JP2006309071A - Lithographic printing original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithographic printing original plate, permitting direct platemaking by scanning exposure, based on a digital signal and having superior printing durability and satisfactory erasure properties in unwanted image parts. <P>SOLUTION: The lithographic printing original plate has an intermediate layer containing a polymer, having at an end a thioether group, having a carbon number of 5 or larger aliphatic group or an aromatic group as a substitute group and an onium group on a side chain and an infrared laser photosensitive positive recording layer are sequentially provided on a support. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a positive lithographic printing plate precursor capable of recording an image by exposure with an infrared laser and changing the solubility of a recording layer in an exposed portion. More specifically, the present invention relates to a positive lithographic printing plate precursor which can be written by exposure in the near infrared region such as an infrared laser, and can be directly made from a digital signal such as a computer, and has excellent printing durability and erasability. .

In recent years, with the development of solid-state lasers and semiconductor lasers having a light emitting region from the near infrared to the infrared, systems using these infrared lasers are attracting attention as a system for making a plate directly from digital data of a computer.
As a positive lithographic printing plate material for an infrared laser for direct plate making, an image in which a substance that absorbs light and generates heat and a positive photosensitive compound such as a quinonediazide compound is added to an aqueous alkali-soluble resin A recording material has been proposed (see, for example, Patent Document 1). In the image area, the positive photosensitive compound functions as a dissolution inhibitor that substantially lowers the solubility of the alkaline aqueous solution-soluble resin, and heat is generated in the non-image area. It decomposes to cause no dissolution inhibiting ability and can be removed by development to form an image.

  On the other hand, it is known that onium salts and compounds capable of forming a hydrogen-bonding network with low alkali solubility have an alkali dissolution inhibiting action of alkali-soluble polymers. As an image recording material for infrared lasers, it is disclosed that a composition using a cationic infrared absorbing dye as a dissolution inhibitor of an alkaline water-soluble polymer exhibits a positive action (for example, see Patent Document 2). . The positive action in this image recording material is an action in which the infrared absorbing dye absorbs the laser light, and the effect of dissolving the polymer film in the irradiated portion is lost by the generated heat to form an image.

  With respect to the support used for such a lithographic printing plate precursor, there has been extensive research on hydrophilicizing the surface of the support in order to prevent contamination of non-image areas. For example, when a metal support such as an aluminum plate is used as a support, an anodized aluminum substrate (support), or the anodized aluminum substrate is subjected to a silicate treatment in order to further increase the hydrophilicity. Various techniques have been proposed. However, various treatments for improving hydrophilicity are not necessarily excellent in affinity with the recording layer, and in some cases, the adhesion between the support and the recording layer formed thereon is lowered. Therefore, the recording layer peels off under severe printing conditions, and there is a problem that sufficient printing durability cannot be obtained.

  Thus, in order to improve the adhesion between the hydrophilic support surface and the recording layer, a method of providing various intermediate layers between the support and the recording layer has been proposed. In such a method, a resin material constituting the recording layer or a material having a functional group excellent in affinity with the support surface is used as an intermediate layer, so that adhesion in the image area is improved and sufficient printing durability is achieved. Is obtained. However, in the non-image area, the recording layer is not quickly removed at the time of development, and remains as a remaining film on the surface of the support, causing ink to adhere to the non-image area and causing stains. was there. For this reason, a support having excellent surface hydrophilicity and satisfying both the adhesion to the recording layer in the image area and the recording layer removability in the non-image area has been desired.

  In order to solve the above problems, the present inventors have proposed a lithographic printing plate provided with an intermediate layer containing a polymer compound containing a specific structural unit such as p-vinylbenzoic acid (Patent Literature). 3). Further, a lithographic printing plate precursor provided with an intermediate layer containing a polymer (random polymer) containing a monomer having an acid group and a monomer having an onium group has been proposed (see Patent Document 4). These have some improvement effect on printing durability, but as a result of realizing the improved adhesion between the intermediate layer and both the support and the recording layer, even after the recording layer is removed after alkali development, If the intermediate layer that is in close contact with the support is not sufficiently removed, or if it is necessary to correct the image, the intermediate layer that is in close contact with the support is sufficiently removed by the erasing liquid even after the image area is erased by treatment with the erasing liquid. However, there is a problem that the ink is deposited on the image area which should have been erased, and stains occur.

JP-A-7-285275 International Publication No. 97/39894 Pamphlet JP-A-10-69092 JP 2000-108538 A

  An object of the present invention, which has been made in consideration of the drawbacks of the above-described conventional techniques, is that direct plate-making by scanning exposure based on digital signals is possible, excellent in printing durability, and erasing unnecessary image portions with an erasing liquid It is to provide a lithographic printing plate precursor having excellent properties.

As a result of extensive research, the present inventors have found that the above problem can be solved by providing an intermediate layer containing a specific polymer between the support and the recording layer, and the present invention has been completed. It came to do.
That is, the lithographic printing plate precursor of the present invention is a polymer having a thioether group having an aliphatic group having 5 or more carbon atoms or an aromatic group as a substituent at the terminal and an onium group in the side chain on a support. And an infrared laser-sensitive positive recording layer are sequentially provided.

  Here, “sequentially provided” means that an intermediate layer and a recording layer are provided in this order on a support, and other layers (for example, a protective layer, a backcoat layer, etc.) provided according to the purpose. ) Is not denied.

Although the operation of the present invention is not clear, it is considered as follows.
That is, the specific polymer contained in the intermediate layer according to the present invention has an ionic onium group in its side chain, so that it can form a strong interaction with the hydrophilized support surface. It is considered that the adhesion between the recording layer and the recording layer is improved, and the printing durability can be improved.
Furthermore, the specific polymer has an aliphatic group having 5 or more carbon atoms, or a thioether group having an aromatic group as a substituent at the end, so that the solubility in an erasing liquid that is an organic solvent is improved and excellent. It is considered that the erasability is expressed.

  According to the present invention, it is possible to provide a lithographic printing plate precursor capable of direct plate making by scanning exposure based on a digital signal, excellent in printing durability, and excellent in erasure of unnecessary image areas by an erasing liquid. Can do.

Hereinafter, the present invention will be described in detail.
The lithographic printing plate precursor according to the invention contains, on a support, a polymer having an aliphatic group having 5 or more carbon atoms or a thioether group having an aromatic group as a substituent at the terminal and an onium group in the side chain. The intermediate layer and the infrared laser-sensitive positive recording layer are sequentially provided.

[Middle layer]
[Specific polymer]
The intermediate layer according to the present invention contains a polymer (specific polymer) having an aliphatic group having 5 or more carbon atoms or a thioether group having an aromatic group as a substituent at the terminal and an onium group in the side chain. The specific polymer is a relatively low molecular weight polymer synthesized using a chain transfer agent. Hereinafter, each monomer for obtaining the specific polymer and a method for synthesizing the specific polymer will be sequentially described.

<Monomer having an onium group>
The specific polymer according to the present invention has an onium group in its side chain, and the onium group can be introduced into the specific polymer by using a monomer having an onium group as a raw material.

  Examples of the monomer having an onium group include, but are not limited to, monomers represented by the following general formula (A) to general formula (C).

In general formulas (A) to (C), J represents a divalent linking group. K represents an aromatic group or a substituted aromatic group. M represents a divalent linking group. Y ¹ represents a group V atom in the periodic table. Y ² represents an atom belonging to Group VI of the periodic table. Z ⁻ represents a counter anion. R ² represents a hydrogen atom, an alkyl group, or a halogen atom. R ³ , R ⁴ , R ⁵ , and R ⁷ each independently represent a hydrogen atom, an alkyl group, an aromatic group, or an aralkyl group, and these may further have a substituent. R ⁶ represents an alkylidine group or a substituted alkylidine group. R ³ and R ⁴ , R ⁶ and R ⁷ may be bonded to each other to form a ring. j, k, and m each independently represent 0 or 1. u represents an integer of 1 to 3.

Among the monomers having an onium group represented by the general formulas (A) to (C), more preferable are the following cases.
J represents -COO- or -CONH-, and K represents a phenylene group or a substituted phenylene group. The substituent introduced when K is a substituted phenylene group is preferably a hydroxyl group, a halogen atom, or an alkyl group.
M is an alkylene group and a divalent linking group having a molecular formula of C _n H _2n O, C _n H _2n S, or C _n H _{2n + 1} N. However, n represents the integer of 1-12 here.
Y ¹ represents a nitrogen atom or a phosphorus atom, and Y ² represents a sulfur atom.
Z ⁻ represents a halogen ion, PF ₆ ⁻ , BF ₄ ⁻ , or R ⁸ SO ₃ ^— .
R ² represents a hydrogen atom or an alkyl group.
R ³ , R ⁴ , R ⁵ , and R ⁷ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms to which a substituent may be bonded. Represents a group or a C7-10 aralkyl group.
R ⁶ is preferably an alkylidine group having 1 to 10 carbon atoms or a substituted alkylidine. R ³ and R ⁴ , R ⁶ and R ⁷ may be bonded to each other to form a ring.
j, k, and m each independently represent 0 or 1, but j and k are preferably not 0 at the same time.
R ⁸ represents an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms to which a substituent may be bonded.

Among the monomers having an onium group represented by the general formulas (A) to (C), particularly preferred are the following cases.
K represents a phenylene group or a substituted phenylene group, and when it is a substituted phenylene group, the substituent represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
M represents an alkylene group having 1 to 2 carbon atoms or an alkylene group having 1 to 2 carbon atoms linked by an oxygen atom.
Z ⁻ represents a chlorine ion or R ⁸ SO ₃ ^— . R ² represents a hydrogen atom or a methyl group. j is 0 and k is 1. R ⁸ represents an alkyl group having 1 to 3 carbon atoms.

  In the specific polymer, the content of the monomer component having an onium group is preferably 1 mol% or more and more preferably 5 mol% or more from the viewpoint of sufficiently exerting the effect of improving printing durability by interaction with the support. Preferably, 8 mol% or more is more preferable.

  Although the specific example of the monomer which has an onium group used suitably for a specific polymer below is given, this invention is not limited to these.

  In addition to the above-mentioned “monomer having an onium group”, the specific polymer according to the present invention contains other monomer components for the purpose of further strengthening the interaction with the support or the interaction with the recording layer. It may be polymerized. As the other monomer component, for example, from the viewpoint of improving the adhesion with the hydrophilic treatment substrate, "monomer having an amino acid group", from the viewpoint of improving the adhesion with the hydrophilic treatment substrate and improving the developer solubility. From the viewpoint of improving the adhesion to the recording layer, “monomer having an acid group”, “monomer having a functional group capable of interacting with the recording layer” and the like can be mentioned.

<Monomer having an amino acid group>
The monomer which has an amino acid group used suitably for a specific polymer is demonstrated.
The monomer having an amino acid group is not particularly limited as long as it has both an N atom and a —COOH group in its structure, but an amino acid group represented by the following general formula (I) is preferable.

  In general formula (I), Y represents a linking group to the polymer main chain skeleton. Examples of the linking group represented by Y include a substituted or unsubstituted divalent hydrocarbon group. The hydrocarbon group may have one or more partial structures containing one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom.

In general formula (I), R ¹ represents a hydrogen atom or a monovalent organic group. Preferred examples of the monovalent organic group include a hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The hydrocarbon group includes a nitrogen atom, an oxygen atom, and a sulfur atom. It may have a partial structure containing one or more heteroatoms selected from the group consisting of.
Among these hydrocarbon groups, an alkyl group or an aryl group is more preferable.
The hydrocarbon group represented by R ¹ may further have a substituent described later, and the substituent is particularly preferably a group composed of a carboxyl group and a salt thereof.
As the hydrocarbon group represented by R ¹ , the most preferred embodiment is an alkyl group and an aryl group having a carboxyl group or a group consisting of a salt thereof.

The hydrocarbon group in R ¹ and the substituent that can be introduced into the hydrocarbon group will be described in detail.
Specific examples of the alkyl group represented by R ¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methyl A hexyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-norbornyl group and the like have 1 to 30 carbon atoms, and examples thereof include a linear, branched, or cyclic alkyl group.

The aryl group represented by R ¹ includes those in which 2 to 4 benzene rings form a condensed ring and those in which a benzene ring and an unsaturated 5-membered ring form a condensed ring.
Specific examples of the aryl group represented by R ¹ include aryl groups having 6 to 30 carbon atoms such as phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acebutenyl group, fluorenyl group, and pyrenyl group. Groups.

The hydrocarbon group represented by R ¹ may be substituted at one or more locations with any substituent. Examples of the substituent that can be introduced into R ¹ include a monovalent nonmetallic atomic group excluding a hydrogen atom. Specific examples include halogen atoms (-F, -Br, -Cl, -I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino 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, acylthio group , Acylamino group, N-alkylacylamino N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl- N'-arylureido group, N-alkylureido group, N-arylureido group, 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 An alkylureido group, an N ′, N′-diaryl-N-arylureido group,

N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxy Carbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and salts thereof A group consisting of: 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, alkyl A sulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its a salt group, alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and the like Group consisting of salt, N-alkylsulfonylsulfamoyl group -SO ₂ NHSO ₂ (alkyl)) and its a salt group, N- aryl sulfonylsulfamoyl group _{(-SO 2 NHSO 2 (aryl)} ) and its a salt group, N- alkylsulfonylcarbamoyl group (-CONHSO ₂ (alkyl)) and a salt thereof,

N-arylsulfonylcarbamoyl group (—CONHSO ₂ (aryl)) and a salt thereof, alkoxysilyl group (—Si (Oalkyl) ₃ ), aryloxysilyl group (—Si (Oaryl) ₃ ), hydroxysilyl group ( -Si (OH) ₃ ) and groups thereof, phosphono groups (-PO ₃ H ₂ ) and groups thereof, dialkylphosphono groups (-PO ₃ (alkyl) ₂ ), diarylphosphono groups (- PO ₃ (aryl) ₂ ), an alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ H (alkyl)) and a salt thereof, a monoarylphosphono group (-PO ₃ H (aryl)) and its a salt group, phosphonooxy group (-OPO ₃ H ₂₎ and its a salt group, a dialkyl Suhonookishi group _{(-OPO 3 (alkyl) 2)} , diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonooxymethyl Group (—OPO ₂ H (alkyl)) and a salt thereof, monoarylphosphonooxy group (—OPO ₃ H (aryl)) and a group thereof, cyano group, nitro group, aryl group, alkyl group Alkenyl group and alkynyl group.

Among these, as the substituent that can be introduced into R ¹ , a group consisting of a carboxyl group and a salt thereof, an alkoxycarbonyl group, and an aryloxycarbonyl group are more preferable, and a group consisting of a carboxyl group and a salt thereof is particularly preferable.

In general formula (I), R ² represents a divalent organic group and may further have a substituent. The organic group is preferably a hydrocarbon group, and the hydrocarbon group may contain one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom.

Examples of the substituent that can be introduced into R ² include the same substituents as those described as the substituent that can be introduced into R ¹ , and the preferred substituents are also the same.

The divalent hydrocarbon group represented by R ² is more preferably an alkylene group which may have a substituent or a phenylene group. Specific examples include a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, an isopropylene group, and an isobutylene group, and a phenylene group. Moreover, as a more preferable form, what substituted the carboxylic acid group to the said alkylene group is mentioned.

  The carboxylic acid group contained in the general formula (I) may form an alkali metal salt or an ammonium salt.

A more preferred structure of the general formula (I) is a hydrocarbon group in which R ¹ is substituted with a carboxylic acid group, and R ² is a hydrocarbon group substituted with a linear hydrocarbon group or a carboxylic acid group This is the case. Furthermore, the most preferable structure of the general formula (I) is a case where R ¹ is an alkyl group substituted with a carboxylic acid group, and R ² is a linear alkylene group.

  As a method for introducing the amino acid group structure represented by the general formula (I) as a side chain into the polymer, for example, a monomer having a structure represented by the general formula (I) is polymerized or copolymerized by a known method. do it. Other methods include a method of reacting poly-p-aminostyrene and chloroacetic acid, and a method of hydrolyzing after reacting polychloromethylstyrene and iminodiacetonitrile. From the viewpoint of more easily controlling the introduction rate of the structure represented by the general formula (I), a method of polymerizing or copolymerizing the monomer having the structure represented by the general formula (I) by a known method is preferable. .

  As a monomer which has a structure represented by general formula (I), what contains the following structures is more preferable.

  Moreover, the following structure is mentioned as a preferable structure of a coupling group with the polymer principal chain skeleton represented by Y.

  Specific examples of the monomer having the structure represented by the general formula (I) include the following compounds, but the present invention is not limited thereto.

<Monomer having an acid group>
The monomer having an acid group that is suitably used for the specific polymer will be described.
The acid group contained in the monomer having an acid group is particularly preferably a carboxylic acid group, a sulfonic acid group, or a phosphonic acid group, but is not limited thereto.

-Monomer having a carboxylic acid group-
The monomer having a carboxylic acid group is not particularly limited as long as it is a polymerizable compound having a carboxylic acid group and a polymerizable double bond in its structure.
Preferable examples of the monomer having a carboxylic acid group include compounds represented by the following general formula (1).

In General Formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group, or an organic group represented by the following General Formula (2), and at least one of R ^{1 to} R ⁴ is: It is an organic group represented by the general formula (2).
Here, from the viewpoint of copolymerizability and raw material availability when producing the specific polymer, R ^{1 to} R ⁴ may have 1 to 2 organic groups represented by the following general formula (2). It is particularly preferable to have one. From the viewpoint of the flexibility of the specific polymer obtained as a result of the polymerization, among R ^{1 to} R ⁴ , in addition to the organic group represented by the following general formula (2), an alkyl group or a hydrogen atom is preferable. Particularly preferred is a hydrogen atom.
For the same reason, when R ^{1 to} R ⁴ are alkyl groups, they are preferably alkyl groups having 1 to 4 carbon atoms, and particularly preferably methyl groups.

  In the general formula (2), X represents a single bond, an alkylene group, an arylene group which may have a substituent, or any one of the following structural formulas (i) to (iii). From the viewpoints of polymerizability, availability, etc., a single bond, an arylene group represented by a phenylene group, or one represented by the following structural formula (i) is preferred, and an arylene group or the following structural formula (i) is preferred. Those represented by the following structural formula (i) are particularly preferred.

In structural formulas (i) to (iii), Y represents a divalent linking group, and Ar represents an arylene group which may have a substituent. Y is preferably an alkylene group having 1 to 16 carbon atoms or a single bond. Methylene (—CH ₂ —) in an alkylene group is an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond (—CONR—; R is a hydrogen atom or an alkyl A bond which may be substituted with a methylene group, an ether bond or an ester bond is particularly preferable.
Among such divalent linking groups, particularly preferred specific examples are listed below.

  Particularly preferable examples of the monomer having a carboxylic acid group represented by the general formula (1) are shown below, but the present invention is not limited thereto.

-Monomers having sulfonic acid groups-
The monomer having a sulfonic acid group is not particularly limited as long as it is a polymerizable compound having a sulfonic acid group and a polymerizable double bond in its structure.
Preferable specific examples of the monomer having a sulfonic acid group include 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and 4-styrene sulfonic acid.

-Monomer having a phosphonic acid group-
The monomer having a phosphonic acid group is not particularly limited as long as it is a polymerizable compound having a phosphonic acid group and a polymerizable double bond in its structure.
Preferable specific examples of the monomer having a phosphonic acid group include acid phosphooxyethyl methacrylate, 3-chloro-2-acid phosphooxypropyl methacrylate, and acid phosphoxypolyoxyethylene glycol monomethacrylate.

<Monomer having a functional group capable of interacting with the recording layer>
Specific examples of the monomer having a functional group capable of interacting with the recording layer that can be introduced into the specific polymer of the present invention will be given below, but the present invention is not limited thereto.

  (1) N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o- or m-bromo-p-hydroxysterene, o- or Acrylamides having an aromatic hydroxyl group such as m-chloro-p-hydroxyquinstyrene, o-, m- or p-hydroxyphenyl acrylate or methacrylate, methacrylamides, acrylic esters, methacrylic esters and hydroxystyrenes ;

  (2) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) naphthyl] acrylamide Acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacryl Amides, methacrylamides such as N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, o-aminosulfonylphenyl acrylate, m-aminosulfonylphenyl Nyl acrylate, p-aminosulfonylphenyl acrylate, unsaturated sulfonamides such as acrylic esters such as 1- (3-aminosulfonylphenylnaphthyl) acrylate, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p- Unsaturated sulphonamides such as methacrylic acid esters such as aminosulfonylphenyl metatalylate and 1- (3-aminosulfonylphenylnaphthyl) methacrylate;

(3) phenylsulfonylacrylamide, which may have a substituent such as tosylacrylamide, and phenylsulfonylmethacrylamide, which may have a substituent such as tosylmethacrylamide;
(4) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate;

  (5) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid-2 -(Substituted) acrylic esters such as chloroethyl, 4-hydroxybutyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate;

  (6) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid-2 -(Substituted) methacrylate esters such as chloroethyl, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate;

  (7) Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-hexyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N- Cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide Acrylamide or methacrylate such as N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide De;

  (8) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether;

(9) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate;
(10) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene;
(11) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone;
(12) Olefin such as ethylene, propylene, isobutylene, butadiene, isoprene;

(13) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc .;
(14) Lactone group-containing monomers such as pantoyl lactone (meth) acrylate, α- (meth) acryloyl-γ-butyrolactone, β- (meth) acryloyl-γ-butyrolactone;
(15) Ethylene oxide group-containing monomers such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and methoxypolyethylene glycol mono (meth) acrylate.

  As a combination of monomer components constituting the specific polymer, among the above-mentioned monomers, a monomer having a carboxylic acid group, a monomer having a phosphonic acid group, (4), (5) acrylic acid ester, (6) methacrylic acid ester , (8) vinyl ethers, (12) vinyl olefins, (13), (14), (15) are preferred, monomers having a carboxylic acid group, (4), (5) acrylic acid ester, (6) methacrylic acid Acid esters, (8) vinyl ethers, (13), (14) and (15) are more preferred.

Moreover, 300-20000 are preferable, as for the weight average molecular weight of a specific polymer, 500-18000 are more preferable, and 1000-15000 are still more preferable.
In addition, when a specific polymer is a copolymer, any of a random copolymer, a block copolymer, or a graft copolymer may be sufficient.

[Synthesis of specific polymers]
The method for synthesizing the specific polymer according to the present invention is not particularly limited, but a monomer having an onium group and other monomers used as required are used as raw materials, and in the presence of a polymerization initiator, the number of carbon atoms is 5 Examples include a method of adding and synthesizing a thiol compound having the above aliphatic group or aromatic group as a substituent (hereinafter referred to as “specific thiol compound” as appropriate). The specific thiol compound is preferably used as a chain transfer agent. The thiol compound may be added all at once, divided or continuously, or the two methods may be used simultaneously. For example, the following methods (a), (b) and (c) can be mentioned.
(A) A method in which all of the monomer mixture and chain transfer agent are charged in a reaction vessel, and copolymerization is performed by adding a polymerization initiator into the reaction vessel.
(B) A method of carrying out copolymerization by charging a part of the monomer mixture into the reaction vessel and adding the chain transfer agent, the polymerization initiator, and the remaining monomer mixture into the reaction vessel.
(C) A method in which a polymerization solvent is charged into a reaction vessel, and all of monomers, a chain transfer agent, and a polymerization initiator are added.

<A thiol compound having an aliphatic group having 5 or more carbon atoms or an aromatic group>
The specific thiol compound used for the synthesis of the specific polymer according to the present invention has an aliphatic group having 5 or more carbon atoms or an aromatic group as a substituent of the thiol group.
The aliphatic group having 5 or more carbon atoms in the specific thiol compound is a linear, branched or cyclic alkyl group having 5 or more carbon atoms (preferably 5 or more and 35 or less, more preferably 5 or more and 30 or less). It is preferable.
Examples of the aromatic group in the specific thiol compound include benzene, naphthalene, phenanthrene, anthracene, pyrene, pyridine, quinoline, isoquinoline, indene, indole, benzofuran, fluorene, dibenzofuran, etc., and in particular, benzene, naphthalene, phenanthrene, pyridine. It is preferable that
In addition, the aliphatic group or aromatic group having 5 or more carbon atoms may further have a substituent, and examples of the substituent that can be introduced include a hydroxyl group, a halogen atom, an alkyl group, and an aryl group. It is done.

Although it does not specifically limit as a specific thiol compound, For example, isoamyl mercaptan, 1-octanethiol, nonyl mercaptan, 1-decanethiol, 1-dodecanethiol, hexadecyl mercaptan, octadecyl mercaptan, 3-methyl-1-propanethiol, Cyclohexyl mercaptan, 1,8-octanedithiol, 1,6-hexanedithiol, 1,9-nonanedithiol, stearyl mercaptan, benzyl mercaptan, 2,4,6-trimethylbenzyl mercaptan, phenethyl mercaptan, 4-methoxy-α-toluene Thiol, cyclopentyl mercaptan, cyclohexyl mercaptan, 2-naphthalenethiol, o-toluenethiol, m-toluenethiol, p-toluenethiol, 5-ter - and butyl-2-methyl-thio phenol.
Among these, from the viewpoint of solubility in the erasing solution, 1-octanethiol, cyclohexyl mercaptan, stearyl mercaptan, nonyl mercaptan, 1-decanethiol, 1-dodecanethiol, hexadecyl mercaptan, octadecyl mercaptan, 3-methyl- 1-propanethiol, benzyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, o-toluenethiol, m-toluenethiol, and p-toluenethiol are preferred.

  As for the specific thiol compound, only one kind may be used, and two or more kinds may be used in combination as long as the effect is not impaired, but the addition amount at the time of synthesis is 1 mol% or more based on the total amount of charged monomers. Preferably, it is 13 mol% or less. A particularly preferred addition amount is 2.5 mol% or more and 10 mol% or less.

<Polymerization initiator>
As polymerization initiators used for the synthesis of specific polymers, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2 , 2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1- Azonitrile-based initiators such as cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, 2,2 ′ Azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-cyclophenyl) -2methyl-propiona Midine] dihydrochloride, 2,2′-azobis [N- (4-hydroxyphenyl) 2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydro Chloride, 2,2′-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N Azoamidine-based initiators such as-(2-hydroxyethyl) -2-methyl-propionamidine] dihydrochloride;

2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (3,4) , 5,6-Tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride 2,2′-azobis [2- (1- (2-hydroxyethyl) -2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2 imidazole) Cyclic amidine-based initiators such as [Rin-2-yl) propane], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2 , 2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide , Azoamide initiators such as 2,2′-azobis (2-methylpropionamide) dihydrate,

Alkyl azo initiators such as 2,2′-azobis (2,4,4-trimethylpropane) and 2,2′-azobis (2-methylpropane), dimethyl 2,2′-azobis (2-methylpro) Pionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis [2- (hydroxymethyl) propionitrile] and the like.
These polymerization initiators are, for example, V-70, V-65, V-60, V-59, V-40, V-30, V-19 (above, azonitrile series) manufactured by Wako Pure Chemical Industries, Ltd. VA-545, VA-546, VA-548, VA-552, VA-553, VA-50, VA-558 (above, azoamidine series), VA-041, VA-044, VA-054, VA-058, VA-059, VA-060, VA-061 (above, cyclic azoamidine series), VA-080, VA-082, VA-086, VA-088 (above, azoamide series), VR-110, VR-160 (above) , Alkylazo series), V-601, V-501, VF-077, and the like, and such commercially available products can also be suitably used for the synthesis of the specific polymer according to the present invention.
Among them, preferably, dimethyl 2,2′-azobis (2-methylpropionate) (as a commercial product, manufactured by Wako Pure Chemical: V-601), 2,2′-azobis (2,4-dimethylvalero) Nitrile) (commercially available product, Wako Pure Chemicals: V-65).

  Such polymerization initiators may be used alone or in combination of two or more according to the purpose. As an addition amount at the time of synthesis, an initiator addition amount at the time of synthesis is preferably 1 mol% or more, and preferably 10 mol% or less. A particularly preferable addition amount is 1.5 mol% or more and 8 mol% or less.

<Polymerization solvent>
As polymerization solvents used in the synthesis, acetone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy -2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, ethyl acetate, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, toluene, water and the like can be mentioned, but are not limited thereto. Not.

The synthesis method of the specific polymer may be performed in the same manner as a known synthesis method, and as the polymerization method, solution polymerization, emulsion polymerization, suspension polymerization, or the like is applied, and the solution polymerization method is preferable.
The specific polymer according to the present invention is adjusted to a relatively low molecular weight by the function of the chain transfer agent (specific thiol compound). The preferred range of the weight average molecular weight in the specific polymer is as described above, but such low molecular weight confirmation is carried out by comparing the viscosity with a polymer synthesized by a method not using a chain transfer agent. be able to.

  Hereinafter, although the specific example (P-1 to P-7) of the specific polymer which concerns on this invention is given, this invention is not limited to these.

  The content of the specific polymer in the intermediate layer is preferably 50 to 100% by mass and more preferably 80 to 100% by mass with respect to the total solid content constituting the intermediate layer.

(Formation of intermediate layer)
The intermediate layer according to the present invention can be provided by applying a coating solution (intermediate layer forming coating solution) in which each component of the above-described intermediate layer is dissolved onto the support described later by various methods. Although there is no restriction | limiting in particular in the method of apply | coating an intermediate | middle layer, The following method is mentioned as a typical thing.
That is, (1) a solution in which the specific polymer in the present invention is dissolved in an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof, or a mixed solvent of these organic solvent and water is placed on a support. Application method that is applied and dried. Alternatively, (2) the support is immersed in a solution in which the specific polymer in the present invention is dissolved in an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof, or a mixed solvent of these organic solvent and water. However, after that, there may be mentioned a coating method in which an intermediate layer is provided by washing and drying with water or air.

  In the application method (1), a solution having a concentration of 0.005 to 10% by mass in total may be applied by various methods. As the coating means, any means such as bar coater coating, spin coating, spray coating, curtain coating, etc. may be used. In the coating method (2), the concentration of the solution is 0.005 to 20% by mass, preferably 0.01% to 10% by mass, and the immersion temperature is 0 ° C. to 70 ° C., preferably 5 to 60 ° C. The infiltration time is 0.1 seconds to 5 minutes, preferably 0.5 seconds to 120 seconds.

The above intermediate layer forming coating solution includes basic substances such as ammonia, triethylamine, potassium hydroxide, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid, organic sulfonic acids such as nitrobenzene sulfonic acid, naphthalene sulfonic acid, Adjust pH with various organic acidic substances such as organic phosphonic acid such as phenylphosphonic acid, organic carboxylic acid such as benzoic acid, coumaric acid and malic acid, organic chloride such as naphthalenesulfonyl chloride, benzenesulfonyl chloride, etc., pH = 0 12, More preferably, it can also be used in the range of pH = 0-6.
In addition, a substance that absorbs ultraviolet light, visible light, infrared light, or the like may be added to the coating solution for forming an intermediate layer in order to improve the tone reproducibility of the lithographic printing plate.

The total coating amount of the intermediate layer in the present invention after drying is appropriately 1 to 100 mg / m ² , and preferably ² to 70 mg / m ² .

[Recording layer]
The infrared laser photosensitive positive recording layer (hereinafter referred to as “recording layer” as appropriate) according to the present invention will be described. The recording layer preferably comprises (A) an alkali-soluble resin, (B) an infrared absorber, and (C) other components as necessary. Hereinafter, each component contained in the recording layer will be sequentially described.

[(A) Alkali-soluble resin]
The recording layer according to the present invention preferably contains an alkali-soluble resin. The alkali-soluble resin includes a homopolymer containing an acidic group in the main chain and / or side chain in the polymer, a copolymer thereof, or a mixture thereof.
Among these, those having an acidic group listed in the following (1) to (6) in the main chain and / or side chain of the polymer are preferable from the viewpoint of solubility in an alkaline developer and expression of dissolution inhibiting ability.

(1) Phenol group (-Ar-OH)
(2) Sulfonamide group (—SO ₂ NH—R)
(3) Substituted sulfonamide acid group (hereinafter referred to as “active imide group”)
[—SO ₂ NHCOR, —SO ₂ NHSO ₂ R, —CONHSO ₂ R]
(4) Carboxylic acid group (—CO ₂ H)
(5) Sulfonic acid group (—SO ₃ H)
(6) Phosphate group (—OPO ₃ H ₂ )

  In the above (1) to (6), Ar represents a divalent aryl linking group which may have a substituent, and R represents a hydrogen atom or a hydrocarbon group which may have a substituent. .

  Among the alkali-soluble resins having an acidic group selected from the above (1) to (6), (1) an alkali-soluble resin having a phenol group, (2) a sulfonamide group, and (3) an active imide group is preferable. An alkali-soluble resin having (1) a phenol group or (2) a sulfonamide group is most preferable from the viewpoint of sufficiently ensuring solubility in an alkaline developer, development latitude, and film strength.

Examples of the alkali-soluble resin having an acidic group selected from the above (1) to (6) include the following.
(1) Examples of the alkali-soluble resin having a phenol group include a condensation polymer of phenol and formaldehyde, a condensation polymer of m-cresol and formaldehyde, a condensation polymer of p-cresol and formaldehyde, m− / p. A novolak resin such as a condensation polymer of mixed cresol and formaldehyde, a condensation polymer of phenol and cresol (any of m-, p-, or m- / p-mixing) and formaldehyde, and pyrogallol and acetone Can be mentioned. Furthermore, the copolymer which copolymerized the compound which has a phenol group in a side chain can also be mentioned. Alternatively, a copolymer obtained by copolymerizing a compound having a phenol group in the side chain can also be used.

  Examples of the compound having a phenol group include acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, and hydroxystyrene having a phenol group.

  (2) As an alkali-soluble resin having a sulfonamide group, for example, a polymer composed of a minimum constituent unit derived from a compound having a sulfonamide group as a main constituent can be mentioned. Examples of the compound as described above include compounds having at least one sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom and one or more polymerizable unsaturated groups in the molecule. Among these, low molecular weight compounds having an acryloyl group, an allyl group, or a vinyloxy group and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group in the molecule are preferable. For example, the following general formulas (i) to (v) The compound represented by these is mentioned.

In general formulas (i) to (v), X ¹ and X ² each independently represent —O— or —NR ⁷ . R ¹ and R ⁴ each independently represents a hydrogen atom or —CH ₃ . R ² , R ⁵ , R ⁹ , R ¹² and R ¹⁶ each independently represent a C 1-12 alkylene group, cycloalkylene group, arylene group or aralkylene group which may have a substituent. R ³ , R ⁷ and R ¹³ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. R ⁶ and R ¹⁷ each independently represent a C 1-12 alkyl group, cycloalkyl group, aryl group, or aralkyl group that may have a substituent. R ⁸ , R ¹⁰ and R ¹⁴ each independently represent a hydrogen atom or —CH ₃ . R ¹¹ and R ¹⁵ each independently represent a C 1-12 alkylene group, cycloalkylene group, arylene group or aralkylene group which may have a single bond or a substituent. Y ¹ and Y ² each independently represent a single bond or CO.

  Among the compounds represented by the general formulas (i) to (v), in the lithographic printing plate precursor according to the invention, in particular, m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- ( p-Aminosulfonylphenyl) acrylamide and the like can be preferably used.

  (3) As an alkali-soluble resin having an active imide group, for example, a polymer composed of a minimum constituent unit derived from a compound having an active imide group as a main constituent can be mentioned. Examples of the compound as described above include compounds each having one or more active imide groups represented by the following structural formula and polymerizable unsaturated groups in the molecule.

  Specifically, N- (p-toluenesulfonyl) methacrylamide, N- (p-toluenesulfonyl) acrylamide and the like can be preferably used.

(4) As an alkali-soluble resin having a carboxylic acid group, for example, a minimum structural unit derived from a compound having at least one carboxylic acid group and polymerizable unsaturated group in the molecule is used as a main constituent component. A polymer can be mentioned.
(5) As an alkali-soluble resin having a sulfonic acid group, for example, a minimum structural unit derived from a compound having one or more sulfonic acid groups and polymerizable unsaturated groups in the molecule is used as a main structural unit. A polymer can be mentioned.
(6) As an alkali-soluble resin having a phosphate group, for example, a minimum structural unit derived from a compound having at least one phosphate group and a polymerizable unsaturated group in the molecule is used as a main constituent component. A polymer can be mentioned.

  The minimum structural unit having an acidic group selected from the above (1) to (6) that constitutes the alkali-soluble resin used in the recording layer is not necessarily limited to one kind, and is the minimum structural unit having the same acidic group. Two or more of these may be used, or two or more of the minimum structural units having different acidic groups may be copolymerized.

  The copolymer preferably contains 10 mol% or more of a compound having an acidic group selected from (1) to (6) to be copolymerized, and is contained in an amount of 20 mol% or more. Those are more preferred. If it is less than 10 mol%, the development latitude tends to be insufficiently improved.

  In this invention, when copolymerizing a compound and using an alkali-soluble resin as a copolymer, the other compound which does not contain the acidic group of said (1)-(6) can also be used as a compound to copolymerize. Examples of other compounds not containing an acidic group of (1) to (6) include the compounds listed in the following (m1) to (m12), but are not limited thereto.

(M1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
(M2) Alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, and glycidyl acrylate.
(M3) Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, and glycidyl methacrylate.
(M4) Acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide.

(M5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(M6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(M7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene.
(M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(M9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.
(M10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(M11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(M12) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.

  The alkali-soluble resin preferably has a phenolic hydroxyl group from the viewpoint of excellent image-forming properties when exposed to infrared laser or the like. For example, a phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- Preferred are novolak resins such as / p-mixed cresol formaldehyde resin and phenol / cresol (m-, p-, or m- / p-mixed) mixed formaldehyde resin and pyrogallol acetone resin.

  Further, as an alkali-soluble resin having a phenolic hydroxyl group, as described in US Pat. No. 4,123,279, a carbon number of 3 such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin is used. And a condensation polymer of phenol and formaldehyde having an alkyl group of ˜8 as a substituent.

  The alkali-soluble resin preferably has a weight average molecular weight of 500 or more from the viewpoint of image forming properties, and more preferably 1,000 to 700,000. The number average molecular weight is preferably 500 or more, and more preferably 750 to 650,000. The dispersity (weight average molecular weight / number average molecular weight) is preferably 1.1 to 10.

Moreover, these alkali-soluble resins may be used alone or in combination of two or more.
In the case of combination, the number of carbon atoms such as a condensation polymer of t-butylphenol and formaldehyde or a condensation polymer of octylphenol and formaldehyde as described in US Pat. No. 4,123,279 is described. A polycondensation product of phenol and formaldehyde having 3 to 8 alkyl groups as substituents, a phenol having an electron-withdrawing group on the aromatic ring described in JP-A-2000-241972 previously filed by the present inventors You may use together alkali-soluble resin etc. which have a structure.

  As the alkali-soluble resin used in the second layer, strong hydrogen bonding occurs in the unexposed area, and some hydrogen bonds are easily released in the exposed area, and the non-silicate developer In view of the large difference in developability between the unexposed area and the exposed area, a polymer compound having a phenolic hydroxyl group is desirable because image forming properties are improved. More preferred is a novolac resin.

  The total content of the alkali-soluble resin contained in the recording layer is preferably from 30 to 98 mass%, more preferably from 40 to 95 mass%, based on the total solid content of the recording layer. When the content is less than 30% by mass, the durability tends to deteriorate. On the other hand, when the content exceeds 98% by mass, the sensitivity and image formability tend to be lowered, which is not preferable.

[(C) Infrared absorber]
The recording layer according to the present invention preferably contains an infrared absorber. As the infrared absorber, any substance that absorbs light energy radiation and generates heat can be used without any limitation in the absorption wavelength range, but from the viewpoint of compatibility with an easily available high-power laser. Is preferably an infrared-absorbing dye or pigment having an absorption maximum at a wavelength of 760 nm to 1200 nm.

  As the infrared absorbing 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, 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, oxonol dyes And dyes such as diimonium dyes, aminium dyes, and croconium dyes.

  Examples of preferable dyes include cyanine dyes described in, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58- Naphthoquinone dyes described in JP-A-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc. Examples include squarylium dyes described in JP-A-58-112792, and cyanine dyes described in British Patent 434,875.

  Further, near infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used, and substituted aryl benzoates described in US Pat. No. 3,881,924 are also preferably used. (Thio) pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, JP-A-58-220143 No. 59-41363, No. 59-84248, No. 59-84249, No. 59-146063, No. 59-146061, JP-A 59-216146 No. 5,13514, a cyanine dye described in US Pat. No. 4,283,475, a pentamethine thiopyrylium salt described in US Pat. No. 4,283,475, and the like. Pyrylium compounds Nos disclosed in Japanese 5-19702 are also preferably used.

  Moreover, as another example preferable as an infrared absorption dye, the near-infrared absorption dye described as Formula (I) and (II) in US Patent 4,756,993 can be mentioned.

  Particularly preferred among these dyes are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes. Furthermore, the dyes represented by the following general formulas (a) to (e) are preferable because they are excellent in photothermal conversion efficiency. Particularly, the cyanine dyes represented by the following general formula (a) are used in the recording layer according to the present invention. In this case, it is most preferable because it gives a high interaction with the alkali-soluble resin and is excellent in stability and economy.

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 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 a carbon atom having 1 to 12 carbon atoms including a hetero atom. Indicates a hydrogen group. 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 when the photosensitive composition of the present invention is used as a recording layer coating solution for a lithographic printing plate precursor, R ¹ and R ² may be a hydrocarbon group having 2 or more carbon atoms. Further, R ¹ and R ² are preferably bonded to each other to form a 5-membered ring or a 6-membered ring.

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, carboxyl 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, Za ⁻ is not necessary when the cyanine dye represented by formula (a) has an anionic substituent in its structure and charge neutralization is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a carboxylate ion, and a sulfonate ion because of the storage stability of the recording layer coating solution. From the viewpoint of solubility and solubility in a coating solution, halogen ions and organic acid ions such as carboxylate ions and sulfonate ions are preferable, sulfonate ions are more preferable, and aryl sulfonate ions are particularly preferable.

  Specific examples of the cyanine dye represented by the general formula (a) that can be suitably used in the present invention include those exemplified below, and paragraph numbers [0017] to [0019] of JP-A No. 2001-133969, Examples thereof include those described in paragraph numbers [0012] to [0038] of JP-A No. 2002-40638 and paragraph numbers [0012] to [0023] of JP-A No. 2002-23360.

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 halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, This represents a substituent selected from an oxy group or an amino group, 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 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 general formula (d), R ²⁹ to R ³¹ 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 bonded to form a ring. R ²⁹ and / or R ³⁰ may be combined with R ³³ and R ³¹ and / or R ³² may be combined with R ³⁴ to form a ring, and when there are a plurality of R ³³ or R ³⁴ it is R ³³ or between R ³⁴ together 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 general formula (e), R ^{35 to} R ⁵⁰ are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, hydroxyl group, carbonyl which may have a substituent. Group, thio group, sulfonyl group, sulfinyl group, oxy group, amino group, and onium salt structure. 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 Three-period transition metals and lanthanoid elements can be mentioned, 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 as the infrared absorbent according to the present invention include commercially available pigments and color index (CI) manuals, “Latest Pigment Handbook” (edited by the Japan Pigment Technical Association, published in 1977), “Latest Pigment Applied Technology”. (CMC Publishing, published in 1986) and “Printing Ink Technology”, published by CMC Publishing, published in 1984).

  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 , Quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like. 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 size 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 size of the pigment is less than 0.01 μm, it is not preferable in terms of stability when the pigment dispersion is used as a recording layer coating liquid for a lithographic printing plate precursor, and when it exceeds 10 μm, the recording layer is uniform. It is not preferable in terms of sex.

  As a method for dispersing the pigment, a known dispersion technique used in 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 pigments or dyes are 0.01 to 50% by mass, preferably 0.1 to 10% by mass, based on the total solid content constituting the recording layer. In the case of a dye, it is particularly preferably 0.5 to 10% by mass, and in the case of a pigment, it is particularly preferably 0.1 to 10% by mass. When the addition amount of the pigment or dye is less than 0.01% by mass, the sensitivity tends to be low. When the addition amount exceeds 50% by mass, the uniformity of the recording layer increases as the blending amount increases. There is a risk of adversely affecting durability.

[(D) Other ingredients]
Various additives can be further added to the recording layer according to the present invention as necessary. In particular, a substance (decomposable solvent inhibitor) that is thermally decomposable, such as an onium salt, an o-quinonediazide compound, and a sulfonic acid alkyl ester, and substantially reduces the solubility of the alkali-soluble resin when not decomposed may be used in combination. It is preferable from the viewpoint of improving dissolution inhibition of the image area in the developer. As the decomposable dissolution inhibitor, onium salts such as diazonium salts, iodonium salts, sulfonium salts, ammonium salts, and o-quinonediazide compounds are preferred, diazonium salts, iodonium salts, onium salts of sulfonium salts are more preferred, and diazonium salts are preferred. It is particularly preferable to add it as a thermally decomposable dissolution inhibitor.

Suitable examples of the onium salt used in the present invention include S.P. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in JP-A-5-158230, U.S. Pat. Nos. 4,069,055, 4,069,056, and JP-A-3-140140. Ammonium salts described in the specification of C. Necker et al, Macromolecules, 17, 2468 (1984), C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055 and 4,069,056; V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, US Pat. No. 5,041,358, US Pat. No. 4,491,628, Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. Iodonium salts described in JP-A-2-296514, J. Org. V. Crivello et al, Polymer J. et al. 17, 73 (1985), J. Am. V. Crivello et al. J. et al. Org. Chem. 43, 3055 (1978); R. Watt et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 22, 1789 (1984), J. Am. V. Crivello et al, Polymer Bull. 14, 279 (1985), J. Am. V. Crivello et al, Macromolecules, 14 (5), 1141 (1981), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. 17, 2877 (1979), European Patent Nos. 370,693, 233,567, 297,443, 297,442, U.S. Pat. No. 4,933,377. No. 3,902,114, No. 5,041,358, No. 4,491,628, No. 4,760,013, No. 4,734,444 No. 2,833,827, German Patent 2,904,626, 3,604,580, 3,604,581 Salt, J.M. 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).
Among these onium salts, diazonium salts are particularly preferable from the viewpoints of dissolution inhibiting ability and thermal decomposability. In particular, the diazonium salt represented by the general formula (I) described in JP-A No. 5-158230 and the diazonium salt represented by the general formula (1) described in JP-A No. 11-143064 are preferable. The diazonium salt represented by the general formula (1) described in JP-A-11-143064 having a small absorption wavelength is most preferable.

  The counter ion of the onium salt includes tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfone Examples include acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, and paratoluenesulfonic acid. Of these, particularly preferred are alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid.

  Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and compounds having various structures can be used. That is, o-quinonediazide helps the solubility of the sensitive material system by both the effect of losing the ability to suppress the dissolution of the binder due to thermal decomposition and the change of o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include J. The compounds described in pages 339 to 352 of “Light-sensitive systems” by John Coley (John Wiley & Sons. Inc.) can be used, and in particular, o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds. The sulfonic acid esters or sulfonic acid amides are preferred. Further, benzoquinone (1,2) -diazidosulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and pyrogallol-acetone resin as described in JP-B-43-28403 Esters of benzoquinone- (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) described in US Pat. Nos. 3,046,120 and 3,188,210. An ester of) -diazide-5-sulfonic acid chloride with a phenol-formaldehyde resin is also preferably used.

  Further, an ester of naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride and phenol formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride and pyrogallol-acetone resin Similarly, the esters are also preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-49-38701, JP-A-48-13354, Japanese Patent Publication Nos. 41-11222, 45-9610, 49-17482, U.S. Pat. Nos. 2,797,213, 3,454,400, and 3,544 No. 323, No. 3,573,917, No. 3,674,495, No. 3,785,825, British Patent No. 1,227,602, No. 1,251,345, No. No. 1,267,005, No. 1,329,888, No. 1,330,932, German Patent No. 854,890 and the like. .

  When the photosensitive composition of the present invention is used for the recording layer of a lithographic printing plate, the amount of onium salt and / or o-quinonediazide compound that is a degradable dissolution inhibitor is preferably added to the total solid content of the recording layer. On the other hand, it is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.2 to 2% by mass. These compounds can be used alone, but may be used as a mixture of several kinds.

  The amount of additives other than the o-quinonediazide compound is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, and particularly preferably 0.1 to 1.5% by mass. The additive and binder used in the present invention are preferably contained in the same layer.

  Further, a dissolution inhibitor having no decomposability may be used in combination, and preferred dissolution inhibitors include sulfonate esters, phosphate esters, and aromatic carboxylic acids described in detail in JP-A-10-268512. Esters, aromatic disulfones, carboxylic anhydrides, aromatic ketones, aromatic aldehydes, aromatic amines, aromatic ethers, etc., as well as lactone skeletons described in detail in JP-A-11-190903, N, N- Examples thereof include an acid color-forming dye having a diarylamide skeleton and a diarylmethylimino skeleton, which also serves as a colorant, and nonionic surfactants described in detail in JP-A No. 2000-105454.

Further, in order to enhance image discrimination (hydrophobic / hydrophilic discrimination) and to enhance resistance to scratches on the surface, carbon described in JP-A-2000-187318 is used. A polymer containing a (meth) acrylate monomer having 2 or 3 perfluoroalkyl groups of 3 to 20 as a polymerization component can be used in combination. The addition amount of such a compound is preferably 0.1 to 10% by mass, more preferably, based on the total solid content of the recording layer when the photosensitive composition of the present invention is used for the recording layer of a lithographic printing plate. Is 0.5-5 mass%.
In the photosensitive composition of the present invention, for the purpose of imparting resistance to scratches, a compound that lowers the static friction coefficient of the surface can also be added. Specific examples include esters of long-chain alkyl carboxylic acids as used in US Pat. No. 6,117,913. As the addition amount of such a compound, when the photosensitive composition of the present invention is used for a recording layer of a lithographic printing plate, it is preferably from 0.1 to 10% by mass, more preferably from the total solid content of the recording layer. 0.5-5 mass%.
Further, the photosensitive composition of the present invention may contain a compound having a low molecular weight acidic group, if necessary. Examples of acidic groups include sulfonic acid groups, carboxylic acid groups, and phosphoric acid groups. Of these, compounds having a sulfonic acid group are preferred. Specific examples include aromatic sulfonic acids such as p-toluenesulfonic acid and naphthalenesulfonic acid, and aliphatic sulfonic acids.

  In addition, for the purpose of further improving sensitivity, cyclic acid anhydrides, phenols, and organic acids can be used in combination. Examples of cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ4-tetrahydrophthalic anhydride described in US Pat. No. 4,115,128, Tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 ″ -Trihydroxytriphenylmethane, 4,4 ′, 3 ″, 4 ″ -tetrahydroxy-3,5,3 ′, 5′-tetramethyltriphenylmethane and the like. There are sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphoric esters and carboxylic acids described in Japanese Laid-Open Patent Publication No. 60-88942 and Japanese Patent Laid-Open No. 2-96755, specifically , P-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate Phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1, 2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid, etc. When added to the recording layer of the lithographic printing plate precursor of the above cyclic acid anhydrides, phenols and organic acids, the recording layer The proportion of the content is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 0.1 to 10% by mass.

  Further, the recording layer according to the present invention has a nonionic surfactant as described in JP-A Nos. 62-251740 and 3-208514 in order to broaden the processing stability against development conditions. , Amphoteric surfactants as described in JP-A-59-121044 and JP-A-4-13149, siloxane-based compounds as described in EP950517, JP-A-11-288093 Fluorine-containing monomer copolymers as described can be added.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like. Specific examples of the double-sided activator include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Type (for example, trade name “Amorgen K” manufactured by Daiichi Kogyo Co., Ltd.) and the like.
The siloxane compound is preferably a block copolymer of dimethylsiloxane and polyalkylene oxide. Specific examples include DBE-224, DBE-621, DBE-712, DBP-732, DBP-534, manufactured by Chisso Corporation. And polyalkylene oxide-modified silicones such as Tego Glide 100 manufactured by Tego, Germany.
The proportion of the nonionic surfactant and the amphoteric surfactant in the recording layer is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

To the recording layer according to the present invention, a print-out agent for obtaining a visible image immediately after heating by exposure, or a dye or pigment as an image colorant can be added.
Typical examples of the printing-out agent include a combination of a compound that releases an acid by heating by exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halides and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, 36223, 54-74728, 60-3626, 61-143748, 61-151644 and 63-58440, and trihalomethyl compounds and salt-forming organic dyes Can be mentioned. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear printout images.

  As the image colorant, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Examples of suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. 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 (oriental chemical industry) Manufactured by Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI522015), and the like. The dyes described in JP-A-62-293247 are particularly preferred. These dyes can be added in a proportion of 0.01 to 10% by mass, preferably 0.1 to 3% by mass, based on the total solid content of the recording layer. Furthermore, a plasticizer is added to the photosensitive composition of the present invention as needed to impart flexibility of the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid These oligomers and polymers are used.

  In addition to these, epoxy compounds, vinyl ethers, and further, phenol compounds having a hydroxymethyl group, phenol compounds having an alkoxymethyl group, and the present inventors described in JP-A-8-276558, A crosslinkable compound having an alkali dissolution inhibiting action described in JP-A-11-160860 proposed in JP-A-11-160860 can be appropriately added depending on the purpose.

[Formation of recording layer]
The recording layer according to the present invention can be formed by dissolving each component constituting the above-described recording layer in a solvent and coating the solution on a suitable support.
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-butyrolactone, and toluene. It is not limited. These solvents are used alone or in combination.
The concentration of the above components (total solid content including additives) in the solvent is preferably 1 to 50% by mass.

The coating amount (solid content) on the support obtained after coating and drying varies depending on the use, but is generally preferably 0.5 to 5.0 g / m ² . As the coating amount decreases, the apparent sensitivity increases, but the film properties of the photosensitive film (recording layer) decrease.
Various methods can be used as the coating method, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.
In the recording layer comprising the photosensitive composition of the present invention, a surfactant for improving the coating property, for example, a fluorosurfactant as described in JP-A-62-170950 is added. can do. A preferable addition amount is 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass in the total solid content of the recording layer.

[Configuration of recording layer]
The recording layer according to the present invention may have a multilayer structure. For example, a resin layer made of an alkali-soluble polymer is used as the lower layer (support side), the recording layer described above is provided as the upper layer, and a two-layer structure is provided. Can do.
As a result, the recording layer (upper layer) whose solubility in an alkaline developer is lowered by exposure is provided on the exposed surface or in the vicinity thereof, whereby the sensitivity to the infrared laser is improved, and the support and the recording layer Since this resin layer (lower layer) exists between them and functions as a heat insulating layer, the heat generated by the infrared laser exposure is not diffused to the support, and the sensitivity can be increased because it is used efficiently.
In the exposed area, the recording layer (upper layer) that has become impermeable to the alkaline developer functions as a protective layer for the resin layer (lower layer). It is considered that an image excellent in nation is formed and stability over time is secured. Further, in the unexposed area, the uncured binder component is quickly dissolved and dispersed in the developer, and the resin layer (lower layer) existing adjacent to the support is made of an alkali-soluble polymer. Therefore, the solubility in the developer is good. For example, even when a developer with reduced activity is used, it dissolves quickly without the formation of a residual film, so that it is considered that the developability is excellent.

[Support]
As the support used in the lithographic printing plate precursor according to the present invention, a dimensionally stable plate-like material is used. For example, paper, paper laminated with plastic (for example, 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.), paper laminated with metal as described above, or vapor-deposited paper, or plastic film.

  As the support according to the present invention, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate that has good dimensional stability and is relatively inexpensive is particularly preferable. A suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, and may be a plastic film on which aluminum is laminated or vapor-deposited. 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 at most 10% by mass. Particularly suitable aluminum in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in the refining technique, and may contain slightly different elements. Thus, the composition of the aluminum plate applied to the present invention is not specified, and a conventionally known and publicly available aluminum plate can be used as appropriate. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

Prior to roughening the aluminum plate, a degreasing treatment with, for example, a surfactant, an organic solvent, or an alkaline aqueous solution 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, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, 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. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

The roughened aluminum plate is subjected to alkali etching treatment and neutralization treatment as necessary, and then subjected to anodization treatment if desired in order to enhance the water retention and wear resistance of the surface. 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, phosphoric 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 treatment conditions for anodization vary depending on the electrolyte used and cannot be specified. However, in general, the concentration of the electrolyte is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / dm. ^{2. A} voltage of 1 to 100 V and an electrolysis time of 10 seconds to 5 minutes are suitable.
When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient, or the non-image part of the planographic printing plate is easily damaged, and the ink adheres to the damaged part during printing. So-called “scratch dirt” is likely to occur.

After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. As the hydrophilization treatment used in the present invention, each specification of US Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734 is disclosed. There is an alkali metal silicate (for example, aqueous sodium silicate) method as disclosed in US Pat. In this method, the support is immersed in an aqueous sodium silicate solution or electrolytically treated. In addition, potassium fluoride zirconate disclosed in Japanese Patent Publication No. 36-22063 and U.S. Pat. Nos. 3,276,868, 4,153,461, and 4,689,272 For example, a method of treating with polyvinylphosphonic acid as disclosed in the literature is used.
As a particularly preferable support treatment, an aluminum plate is subjected to mechanical surface roughening treatment, alkali etching treatment, desmutting treatment with an acid, electrochemical surface roughening treatment using an electrolytic solution containing nitric acid, and an aqueous solution containing hydrochloric acid. It is preferable to sequentially perform an electrochemical surface roughening treatment using. A support subjected to such treatment has a very high surface area.

  The reason why the intermediate layer according to the present invention exhibits a more preferable effect on the support subjected to the above treatment is not well understood, but the intermediate layer according to the present invention is a substrate even for a support having a very high surface area. It is considered that the surface of the substrate can be sufficiently covered by the effect of interacting with the substrate, so that the adhesion between the recording layer (photosensitive layer) and the support can be further improved and good non-image area smearing can be achieved.

  The lithographic printing plate precursor of the present invention is converted into a lithographic printing plate by various processing methods corresponding to the recording layer. The developer is substantially free of alkali metal silicate as follows. A lithographic printing plate is preferred depending on the developing method. That is, the lithographic printing plate precursor according to the invention is preferably a lithographic printing plate precursor to be treated with a developer containing substantially no alkali metal silicate. This method is described in detail in JP-A No. 11-109637, and in the present invention, the contents described in the publication can be used.

The positive lithographic printing plate precursor produced as described above is usually subjected to image exposure and development processing.
As the light source of the light beam used for image exposure, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser or a semiconductor laser is particularly preferable.

As a developer and a replenisher for a lithographic printing plate precursor using the photosensitive composition of the present invention as a recording layer, conventionally known alkaline aqueous solutions can be used.
For example, sodium silicate, potassium, trisodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, Examples include inorganic alkali salts such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. In addition, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used. These alkali agents are used alone or in combination of two or more.
Among these alkali agents, particularly preferred developers are aqueous silicate solutions such as sodium silicate and potassium silicate. The reason is that the developability can be adjusted by the ratio and concentration of silicon oxide SiO ₂ and alkali metal oxide M ₂ O, which are silicate components. For example, Japanese Patent Application Laid-Open No. 54-62004, Alkali metal silicates as described in JP-B-57-7427 are effectively used.

Furthermore, when developing using an automatic developing machine, an aqueous solution (replenisher) having a higher alkali strength than that of the developer is added to the developer so that the developer in the developer tank is not changed for a long time. It is known that the PS version can be processed. This replenishment method is also preferably applied in the present invention. Various surfactants and organic solvents can be added to the developer and replenisher as necessary for the purpose of promoting and suppressing developability, dispersing development residue, and improving ink affinity of the printing plate image area.
Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. If necessary, the developer and replenisher may contain reducing agents such as hydroquinone, resorcin, sulfurous acid, bisulfite, and other inorganic acids such as sodium and potassium salts, organic carboxylic acids, antifoaming agents, and hard water softeners. It can also be added.

  The printing plate developed using the developer and the replenisher is post-treated with water-washing water, a rinsing solution containing a surfactant and the like, a desensitizing solution containing gum arabic and starch derivatives. As the post-process applied to the present invention, these processes can be used in various combinations.

  In recent years, automatic developing machines for printing plates have been widely used in the plate making and printing industries in order to rationalize and standardize plate making operations. This automatic developing machine is generally composed of a developing unit and a post-processing unit, and includes an apparatus for transporting the printing plate, each processing liquid tank and a spray device, and each pumped up by a pump while transporting the exposed printing plate horizontally. The processing liquid is sprayed from the spray nozzle and developed. In addition, recently, a method is also known in which a printing plate is dipped and conveyed by a submerged guide roll or the like in a processing liquid tank filled with the processing liquid. In such automatic processing, each processing solution can be processed while being supplemented with a replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable processing method in which processing is performed with a substantially unused processing solution can also be applied.

(Erase processing)
In the lithographic printing plate precursor according to the invention, image portions unnecessary for the lithographic printing plate obtained by image exposure, development, washing and / or rinsing and / or gumming (for example, film edge marks of the original film, etc.) ), Unnecessary image portions are erased.
In the present invention, even when the intermediate layer having excellent adhesion with the recording layer remains in the side edge portion or the non-image portion, it is easily removed by such an erasing process, and the non-image portion is not stained. An excellent image is formed, and the planographic printing plate precursor of the present invention is excellent in erasability. The erasing process is preferably performed by applying an erasing solution to unnecessary image portions as described in, for example, Japanese Patent Publication No. 2-13293, leaving it for a predetermined time, and then washing with water. A method of developing after irradiating an unnecessary image portion with an actinic ray guided by an optical fiber as described in JP-A-59-174842 can also be used.

Hereinafter, the general composition of the erasing liquid used in the erasing process will be described.
In general, the erasing liquid preferably contains an organic solvent for dissolving the recording layer, an acidic substance for preventing contamination, and a fluorosurfactant. Further, the erasing liquid further contains water, printing ink, a solvent for removing developing ink such as image portion protection, a wetting agent, a viscosity modifier, a colorant, and a surfactant other than the above-mentioned fluorosurfactant as necessary. be able to.

  Examples of the organic solvent for dissolving the recording layer include lactones such as propiolactone, butyrolactone, valerolactone, and hexanolactone (common names: cyclic intramolecular esters), glycols such as methoxy glycol and ethoxy glycol, and methyl- Ketones such as isobutyl ketone, ethyl-isobutyl ketone and cyclohexanone, esters such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, ethyl acetate and butyl acetate, ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether, and other dimethyl sulfoxides And special solvents such as dimethylformamide. These organic solvents can be used alone or in combination of two or more, but it is preferable to add 25 to 99.89% by mass with respect to all components of the erasing solution.

Examples of the acidic substance for preventing dirt include fluorine-containing compounds such as phosphoric acid, hydrogen fluoride, and zirconic fluoride, citric acid, and lactic acid. Among these, phosphoric acid and fluorine-containing compounds are preferable, Among these, it is particularly preferable to use phosphoric acid from the viewpoint of ease of post-drainage treatment.
These acidic substances can also be used alone or in combination of two or more. The addition amount is preferably 0.1 to 20% by mass, and in the case of phosphoric acid, 0.5 to 15% by mass is preferable.
In addition, when 1 to 20% by mass of water is added to the erasing solution, the acidity increases and the effect of preventing dirt is improved. There is an advantage that the erasing operation can be performed without removing it with water in advance.

As the fluorosurfactant used in the erasing solution, an anionic or nonionic fluorosurfactant is preferable, but a nonionic fluorosurfactant is particularly preferable. Particularly preferred examples of the nonionic fluorosurfactant include fluoroaliphatic oligomers having a fluoroaliphatic group and a polyoxyalkylene group represented by the following general formula (A) or (B).
(R _f ) _m Q [(OR) _x Q′A] _n (A)
[(R _f ) _m Q {(OR) _x Q′A ′} _n ] ₂ (B)
Here, R _f represents a fluoroaliphatic group, Q represents a linking group for covalently bonding R and OR, OR represents a polyoxyalkylene group, A represents a monovalent terminal organic group such as an acyl group, An alkyl group, an aryl group, etc., A ′ represents A or a single bond, provided that at least one R bonded to Q binds to another Q, and Q ′ represents A or A ′ and R , M represents an integer of 2 or more, n represents an integer of 2 or more, and x represents an integer of 5 or more.
The fluorosurfactant used in the erasing solution suitably used in the present invention can be obtained as a commercial product. Specific examples include FC-430, FC-431 (manufactured by 3M), Megafuck F-141, F-142, F-142D, F-143, F-144, F-144D, F-528, F-170, F-171, F-172 F-173, F-177, F-183, F-184 (manufactured by Dainippon Ink & Chemicals, Inc.). The addition amount of the fluorosurfactant varies depending on the solvent used and other additives, but is preferably 0.01 to 5% by mass, particularly preferably 0.05 to 2% by mass in the total composition of the erasing liquid.

As a preferred type of wetting agent which is an optional component contained in the erasing solution, water-soluble polyhydric alcohols such as glycerin, glycol and polyglycol are useful. By adding a wetting agent, it is possible to help prevent drying due to evaporation of the organic solvent in the erased portion, or to maintain hydrophilicity until the eraser is removed with water or a developer.
Viscosity modifiers are almost unnecessary in the erasing liquid used before development, but in the erasing liquid after development, when the erasing liquid is applied to the area to be erased, the erasing liquid is reduced by reducing the fluidity of the erasing liquid It can be added in order to assist in reducing bleeding, to suppress sagging from an application tool such as a brush during coating, and to improve handling properties. Such a viscosity modifier is preferably one that can be completely removed with running water after treatment, and is preferably a water-soluble resin that is soluble in other erasing liquid components.
Specifically, for example, modified cellulose such as polyvinyl pyrrolidone, polyethylene oxide, carboxymethyl cellulose, methyl cellulose, polyvinyl acetate / maleic anhydride copolymer, polyvinyl methyl ether / maleic anhydride copolymer, etc. A substance having the trade name of Aerosil with fine silicon powder can also be used as a viscosity modifier.
Such an erasing liquid is continuously used when correction is required in various image forming processes, for example, when a part of an original image is erased and an undesired residual film is generated in a non-image area. It is used when the boundary surface between images remains unexposed during processing, and has a great influence on the image quality of the formed image.

The lithographic printing plate obtained as described above can be subjected to a printing process after applying a desensitized gum if desired. However, if it is desired to obtain a lithographic printing plate with a higher printing durability, it is desired. The burning process is performed.
In the case of burning a lithographic printing plate, before burning, an adjustment as described in JP-B-61-2518, JP-A-55-28062, JP-A-62-31859, JP-A-61-159655 is used. It is preferable to treat with a surface liquid.
As its method, with a sponge or absorbent cotton soaked with the surface-adjusting liquid, it is applied onto a lithographic printing plate, or a method in which the printing plate is immersed and applied in a vat filled with the surface-adjusting liquid, Application by an automatic coater is applied. Further, it is more preferable to make the coating amount uniform with a squeegee or a squeegee roller after coating.

In general, the amount of the surface-adjusting solution applied is suitably 0.03 to 0.8 g / m ² (dry mass). The lithographic printing plate coated with the surface-adjusting liquid is dried if necessary and then heated to a high temperature with a burning processor (for example, burning processor “BP-1300” sold by Fuji Photo Film Co., Ltd.). Is done. The heating temperature and time in this case are preferably in the range of 180 to 300 ° C. and in the range of 1 to 20 minutes, although depending on the type of components forming the image.

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

[Synthesis of Specific Polymer (P-1)]
In a 200 ml three-necked flask containing 13.28 g of dimethyl sulfoxide (DMSO) and 8.85 g of methanol, 11.91 g (70.0 mmol) of α-methacryloyloxy-γ-butyrolactone and vinylbenzyltriethyl were added in a nitrogen atmosphere at 75 ° C. 7.61 g (30.0 mmol) of ammonium chloride, initiator: V601 [dimethyl 2,2′-azobis (2-methylpropionate), manufactured by Wako Pure Chemical Industries, Ltd.] 1.1513 g (5.0 mmol), chain transfer agent: A solution of 2.38 g (8.3 mmol) of 1-octadecanethiol, 53.11 g of DMSO, and 35.41 g of methanol was added dropwise over 2 hours, and further reacted for 4 hours to obtain a specific polymer (P-1).

[Examples 1-3, 6, 7, Comparative Example 1]
(Production of support)
The support body 1 and the support body 2 were produced by performing the process shown below using a JIS A 1050 aluminum plate having a thickness of 0.3 mm.

(A) Mechanical surface roughening treatment While supplying a suspension of abrasive (silica sand) having a specific gravity of 1.12. Roughening was performed. The average particle size of the abrasive was 8 μm, and the maximum particle size was 50 μm. The material of the nylon brush was 6 · 10 nylon, the hair length was 50 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers (φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.

(B) Alkali etching treatment The aluminum plate obtained above was sprayed with an aqueous NaOH solution at a temperature of 70 ° C. (concentration 26 mass%, aluminum ion concentration 6.5 mass%) to perform an etching treatment, and the aluminum plate was 6 g / m. ² dissolved. Thereafter, washing with water was performed using well water.

(C) Desmutting treatment Desmutting treatment was performed by spraying with a 1% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by weight of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in nitric acid aqueous solution.

(D) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a nitric acid 10.5 g / liter aqueous solution (aluminum ion 5 g / liter) at a temperature of 50 ° C. The AC power supply waveform is electrochemically roughened using a carbon electrode as the counter electrode, using a trapezoidal rectangular wave alternating current with a time TP of 0.8 msec until the current value reaches a peak from zero, a DUTY ratio of 1: 1. went. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type.
The current density was 30 A / dm ² at the peak current value, and the amount of electricity was 220 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode.
Thereafter, washing with water was performed using well water.

(E) Alkaline etching treatment An aluminum plate is etched by spraying at a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C., 0.20 g / m ^{2 of the} aluminum plate is dissolved, The smut component mainly composed of aluminum hydroxide generated when electrochemical surface roughening was used was removed, and the edge portion of the generated pit was melted to smooth the edge portion. Thereafter, washing with water was performed using well water.

(F) Desmut treatment Desmut treatment was performed by spraying with a 15% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (containing 4.5% by weight of aluminum ions), and then washed with water using well water. The nitric acid aqueous solution used for the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in nitric acid aqueous solution.

(G) Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a hydrochloric acid 7.5 g / liter aqueous solution (containing 5 g / liter of aluminum ions) at a temperature of 35 ° C. The AC power supply waveform was a rectangular wave, and an electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type.
The current density was 25 A / dm ² at the peak current value, and the amount of electricity was 50 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode.
Thereafter, washing with water was performed using well water.

(H) Alkali etching treatment The aluminum plate was sprayed at a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C. to dissolve the aluminum plate at 0.10 g / m ² , The smut component mainly composed of aluminum hydroxide generated during the electrochemical surface roughening treatment was removed, and the edge portion of the generated pit was dissolved to smooth the edge portion. Thereafter, washing with water was performed using well water.

(I) Desmut treatment A desmut treatment by spraying was performed with a 25% by mass aqueous solution of sulfuric acid having a temperature of 60 ° C. (containing 0.5% by mass of aluminum ions), and then water washing by spraying was performed using well water.

(J) Anodizing treatment As the electrolytic solution, sulfuric acid was used. The electrolyte solutions all had a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions), and the temperature was 43 ° C. Thereafter, washing with water was performed using well water.
Both current densities were about 30 A / dm ² . The final oxide film amount was 2.7 g / m ² .

(K) Alkali metal silicate treatment Alkali metal silicate is obtained by immersing the aluminum support obtained by anodizing treatment into a treatment layer of a 1 mass% aqueous solution of sodium silicate 3 at a temperature of 30 ° C for 10 seconds. Salt treatment (silicate treatment) was performed. Then, the water washing by the spray using well water was performed. The amount of silicate adhering at that time was 3.5 mg / dm ² .

<Support 1>
The above-described steps (a) to (k) were sequentially performed, and the support 1 was produced so that the etching amount in the step (e) was 3.5 g / m ² .

<Support 2>
Except for omitting the steps (g), (h), and (i) among the above steps, each step was performed in order to prepare the support 2.

(Formation of intermediate layer)
On the support obtained as described above (which support was used is described in Table 1), the following intermediate layer forming coating solution was applied and then dried at 80 ° C. for 15 seconds to provide an intermediate layer. . The coating amount after drying was 15 mg / m ² .

<Intermediate layer forming coating solution>
・ 0.3 g of polymers listed in Table 1
・ Methanol 100g
・ Water 1g

  In addition, the polymers (P-1) to (P-6) described in Table 1 are polymers listed above as specific examples of the specific polymer. Moreover, the structure of the polymer (PA-0) for a comparison is shown below.

[Formation of recording layer]
-Synthesis of Copolymer 1-
A 500 ml three-necked flask equipped with a stirrer, a condenser tube and a dropping funnel is charged with 31.0 g (0.36 mol) of methacrylic acid, 39.1 g (0.36 mol) of ethyl chloroformate and 200 ml of acetonitrile and cooled in an ice water bath. The mixture was stirred while. To this mixture, 36.4 g (0.36 mol) of triethylamine was dropped with a dropping funnel over about 1 hour. After completion of the dropwise addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes.

  To this reaction mixture, 51.7 g (0.30 mol) of p-aminobenzenesulfonamide was added, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, the mixture was added to 1 liter of water with stirring, and the resulting mixture was stirred for 30 minutes. The mixture was filtered to take out a precipitate, which was slurried with 500 ml of water, then the slurry was filtered, and the obtained solid was dried to dry a white solid of N- (p-aminosulfonylphenyl) methacrylamide. Was obtained (yield 46.9 g).

  Next, 4.61 g (0.0192 mol) of N- (p-aminosulfonylphenyl) methacrylamide and 2.58 g of ethyl methacrylate (0.0258 mol) were added to a 200 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel. ), 0.80 g (0.015 mol) of acrylonitrile and 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while heating to 65 ° C. with a hot water bath. To this mixture, 0.15 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (trade name: “V-65”, manufactured by Wako Pure Chemical Industries, Ltd.) was added as a polymerization initiator and maintained at 65 ° C. The mixture was stirred for 2 hours under a nitrogen stream. To this reaction mixture, 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide, 2.58 g of methyl methacrylate, 0.80 g of acrylonitrile, 20 g of N, N-dimethylacetamide and 0.15 g of the above “V-65” were added. The mixture was added dropwise via a dropping funnel over 2 hours. After completion of the dropwise addition, the resulting mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, 40 g of methanol was added to the mixture, cooled, and the resulting mixture was added to 2 liters of water while stirring the water. After stirring the mixture for 30 minutes, the precipitate was removed by filtration and dried. 15 g of a white solid was obtained. It was 54,000 when the weight average molecular weight (polystyrene standard) of this specific copolymer 1 was measured by the gel permeation chromatography.

On the support after forming the intermediate layer, the following recording layer forming coating solution 1 was applied so that the coating amount was 0.85 g / m ^2, and then Wind Control 7 was manufactured by TABAI, PERFECT OPENPH200. And dried at 110 ° C. for 50 seconds. Thereafter, the recording layer forming coating solution 2 was applied so that the coating amount was 0.30 g / m ^2, and then dried at 120 ° C. for 1 minute. The planographic printing of Examples 1 to 3, 6, 7 and Comparative Example 1 I got the original version.

<Recording layer forming coating solution 1>
-Copolymer 1 2.133 g
・ Cyanine dye A (the following structure) 0.109 g
・ 4,4'-bishydroxyphenylsulfone 0.126g
・ Tetrahydrophthalic anhydride 0.190g
・ 0.008 g of p-toluenesulfonic acid
・ 3-methoxy-4-diazodiphenylamine hexafluorophosphate 0.030 g
・ The counter ion of ethyl violet is changed to the anion of 6-hydroxy-2-naphthalenesulfonic acid
0.100g
・ Megafac F780, manufactured by Dainippon Ink & Chemicals, Inc. (Coated surface-modified fluorine-based surfactant) 0.035 g
・ Methyl ethyl ketone 25.38g
・ 13.0 g of 1-methoxy-2-propanol
・ Γ-butyrolactone 13.2 g

<Recording layer forming coating solution 2>
・ M, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 4500, containing 0.8% by mass of unreacted cresol) 0.3478 g
・ The cyanine dye A 0.0192g
・ The following onium salt B 0.0115g
・ Megafac F780 (20%), manufactured by Dainippon Ink & Chemicals, Inc. (Surface improving surfactant) 0.022 g
・ Methyl ethyl ketone 13.07g
1-methoxy-2-propanol 6.79g

[Examples 4 and 5]
(Formation of recording layer)
An intermediate layer was formed on the support (which support was used is described in Table 1) in the same manner as in Examples 1-3, 6 and 7, and then the following recording layer forming coating solution 3 was dried. The subsequent coating amount was applied to 1.2 g / m ² to obtain lithographic printing plate precursors of Examples 4 and 5.

<Recording layer forming coating solution 3>
・ M, p-cresol novolak 0.93g
(M / p ratio = 6/4, weight average molecular weight 7,300,
Unreacted cresol 0.4% by mass
・ The following vinyl polymer (1) 0.07g
・ The following infrared absorber (cyanine dye A) 0.017 g
・ The following infrared absorber (cyanine dye B) 0.023 g
・ 2,4,6-Tris (hexyloxy)
Benzenediazonium-2-hydroxy-4-methoxybenzophenone-5-sulfonate 0.01 g
・ 0.003 g of p-toluenesulfonic acid
・ Cyclohexane-1,2-dicarboxylic anhydride 0.06g
・ Counter anion of Victoria Pure Blue BOH
0.015 g of dye converted to 1-naphthalenesulfonic acid anion
・ Fluorine surfactant 0.02g
(Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 15g
・ 7g of 1-methoxy-2-propanol

[Evaluation]
The lithographic printing plate precursors of Examples 1 to 7 and Comparative Example 1 thus obtained were evaluated as follows with respect to printing durability and erasability.

1. Printing durability Each of the lithographic printing plate precursors obtained in Examples 1 to 7 and Comparative Example 1 was subjected to imagewise exposure using a TrendSetter 3244 manufactured by CREO at a plate surface energy amount of 140 mJ / cm ² .
Next, for the lithographic printing plate precursors of Examples 1 to 4, 7 and Comparative Example 1, a developer for PS plate manufactured by Fuji Photo Film Co., Ltd., which is a developer substantially free of alkali metal silicate. Using DT-1 "or" DT-2 "under standard operating conditions, development was performed with an automatic developing machine 900NP to obtain a lithographic printing plate.
Further, the planographic printing plate precursors of Examples 5 and 6 were developed in the same manner as described above using a developer containing alkali metal silicate (PS plate developer “DP-4” manufactured by Fuji Photo Film). ,evaluated.
Each obtained lithographic printing plate is printed with DIC-GEOS (N) ink manufactured by Dainippon Ink & Chemicals, Inc. using a Lithrone printing machine manufactured by Komori Corporation, and the density of the solid image begins to decrease. The printing durability was evaluated based on the number of printed sheets when visually confirmed. The results are shown in Table 3.

2. Erasability Using each lithographic printing plate obtained by developing and developing in the same manner as in 1 above, an erasing liquid of the following formulation is included in the brush depending on the application area, or oozed out of the pen and lithographic printing After the film edge on the plate was applied to an area where an image remained as an image or an unnecessary image portion, the film edge was left for 30 seconds and then washed away by spraying water. The resulting lithographic printing plate after erasing is printed on a Lithrone printing machine made by Komori Corporation using DIC-GEOS (N) ink made by Dainippon Ink and Chemicals, and unnecessary image parts are erased. The properties were visually confirmed from the printed matter and evaluated according to the following criteria. The results are shown in Table 3.
○: Unnecessary image area is completely removed ×: Unnecessary image area is not completely removed and stain is generated <Erase Solution Composition>
-Propylene carbonate 10.0 mass parts-Ethylene carbonate 40.0 mass parts-Dimethyl sulfoxide 33.3 mass parts-Pure water 8.4 mass parts-Zircon hydrofluoric acid (40 wt% aqueous solution) 2.4 mass parts-Triethanol 1.2 parts by weight of amine, 4.7 parts by weight of powdered silicon dioxide

  As shown in Table 3, it can be seen that each lithographic printing plate precursor of the example containing the specific polymer in the intermediate layer is excellent in printing durability and erasability.

Claims (1)

  On the support, an intermediate layer containing a polymer having an aliphatic group having 5 or more carbon atoms or a thioether group having an aromatic group as a substituent at the terminal and an onium group in the side chain, and infrared laser sensitivity A lithographic printing plate precursor comprising a positive recording layer and a lithographic printing plate precursor.