensitive layer and diffusion to other layers are avoided, and it has excellent storage stability and high sensitivity and high printing durability. A lithographic printing plate precursor is obtained.

  In general formula (13), R represents an alkyl group which may have a substituent, or an aryl group which may have a substituent, and A represents a 5-membered ring having a carbon atom together with an N = CN moiety. Alternatively, it represents an atomic group that forms a 6-membered heterocyclic ring, and A may further have a substituent.

  More preferably, those represented by the following general formula (13A) or general formula (13B) are used.

  In general formula (13A) and formula (13B), R represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and X represents a halogen atom, an alkoxyl group or a substituent. The alkyl group which may have or the aryl group which may have a substituent is represented.

  Specific examples include 1-methyl-2-mercaptobenzimidazole, 1-propyl-2-mercaptobenzimidazole, 1-hexyl-2-mercaptobenzimidazole, 1-hexyl-2-mercapto-5-chlorobenzimidazole. 1-pentyl-2-mercaptobenzimidazole, 1-octyl-2-mercaptobenzimidazole, 1-octyl-2-mercapto-5-methoxybenzimidazole, 1-cyclohexyl-2-mercaptobenzimidazole, 1-phenyl-2 -Mercaptobenzimidazole, 1-phenyl-2-mercapto-5-methylsulfonylbenzimidazole, 1- (p-tolyl) -2-mercaptobenzimidazole, 1-methoxyethyl-2-mercaptobenzimidazole, 1- Til-2-mercaptonaphthimidazole, 1-methyl-2-mercapto-5-phenyl-1,3,5-triazole, 1-butyl-2-mercapto-5-phenyl-1,3,5-triazole, 1- Heptyl-2-mercapto-5-phenyl-1,3,5-triazole, 1-phenyl-2-mercapto-5-phenyl-1,3,5-triazole, 1-benzyl-2-mercapto-5-phenyl- 1,3,5-triazole, 1-phenethyl-2-mercapto-5-phenyl-1,3,5-triazole, 1-cyclohexyl-2-mercapto-5-phenyl-1,3,5-triazole, 1 -Phenethyl-2-mercapto-5- (3-fluorophenyl) -1,3,5-triazole, 1-phenethyl-2-mercapto-5- (3 Trifluoromethylphenyl) -1,3,5-triazole, 1-benzyl-2-mercapto-5- (p-tolyl) -1,3,5-triazole, 1-benzyl-2-mercapto-5- (4 -Methoxyphenyl) -1,3,5-triazole, 1-benzyl-2-mercapto-5- (p-trifluoromethylphenyl) -1,3,5-triazole, 1-benzyl-2-mercapto-5 (3,5-dichlorophenyl) -1,3,5-triazole, 1-phenyl-2-mercapto-5- (p-tolyl) -1,3,5-triazole, 1-phenyl-2-mercapto-5 (4-methoxyphenyl) -1,3,5-triazole, 1- (1-naphthyl) -2-mercapto-5-phenyl-1,3,5-triazole, 1- (4-bromopheny ) -2-mercapto-5-phenyl-1,3,5-triazole, 1- (4-trifluorophenyl) -2-mercapto-5-phenyl-1,3,5-triazole, and the like.

  The amount of these chain transfer agents to be used is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the photosensitive layer. More preferably, it is 1.0-10 mass%.

<Formation of photosensitive layer>
The photosensitive layer in the present invention is formed by preparing or applying a coating solution by dispersing or dissolving the necessary components described above in a solvent, and coating and drying the coating solution.
Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Examples include ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyllactone, toluene, water, and the like. However, the present invention is not limited to this. These solvents are used alone or in combination. The solid content concentration of the coating solution is preferably 1 to 50% by mass.

  In the present invention, the photosensitive layer may be prepared by preparing a plurality of coating solutions in which the same or different components are dispersed or dissolved in the same or different solvents, and repeating a plurality of coating and drying steps to form a multilayered photosensitive layer. Is possible.

Moreover, although the photosensitive layer coating amount (solid content) on the support obtained after coating and drying varies depending on the application, it is generally preferably 0.3 to 3.0 g / m ² . Within this range, good sensitivity and good film properties of the photosensitive layer can be obtained.
Various methods can be used as the coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

(Protective layer)
The lithographic printing plate precursor according to the invention preferably has a protective layer (overcoat layer) on the photosensitive layer. In addition to the function of suppressing the image formation inhibition reaction by blocking oxygen, the protective layer also has functions such as preventing scratches in the photosensitive layer and preventing ablation during high-illuminance laser exposure. Hereinafter, components constituting the protective layer will be described.

  Usually, the exposure processing of a lithographic printing plate is carried out in the atmosphere. The image forming reaction in the photosensitive layer caused by the exposure process can be inhibited by low molecular compounds such as oxygen and basic substances present in the atmosphere. The protective layer prevents low molecular compounds such as oxygen and basic substances from entering the photosensitive layer, and as a result, suppresses image formation inhibition reaction in the air. Therefore, the properties desired for the protective layer are to reduce the permeability of low-molecular compounds such as oxygen, furthermore, the transparency of light used for exposure is good, the adhesiveness to the photosensitive layer is excellent, and It can be easily removed in the on-press development process after exposure. The protective layer having such characteristics is described in, for example, US Pat. No. 3,458,311 and JP-B-55-49729.

As a material used for the protective layer, either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used. Specifically, for example, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl imidazole, polyacrylic acid, polyacrylamide, partially saponified product of polyvinyl acetate, ethylene-vinyl alcohol copolymer, water-soluble cellulose derivative, gelatin, Examples thereof include water-soluble polymers such as starch derivatives and gum arabic, and polymers such as polyvinylidene chloride, poly (meth) acrylonitrile, polysulfone, polyvinyl chloride, polyethylene, polycarbonate, polystyrene, polyamide, and cellophane.
These may be used in combination of two or more as required.

  Examples of relatively useful materials among the above materials include water-soluble polymer compounds having excellent crystallinity. Specifically, water-soluble acrylic resins such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl imidazole, and polyacrylic acid, gelatin, gum arabic, and the like are suitable. Among these, water can be applied as a solvent, and at the time of printing Polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl imidazole are preferable from the viewpoint that they are easily removed by the fountain solution. Among them, polyvinyl alcohol (PVA) gives the best results for basic properties such as oxygen barrier properties and development removability.

  The polyvinyl alcohol that can be used in the protective layer may be partially substituted with esters, ethers, and acetals as long as they contain a substantial amount of unsubstituted vinyl alcohol units having the required water solubility. Similarly, a part may contain other copolymerization components. For example, various hydrophilic modification sites such as anion modification sites modified with anions such as carboxy groups and sulfo groups, cation modification sites modified with cations such as amino groups and ammonium groups, silanol modification sites, and thiol modification sites are randomly selected. Polyvinyl alcohol having various degrees of polymerization, the anion-modified site, the cation-modified site, the silanol-modified site, the thiol-modified site, the alkoxyl-modified site, the sulfide-modified site, and the ester modification of vinyl alcohol and various organic acids. Polyvinyl alcohol having various degrees of polymerization having various modified sites such as a site, an ester-modified site of the anion-modified site and alcohols, an epoxy-modified site, etc. at the polymer chain end is also preferably used.

Suitable examples of the modified polyvinyl alcohol include compounds having a hydrolysis degree of 71 to 100 mol% and a polymerization degree in the range of 300 to 2400. Specifically, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, manufactured by Kuraray Co., Ltd. PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8, and the like.
Moreover, as modified polyvinyl alcohol, all made by Kuraray Co., Ltd., KL-318, KL-118, KM-618, KM-118, SK-5102 having anion-modified sites, C having a cation-modified site. -318, C-118, CM-318, M-205, M-115 with terminal thiol modification sites, MP-103, MP-203, MP-102, MP-202 with terminal sulfide modification sites, high grade Examples thereof include HL-12E and HL-1203 having an ester-modified site with a fatty acid at the end, and R-1130, R-2105, R-2130 having other reactive silane-modified sites.

The protective layer preferably contains an inorganic layered compound, that is, a compound that is an inorganic compound, has a layered structure, and has a flat plate shape. By using such an inorganic layered compound in combination, the oxygen barrier property is further increased and the printing durability is remarkably improved. Further, the film strength of the protective layer is further improved and scratch resistance is improved, and matting properties can be imparted to the protective layer.
As an inorganic layered compound, for example, the following general formula A (B, C) 2-5D ₄ O ₁₀ (OH, F, O) ₂ [where A is Li, K, Na, Ca, Mg, organic cation Any one of B and C is any one of Fe (II), Fe (III), Mn, Al, Mg, and V, and D is Si or Al. And mica groups such as natural mica and synthetic mica, talc, teniolite, montmorillonite, saponite, hectorite, zirconium phosphate and the like represented by the formula 3MgO.4SiO.H ₂ O.

Among the mica compounds, natural mica includes muscovite, soda mica, phlogopite, biotite and sericite. Synthetic mica includes non-swellable mica such as fluorine phlogopite mica ₃ (AlSi ₃ O ₁₀ ) F ₂ , potassium tetrasilicon mica KMg _2.5 Si ₄ O ₁₀ ) F ₂ , and Na tetrasilicic mica NaMg _2.5 ( Si ₄ O ₁₀ ) F ₂ , Na or Li teniolite (Na, Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , montmorillonite-based Na or Li hectorite (Na, Li) _1/8 Mg _2/5 Li Examples thereof include swelling mica such as _1/8 (Si ₄ O ₁₀ ) F ₂ . Synthetic smectite is also useful.

Of the mica compounds, fluorine-based swellable mica, which is a synthetic layered compound, is particularly useful. That is, swellable clay minerals such as mica, montmorillonite, saponite, hectorite, bentonite, etc. have a laminated structure composed of unit crystal lattice layers with a thickness of about 10 to 15 mm, and metal atom substitution in the lattice is other than It is significantly larger than clay minerals. As a result, the lattice layer has a shortage of positive charge, and in order to compensate for it, Li ⁺ , Na ⁺ , Ca ²⁺ , Mg ²⁺ , amine salts, quaternary ammonium salts, phosphonium salts, sulfonium salts, etc. Adsorbs organic cation cations. These layered compounds swell with water. If shear is applied in this state, it will easily cleave and form a stable sol in water. Bentonite and swellable synthetic mica have a strong tendency and are useful in the present invention. In particular, swellable synthetic mica is preferably used from the viewpoint of availability and quality uniformity.

  The shape of the layered compound is a flat plate, and from the viewpoint of diffusion control, the thinner the better, the larger the plane size as long as it does not hinder the smoothness of the coated surface or the transmittance of actinic rays. . Accordingly, the aspect ratio is 20 or more, preferably 100 or more, particularly preferably 200 or more. The aspect ratio is the ratio of the thickness to the major axis of the particle, and can be measured, for example, from a projected view of the particle by a micrograph. The larger the aspect ratio, the greater the effect that can be obtained.

  As for the particle diameter of the layered compound, the average major axis is 0.3 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 1 to 5 μm. If the particle diameter is 0.3 μm or more, it is preferable that the permeation of oxygen and moisture is sufficiently suppressed and the effect can be sufficiently exhibited. Moreover, if it is 20 micrometers or less, the dispersion stability in a coating liquid is enough, and stable application | coating can be performed and it is preferable. The average thickness of the particles is 0.1 μm or less, preferably 0.05 μm or less, particularly preferably 0.01 μm or less. For example, among inorganic layered compounds, the size of the swellable synthetic mica that is a representative compound is about 1 to 50 nm in thickness and about 1 to 20 μm in surface size.

  When particles of inorganic layered compounds having a large aspect ratio are contained in the protective layer in this way, the coating film strength is improved and oxygen and moisture permeation can be effectively prevented. Deterioration is prevented, and even when stored for a long time under high-humidity conditions, the storage stability of the planographic printing plate precursor does not deteriorate due to changes in humidity, and the storage stability is excellent.

Next, an example of a general dispersion method when a layered compound is used for the protective layer will be described.
First, 5 to 10 parts by mass of the swellable laminar compound mentioned above as a preferred laminar compound is added to 100 parts by mass of water, and the mixture is thoroughly swelled and swollen. Examples of the disperser used here include various mills that disperse mechanically by applying a direct force, a high-speed stirring disperser having a large shearing force, and a disperser that provides high-intensity ultrasonic energy. Specifically, ball mill, sand grinder mill, visco mill, colloid mill, homogenizer, tisol bar, polytron, homomixer, homo blender, ketdy mill, jet agitator, capillary emulsifier, liquid siren, electrostrictive ultrasonic generator, An emulsifying device having a Paulman whistle can be used. A dispersion of 5 to 10% by mass of the inorganic stratiform compound dispersed by the above method is highly viscous or gelled and has very good storage stability.
When preparing a coating solution for the protective layer using this dispersion, it is preferably prepared by diluting with water and stirring sufficiently, and then blending with a polymer solution such as polyvinyl alcohol.

  It is preferable that content of the inorganic stratiform compound in a protective layer is 5/1-1/100 by mass ratio with respect to the quantity of the said polymer used for a protective layer. Even when a plurality of kinds of inorganic layered compounds are used in combination, it is preferable that the total amount of these inorganic layered compounds is compatible with the above-described mass ratio.

  As other additives for the protective layer, for example, glycerin, dipropylene glycol, propionamide, cyclohexanediol, sorbitol and the like are added in an amount corresponding to several mass% with respect to the water-soluble or water-insoluble polymer to impart flexibility. be able to. Moreover, well-known additives, such as a water-soluble (meth) acrylic polymer and a water-soluble plasticizer, can be added for improving the physical properties of the film.

Further, the protective layer in the present invention is formed using a coating solution for a protective layer as described later. This coating solution is known for improving the adhesion to the photosensitive layer and the stability of the coating solution over time. The additive may be added.
That is, the protective layer coating solution includes an anionic surfactant, a nonionic surfactant, a cationic surfactant, and a fluorosurfactant for improving coating properties, specifically, sodium alkyl sulfate, alkyl sulfonic acid. Anionic surfactants such as sodium; amphoteric surfactants such as alkylaminocarboxylates and alkylaminodicarboxylates; nonionic surfactants such as polyoxyethylene alkylphenyl ether can be added. These surfactants can be added in an amount of 0.1 to 100% by mass relative to the water-soluble or water-insoluble polymer.

  In order to improve the adhesion to the image area, for example, JP-A-49-70702 and British Patent Application No. 1303578 disclose an acrylic polymer in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesiveness can be obtained by mixing 20 to 60% by mass of solid particles such as a polymer based polymer, a water-insoluble vinylpyrrolidone-vinyl acetate copolymer, and polyfluoroethylene and laminating them on a photosensitive layer. ing. Any of these known techniques can be used in the present invention.

  Furthermore, a sensitizer such as the low molecular nitrogen compound or ammonium salt-containing polymer can be added to the protective layer. With these additions, a further effect of improving the inking property can be obtained. The amount of addition of the sensitizer to the protective layer is preferably in the range of 0.5 to 30% by mass.

Furthermore, other functions can be imparted to the protective layer. For example, by adding a colorant (for example, a water-soluble dye) that is excellent in the transparency of infrared rays used for exposure and that can efficiently absorb light of other wavelengths, safe light is not caused. Suitability can be improved. Further, for the purpose of controlling the slipperiness of the outermost surface of the lithographic printing plate precursor, it may contain spherical inorganic fine particles such as those added to the aforementioned photosensitive layer. Preferred examples of the inorganic fine particles include silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, and a mixture thereof. The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 50 nm to 3 μm. The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 40% by mass or less, and more preferably 20% by mass or less, based on the total solid content of the protective layer.

The protective layer is formed by applying and drying a protective layer coating solution prepared by dispersing or dissolving the protective layer component in a solvent on the photosensitive layer.
The coating solvent can be appropriately selected in relation to the polymer to be used, but when a water-soluble polymer is used, it is preferable to use distilled water or purified water.

The method for applying the protective layer is not particularly limited, and a known method such as the method described in US Pat. No. 3,458,311 or Japanese Patent Publication No. 55-49729 can be applied. .
Specifically, for example, when the protective layer is formed, a blade coating method, an air knife coating method, a gravure coating method, a roll coating coating method, a spray coating method, a dip coating method, a bar coating method, or the like is used.

The coating amount of the protective layer, the coating amount after drying is preferably in the range of 0.01 to 10 g / m ^2, more preferably in the range of 0.02 to 3 g / m ^2, and most preferably 0. It is in the range of 02 to 1 g / m ² .

(Undercoat layer)
In the planographic printing plate precursor, an undercoat layer (sometimes referred to as an intermediate layer) is provided between the photosensitive layer and the support, if necessary. The undercoat layer enhances the adhesion between the support and the photosensitive layer in the exposed area, and easily peels off the photosensitive layer from the support in the unexposed area, thus improving developability without impairing the printing durability. Contribute to In addition, in the case of infrared laser exposure, since the undercoat layer functions as a heat insulating layer, the heat generated by exposure does not diffuse to the support and can be used efficiently, so that the sensitivity can be increased. is there. Below, the component etc. which are used for the undercoat of this invention are demonstrated.

Specific examples of the undercoat layer compound include a silane coupling agent having an addition polymerizable ethylenic double bond reactive group described in JP-A-10-282679, and JP-A-2-304441. The phosphorus compound etc. which have the ethylenic double bond reactive group of gazette publication are mentioned suitably.
As the most preferable undercoat layer compound, a polymer resin having an adsorptive group, a hydrophilic group, and a crosslinkable group can be mentioned. This polymer resin is preferably formed by copolymerization of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group.

The polymer resin for the undercoat layer preferably has an adsorptive group on the surface of the hydrophilic support. The presence or absence of adsorptivity to the surface of the hydrophilic support can be determined, for example, by the following method.
A coating night is prepared by dissolving the test compound in a readily soluble solvent, and the coating night is coated and dried on the support so that the coating amount after drying is 30 mg / m ² . Next, after the support coated with the test compound is sufficiently washed with an easily soluble solvent, the residual amount of the test compound that has not been removed by washing is measured to calculate the support adsorption amount. Here, the measurement of the remaining amount may be performed by directly quantifying the amount of the remaining compound or by quantifying the amount of the test compound dissolved in the cleaning liquid. The compound can be quantified by, for example, fluorescent X-ray measurement, reflection spectral absorbance measurement, liquid chromatography measurement and the like. A compound having a support adsorptivity is a compound that remains at 1 mg / m ² or more even after the washing treatment as described above.

The adsorptive group on the surface of the hydrophilic support is a substance (for example, metal, metal oxide) present on the surface of the hydrophilic support, or a functional group (for example, a hydroxy group) and a chemical bond (for example, an ionic bond, It is a functional group capable of causing a hydrogen bond, a coordinate bond, and a bond due to intermolecular force. The adsorptive group is preferably an acid group or a cationic group.
The acid group preferably has an acid dissociation constant (pKa) of 7 or less. Examples of the acid group include a phenolic hydroxy group, a carboxy group, —SO ₃ H, —OSO ₃ H, —PO ₃ H ₂ , —OPO ₃ H ₂ , —CONHSO ₂ —, —SO ₂ NHSO ₂ , —COCH _2. COCH ₃ may be mentioned. Of these, —OPO ₃ H ₂ and PO ₃ H ₂ are particularly preferable. These acid groups may be metal salts.
The cationic group is preferably an onium group. Examples of the onium group include an ammonium group, a phosphonium group, an arsonium group, a stibonium group, an oxonium group, a sulfonium group, a selenonium group, a stannonium group, and an iodonium group. Among these, an ammonium group, a phosphonium group, and a sulfonium group are preferable, an ammonium group and a phosphonium group are more preferable, and an ammonium group is most preferable.

  As a particularly preferred example of the monomer having an adsorptive group used when synthesizing a polymer resin suitable as a compound for the undercoat layer, a compound represented by the following general formula (U1) or general formula (U2) can be given. It is done.

In the general formulas (U1) and (U2), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.
R ¹ , R ² and R ³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. More preferably, it is most preferably a hydrogen atom or a methyl group. R ² and R ³ are particularly preferably a hydrogen atom.
Z is a functional group adsorbed on the surface of the hydrophilic support, and the adsorptive functional group is as described above.

  In the general formulas (U1) and (U2), L is a single bond or a divalent linking group. L is a divalent aliphatic group (alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (arylene group, substituted arylene group), or divalent Or an oxygen atom (—O—), a sulfur atom (—S—), an imino (—NH—), a substituted imino (—NR—, R is an aliphatic group, an aromatic group Group or heterocyclic group) or a combination with carbonyl (—CO—).

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. The divalent aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Furthermore, the divalent aliphatic group may have a substituent, and examples of the substituent include a halogen atom, a hydroxy group, an aromatic group, and a heterocyclic group.
The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10. In addition, the divalent aromatic group may have a substituent, and examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group, and a heterocyclic group.
The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocycle. In addition, another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. The divalent heterocyclic group may have a substituent, and examples of the substituent include a halogen atom, a hydroxy group, an oxo group (═O), a thioxo group (═S), an imino group (═NH ), A substituted imino group (= N—R, R is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, or a heterocyclic group.

In the present invention, L is preferably a divalent linking group containing a plurality of polyoxyalkylene structures. The polyoxyalkylene structure is more preferably a polyoxyethylene structure. In other words, L preferably contains — (OCH ₂ CH ₂ ) _n — (n is an integer of 2 or more).
In General Formula (U1), X is an oxygen atom (—O—) or imino (—NH—). X is more preferably an oxygen atom.
In general formula (U2), Y is a carbon atom or a nitrogen atom. When Y is a nitrogen atom and L is linked to Y to form a quaternary pyridinium group, Z itself is adsorbable, so Z is not essential and Z may be a hydrogen atom.

  Examples of typical compounds represented by general formula (U1) or general formula (U2) are shown below.

  The polymer resin suitable as the compound for the undercoat layer preferably has a hydrophilic group. Examples of the hydrophilic group include a hydroxy group, a carboxy group, a carboxylate group, a hydroxyethyl group, a polyoxyethyl group, and a hydroxypropyl group. Preferred examples include a group, a polyoxypropyl group, an amino group, an aminoethyl group, an aminopropyl group, an ammonium group, an amide group, a carboxymethyl group, a sulfo group, and a phosphoric acid group. Of these, a sulfo group exhibiting high hydrophilicity is preferable.

Specific examples of the monomer having a sulfo group include methallyloxybenzenesulfonic acid, allyloxybenzenesulfonic acid, allylsulfonic acid, vinylsulfonic acid, p-styrenesulfonic acid, methallylsulfonic acid, acrylamide t-butylsulfonic acid, Examples include 2-acrylamido-2-methylpropanesulfonic acid, sodium salt of (3-acryloyloxypropyl) butylsulfonic acid, and amine salt. Among them, 2-acrylamido-2-methylpropanesulfonic acid sodium salt is preferable from the viewpoint of hydrophilic performance and handling of synthesis.
These are suitably used when synthesizing a polymer resin suitable as a compound for the undercoat layer.

  The polymer resin for the undercoat layer in the present invention preferably has a crosslinkable group. The crosslinkable group can improve the adhesion with the image area. In order to make the polymer resin for the undercoat layer crosslinkable, a crosslinkable functional group such as an ethylenically unsaturated bond is introduced into the side chain of the polymer, or the polar substituent of the polymer resin is countercharged. Or a compound having an ethylenically unsaturated bond may be introduced by forming a salt structure.

  An example of a polymer having an ethylenically unsaturated bond in the side chain of the molecule is an ester or amide polymer of acrylic acid or methacrylic acid, wherein the ester or amide residue (-COOR or CONHR R) is ethylene. The polymer which has an ionic unsaturated bond can be mentioned.

Examples of the residue (the R) having an ethylenically unsaturated _{bond, - (CH 2) n CR} 1 = CR 2 R 3, - (CH 2 O) n CH 2 CR 1 = CR 2 R 3, - _{(CH 2 CH 2 O) n} CH 2 CR 1 = CR 2 R 3, - (CH 2) n NH-CO-O-CH 2 CR 1 = CR 2 R 3, - (CH 2) n -O-CO —CR ¹ ═CR ² R ³ and (CH ₂ CH ₂ O) ₂ —X (wherein R ^{1 to} R ³ are each a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, Represents an alkoxy group or an aryloxy group, and R ¹ and R ² or R ³ may combine with each other to form a ring, n represents an integer of 1 to 10. X represents dicyclopentadienyl. Represents a residue).
Specific examples of the ester _{residue, -CH 2 CH = CH 2,} ( described in JP Kokoku _{7-21633.) - CH 2 CH 2} O-CH 2 CH = CH 2, -CH 2 C _{(CH 3) = CH 2,} -CH 2 CH = CH-C 6 H 5, -CH 2 CH 2 OCOCH = CH-C 6 H 5, -CH 2 CH 2 NHCOO-CH 2 CH = CH 2, and CH ₂ CH ₂ O—X (wherein X represents a dicyclopentadienyl residue).
Specific examples of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ O—Y (wherein Y represents a cyclohexene residue), —CH ₂ CH ₂ OCO—CH═CH _2. Is mentioned.
As the monomer having a crosslinkable group of the polymer resin for the undercoat layer, an ester or amide of acrylic acid or methacrylic acid having the crosslinkable group is preferable.

  The content of the crosslinkable group in the polymer resin for the undercoat layer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.1 to 10.0 mmol per 1 g of the polymer resin. Preferably it is 1.0-7.0 mmol, Most preferably, it is 2.0-5.5 mmol. Within this range, both good sensitivity and dirtiness and good storage stability can be obtained.

The polymer resin for the undercoat layer preferably has a mass average molar mass of 5000 or more, more preferably 10,000 to 300,000, and a number average molar mass of 1000 or more is preferable. More preferably, it is ˜250,000. The polydispersity (mass average molar mass / number average molar mass) is preferably 1.1 to 10.
The polymer resin for the undercoat layer may be any of a random polymer, a block polymer, a graft polymer, and the like, but is preferably a random polymer.

  The polymer resin for undercoating may be used alone or in combination of two or more.

  The undercoat layer of the present invention can contain a secondary or tertiary amine or a polymerization inhibitor in order to prevent contamination of the raw plate (unexposed lithographic printing plate precursor) over time. Secondary or tertiary amines include imidazole, 4-dimethylaminopyridine, 4-dimethylaminobenzaldehyde, tris (2-hydroxy-1-methyl) amine, 1,4-diazabicyclo [2,2,2] octane ( DABCO), 1,5,7-triazabicyclo [4,4,0] dec-5-ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,10-phenanthroline, 1 , 8-bis (dimethylamino) naphthalene, 4,4′-bis (dimethylamino) biphenyl, diphenylamine, 1,3-diphenylguanidine, 4-phenylpyridine, N, N′-ethylenebis (2,2,5,5) 5-tetramethylpyrrolidine) and the like.

Examples of the polymerization inhibitor include known thermal polymerization inhibitors. Among them, preferred polymerization inhibitors are phenolic hydroxy group-containing compounds, quinone compounds, N-oxide compounds, piperidine-1-oxyl free radical compounds, pyrrolidine-1-oxyl free radical compounds, N-nitrosophenylhydroxyl. It is a compound selected from the group consisting of amines, diazonium compounds, cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, and transition metal compounds such as FeCl ₃ and CuCl ₂ . Of the above compounds, quinone compounds are particularly preferred. Specific examples of the quinone compounds include 1,4-benzoquinone, 2,3,5,6-tetrahydroxy-1,4-benzoquinone 2,5-dihydroxy-1,4-benzoquinone, chloranil, and 2,3-dichloro. -5,6-dicyano-1,4-benzoquinone, naphthoquinone, 2-fluoro-1,4-naphthoquinone, 2-hydroxyethyl-1,4-naphthoquinone, anthraquinone, 1,2,4-trihydroxyanthraquinone, 2, And 6-dihydroxyanthraquinone.

  The amount of these compounds added to the undercoat layer is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, and most preferably from 30 to 70% by mass, based on the components of the undercoat layer.

In addition, a compound having an amino group or a functional group having a polymerization inhibiting ability and a group that interacts with the aluminum support surface can also be used as a compound that is effective for preventing stains during aging. Examples of the group that interacts with the surface of the aluminum support include trialkoxysilyl group, onium group, phenolic hydroxy group, carboxy group, —SO ₃ H, —OSO ₃ H, —PO ₃ H ₂ , —OPO ₃ H _2. , —CONHSO ₂ —, —SO ₂ NHSO ₂ — and COCH ₂ CO—, an acid group or a metal salt thereof.

  Examples of the compound having an interaction group between the amino group and the aluminum support surface include a salt of 1,4-diazabicyclo [2,2,2] octane and an acid, 4-aza-1-azoniabicyclo [2,2 , 2] Compound having at least one octane structure (for example, 1-methyl-4-aza-1-azoniabicyclo [2,2,2] octane = p-toluenesulfonate), ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid , Dihydroxyethylethylenediaminediacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethyliminodiacetic acid, and the like. As a compound having a functional group having a polymerization inhibiting ability and a group that interacts with the surface of the aluminum support, 2-trimethoxysilylpropylthio-1,4-benzoquinone, 2,5-bis (trimethoxysilylpropylthio)- 1,4-benzoquinone, 2-carboxyanthraquinone, 2-trimethylammonioanthraquinone = chloride and the like.

The undercoat layer coating solution is obtained by dissolving the above-described undercoat polymer resin and necessary additives in an organic solvent (for example, methanol, ethanol, acetone, methyl ethyl ketone, etc.) and / or water. The undercoat layer coating solution may contain an infrared absorber.
Various known methods can be used as a method of applying the undercoat layer coating solution to the support. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.
The coating amount (solid content) of the undercoat layer is preferably from 0.1-100 mg / m ^2, and more preferably 1 to 30 mg / m ^2.

(Support)
The support used for the lithographic printing plate precursor according to the invention is not particularly limited as long as it is a dimensionally stable plate-like material. For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate) Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or deposited. Preferable supports include a polyester film and an aluminum plate. Among these, an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable.

  The aluminum plate is a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or a plastic laminated on a thin film of aluminum or an aluminum alloy. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is preferably 10% by mass or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to manufacture in terms of refining technology, and therefore may contain a slightly different element. The composition of the aluminum plate is not specified, and a publicly known material can be used as appropriate.

  The thickness of the support is preferably from 0.1 to 0.6 mm, more preferably from 0.15 to 0.4 mm.

  Prior to using the aluminum plate, it is preferable to perform surface treatment such as roughening treatment or anodizing treatment. By the surface treatment, it becomes easy to improve hydrophilicity and secure adhesion between the photosensitive layer and the support. Prior to the roughening treatment of the aluminum plate, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like for removing rolling oil on the surface is performed as desired.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, mechanical surface roughening treatment, electrochemical surface roughening treatment (electrochemical surface roughening treatment that dissolves the surface), chemical treatment, etc. Surface roughening treatment (roughening treatment that chemically selectively dissolves the surface).
As a method for the mechanical surface roughening treatment, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Moreover, the transcription | transfer method which transfers an uneven | corrugated shape with the roll which provided the unevenness | corrugation in the rolling stage of aluminum can also be used.
Examples of the electrochemical surface roughening treatment include a method in which an alternating current or a direct current is used in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Another example is a method using a mixed acid as described in JP-A-54-63902.

  The surface-roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide, sodium hydroxide or the like, if necessary, and further neutralized, and if desired, wear resistant. In order to increase the anodic oxidation treatment.

As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.
The conditions of anodizing treatment vary depending on the electrolyte used, and thus cannot be specified in general. In general, however, an electrolyte concentration of 1 to 80% by mass solution, a liquid temperature of 5 to 70 ° C., a current density of 5 to 60 A / dm ² , voltage 1 to 100 V, and electrolysis time 10 seconds to 5 minutes are preferable. The amount of the anodized film formed is preferably from 1.0 to 5.0 g / m ^2, and more preferably 1.5 to 4.0 g / m ^2. Within this range, good printing durability and good scratch resistance of the non-image area of the lithographic printing plate can be obtained.

  As the support used in the present invention, the substrate having the above-mentioned surface treatment and having an anodized film may be used as it is. However, in order to further improve the adhesiveness with the upper layer, hydrophilicity, dirt resistance, heat insulation and the like. If necessary, it is immersed in an aqueous solution containing a hydrophilic compound and a micropore enlargement treatment or sealing treatment of an anodized film described in JP-A-2001-253181 or JP-A-2001-322365. The surface hydrophilization treatment to be performed can be appropriately selected and performed. Of course, the enlargement process and the sealing process are not limited to those described above, and any conventionally known methods can be performed. For example, as the sealing treatment, in addition to the vapor sealing, a single treatment with fluorinated zirconic acid, a treatment with sodium fluoride, and a vapor sealing with addition of lithium chloride are possible.

  The sealing treatment used in the present invention is not particularly limited, and a conventionally known method can be used. Among them, sealing treatment with an aqueous solution containing an inorganic fluorine compound, sealing treatment with water vapor, and hot water. Sealing treatment is preferred. Each will be described below.

<1> Sealing treatment with an aqueous solution containing an inorganic fluorine compound As the inorganic fluorine compound used for the sealing treatment with an aqueous solution containing an inorganic fluorine compound, a metal fluoride is preferably exemplified.
Specifically, for example, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, sodium fluoride zirconate, potassium fluoride zirconate, sodium fluoride titanate, potassium fluoride titanate, zircon fluoride Ammonium acid, ammonium fluoride titanate, potassium fluoride titanate, zirconate fluoride, titanate fluoride, hexafluorosilicic acid, nickel fluoride, iron fluoride, phosphor fluoride, ammonium fluoride phosphate It is done. Of these, sodium fluorinated zirconate, sodium fluorinated titanate, fluorinated zirconic acid, and fluorinated titanic acid are preferable.

  The concentration of the inorganic fluorine compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of sufficiently sealing the micropores of the anodized film. Further, in terms of stain resistance, it is preferably 1% by mass or less, and more preferably 0.5% by mass or less.

  It is preferable that the aqueous solution containing an inorganic fluorine compound further contains a phosphate compound. When the phosphate compound is contained, the hydrophilicity of the surface of the anodized film is improved, so that on-machine developability and stain resistance can be improved.

Suitable examples of the phosphate compound include phosphates of metals such as alkali metals and alkaline earth metals.
Specifically, for example, zinc phosphate, aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, dihydrogen phosphate Potassium, dipotassium hydrogen phosphate, calcium phosphate, sodium ammonium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, sodium phosphate, hydrogen phosphate Disodium, lead phosphate, diammonium phosphate, calcium dihydrogen phosphate, lithium phosphate, phosphotungstic acid, ammonium phosphotungstate, sodium phosphotungstate, ammonium phosphomolybdate, sodium phosphomolybdate, sodium phosphite , Tripolyphosphate Potassium, and sodium pyrophosphate. Of these, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate are preferable.
The combination of the inorganic fluorine compound and the phosphate compound is not particularly limited, but the aqueous solution contains at least sodium zirconate fluoride as the inorganic fluorine compound and contains at least sodium dihydrogen phosphate as the phosphate compound. Is preferred.

  The concentration of the phosphate compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of improving on-press developability and stain resistance. Further, in terms of solubility, it is preferably 20% by mass or less, and more preferably 5% by mass or less.

The ratio of each compound in the aqueous solution is not particularly limited, but the mass ratio of the inorganic fluorine compound and the phosphate compound is preferably 1/200 to 10/1, and preferably 1/30 to 2/1. Is more preferable.
Further, the temperature of the aqueous solution is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
Further, the aqueous solution preferably has a pH of 1 or more, more preferably has a pH of 2 or more, preferably has a pH of 11 or less, and more preferably has a pH of 5 or less.
A method for sealing with an aqueous solution containing an inorganic fluorine compound is not particularly limited, and examples thereof include an immersion method and a spray method. These may be used alone or in combination, or may be used in combination of two or more.
Of these, the dipping method is preferred. When the treatment is performed using the dipping method, the treatment time is preferably 1 second or longer, more preferably 3 seconds or longer, more preferably 100 seconds or shorter, and 20 seconds or shorter. More preferred.

<2> Sealing treatment with water vapor The sealing treatment with water vapor includes, for example, a method in which pressurized or normal pressure water vapor is contacted with the anodized film continuously or discontinuously.
The temperature of the water vapor is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 105 ° C. or lower.
The pressure of the water vapor is preferably in a range (1.008 × 10 ^{5 to} 1.043 × 10 ⁵ Pa) from (atmospheric pressure−50 mmAq) to (atmospheric pressure + 300 mmAq).
Further, the time for which the water vapor is contacted is preferably 1 second or longer, more preferably 3 seconds or longer, 100 seconds or shorter, more preferably 20 seconds or shorter.

<3> Sealing treatment with hot water Examples of the sealing treatment with hot water include a method in which an aluminum plate on which an anodized film is formed is immersed in hot water.
The hot water may contain an inorganic salt (for example, phosphate) or an organic salt.
The temperature of the hot water is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 100 ° C. or lower.
Further, the time of immersion in hot water is preferably 1 second or longer, more preferably 3 seconds or longer, more preferably 100 seconds or shorter, and even more preferably 20 seconds or shorter.

  The hydrophilization treatment is described in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. There are alkali metal silicate methods. In this method, the support is subjected to immersion treatment or electrolytic treatment with an aqueous solution such as sodium silicate. In addition, the treatment with potassium zirconate fluoride described in JP-B 36-22063, U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689, And a method of treating with polyvinylphosphonic acid as described in each specification of No.272.

  When using a support with insufficient surface hydrophilicity such as a polyester film as the support of the present invention, it is desirable to apply a hydrophilic layer to make the surface hydrophilic. As the hydrophilic layer, at least one element selected from beryllium, magnesium, aluminum, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony, and a transition metal described in JP-A-2001-199175 A hydrophilic layer obtained by coating a coating solution containing a colloid of oxide or hydroxide, or an organic hydrophilic polymer obtained by crosslinking or pseudo-crosslinking an organic hydrophilic polymer described in JP-A No. 2002-79772 A hydrophilic layer having a hydrophilic matrix, a hydrophilic layer having an inorganic hydrophilic matrix obtained by sol-gel conversion comprising hydrolysis and condensation reaction of polyalkoxysilane, titanate, zirconate or aluminate, or a metal oxide A hydrophilic layer comprising an inorganic thin film having a surface Preferred. Among these, a hydrophilic layer formed by applying a coating solution containing a silicon oxide or a hydroxide colloid is preferable.

  Moreover, when using a polyester film etc. as a support body of this invention, it is preferable to provide an antistatic layer in the hydrophilic layer side of a support body, the opposite side, or both sides. In the case where the antistatic layer is provided between the support and the hydrophilic layer, it also contributes to improving the adhesion with the hydrophilic layer. As the antistatic layer, a polymer layer in which metal oxide fine particles or a matting agent are dispersed as described in JP-A-2002-79772 can be used.

  The support preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the photosensitive layer, good printing durability and good stain resistance can be obtained.

(Back coat layer)
After the surface treatment is performed on the support or after the undercoat layer is formed, a backcoat layer can be provided on the back surface of the support, if necessary.
As the back coat layer, for example, an organic polymer compound described in JP-A-5-45885, an organometallic compound or an inorganic metal compound described in JP-A-6-35174 is hydrolyzed and polycondensed. Preferable examples include a coating layer made of a metal oxide. Of these, the use of silicon alkoxy compounds such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) _4, etc. is inexpensive. It is preferable in that it is easily available.

(Plate making method)
The lithographic printing plate precursor according to the invention is subjected to image exposure and then plate-making in a development processing step using a developer, or plate-making by on-press development. On-press development is more preferred from the viewpoint of simplification of processing.
Hereinafter, the plate making method will be described in detail.

<Exposure>
As the exposure method for the lithographic printing plate precursor according to the invention, known methods can be used without limitation.
As a light source for exposing the lithographic printing plate precursor according to the invention, a known light source can be used without limitation. The wavelength of the light source may be 300 nm to 1200 nm. Specifically, various lasers can be used as the light source, and among them, a semiconductor laser that emits infrared light having a wavelength of 760 nm to 1200 nm can be used.

A laser is preferred as the light source. For example, the following can be used as an available laser light source having a wavelength of 350 to 450 nm.
As a gas laser, Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), He—Cd laser (441 nm, 325 nm, 1 mW to 100 mW), and solid laser as Nd : Combination of YAG (YVO ₄ ) and SHG crystal × 2 times (355 mm, 5 mW to 1 W), combination of Cr: LiSAF and SHG crystal (430 nm, 10 mW). As the semiconductor laser system, KNbO ₃ , ring resonator (430 nm, 30 mW), waveguide type wavelength conversion element and AlGaAs, combination of InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), waveguide type wavelength conversion element and AlGaInP, Combination of AlGaAs semiconductors (300 nm to 350 nm, 5 mW to 100 mW), AlGaInN (350 nm to 450 nm, 5 mW to 30 mW), other pulse lasers such as N ₂ laser (337 nm, pulse 0.1 to 10 mJ), XeF (351 nm, pulse 10 ~ 250 mJ).
In particular, an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost.

In addition, as an available light source of 450 nm to 700 nm, Ar ⁺ laser-(488 nm), YAG-SHG laser (532 nm), He-Ne laser (633 nm), He-Cd laser, red semiconductor laser (650-690 nm), Moreover, as an available light source of 700 nm to 1200 nm, a semiconductor laser (800 to 850 nm) and an Nd-YAG laser (1064 nm) can be suitably used.

In addition, ultra high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, ultraviolet laser lamp (ArF excimer laser, KrF excimer laser, etc.), various visible laser lamps, fluorescence An electron beam, an X-ray, an ion beam, a far-infrared ray, or the like can be used as the radiation, such as a lamp, a tungsten lamp, or sunlight.
Among the above, the light source used for image exposure of the image recording material according to the present invention is preferably a light source having an emission wavelength in the near infrared to infrared region, and a solid laser or a semiconductor laser is particularly preferable.

  The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.

<On-machine development>
The exposed lithographic printing plate precursor is mounted on a plate cylinder of a printing machine. In the case of a printing press equipped with a laser exposure device, imagewise exposure is performed after a lithographic printing plate precursor is mounted on a plate cylinder of the printing press.

After the lithographic printing plate precursor is imagewise exposed with a laser, printing is performed by supplying dampening water and printing ink without passing through a development processing step such as a wet development processing step. The photosensitive layer cured by forming a printing ink receiving part having an oleophilic surface. On the other hand, in the unexposed area, the uncured photosensitive layer is removed by dissolution or dispersion by the supplied dampening water and / or printing ink, and a hydrophilic surface is exposed in that area. As a result, the fountain solution adheres to the exposed hydrophilic surface, and the printing ink is deposited on the photosensitive layer in the exposed area and printing is started.
Here, dampening water or printing ink may be supplied to the printing plate first, but the printing ink is first supplied in order to prevent the dampening water from being contaminated by the removed photosensitive layer components. Is preferably supplied. As the fountain solution and printing ink, normal lithographic fountain solution and printing ink are used.

  In this way, the lithographic printing plate precursor is subjected to on-press development on an offset printing machine and used as it is for printing a large number of sheets.

<Development processing>
The lithographic printing plate precursor according to the present invention is excellent in on-press developability. You can also take a method. Hereinafter, a plate making method in the case of performing alkali development processing will be described.
Preferred developers used in the present invention include developers described in JP-B-57-7427, such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide. , Inorganic alkaline agents such as sodium triphosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia etc. and monoethanolamine or diethanolamine An aqueous solution of such an organic alkali agent is suitable. It is added so that the concentration of such an alkaline solution is 0.1 to 10% by mass, preferably 0.5 to 5% by mass.

Such an alkaline aqueous solution can contain a small amount of an organic solvent such as a surfactant, benzyl alcohol, 2-phenoxyethanol, or 2-butoxyethanol as necessary. Examples thereof include those described in US Pat. Nos. 3,375,171 and 3,615,480.
Further, the developers described in JP-A-50-26601, 58-54341, JP-B-56-39464, and 56-42860 are also excellent.
In addition, it is more preferable in terms of developability to use a specific aromatic nonionic surfactant-containing developer described in JP-A-2002-202616 as the developer.

  Further, after the lithographic printing plate precursor of the present invention is imagewise exposed with a laser, a development treatment may be performed using a non-alkaline aqueous solution having a pH of 10 or less as a developer. As the non-alkaline aqueous solution that can be used here, for example, water alone or an aqueous solution containing water as a main component (containing 60% by mass or more of water) is preferable. The aqueous solution containing an aqueous solution or a surfactant (anionic, nonionic, cationic, etc.) is preferred. The pH of the developer is preferably from 2 to 10, more preferably from 3 to 9, and even more preferably from 5 to 9. .

The non-alkali aqueous solution that can be used as the developer may contain an organic acid, an inorganic acid, an inorganic salt, or the like.
Examples of the organic acid include citric acid, acetic acid, succinic acid, malonic acid, salicylic acid, caprylic acid, tartaric acid, malic acid, lactic acid, levulinic acid, p-toluenesulfonic acid, xylenesulfonic acid, phytic acid, and organic phosphonic acid. . The organic acid can also be used in the form of its alkali metal salt or ammonium salt. The content in the developer is preferably 0.01 to 5% by mass.

  Examples of inorganic acids and inorganic salts include phosphoric acid, metaphosphoric acid, primary ammonium phosphate, secondary ammonium phosphate, primary sodium phosphate, secondary sodium phosphate, primary potassium phosphate, secondary potassium phosphate, Examples include sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, ammonium sulfite, sodium hydrogen sulfate, nickel sulfate and the like. The content in the developer is preferably 0.01 to 5% by mass.

  Examples of the anionic surfactant that can be used in the developer used in the present invention include fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, dialkylsulfosuccinic acid salts, linear alkylbenzenesulfonic acid salts, Branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid monoamides Sodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef tallow oil, fatty acid alkyl ester sulfate esters, alkyl sulfate esters, polyoxyethylene alkyl ether sulfates Ester salts, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkylphenyl ether phosphates Examples thereof include ester salts, partially saponified products of styrene-maleic anhydride copolymer, partially saponified products of olefin-maleic anhydride copolymer, and naphthalene sulfonate formalin condensates. Among these, dialkyl sulfosuccinates, alkyl sulfate esters and alkyl naphthalene sulfonates are particularly preferably used.

  The cationic surfactant that can be used in the developer used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

Nonionic surfactants that can be used in the developer used in the present invention include polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide Adducts, higher alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, fat and oil ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, dimethylsiloxane-ethylene oxide block copolymers, dimethylsiloxane- (propylene oxide-ethylene oxide) Block copolymer, fatty acid ester of polyhydric alcohol glycerol, fatty acid ester of pentaerythritol, Bitoru and fatty acid esters of sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines.
These nonionic surfactants may be used alone or in combination of two or more. In the present invention, ethylene oxide adduct of sorbitol and / or sorbitan fatty acid ester, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer, polyhydric alcohol Fatty acid esters are more preferred.

Moreover, from the viewpoint of stable solubility or turbidity in water, the nonionic surfactant used in the developer of the present invention preferably has an HLB (Hydrophile-Lipophile Balance) value of 6 or more, and 8 More preferably.
Furthermore, the ratio of the nonionic surfactant contained in the developer is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass.
Further, acetylene glycol-based and acetylene alcohol-based oxyethylene adducts, fluorine-based and silicon-based surfactants can be used in the same manner.
As the surfactant used in the developer of the present invention, a nonionic surfactant is particularly suitable from the viewpoint of foam suppression.

The developer used in the present invention may contain an organic solvent. Examples of the organic solvent that can be contained here include aliphatic hydrocarbons (hexane, heptane, “Isopar E, H, G” (produced by Esso Chemical Co., Ltd.) or gasoline, kerosene, etc.), aromatic hydrocarbons, and the like. (Toluene, xylene, etc.), halogenated hydrocarbons (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.) and the following polar solvents.
Examples of polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol mono Ethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl Alcoa Etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl) Acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl levulinate, etc.) and others (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine, N-phenyldiethanolamine, etc.).

  When the organic solvent is insoluble in water, it can be used after being solubilized in water using a surfactant or the like. When the developer contains an organic solvent, the concentration of the solvent is preferably less than 40% by mass from the viewpoint of safety and flammability.

  In the developer used in the present invention, as a water-soluble polymer compound, soybean polysaccharide, modified starch, gum arabic, dextrin, fiber derivative (for example, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, etc.) and modified products thereof, Pullulan, polyvinyl alcohol and its derivatives, polyvinyl pyrrolidone, polyacrylamide and acrylamide copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, styrene / maleic anhydride copolymer, etc. Can be contained.

  A well-known thing can be used for the said soybean polysaccharide, for example, there exists a brand name Soya Five (made by Fuji Oil Co., Ltd.) as a commercial item, and the thing of various grades can be used. What can be preferably used is one in which the viscosity of a 10% by mass aqueous solution is in the range of 10 to 100 mPa / sec.

As the modified starch, known ones can be used, and starch such as corn, potato, tapioca, rice and wheat is decomposed with acid or enzyme in the range of 5 to 30 glucose residues per molecule, and further in an alkali. It can be made by a method of adding oxypropylene.
Two or more water-soluble polymer compounds can be used in combination. The content of the water-soluble polymer compound in the developer is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass.

  In addition to the above, the developer used in the present invention may contain a preservative, a chelate compound, an antifoaming agent and the like.

  Preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzisothiazolin-3-one, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyridine, Derivatives such as quinoline and guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives, nitrobromoalcohol-based 2-bromo-2-nitropropane-1,3diol, 1,1-dibromo-1-nitro-2-ethanol, 1,1-dibromo-1-nitro-2-propanol and the like can be preferably used.

  Examples of the chelate compound include ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, potassium salt thereof, sodium salt thereof, hydroxyethylethylenediaminetriacetic acid Nitrilotriacetic acid, sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, potassium salt, sodium salt; aminotri (methylenephosphonic acid), potassium salt, sodium salt And organic phosphonic acids and phosphonoalkanetricarboxylic acids. Organic amine salts are also effective in place of the sodium and potassium salts of the chelating agents.

  As the antifoaming agent, a general silicon-based self-emulsifying type, emulsifying type, or nonionic surfactant having a HLB of 5 or less can be used. Silicon antifoaming agents are preferred. Among them, emulsification dispersion type and solubilization can be used.

The development processing with a non-alkaline aqueous solution in the present invention can be preferably carried out by an automatic processor equipped with a developer supply means and a rubbing member. As the automatic processor, for example, an automatic processor described in JP-A-2-220061 and JP-A-60-59351, which performs rubbing while conveying a lithographic printing plate precursor after image recording, Automatic processing for rubbing the lithographic printing plate precursor after image recording set on the cylinder described in the specifications of Patent No. 5148746, US Pat. No. 5,568,768 and British Patent No. 2297719, while rotating the cylinder Machine. Among these, an automatic processor using a rotating brush roll as the rubbing member is particularly preferable. In the present invention, the lithographic printing plate after the rubbing treatment can be optionally washed with water, dried and desensitized.
Although the temperature of the developer can be used at any temperature, it is preferably 10 ° C to 50 ° C.

  The printing plate developed using the developer and the replenisher is treated with a rinsing solution containing washing water, a surfactant, etc. to remove the developer, and then contains insensitive gum arabic and starch derivatives. It is post-treated with an oil. As the post-treatment of the lithographic printing plate precursor according to the invention, these treatments can be used in various combinations.

In addition, as the plate making process of the lithographic printing plate precursor, the entire surface may be heated before exposure, during exposure, and between exposure and development, if necessary. In particular, in the case of a lithographic printing plate precursor subjected to on-press development, it is preferable to perform full exposure or full heating before exposure to the printing step. By such heating or exposure, an image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. Usually, the heating or exposure performed before the development or printing process is preferably performed under mild conditions that do not affect the non-image in order to suppress fogging in the non-image area. From such a point of view, heating is generally performed with a temperature image of 150 ° C. or lower.
Further, in the plate making process in which the development process is performed, it is also effective to perform entire post-heating or entire exposure on the developed image for the purpose of improving image strength and printing durability.
Since there is no limitation on the heating after development before the development, very strong conditions can be used, and the temperature is usually 200 to 500 ° C. In this temperature range, a sufficient image strengthening effect is exhibited, and problems such as deterioration of the support and thermal decomposition of the image portion do not occur.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

[Synthesis Example 1: Synthesis of curable polymer compound (P-1)]
A 2000 ml flask equipped with a condenser and a stirrer was charged with 306.0 g of 1-methoxy-2-propanol and heated to 72.5 ° C. under a nitrogen stream. Methyl methacrylate: 60.1 g, diethylene glycol monomethyl ether methacrylate: 150.6 g, methacrylic acid: 51.65 g, polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.): 5.5 g of 1-methoxy-2 -Propanol: 312.6 g solution was added dropwise over 2.5 hours. After completion of the dropwise addition, the mixture was stirred at 72.5 ° C for 2 hours, V-601: 2.3 g was added, the temperature was raised to 90 ° C, and the mixture was further stirred for 2 hours. The reaction solution was cooled to room temperature to obtain a polymer compound (1) having an acid group.
In the reaction solution of the polymer compound (1) having an acid group, glycidyl methacrylate: 102.3 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical: 0.73 g, tetra Butylammonium trifluoroacetate (O-1): 2.6 g was added, heated again to 90 ° C., and stirred for 8 hours to obtain a curable polymer compound P-1.
The mass average molar mass of the obtained curable polymer compound (P-1) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 1.1 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 2: Synthesis of curable polymer compound (P-1)]
In a reaction solution of the polymer compound (1) having an acid group synthesized by the same method as in Synthesis Example 1, glycidyl methacrylate: 102.3 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 -Oxyl Free radical: 0.73 g, tetramethylammonium trifluoroacetate (O-2): 2.6 g was added, heated again to 90 ° C., and stirred for 8 hours to obtain a curable polymer compound P-1. It was.
The mass average molar mass of the obtained curable polymer compound (P-1) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of the acid value titration, the acid value was 2.8 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 3: Synthesis of Curable Polymer Compound (P-1)]
In a reaction solution of the polymer compound (1) having an acid group synthesized by the same method as in Synthesis Example 1, glycidyl methacrylate: 102.3 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 -Oxyl Free radical: 0.73 g, tetrabutylammonium nonafluorobutanate (O-3): 2.6 g was added, and the mixture was heated again to 90 ° C. and stirred for 8 hours to obtain a curable polymer compound P-1. It was.
The mass average molar mass of the obtained curable polymer compound (P-1) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 2.2 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 4: Synthesis of Curable Polymer Compound (P-1)]
In a reaction solution of the polymer compound (1) having an acid group synthesized by the same method as in Synthesis Example 1, glycidyl methacrylate: 102.3 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 -Oxyl Free radical: 0.73 g, tetrabutylammonium pentafluorobenzoate (O-4): 2.6 g was added, heated again to 90 ° C., and stirred for 8 hours to obtain a curable polymer compound P-1. It was.
The mass average molar mass of the obtained curable polymer compound (P-1) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 2.97 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 5: Synthesis of Curable Polymer Compound (P-1)]
In a reaction solution of the polymer compound (1) having an acid group synthesized by the same method as in Synthesis Example 1, glycidyl methacrylate: 102.3 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 -Oxyl Free radical: 0.73 g, ethyltriphenylphosphonium trifluoroacetate (O-5): 2.6 g was added, heated again to 90 ° C., stirred for 8 hours, and curable polymer compound P-1 was added. Obtained.
The mass average molar mass of the obtained curable polymer compound (P-1) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of the acid value titration, the acid value was 2.8 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 6: Synthesis of Curable Polymer Compound (P-1)]
In a reaction solution of the polymer compound (1) having an acid group synthesized by the same method as in Synthesis Example 1, glycidyl methacrylate: 102.3 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 -Oxyl free radical: 0.73 g, tetrabutylammonium bromoacetate (O-6): 2.6 g was added, and the mixture was heated again to 90 ° C. and stirred for 8 hours to obtain a curable polymer compound P-1. .
The mass average molar mass of the obtained curable polymer compound (P-1) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of the acid value titration, the acid value was 2.8 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 7: Synthesis of curable polymer compound (P-2)]
In a 2000 ml flask equipped with a condenser and a stirrer, 312.6 g of 1-methoxy-2-propanol was placed and heated to 72.5 ° C. under a nitrogen stream. Methyl methacrylate: 100.12 g, diethylene glycol monomethyl ether methacrylate: 150.6 g, methacrylic acid: 17.2 g, V-601: 5.5 g of 1-methoxy-2-propanol: 312.6 g solution over 2.5 hours And dripped. After completion of the dropwise addition, the mixture was stirred at 72.5 ° C for 2 hours, V-601: 2.3 g was added, the temperature was raised to 90 ° C, and the mixture was further stirred for 2 hours. The reaction solution was cooled to room temperature to obtain a polymer compound (2) having an acid group.
In the reaction solution of the polymer compound (2) having an acid group, glycidyl methacrylate: 34.1 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical: 0.60 g, tetra Butylammonium trifluoroacetate (O-1): 2.7 g was added, and the mixture was heated again to 90 ° C. and stirred for 8 hours to obtain a curable polymer compound P-2.
The obtained curable polymer compound (P-2) was measured for mass average molar mass by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 0.56 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 8: Synthesis of Curable Polymer Compound (P-3)]
Cyclomer M100 (manufactured by Daicel Industries, Ltd.): 47.1 g, 4-hydroxy-2,2, and a reaction solution of the polymer compound (2) having an acid group synthesized by the same method as in Synthesis Example 7 above. 6,6-tetramethylpiperidine-1-oxyl free radical: 0.63 g, tetrabutylammonium trifluoroacetate (O-1): 2.7 g was added, heated again to 90 ° C., stirred for 8 hours, and cured. Functional polymer compound P-3 was obtained.
The mass average molar mass of the obtained curable polymer compound (P-3) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 0.56 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 9: Synthesis of Curable Polymer Compound (P-4)]
In a reaction solution of the polymer compound (2) having an acid group synthesized by the same method as in Synthesis Example 7, allyl glycidyl ether: 27.4 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine- 1-oxyl free radical: 0.59 g, tetrabutylammonium trifluoroacetate (O-1): 2.7 g are added, heated again to 90 ° C., stirred for 8 hours, and curable polymer compound P-4 is obtained. Obtained.
The mass average molar mass of the obtained curable polymer compound (P-4) measured by gel permeation chromatography (GPC) using polystyrene as a standard substance was 62,000. Has been confirmed. As a result of acid value titration, the acid value was 0.56 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 10: Synthesis of Curable Polymer Compound (P-5)]
A 2000 ml flask equipped with a condenser and a stirrer was charged with 346.2 g of 1-methoxy-2-propanol and heated to 72.5 ° C. under a nitrogen stream. Methyl methacrylate: 100.12 g, diethylene glycol monomethyl ether methacrylate: 150.6 g, 4- [2- (methacryloyloxy) ethoxy] -4-oxobutanoic acid: 46.0 g, V-601: 5.5 g of 1-methoxy- 2-Propanol: 346.2 g solution was added dropwise over 2.5 hours. After completion of the dropwise addition, the mixture was stirred at 72.5 ° C for 2 hours, V-601: 2.3 g was added, the temperature was raised to 90 ° C, and the mixture was further stirred for 2 hours. The reaction solution was cooled to room temperature to obtain a polymer compound (3) having an acid group.
In the reaction solution of the polymer compound having an acid group (3), glycidyl methacrylate: 27.2 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical: 0.65 g, tetra Butylammonium trifluoroacetate (O-1): 3.0 g was added, heated again to 90 ° C., and stirred for 16 hours to obtain a curable polymer compound P-5.
The obtained curable polymer compound (P-5) was measured for mass average molar mass by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of the acid value titration, the acid value was 2.8 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Comparative Synthesis Example 1]
The curable polymer was synthesized in the same manner as in Synthesis Example 1 except that 2.6 g of tetrabutylammonium trifluoroacetate (O-1) in Synthesis Example 1 was changed to 2.6 g of tetraethylammonium chloride. Compound (R-1) was obtained. As a result of measuring the mass average molar mass (Mw) of the obtained curable polymer compound (R-1) by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 165,000. It was confirmed that Mw increased abnormally. As a result of the acid value titration, the acid value was 1.1 mgKOH / g. It was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Comparative Synthesis Example 2]
Synthesis was performed in the same manner as in Synthesis Example 1 except that 2.6 g of tetrabutylammonium trifluoroacetate (O-1): 2.6 g in Synthesis Example 1 was changed to tetraethylammonium acetate: 2.6 g. A molecular compound (R-2) was obtained. The mass average molar mass of the obtained curable polymer compound (R-2) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 8.4 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Comparative Synthesis Example 3]
The curable polymer was synthesized in the same manner as in Synthesis Example 1 except that 2.6 g of tetrabutylammonium trifluoroacetate (O-1) in Synthesis Example 1 was changed to 2.6 g of triphenylphosphine. Compound (R-3) was obtained. The mass average molar mass of the obtained curable polymer compound (R-3) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 72.9 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Comparative Synthesis Example 4]
The curable polymer was synthesized in the same manner as in Synthesis Example 1 except that 2.6 g of tetrabutylammonium trifluoroacetate (O-1) in Synthesis Example 1 was changed to 2.6 g of dimethylbenzylamine. Compound (R-4) was obtained. The mass average molar mass of the obtained curable polymer compound (R-4) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 10.1 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Comparative Synthesis Example 5]
Synthesis and curing were conducted in the same manner as in Synthesis Example 1 except that 2.6 g of tetrabutylammonium trifluoroacetate (O-1) in Synthesis Example 1 was changed to 2.6 g of tetraethylammonium trifluoropropionate: 2.6 g. Functional polymer compound (R-5) was obtained. The obtained curable polymer compound (R-5) was measured for mass average molar mass by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 10.1 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 11: Synthesis of Curable Polymer Compound (P-6)]
In a 2000 ml flask equipped with a condenser and a stirrer, 215.6 g of 1-methoxy-2-propanol was placed and heated to 72.5 ° C. under a nitrogen stream. A solution of methyl methacrylate: 90.1 g, methacrylic acid: 94.7 g, and V-601: 5.5 g of 1-methoxy-2-propanol: 215.6 g was added dropwise over 2.5 hours. After completion of the dropwise addition, the mixture was stirred at 72.5 ° C for 2 hours, V-601: 2.3 g was added, the temperature was raised to 90 ° C, and the mixture was further stirred for 2 hours. The reaction solution was cooled to room temperature to obtain a polymer compound (4) having an acid group.
In the reaction solution of the polymer compound having an acid group (4), glycidyl methacrylate: 95.5 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical: 0.56 g, tetra Butylammonium trifluoroacetate (O-1): 1.65 g was added, and the mixture was heated again to 90 ° C. and stirred for 6 hours to obtain a curable polymer compound P-6.
The obtained curable polymer compound (P-6) was measured to have a mass average molar mass by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. Moreover, the acid value was 109 mgKOH / g as a result of acid value titration. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 12: Synthesis of Curable Polymer Compound (P-7)]
In a 2000 ml flask equipped with a condenser and a stirrer, 218.9 g of 1-methoxy-2-propanol was placed and heated to 72.5 ° C. under a nitrogen stream. Methyl methacrylate: 110.1 g, methacrylic acid: 77.5 g, V-601: 5.5 g of 1-methoxy-2-propanol: 218.9 g solution was added dropwise over 2.5 hours. After completion of the dropwise addition, the mixture was stirred at 72.5 ° C for 2 hours, V-601: 2.3 g was added, the temperature was raised to 90 ° C, and the mixture was further stirred for 2 hours. The reaction solution was cooled to room temperature to obtain a polymer compound (5) having an acid group.
In the reaction solution of the polymer compound (5) having an acid group, glycidyl methacrylate: 68.2 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical: 0.51 g, tetra Butylammonium trifluoroacetate (O-1): 1.68 g was added, and the mixture was again heated to 90 ° C. and stirred for 6 hours to obtain a curable polymer compound P-7.
The mass average molar mass of the obtained curable polymer compound (P-7) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 118 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 13: Synthesis of Curable Polymer Compound (P-8)]
In a 2000 ml flask equipped with a condenser and a stirrer, 218.2 g of 1-methoxy-2-propanol was placed and heated to 72.5 ° C. under a nitrogen stream. Methyl methacrylate: 106.1 g, methacrylic acid: 80.9 g, V-601: 5.5 g of 1-methoxy-2-propanol: 218.9 g solution was added dropwise over 2.5 hours. After completion of the dropwise addition, the mixture was stirred at 72.5 ° C for 2 hours, V-601: 2.3 g was added, the temperature was raised to 90 ° C, and the mixture was further stirred for 2 hours. The reaction solution was cooled to room temperature to obtain a polymer compound (6) having an acid group.
Cyclomer M100 (manufactured by Daicel Industries, Ltd.): 94.2 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1- Oxyl free radical: 0.56 g, tetrabutylammonium trifluoroacetate (O-1): 1.64 g were added, heated again to 90 ° C., stirred for 6 hours, and curable polymer compound (P-8) was added. Obtained.
The mass average molar mass of the obtained curable polymer compound (P-8) measured by gel permeation chromatography (GPC) using polystyrene as a standard substance was 63,000. Has been confirmed. As a result of acid value titration, the acid value was 117 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 14: Synthesis of Curable Polymer Compound (P-9)]
In a 2000 ml flask equipped with a condenser and a stirrer, 219.2 g of 1-methoxy-2-propanol was placed and heated to 72.5 ° C. under a nitrogen stream. Methyl methacrylate: 112.1 g, methacrylic acid: 75.8 g, V-601: 5.5 g of 1-methoxy-2-propanol: 219.2 g solution was added dropwise over 2.5 hours. After completion of the dropwise addition, the mixture was stirred at 72.5 ° C for 2 hours, V-601: 2.3 g was added, the temperature was raised to 90 ° C, and the mixture was further stirred for 2 hours. The reaction solution was cooled to room temperature to obtain a polymer compound (7) having an acid group.
In the reaction solution of the polymer compound having an acid group (7), allyl glycidyl ether: 54.8 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical: 0.49 g, Tetrabutylammonium trifluoroacetate (O-1): 1.64 g was added, and the mixture was heated again to 90 ° C. and stirred for 6 hours to obtain a curable polymer compound P-9.
The obtained curable polymer compound (P-9) was measured for mass average molar mass by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 118 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Synthesis Example 15: Synthesis of Curable Polymer Compound (P-10)]
A 2000 ml flask equipped with a condenser and a stirrer was charged with 317.7 g of 1-methoxy-2-propanol and heated to 72.5 ° C. under a nitrogen stream. Methyl methacrylate: 102.1 g, 4- [2- (methacryloyloxy) ethoxy] -4-oxobutanoic acid: 225.6 g, V-601: 5.5 g of 1-methoxy-2-propanol: 327.7 g The solution was added dropwise over 2.5 hours. After completion of the dropwise addition, the mixture was stirred at 72.5 ° C for 2 hours, V-601: 2.3 g was added, the temperature was raised to 90 ° C, and the mixture was further stirred for 2 hours. The reaction solution was cooled to room temperature to obtain a polymer compound (8) having an acid group.
In the reaction solution of the polymer compound (8) having an acid group, glycidyl methacrylate: 55.2 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical: 0.77 g, tetra Butylammonium trifluoroacetate (O-1): 2.9 g was added, heated again to 90 ° C., and stirred for 6 hours to obtain a curable polymer compound (P-10).
The mass average molar mass of the obtained curable polymer compound (P-10) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Has been confirmed. As a result of acid value titration, the acid value was 88 mgKOH / g. Furthermore, it was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

[Comparative Synthesis Example 6]
Synthesis was performed in the same manner as in Synthesis Example 10 except that tetrabutylammonium trifluoroacetate (O-1) in Synthesis Example 10 was changed to tetraethylammonium chloride: 1.62 g, and a curable polymer compound (R— 6) was obtained. As a result of measuring the mass average molar mass (Mw) of (R-6) by a gel permeation chromatography method (GPC) using polystyrene as a standard substance, it was 153,000, and Mw increased abnormally. It was confirmed. As a result of acid value titration, the acid value was 125.8 mgKOH / g. It was confirmed from the NMR spectrum that a methacryl group was introduced into the side chain by a polymer reaction.

  The structural formulas of the catalysts used in the synthesis examples and the curable polymer compounds P-1 to P-10 obtained in the synthesis examples are shown below. The number described under each structural unit of the curable polymer compound is a polymerization molar ratio.

[Method for evaluating solution stability of synthesized polymer]
The synthesized polymer solution was heated in an oven at 60 ° C. for 3 days, cooled to room temperature, then subjected to NMR measurement, and the presence or absence of a methacryl group was confirmed to confirm the polymer solution stability.
The evaluation results are shown in Table 1. The case where the methacryl group is still introduced is described as “◯”, and the case where the methacryl group is decomposed and the methacryl group content is decreased is described as “X”.

  Table 1 below summarizes the reactivity and storage stability of the curable polymer compound synthesized under the above synthesis examples.

  As apparent from Table 1 above, according to the production method of the present invention using a carboxylic acid salt having a pKa of 3.0 or less as a catalyst, there is no abnormal increase in Mw, and the epoxy group and acid group are high. The resulting curable polymer compound is stable even when it is stored in the solution after the reaction.

[Examples 1 to 5 and Comparative Example 1]
(1) Preparation of curable polymer compound composition The curable polymer compounds (P-6 to P-10) synthesized in Synthesis Examples 11 to 15 were prepared in a 30% by mass 1-methoxy-2-propanol solution. did. It hardens | cures by mix | blending the trimethylol propane triacrylate (brand name TMP-A Kyoeisha Chemical Co., Ltd. product), a photoinitiator, and a thiol compound with the composition shown in the following Table 2 to the prepared polymer compound solution. Functional polymer compound compositions (Examples 1 to 5) were prepared. In Comparative Example 1, a composition was similarly prepared using the curable polymer compound (R-6) obtained in Comparative Synthesis Example 6 as the curable polymer compound.

(Light sensitivity evaluation)
The curable polymer compound composition of Table 2 and the comparative curable polymer compound composition were applied to a glass substrate having a size of 100 × 100 × 1 mm so that the dry film thickness was about 15 μm using a spin coater. Furthermore, after drying each coated plate with a hot air circulation dryer at 70 ° C. for 30 minutes, a 21-step step tablet (Hitachi Chemical Industry Co., Ltd.) is placed on each coating film, and an ultra-high pressure mercury lamp is installed. It exposed so that it might become 200 mJ / cm < ² > with the built-in exposure apparatus (Ushio Electric Co., Ltd. make, brand name Multilight ML-251A / B). The amount of irradiated ultraviolet rays was measured with a UV integrated light meter UIT-150 (light receiving unit UVD-S365) manufactured by USHIO INC. After the exposure, each coated plate was developed with a 1% by mass aqueous sodium carbonate solution at 30 ° C., then washed with water and dried with an air gun. After that, the number of steps where the coating film remained completely was read. The development time of 1 minute was designated as photosensitivity evaluation-1, and the development time of 2 minutes was designated as photosensitivity evaluation-2. Here, the greater the number of steps, the higher the photosensitivity. Further, the shape of the remaining film was observed with an optical microscope to determine whether it was acceptable. The results are shown in Table 2.

(Evaluation of developability)
Each of the above-mentioned coated plates was developed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. for 30 seconds without being exposed, and then washed with water, dried with an air gun, and the residue of the curable polymer compound composition applied visually was found. The development was evaluated by observing whether it was present. Visually, nothing was present as ○, and there was a residue as ×. The results are shown in Table 2.

  From the results shown in Table 2, the curable polymer compound synthesized by the production method of the present invention has good radical polymerizability and alkali development properties, and therefore can form a coating film having excellent surface curability and alkali developability. A composition can be prepared. On the other hand, since the polymer compound composition of Comparative Example 1 uses a polymer compound in which a crosslinking reaction has progressed during the reaction and Mw has increased, it can be seen that the developability is greatly reduced.

[Examples 6 to 10 and Comparative Example 2]
-Preparation and evaluation of alkali development negative lithographic printing plate precursors-
(1) Manufacture of support JIS A1050 alloy containing 99.5% by mass or more of aluminum, Fe 0.30% by mass, Si 0.10% by mass, Ti 0.02% by mass, and Cu 0.013% by mass The molten metal was cleaned and cast. In the cleaning process, a degassing process was performed to remove unnecessary gases such as hydrogen in the molten metal, and a ceramic tube filter process was performed. The casting method was a DC casting method. The solidified 500 mm thick ingot was chamfered 10 mm from the surface and homogenized at 550 ° C. for 10 hours so as not to coarsen the intermetallic compound. Next, after hot rolling at 400 ° C. and intermediate annealing at 500 ° C. for 60 seconds in a continuous annealing furnace, cold rolling was performed to obtain an aluminum rolled plate having a plate thickness of 0.30 mm. By controlling the roughness of the rolling roll, the centerline average surface roughness Ra after cold rolling was controlled to 0.2 μm. Then, it applied to the tension leveler in order to improve planarity.

  Next, the surface treatment for making a lithographic printing plate support was performed. First, in order to remove the rolling oil on the surface of the aluminum plate, degreasing treatment was carried out with a 10% by mass sodium aluminate aqueous solution at 50 ° C. for 30 seconds, and neutralization and smut removal treatment were conducted with a 30% by mass sulfuric acid aqueous solution at 50 ° C. for 30 seconds.

Next, in order to improve the adhesion between the support and the photosensitive layer and to provide water retention to the non-image rear portion, a so-called graining treatment was performed to roughen the surface of the support. An aqueous solution containing 1% by mass of nitric acid and 0.5% by mass of aluminum nitrate is kept at 45 ° C., and an aluminum web is allowed to flow in the aqueous solution, while an indirect power feeding cell has a current density of 20 A / dm ² and a duty ratio of 1: 1. Electrolytic graining was performed by applying an anode side electric quantity of 240 C / dm ² in an alternating waveform. Thereafter, an etching treatment was performed with a 10% by mass aqueous sodium aluminate solution at 50 ° C. for 30 seconds, and a 30% by mass sulfuric acid aqueous solution was subjected to neutralization and smut removal treatment at 50 ° C. for 30 seconds.

Furthermore, in order to improve wear resistance, chemical resistance and water retention, an oxide film was formed on the support by anodic oxidation. An anodization of 2.5 g / m ² by using a 20% by weight aqueous solution of sulfuric acid as an electrolyte at 35 ° C. and carrying out an electrolytic treatment with a direct current of 14 A / dm ² by an indirect feeding cell while carrying the aluminum web into the electrolyte. A film was prepared.

Thereafter, a silicate treatment was performed to ensure hydrophilicity as a non-image portion of the printing plate. The treatment was carried in such a way that a 1.5 mass% aqueous solution of sodium silicate 3 was maintained at 70 ° C. so that the contact time of the aluminum web was 15 seconds, and further washed with water. The adhesion amount of Si was 10 mg / m ² . Ra (center line surface roughness) of the support prepared as described above was 0.25 μm.

(2) Formation of photosensitive layer The following photosensitive layer coating solution (P-1) was prepared, applied to the aluminum support obtained as described above using a wire bar, and 115 ° C. in a hot air dryer. Was dried for 45 seconds to form a photosensitive layer, and a lithographic printing plate precursor was obtained. The coating amount after drying was in the range of 1.2 to 1.3 g / m ² .
The alkali-soluble polymer compound used in the examples was prepared by preparing the curable polymer compound obtained in the above synthesis example in a 30% by mass 1-methoxy-2-propanol solution.

<Photosensitive layer coating solution (P-1)>
・ Alkali-soluble polymer compound: curable polymer compound (described in Table 3) 6.7 g
Radical polymerizable compound: Pentaerythritol tetraacrylate 1.0 g
・ Infrared absorber “IR-6” [structure shown below] 0.08 g
・ Sulphonium salt “S-1” [the following structure] 0.30 g
・ Victoria Pure Blue Naphthalenesulfonate 0.04g
・ Fluorine-based surfactant 0.01g
(Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 9.0g
・ Methanol 10.0g
1-methoxy-2-propanol 8.0g

(Evaluation of lithographic printing plate precursor)
(1) Exposure The obtained lithographic printing plate precursor was subjected to the conditions of 9 W output, 210 rpm external drum rotation speed, 100 mJ / cm ² plate surface energy, and 2400 dpi resolution on a Trendsetter 3244VFS manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser. Exposed.

(2) Development processing After the exposure, development processing was performed using an automatic developing machine Stablon 900N manufactured by Fuji Film Co., Ltd. As the developer, a 1: 1 water dilution of DN-3C manufactured by Fuji Film Co., Ltd. was used for both the charging solution and the replenisher. The temperature of the developing bath was 30 ° C. As the finisher, a 1: 1 water dilution of FN-6 manufactured by Fuji Film Co., Ltd. was used.

(3) Evaluation of printing durability Next, printing was performed using a printing press Lislon manufactured by Komori Corporation. At this time, the number of sheets that can be printed while maintaining a sufficient ink density was measured visually to evaluate the printing durability. The results are shown in Table 3 above.

(4) Evaluation of stain resistance of non-image area After the obtained lithographic printing plate precursor was stored at 60 ° C. for 3 days and forced to age, the same printing as described above was performed to evaluate the stain resistance of the non-image area. . The results are shown in Table 3.

  From Table 3, the lithographic printing plate precursor using the curable polymer compound of the present invention for the photosensitive layer has no stain on the non-image area, is excellent in printing durability, and is stored in a high temperature and high humidity environment. It was also found that the non-image area stainability did not decrease and the stability over time was excellent.

[Examples 11 to 19 and Comparative Examples 3 to 5]
-Production and evaluation of on-press development type lithographic printing plate precursor-
(1) Preparation of support In order to remove rolling oil on the surface of an aluminum plate (material JIS A 1050) having a thickness of 0.3 mm, degreasing treatment was performed at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution. After that, the aluminum surface was grained using ^three bundle-planted nylon brushes having a bristle diameter of 0.3 mm and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and washed thoroughly with water. . This plate was etched by being immersed in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washed with water, further immersed in 20 mass% nitric acid at 60 ° C for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .

Next, an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass of aluminum ions) and a liquid temperature of 50 ° C. The AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. Went. Ferrite was used for the auxiliary anode. The current density was 30 A / dm ² at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode.
The amount of electricity in the nitric acid electrolysis was 175 C / dm ² when the aluminum plate was the anode. Then, water washing by spraying was performed.

Next, a 0.5% by mass hydrochloric acid aqueous solution (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. and nitric acid electrolysis under the condition of an electric quantity of 50 C / dm ² when the aluminum plate is an anode. In the same manner as above, an electrochemical surface roughening treatment was performed, followed by washing with water by spraying.
Next, the plate was provided with a DC anodized film of 2.5 g / m ² at a current density of 15 A / dm ² using 15% by mass sulfuric acid (containing 0.5% by mass of aluminum ions) as an electrolyte, and then washed with water. Dried.

Then, in order to ensure the hydrophilic property of a non-image part, the silicate process was performed for 12 second at 70 degreeC using 2.5 mass% 3 sodium silicate aqueous solution. The adhesion amount of Si was 10 mg / m ² . Then, it washed with water and the support body (1) was obtained. The centerline average roughness (Ra) of this substrate was measured using a needle having a diameter of 2 μm and found to be 0.51 μm.

(2) Formation of undercoat layer Next, the following undercoat layer coating solution (1) was applied onto the support (1) so that the dry coating amount was 28 mg / m ² , thereby providing an undercoat layer.

<Coating liquid for undercoat layer (1)>
-Undercoat layer compound (1) having the following structure: 0.18 g
・ Hydroxyethyliminodiacetic acid 0.10g
・ Methanol 55.24g
・ Water 6.15g

(3) Formation of photosensitive layer On the undercoat layer formed as described above, a photosensitive layer coating solution having the following composition was bar coated, followed by oven drying at 100 ° C. for 60 seconds, and a dry coating amount of 1.0 g / m. ^Two photosensitive layers were formed.
The photosensitive layer coating solution was obtained by mixing and stirring the following photosensitive solution (1) and microgel solution (1) immediately before coating. The polymer compound used in the examples was prepared by preparing the curable polymer compound obtained in the above synthesis example in a 30% by mass 1-methoxy-2-propanol solution.

<Photosensitive solution (1)>
・ Curable polymer compound
(Compounds listed in Table 4, 30% by mass of 1-methoxy-2-propanol solution)
0.800g
Infrared absorber (1) [the following structure] 0.030 g
-Radical polymerization initiator (1) [the following structure] 0.162 g
Polymerizable compound tris (acryloyloxyethyl) isocyanurate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.192 g
・ Tris (2-hydroxyethyl) isocyanurate 0.062g
・ Low molecular weight hydrophilic compound (1) [the following structure] 0.050 g
-Sensitizing agent Phosphonium compound (1) [the following structure] 0.055 g
・ Sensitizer Benzyl-dimethyl-octylammonium ・ PF ₆ salt 0.018g
・ Fluorosurfactant (1) [The following structure] 0.008g
・ Methyl ethyl ketone 1.091g
・ 1-methoxy-2-propanol 8.609g

<Microgel solution (1)>
・ Microgel (1) 2.640 g
・ Distilled water 2.425g

  The structures of the above infrared absorber (1), radical polymerization initiator (1), phosphonium compound (1), low molecular weight hydrophilic compound (1), and fluorine-based surfactant (1) are as shown below. It is.

  The microgel (1) described above is synthesized as follows.

<Synthesis of Microgel (1)>
As an oil phase component, trimethylolpropane and xylene diisocyanate adduct (manufactured by Mitsui Takeda Chemical Co., Ltd., Takenate D-110N), 10 g of pentaerythritol triacrylate [(C) component] (manufactured by Nippon Kayaku Co., Ltd., SR444) 3.15 g and Piionin A-41C (manufactured by Takemoto Yushi Co., Ltd.) 0.1 g were dissolved in ethyl acetate 17 g. As an aqueous phase component, 40 g of a 4% by mass aqueous solution of PVA-205 was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12,000 rpm using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours. The microgel solution thus obtained was diluted with distilled water to a solid content concentration of 15% by mass, and this was designated as the microgel (1). When the average particle size of the microgel was measured by a light scattering method, the average particle size was 0.2 μm.

(4) Formation of Protective Layer After the bar coating of the protective layer coating solution (1) having the following composition is applied on the photosensitive layer formed as described above, it is oven-dried at 120 ° C. for 60 seconds to obtain a dry coating amount. A protective layer of 0.15 g / m ² was formed to obtain lithographic printing plate precursors (1) to (9) and (R-1) to (R-3).

<Coating liquid for protective layer (1)>
・ Inorganic layered compound dispersion (1) 1.5 g
-Polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. CKS50, sulfonic acid modification,
Saponification degree 99 mol% or more, polymerization degree 300) 6% by mass aqueous solution 0.55 g
・ Polyvinyl alcohol (PVA-405 manufactured by Kuraray Co., Ltd.)
Degree of saponification 81.5 mol%, degree of polymerization 500) 6% by weight aqueous solution 0.03 g
・ Nippon Emulsion Co., Ltd. surfactant (Emalex 710) 1 mass% aqueous solution 8.60 g
・ Ion-exchanged water 6.0g

(Preparation of inorganic layered compound dispersion (1))
6.4 g of synthetic mica Somasif ME-100 (manufactured by Coop Chemical Co., Ltd.) was added to 193.6 g of ion-exchanged water, and dispersed using an homogenizer until the average particle size (laser scattering method) became 3 μm. The aspect ratio of the obtained dispersed particles was 100 or more.

(5) Evaluation of lithographic printing plate precursor The on-press developability and printing durability of the obtained lithographic printing plate precursors (1) to (9) and (R-1) to (R-3) are as follows. evaluated. The results are shown in Table 4.

<On-press developability>
The resulting lithographic printing plate precursor was exposed with a Luxel PLASETTER T-6000III manufactured by FUJIFILM Corporation equipped with an infrared semiconductor laser under conditions of an outer drum rotation speed of 1000 rpm, a laser output of 70%, and a resolution of 2400 dpi. The exposure image includes a solid image and a 50% dot chart of a 20 μm dot FM screen.
The obtained exposed original plate was attached to a plate cylinder of a printing machine LITHRONE 26 manufactured by Komori Corporation without developing. Equality-2 (manufactured by FUJIFILM Corporation) / tap water = 2/98 (volume ratio) dampening water and Values-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.) After dampening water and ink were supplied by the standard automatic printing start method of LITHRONE 26 and developed on the machine, 100 sheets were printed on Tokuhishi Art (76.5 kg) paper at a printing speed of 10,000 sheets per hour.

  The number of print sheets required until the on-press development on the printing machine of the unexposed portion of the photosensitive layer was completed and the ink was not transferred to the non-image portion was measured as on-press developability. The results are shown in Table 4.

<Print durability>
After the on-press developability was evaluated, printing was further continued. As the number of printed sheets was increased, the photosensitive layer was gradually worn out, so that the ink density on the printed material decreased. Printing durability was evaluated using the number of printed copies when the value measured by the Gretag densitometer for the 50% halftone dot area ratio of the FM screen in the printed material was 5% lower than the measured value for the 100th printed sheet. . The results are shown in Table 4.

<Dirty>
The obtained lithographic printing plate precursor was left in a constant temperature and humidity chamber set at 60 ° C. and a relative humidity of 75% for 2 days, then exposed and printed in the same manner as described above, and spot-like stains appearing on the non-image area were observed. Numbers were counted visually. The results are shown in Table 4.

  As can be seen from Table 4, the lithographic printing plate precursor using the curable polymer compound obtained by the production method of the present invention has good on-press developability and printing durability, and excellent stain resistance. ing.

Claims (9)

  A method for producing a curable polymer compound in which an epoxy compound having an ethylenically unsaturated group is added to an acid group present in a polymer compound, wherein a carboxylic acid salt having a pKa of 3.0 or less is used as a catalyst. A method for producing a curable polymer compound, which is characterized by being used.   2. The method for producing a curable polymer compound according to claim 1, wherein the carboxylic acid salt is an onium salt of a carboxylic acid.   The method for producing a curable polymer compound according to claim 1 or 2, wherein the carboxylic acid has at least one fluorine atom. The above-mentioned 1-3, wherein the epoxy compound having an ethylenically unsaturated group is at least one selected from a compound represented by the following general formula (A) and a compound represented by the following general formula (B) The manufacturing method of the curable high molecular compound in any one of.

[In General Formula (A), R ^{1 to} R ⁸ each independently represents a hydrogen atom, a carbonyl group, an alkyloxy group, an alkyl group, an aryl group, a heterocyclic group, or a hydroxy group. Y ¹ represents a single bond or a divalent linking group. In General Formula (B), R ^{9 to} R ¹⁸ each independently represent a hydrogen atom, a carbonyl group, an alkyloxy group, an alkyl group, an aryl group, a heterocyclic group, or a hydroxy group. Y ² represents a single bond or a divalent linking group. ] The curable polymer compound is a polymer compound having at least one selected from the group represented by the following general formula (1) and the group represented by the following general formula (2) in the side chain. The manufacturing method of the curable high molecular compound in any one of Claims 1-4.

[In General Formula (1), R ^{1 to} R ⁸ each independently represents a hydrogen atom, a carbonyl group, an alkyloxy group, an alkyl group, an aryl group, a heterocyclic group, or a hydroxy group. Y ¹ represents a single bond or a divalent linking group. In General Formula (2), R ^{9 to} R ¹⁸ each independently represent a hydrogen atom, a carbonyl group, an alkyloxy group, an alkyl group, an aryl group, a heterocyclic group, or a hydroxy group. Y ² represents a single bond or a divalent linking group. ]   6. The method for producing a curable polymer compound according to claim 1, wherein the acid value of the curable polymer compound is less than 3.0 mgKOH / g.   A curable polymer compound composition comprising the curable polymer compound obtained by the production method according to claim 1.   A lithographic printing plate precursor comprising a curable polymer compound obtained by the production method according to claim 1.   The lithographic printing plate precursor according to claim 8 has a photosensitive layer capable of forming an image on a support by supplying printing ink and fountain solution on a printing machine after exposure to remove unexposed portions. A lithographic printing plate precursor characterized by.