JP2005231347A - Lithographic printing plate precursor and lithographic printing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithographic printing plate precursor and a lithographic printing method employing the lithographic printing plate precursor capable of performing image recording by infrared laser scanning and on-press development and excellent in fine line reproducibility and printing durability while maintaining good on-press developing properties. <P>SOLUTION: The lithographic printing method employs the lithographic printing plate precursor. The lithographic printing plate precursor comprises a support having thereon an image recording layer capable of being removed by a printing ink and/or a fountain solution, in which the image recording layer comprises an infrared absorber and a graft polymer having a graft chain containing a hydrophilic segment, wherein the hydrophilic segment is a polymer containing specific monomer units by 50 mol% or more or a graft polymer having a hydrophilic main chain and a graft chain containing hydrophobic segment. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a lithographic printing plate precursor and a lithographic printing method using the same. Specifically, a lithographic printing plate precursor capable of direct plate making that can be directly made by scanning an infrared laser based on a digital signal from a computer or the like, and the lithographic printing plate precursor subjected to a development processing step The present invention also relates to a lithographic printing method in which development is performed directly on a printing press.

In general, a lithographic printing plate comprises an oleophilic image area that receives ink in the printing process and a hydrophilic non-image area that receives dampening water. Lithographic printing utilizes the property that water and oil-based inks repel each other, so that the oleophilic image area of the lithographic printing plate is the ink receiving area, and the hydrophilic non-image area is dampened with the water receiving area (ink non-receiving area). In this method, a difference in ink adhesion is caused on the surface of the lithographic printing plate, and after ink is applied only to the image area, the ink is transferred to a printing medium such as paper and printed.
In order to produce this lithographic printing plate, conventionally, a lithographic printing plate precursor (PS plate) in which an oleophilic photosensitive resin layer (image recording layer) is provided on a hydrophilic support has been widely used. Normally, after exposing a lithographic printing plate precursor through an original image such as a lithographic film, the image recording layer in the image area remains, and the image recording layer in the non-image area is dissolved with an alkaline developer or an organic solvent. The lithographic printing plate is obtained by carrying out plate making by a method of exposing the surface of the hydrophilic support by removing it.

  In the conventional plate-making process of a lithographic printing plate precursor, a step of dissolving and removing the non-image area with a developing solution or the like corresponding to the image recording layer is necessary after exposure. One of the problems is to make the system unnecessary or simplified. In particular, in recent years, disposal of waste liquids discharged with wet processing has become a major concern for the entire industry due to consideration for the global environment, and therefore, the demand for solving the above-mentioned problems has become stronger.

On the other hand, as one of simple plate making methods, an image recording layer that can remove a non-image portion of a lithographic printing plate precursor in a normal printing process is used. A method called on-press development has been proposed in which a part is removed to obtain a lithographic printing plate.
As a specific method of on-press development, for example, a method of using a lithographic printing plate precursor having an image recording layer that can be dissolved or dispersed in dampening water, an ink solvent, or an emulsion of dampening water and ink , A method of mechanically removing the image recording layer by contact with rollers or a blanket cylinder of a printing press, cohesion of the image recording layer by penetration of dampening water, ink solvent, etc. There is a method in which after the adhesive force is weakened, the image recording layer is mechanically removed by contact with rollers or a blanket cylinder.
In the present invention, unless otherwise specified, the “development process step” refers to using a device other than a printing press (usually an automatic developing machine) and bringing a liquid (usually an alkaline developer) into contact therewith. Refers to the step of removing the unexposed portion of the lithographic printing plate precursor from the infrared laser to expose the surface of the hydrophilic support, and “on-press development” refers to a process using a printing machine (typically printing ink and / or printing ink). Or a dampening solution) to remove the infrared laser unexposed portion of the lithographic printing plate precursor and expose the surface of the hydrophilic support.

  However, when an image recording layer of a conventional image recording system using ultraviolet rays or visible light is used, the image recording layer does not fix even after exposure. For example, the lithographic plate after exposure until it is mounted on a printing press. It was necessary to take a time-consuming method such as storing the printing plate precursor completely in a light-shielded state or under constant temperature conditions.

  On the other hand, in recent years, digitization technology for electronically processing, storing, and outputting image information by a computer has become widespread, and various new image output methods corresponding to such digitization technology will be put into practical use. It is becoming. Along with this, digitized image information is carried by high-convergence radiation such as laser light, and the lithographic printing plate precursor is scanned and exposed with that light, directly without using a lithographic film. Computer-to-plate technology for manufacturing is attracting attention. Therefore, obtaining a lithographic printing plate precursor adapted to such a technique is one of the important technical issues.

  As described above, in recent years, the simplification, drying, and no processing of plate making operations have become more desirable than ever in terms of consideration for the global environment and adaptation to digitalization. It is coming.

Recently, high-power lasers such as semiconductor lasers that emit infrared rays having a wavelength of 760 to 1200 nm, YAG lasers, etc. have become available at a low cost. Therefore, a method using these high-power lasers as an image recording means has been considered promising.
In the conventional plate-making method, imagewise exposure is performed on a photosensitive lithographic printing plate precursor at low to medium illuminance, and image recording is performed by image-like physical property change due to a photochemical reaction in an image recording layer. In contrast, in the method using the above-described high-power laser, a large amount of light energy is irradiated to the exposure region in an extremely short time, and the light energy is efficiently converted into heat energy. In the process, a thermal change such as a chemical change, a phase change, a change in form or structure is caused, and the change is used for image recording. Accordingly, image information is input by light energy such as laser light, but image recording is performed in a state in which reaction by heat energy is taken into account in addition to light energy. Usually, such a recording method using heat generated by high power density exposure is called heat mode recording, and changing light energy to heat energy is called photothermal conversion.

  The major advantages of the plate making method using heat mode recording are that the image recording layer is not exposed to light at a normal illuminance level such as indoor lighting, and that fixing of images recorded by high illuminance exposure is not essential. is there. That is, the lithographic printing plate precursor used for heat mode recording is not likely to be exposed to room light before exposure, and image fixing is not essential after exposure. Therefore, for example, if an image recording layer that is insolubilized or solubilized by exposure using a high-power laser is used, and the plate making process in which the exposed image recording layer is imaged to form a lithographic printing plate is performed by on-machine development, exposure is performed. Later, a printing system is possible in which the image is not affected even if it is exposed to ambient light in the room. Therefore, if heat mode recording is used, it is expected that a lithographic printing plate precursor suitably used for on-press development can be obtained.

On the other hand, for example, Patent Document 1 describes a lithographic printing plate precursor in which an image forming layer in which hydrophobic thermoplastic polymer particles are dispersed in a hydrophilic binder is provided on a hydrophilic support. Yes. In this Patent Document 1, the above lithographic printing plate precursor is exposed by an infrared laser, and the hydrophobic thermoplastic polymer particles are coalesced by heat to form an image, which is then mounted on a cylinder of a printing press and moistened. It is described that it is possible to perform on-press development with water and / or ink.
In this way, the method of forming an image by mere thermal fusion of fine particles shows good on-press developability, but the image strength (adhesion with the support) is extremely weak and the printing durability is insufficient. Had the problem of being.

Patent Documents 2 and 3 describe lithographic printing plate precursors having an image recording layer (thermosensitive layer) containing microcapsules encapsulating a polymerizable compound on a hydrophilic support.
Patent Document 4 describes a lithographic printing plate precursor in which an image recording layer (photosensitive layer) containing an infrared absorber, a radical polymerization initiator, and a polymerizable compound is provided on a support.
The method using such a polymerization reaction has a feature that the image strength is relatively good because the chemical bond density of the image portion is higher than that of the image portion formed by thermal fusion of polymer fine particles. From a general point of view, all of on-press developability, fine line reproducibility and printing durability are still insufficient and have not been put into practical use.

Further, in Patent Document 5, on-press development is possible in which an image recording layer containing a polymerizable compound and a graft polymer having a polyethylene oxide chain in the side chain or a block polymer having a polyethylene oxide block is provided on a support. A planographic printing plate precursor is described.
However, this technology has good on-press developability, but fine line reproducibility and printing durability are still insufficient.
Japanese Patent No. 2938397 JP 2001-277740 A JP 2001-277742 A JP 2002-287334 A US Patent Application Publication No. 2003/0064318

  The present invention has been made to remedy the above-mentioned drawbacks of the prior art. That is, the object of the present invention is to enable lithographic printing plate precursors capable of image recording and on-press development by infrared laser scanning, having excellent on-press developability, and having excellent fine line reproducibility and printing durability, and Another object of the present invention is to provide a lithographic printing method using the lithographic printing plate precursor.

The present invention is as follows.
1. A lithographic printing plate precursor comprising an infrared ray absorbent and a graft polymer having a hydrophilic segment graft chain on a support, and having an image recording layer removable by printing ink and / or fountain solution, The hydrophilic segment is at least selected from an amide group-containing monomer, an acid group-containing monomer, an alkali metal salt of an acid group-containing monomer, a quaternary ammonium salt-containing monomer, and a hydroxyl group-containing monomer. A lithographic printing plate precursor comprising a polymer containing 50 mol% or more of one monomer unit.
2. A lithographic printing plate precursor having an image recording layer containing an infrared absorbent and a graft polymer having a hydrophilic main chain and a hydrophobic segment graft chain on a support.
3. 3. The lithographic printing plate precursor as described in 1 or 2 above, wherein the image recording layer contains a polymerization initiator and a polymerizable compound.
4). 3. The lithographic printing plate precursor as described in 2 above, wherein the image recording layer can be removed with printing ink and / or fountain solution.
5). The lithographic printing plate precursor as described in 1 or 2 above is mounted on a printing press and imagewise exposed with an infrared laser, or after imagewise exposure with an infrared laser and mounted on a printing press, and the lithographic printing A lithographic printing method in which an oil-based ink and an aqueous component are supplied to a plate precursor to remove an infrared unexposed portion of the image recording layer and print.

The mechanism of action of the graft polymer having a hydrophilic graft chain is not clear, but the presence of the graft polymer localizes the hydrophilic part in the unexposed area of the image recording layer and increases the water permeability. In addition, it is estimated that the on-press development type lithographic printing plate precursor can be obtained because the on-press developability is improved and the periphery of the hydrophilic part is also polymerized and cured in the exposed portion of the image recording layer, so that the water permeability is suppressed. The In the present invention, it is possible to improve the mechanical strength of the portion corresponding to the skeleton of the hydrophilic part by using a hydrophilic graft chain having a high glass transition temperature. It is considered that the printing durability can be made to a good level while maintaining the on-press developability.
The mechanism of action of the graft polymer of the hydrophilic main chain / hydrophobic segment graft chain is not clear, but the presence of the graft polymer causes the hydrophilic part and the hydrophobic part in the image recording layer. In the unexposed area of the image recording layer, the water permeability is increased by the localized hydrophilic part, so that the on-machine developability is improved. In the exposed area of the image recording layer, the periphery of the hydrophilic part is also polymerized and cured. Therefore, it is estimated that water permeability is suppressed and a good image is formed. In addition, since the graft chain occupying most of the graft polymer in quantity is hydrophobic, an image generated by polymerization and curing around the graft chain has sufficient water resistance and mechanical strength. Unlike the case where the hydrophilic polyethylene oxide chain / hydrophobic main chain graft polymer described in 5 is used, it is presumed that fine line reproducibility and printing durability are excellent.

  According to the present invention, a lithographic printing plate precursor capable of image recording by infrared rays and having excellent on-press developability and excellent fine line reproducibility and printing durability, and lithographic printing using the lithographic printing plate precursor Can provide a method.

In the first embodiment, the lithographic printing plate precursor according to the present invention is a lithographic printing plate precursor capable of image recording with an infrared laser and capable of on-press development, wherein an infrared absorber and a specific hydrophilic property are formed on a support. And an image recording layer containing a graft polymer having a graft chain of a sex segment.
In the second embodiment, the lithographic printing plate precursor according to the present invention is a lithographic printing plate precursor capable of image recording with an infrared laser and capable of on-press development, wherein an infrared absorber and a hydrophilic material are formed on a support. It has an image recording layer containing a main chain and a graft polymer having a graft chain of a hydrophobic segment.
Further, the lithographic printing method of the present invention is a method in which the lithographic printing plate precursor is mounted on a printing press and imagewise exposed with an infrared laser, or imagewise exposed with an infrared laser and then mounted on a printing press. The lithographic printing plate precursor is supplied with oil-based ink and fountain solution to remove the infrared unexposed portion of the image recording layer and perform printing.
Hereinafter, the components and printing method of the planographic printing plate precursor according to the invention will be described in detail.

(Image recording layer)
First, the first embodiment will be described.
<Graft Polymer Having Hydrophilic Segment Graft Chain>
In the first embodiment, the graft polymer is a graft polymer having a hydrophilic segment as a branch on a hydrophobic trunk, and the hydrophilic segment comprises an amide group-containing monomer, an acid group-containing monomer, an acid It is a polymer containing at least 50 mol% of at least one hydrophilic monomer unit selected from an alkali metal salt of a group-containing monomer, a quaternary ammonium salt-containing monomer, and a hydroxyl group-containing monomer. Features. The hydrophilic segment more preferably contains 70 mol% or more of the hydrophilic monomer unit.
Further, the hydrophilic segment may be a polymer in which the hydrophilicity is adjusted by copolymerizing a hydrophobic monomer in addition to the hydrophilic monomer, and the hydrophobic segment in the hydrophilic segment in that case The sex monomer is preferably less than 50 mol%, more preferably less than 30 mol%.
By using a graft polymer having a hydrophilic segment as described above, a lithographic printing plate precursor excellent in fine line reproducibility and printing durability can be obtained while maintaining good on-press developability.

The synthesis of the graft polymer is basically as follows: 1. Polymerize the branch monomer from the trunk polymer. 2. Link the branch polymer to the trunk polymer. It can be divided into three methods of copolymerizing a branch polymer with a trunk polymer (macromer method).
Any of these three methods can be used to synthesize the graft polymer of the present invention, but “3. Macromer method” is particularly excellent from the viewpoints of manufacturability and ease of synthesis. The synthesis of graft polymers using macromers is described in “New Polymer Experiment 2, Polymer Synthesis and Reaction” published by Kyoritsu Shuppan Co., Ltd., edited by the Society of Polymer Science. It is also described in detail in Yuya Yamashita, et al. In the first embodiment, the graft polymer has a hydrophilic segment at the branch and is easily obtained by copolymerization of a hydrophilic macromer and a hydrophobic monomer.

<Hydrophilic macromer>
In the first embodiment, the hydrophilic segment of the hydrophilic macromer (also referred to as macromonomer) used is an amide group-containing monomer, an acid group-containing monomer, an alkali metal salt of an acid group-containing monomer, It is a polymer containing 50 mol% or more of at least one monomer unit selected from a quaternary ammonium salt-containing monomer and a hydroxyl group-containing monomer.
The hydrophilic macromer used in the present invention is obtained by bonding a polymerizable group to the end of this hydrophilic segment.

  Specific examples of the amide group-containing monomer include acrylamide-t-butylsulfonic acid, N, N-dimethylacrylamide, acrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N -Methylol acrylamide, N-vinyl pyrrolidone, N-vinyl acetamide, etc. are mentioned.

  Examples of the acid group-containing monomer include methacrylic acid, acrylic acid, styrene sulfonic acid and the like. Examples of alkali metal salts of acid group-containing monomers include sodium salt of methacrylic acid, sodium salt of acrylic acid, sodium styrenesulfonate, sodium ethoxymethacrylate sulfonate, sodium ethoxyacrylate sulfonate, and mono-2-acryloyloxyethyl acid phosphate. And the sodium salt thereof.

  Examples of the quaternary ammonium base-containing monomer include hydroxyethyltrimethylammonium methacrylate methacrylate, hydroxypropyltrimethylammonium methacrylate methacrylate, and hydroxyethyltrimethylammonium chloride acrylate.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, and 2,3-dihydroxypropyl methacrylate.

  Hydrophobic monomers used to adjust the hydrophilicity of the hydrophilic segment include acrylic esters, methacrylic acids, vinyl esters, styrenes, acrylonitrile, methacrylonitrile, maleic anhydride, maleic imide And the like, and known hydrophobic monomers.

  Specific examples of acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, chloroethyl acrylate, cyclohexyl acrylate, allyl Acrylate, benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, Examples include 2- (hydroxyphenylcarbonyloxy) ethyl acrylate It is.

  Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Chloroethyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl Methacrylate, sulfa Examples include moylphenyl methacrylate and 2- (hydroxyphenylcarbonyloxy) ethyl methacrylate.

  Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like.

  Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

  The preferred molecular weight of these hydrophilic macromers is in the range of 400 to 100,000, more preferably 1000 to 50,000, and particularly preferably 1500 to 20,000. Within the range of this molecular weight, the effect of the present invention can be exhibited without impairing the polymerizability with the copolymer monomer forming the trunk.

<Hydrophobic monomer>
Particularly useful hydrophobic monomers that copolymerize with hydrophilic macromers include known acrylic esters, methacrylic acids, vinyl esters, styrenes, acrylonitrile, methacrylonitrile, maleic anhydride, maleic imide, and the like. Examples include hydrophobic monomers. A graft polymer can be synthesized by appropriately selecting one or two or more of these monomers.

  Specific examples of acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, chloroethyl acrylate, cyclohexyl acrylate, allyl acrylate, benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl Acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate Rate, 2- (hydroxyphenylcarbonyloxy) ethyl acrylate and the like.

Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl Methacrylate, chlorophenyl Examples include methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenylcarbonyloxy) ethyl methacrylate, and the like.

  Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like.

  Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

The hydrophobic monomer may further have a substituent. As the substituent, a monovalent nonmetallic atomic group excluding hydrogen is used. Preferred 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-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, ア ル キ ル -alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-aryl Acylamino 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-alkylureate group, N', N'-dialkyl- N-arylureido group, N′-aryl-Ν-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, 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-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino Group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group , N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group (hereinafter referred to as sulfonato group), Al Xylsulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N- Alkyl-N-arylsulfamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N - alkyl -N- arylsulfamoyl group, a phosphono group (-PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphono group (-PO ₃ (alkyl) _2), Jiariruhosu Phono group (—PO ₃ (aryl) ₂ ), alkylaryl phosphono group (—PO ₃ (a lkyl) (aryl)), monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) ) And conjugated base groups thereof (hereinafter referred to as aryl phosphonate groups), phosphonooxy groups (—OPO ₃ H ₂ ) and conjugated base groups thereof (hereinafter referred to as phosphonateoxy groups), dialkylphosphonooxy groups ( -OPO ₃ (alkyl) _2), diaryl phosphonooxy group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphonooxy group (-OPO (alkyl) (aryl) ), monoalkyl phosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), Monoariruho Fonookishi group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), Moruhoruno group, a cyano group, a nitro group, an aryl group, an alkenyl group, an alkynyl group.

Specific examples of the alkyl group in these substituents include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t -Butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like can be mentioned. Among these, a hydrogen atom, a methyl group, and an ethyl group are more preferable from the viewpoints of effects and availability. Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl 2, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group , Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl , Can be exemplified phosphonophenyl phenyl group. Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1-butenyl, A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ₁ in the acyl group (G ₁ CO—) include hydrogen and the above alkyl groups and aryl groups.

  Among these substituents, more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkyls. Amino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfamoy Group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group Group, phosphonooxy group, phosphonatooxy group, aryl group, and alkenyl group.

On the other hand, examples of the alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyl group. Oxymethyl group, phenoxymethyl group, methylthiomethyl, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy Carbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) ) Caravamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N- Methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphospho Hexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, Cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like can be mentioned.

In the first form, the hydrophilic macromer content in the graft polymer is preferably 10 to 90% by mass, more preferably 15 to 85% by mass.
Moreover, 5000-1 million are preferable and, as for the weight average molecular weight of the graft polymer of this invention, More preferably, it is 10,000-500,000.

  In the first embodiment, the content of the graft polymer in the image recording layer is 10 to 90% by mass, preferably 15 to 80% by mass, based on the total solid content of the image recording layer. 70 mass% is more preferable. Within these ranges, the effects of the present invention that improve both the on-press developability, fine line reproducibility and printing durability can be obtained.

Next, the second embodiment will be described.
<Graft polymer having graft chains of hydrophobic segments>
In the second embodiment, the graft polymer is a graft polymer having a hydrophilic main chain (trunk) with a graft chain of a hydrophobic segment as a branch. By using this graft polymer, it is possible to provide a lithographic printing plate precursor having excellent fine line reproducibility and printing durability while maintaining good on-press developability.

  Also in the second embodiment, the above-mentioned “3. Macromer method” is excellent for the synthesis of the graft polymer. In the second form, the graft polymer has a hydrophobic segment at the branch, and is easily obtained by copolymerization of a hydrophobic macromer and a hydrophilic monomer constituting the trunk.

<Hydrophobic macromer>
The hydrophobic segment of the hydrophobic macromer (also referred to as macromonomer) used in the present invention includes acrylic esters, methacrylic esters, vinyl esters, styrenes, acrylonitrile, methacrylonitrile, maleic anhydride, maleic Examples thereof include those obtained by polymerizing one kind selected from known hydrophobic monomers such as acid imides, and those obtained by copolymerizing two or more kinds. The hydrophobic macromer of the present invention is obtained by attaching a polymerizable group to the end of this hydrophobic segment.

  Specific examples of the acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate , Dodecyl acrylate, chloroethyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl acrylate, furfuryl Acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydro Examples include xylphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, and 2- (hydroxyphenylcarbonyloxy) ethyl acrylate.

  Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate , Tetrahydrofurfurylmethac Examples include relate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, and 2- (hydroxyphenylcarbonyloxy) ethyl methacrylate.

  Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like.

  Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

The hydrophobic monomer may further have a substituent. As the substituent, a monovalent nonmetallic atomic group excluding hydrogen is used. Preferred 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-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, ア ル キ ル -alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-aryl Acylamino 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-alkylureate group, N', N'-dialkyl- N-arylureido group, N′-aryl-Ν-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, 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-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino Group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group , N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group (hereinafter referred to as sulfonato group), Al Xylsulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N- Alkyl-N-arylsulfamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N - alkyl -N- arylsulfamoyl group, a phosphono group (-PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphono group (-PO ₃ (alkyl) _2), Jiariruhosu Phono group (—PO ₃ (aryl) ₂ ), alkylaryl phosphono group (—PO ₃ (a lkyl) (aryl)), monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) ) And conjugated base groups thereof (hereinafter referred to as aryl phosphonate groups), phosphonooxy groups (—OPO ₃ H ₂ ) and conjugated base groups thereof (hereinafter referred to as phosphonateoxy groups), dialkylphosphonooxy groups ( -OPO ₃ (alkyl) _2), diaryl phosphonooxy group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphonooxy group (-OPO (alkyl) (aryl) ), monoalkyl phosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), Monoariruho Fonookishi group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), Moruhoruno group, a cyano group, a nitro group, an aryl group, an alkenyl group, an alkynyl group.

Specific examples of the alkyl group in these substituents include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t -Butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like can be mentioned. Among these, a hydrogen atom, a methyl group, and an ethyl group are more preferable from the viewpoints of effects and availability. Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl 2, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group , Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl , Can be exemplified phosphonophenyl phenyl group. Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1-butenyl, A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ₁ in the acyl group (G ₁ CO—) include hydrogen and the above alkyl groups and aryl groups.

  Among these substituents, more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkyls. Amino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfamoy Group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group Group, phosphonooxy group, phosphonatooxy group, aryl group, and alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyl group. Oxymethyl group, phenoxymethyl group, methylthiomethyl, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy Carbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) ) Caravamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N- Methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphospho Hexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, Cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like can be mentioned.

  The preferred molecular weight of these hydrophobic macromers is in the range of 400 to 100,000, more preferably 1000 to 50,000, and particularly preferably 1500 to 20,000. Within the range of this molecular weight, the effect of the present invention can be exhibited without impairing the polymerizability with the copolymerization monomer forming the main chain.

<Hydrophilic monomer>
In the second embodiment, as the hydrophilic monomer forming the main chain, an amide group-containing monomer, an acid group-containing monomer, an alkali metal salt of an acid group-containing monomer, a quaternary ammonium salt-containing monomer And known hydrophilic monomers such as monomers and hydroxyl group-containing monomers. A graft polymer can be synthesized by copolymerizing one or more selected from these hydrophilic monomers with one or more of the above hydrophobic macromers.

  Specific examples of the amide group-containing monomer include 2-acrylamide-2-methylpropanesulfonic acid, N, N-dimethylacrylamide, acrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylol acrylamide etc. are mentioned.

  Examples of the acid group-containing monomer include methacrylic acid, acrylic acid, styrene sulfonic acid and the like. Examples of alkali metal salts of acid group-containing monomers include sodium salt of methacrylic acid, sodium salt of acrylic acid, sodium styrenesulfonate, sodium ethoxymethacrylate sulfonate, sodium ethoxyacrylate sulfonate, and mono-2-acryloyloxyethyl acid phosphate. And the sodium salt thereof.

  Examples of the quaternary ammonium base-containing monomer include hydroxyethyltrimethylammonium methacrylate methacrylate, hydroxypropyltrimethylammonium methacrylate methacrylate, and hydroxyethyltrimethylammonium chloride acrylate.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, and 2,3-dihydroxypropyl methacrylate.

  In the present invention, the amount of the hydrophilic monomer introduced is preferably less than 50% by mass, more preferably less than 30% by mass.

  In the second embodiment, the hydrophilicity of the main chain can be appropriately adjusted by copolymerizing a hydrophobic monomer in addition to the hydrophilic monomer to the main chain of the graft polymer. Specific examples of the hydrophobic monomer include the hydrophobic monomers exemplified in the above-mentioned <Hydrophobic macromer> column. The introduction amount of the hydrophobic monomer in the main chain is preferably 0 to 50 mol%, more preferably 0 to 30 mol%.

In the second embodiment, the hydrophobic macromer content in the graft polymer is preferably 10 to 90% by mass, more preferably 15 to 85% by mass.
Moreover, as a weight average molecular weight of a graft polymer, 5000-1 million are preferable, More preferably, it is 10,000-500,000.

  In the second embodiment, the content of the graft polymer in the image recording layer is 10 to 90% by mass, preferably 15 to 80% by mass, based on the total solid content of the image recording layer. 70 mass% is more preferable. Within these ranges, the effects of the present invention that improve both the on-press developability, fine line reproducibility and printing durability can be obtained.

<Infrared absorber>
When forming an image of the lithographic printing plate precursor according to the present invention with a laser that emits infrared rays of 760 to 1200 nm using a light source, it is usually essential to use an infrared absorber. The infrared absorber has a function of converting absorbed infrared rays into heat. Due to the heat generated at this time, a polymerization initiator (radical generator) described later is thermally decomposed to generate radicals. The infrared absorber used in the present invention is a dye or pigment having an absorption maximum at a wavelength of 760 to 1200 nm.

  As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.

  Examples of preferable dyes include cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-60-78787, JP-A-58-173696, Methine dyes described in JP-A Nos. 58-181690 and 58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59-48187, JP-A Naphthoquinone dyes described in JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., squarylium dyes described in JP-A-58-112792, etc., British Patent No. And cyanine dyes described in the specification of 434,875.

In addition, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also suitable. ) Pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59- 41363, 59-84248, 59-84249, 59-146063, 59-146061, pyranyl compounds described in JP-A-59-216146, cyanine dyes described in US Pat. It is disclosed in the pentamethine thiopyrylium salt described in Japanese Patent No. 4,283,475, and Japanese Patent Publication Nos. 5-13514 and 5-19702. Pyrylium compounds are also preferably used. Another example of a preferable dye is a near-infrared absorbing dye described in U.S. Pat. No. 4,756,993 as formulas (I) and (II).
Other preferable examples of the infrared absorbing dye of the present invention include specific indolenine cyanine dyes described in JP-A-2002-278057 as exemplified below.

  Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and one particularly preferred example is a cyanine dye represented by the following general formula (I).

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

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

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms, 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 (I) has an anionic substituent in its structure and neutralization of charge is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, a hexagonal salt, in view of the storage stability of the recording layer coating solution. Fluorophosphate ions and aryl sulfonate ions.

Specific examples of the cyanine dye represented by formula (I) that can be suitably used in the present invention include those described in paragraph numbers [0017] to [0019] of JP-A No. 2001-133969. be able to.
Further, other particularly preferable examples include specific indolenine cyanine dyes described in JP-A-2002-278057 described above.

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

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

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

  The particle diameter of the pigment is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 1 μm, and particularly preferably in the range of 0.1 to 1 μm. Within this range, good stability of the pigment dispersion in the image recording layer coating solution and good uniformity of the image recording layer can be obtained.

  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 infrared absorbers may be added to the same layer as other components, or may be added to another layer provided, but when a negative planographic printing plate precursor is prepared, image recording is performed. It is preferable to add such that the absorbance at the maximum absorption wavelength in the wavelength range of 760 nm to 1200 nm of the layer is in the range of 0.3 to 1.2 by reflection measurement, more preferably 0.4 to 1. 1 range. Within this range, a uniform polymerization reaction in the depth direction of the image recording layer proceeds, and good film strength of the image area and adhesion to the support can be obtained.
The absorbance of the image recording layer can be adjusted by the amount of infrared absorber added to the image recording layer and the thickness of the image recording layer. Absorbance can be measured by a conventional method. As a measuring method, for example, on a reflective support such as aluminum, an image recording layer having a thickness appropriately determined in a range in which the coating amount after drying is necessary as a lithographic printing plate is formed, and the reflection density is set to the optical density. And a method of measuring with a spectrophotometer by a reflection method using an integrating sphere.
The content of the infrared absorber used in the present invention is preferably 0.1 to 50% by mass with respect to the total solid content constituting the image recording layer, from the viewpoint of sensitivity and contamination of non-image areas that occur during printing. More preferably, it is 0.5-30 mass%, Most preferably, it is 1-20 mass%.

<Other image recording layer components>
The image recording layer of the present invention preferably contains a polymerization initiator that generates radicals and a polymerizable compound that is polymerized and cured by radicals. Furthermore, additives such as a binder polymer, a surfactant, a colorant, a bake-out agent, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, inorganic fine particles, and a low molecular weight hydrophilic compound can be contained as necessary. . These will be described below.

<Polymerization initiator>
The image recording layer of the present invention preferably contains a polymerization initiator that generates radicals by heat, light, or both, and initiates and advances the curing reaction of the polymerizable compound described later. Among them, a pyrolytic radical generator that decomposes by heat to generate radicals is useful. When such a radical generator is used in combination with the above-described infrared absorber, the infrared absorber generates heat when irradiated with an infrared laser, and a radical is generated by the heat, thereby enabling heat mode recording.
Examples of the radical generator include an onium salt, a triazine compound having a trihalomethyl group, a peroxide, an azo polymerization initiator, an azide compound, and a quinonediazide, and an onium salt is preferable because it has high sensitivity. Below, the onium salt which can be used suitably as a radical polymerization initiator in this invention is demonstrated. Preferred onium salts include iodonium salts, diazonium salts, and sulfonium salts. In the present invention, these onium salts function not as acid generators but as radical polymerization initiators. The onium salts particularly preferably used in the present invention are onium salts represented by the following general formulas (II) to (IV).

In formula (II), Ar ¹¹ and Ar ¹² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a group having 12 or less carbon atoms. An aryloxy group is mentioned. Z ¹¹⁻ represents a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a carboxylate ion, and a sulfonate ion, preferably a perchlorate ion, Hexafluorophosphate ions, carboxylate ions, and aryl sulfonate ions.

In the formula (III), Ar ²¹ represents an aryl group having 20 or less carbon atoms which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. Z ^21- represents a counter ion having the same ^meaning as Z ^11- .

In the formula (IV), R ³¹ , R ³² and R ³³ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. Z ^31- represents a counter ion having the same ^meaning as Z ^11- .

  Specific examples of onium salts that can be suitably used as a radical generator in the present invention include those described in JP-A Nos. 2001-133969, 2001-343742, and 2002-148790. Etc. In the present invention, onium salts represented by general formula (II) ([OI-1] to [OI-10]) and onium salts represented by general formula (III) ([ON] which can be suitably used in the present invention are shown below. -1] to [ON-5]), and specific examples of the onium salts ([OS-1] to [OS-10]) represented by the general formula (IV), are not limited thereto. .

  Other preferred polymerization initiators include specific aromatic sulfonium salts described in JP-A No. 2002-6482.

  The radical generator used in the present invention preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less. By making the absorption wavelength in the ultraviolet region in this way, the lithographic printing plate precursor can be handled under white light.

These polymerization initiators are added in a proportion of 0.1 to 50% by mass, preferably 0.5 to 30% by mass, particularly preferably 1 to 20% by mass, based on the total solid content constituting the image recording layer. Can do. Within this range, good sensitivity and good stain resistance of the non-image area during printing can be obtained. These polymerization initiators may be used alone or in combination of two or more. Moreover, these polymerization initiators may be added to the same layer as other components, or another layer may be provided and added thereto.

<Polymerizable compound>
The image recording layer of the present invention preferably contains a polymerizable compound in order to perform an efficient curing reaction. The polymerizable compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. To be elected. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

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

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

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

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (V) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

_{CH 2 = C (R 4)} COOCH 2 CH (R 5) OH (V)
(However, R ₄ and R ₅ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

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

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

  The polymerizable compound is preferably used in the range of 5 to 80% by mass, more preferably 25 to 75% by mass with respect to the nonvolatile component in the image recording layer. These may be used alone or in combination of two or more. In addition, the use method of the addition polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

<Binder polymer>
The image recording layer of the present invention may contain a binder polymer in addition to the graft polymer. As the binder polymer that can be used in the present invention, conventionally known binder polymers can be used without limitation, and a linear organic polymer having a film property is preferable. Examples of such binder polymers include acrylic resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, polyimide resins, polyamide resins, epoxy resins, methacrylic resins, polystyrene resins, novolac phenolic resins, polyester resins, and synthetic rubbers. And natural rubber.

  The binder polymer preferably has crosslinkability in order to improve the film strength of the image area. In order to impart crosslinkability to the binder polymer, a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or side chain of the polymer. The crosslinkable functional group may be introduced by copolymerization.

Examples of the polymer having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene and poly-1,4-isoprene.
Examples of polymers having an ethylenically unsaturated bond in the side chain of the molecule are polymers of esters or amides of acrylic acid or methacrylic acid where the ester or amide residue (R of -COOR or -CONHR) is Mention may be made of polymers having an ethylenically unsaturated bond.

Examples of the residue (the R) having an ethylenically unsaturated _{bond, - (CH 2) n CR} 1 = CR 2 R 3, - (CH 2 O) n CH 2 CR 1 = CR 2 R 3, - _{(CH 2 CH 2 O) n} CH 2 CR 1 = CR 2 R 3, - (CH 2) n NH-CO-O-CH 2 CR 1 = CR 2 R 3, - (CH 2) n -O-CO —CR ¹ ═CR ² R ³ and — (CH ₂ CH ₂ O) ₂ —X (wherein R ^{1 to} R ³ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, Represents an alkoxy group or an aryloxy group, and R ¹ and R ² or R ³ may combine with each other to form a ring, n represents an integer of 1 to 10. X represents dicyclopentadienyl. Represents a residue).

Specific examples of the ester _{residue, -CH 2 CH = CH 2,} ( described in JP Kokoku _{7-21633.) - CH 2 CH 2} O-CH 2 CH = CH 2, -CH 2 C _{(CH 3) = CH 2,} -CH 2 CH = CH-C 6 H 5, -CH 2 CH 2 OCOCH = CH-C 6 H 5, -CH 2 CH 2 -NHCOO-CH 2 CH = CH 2 and - CH ₂ CH ₂ O—X (wherein X represents a dicyclopentadienyl residue).
Specific examples of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ —Y (wherein Y represents a cyclohexene residue), —CH ₂ CH ₂ —OCO—CH═CH _2. Is mentioned.

  In the case of a binder polymer having crosslinkability, for example, free radicals (polymerization initiation radicals or growth radicals in the polymerization process of a polymerizable compound) are added to the crosslinkable functional group, and a polymerization chain of a polymerizable compound is formed directly between polymers. Through addition polymerization, a cross-link is formed between the polymer molecules and cured. Alternatively, atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group) are abstracted by free radicals to form polymer radicals that are bonded to each other so that crosslinking between the polymer molecules occurs. Forms and cures.

  The content of the crosslinkable group in the binder polymer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.1 to 10.0 mmol, more preferably 1.0, per 1 g of the binder polymer. -7.0 mmol, most preferably 2.0-5.5 mmol. Within this range, good sensitivity and good storage stability can be obtained.

From the viewpoint of improving the on-press developability, the binder polymer preferably has high solubility or dispersibility in ink and / or fountain solution.
In order to improve the solubility or dispersibility in ink, the binder polymer is preferably lipophilic, and in order to improve the solubility or dispersibility in dampening water, the binder polymer is hydrophilic. Is preferred. Therefore, in the present invention, it is also effective to use a lipophilic binder polymer and a hydrophilic binder polymer in combination.

  Examples of hydrophilic binder polymers include hydroxy groups, carboxyl groups, carboxylate groups, hydroxyethyl groups, polyoxyethyl groups, hydroxypropyl groups, polyoxypropyl groups, amino groups, aminoethyl groups, aminopropyl groups, and ammonium. Preferred are those having a hydrophilic group such as a group, an amide group, a carboxymethyl group, a sulfonic acid group, and a phosphoric acid group.

Specific examples include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and their salts, Polymethacrylic acids and their salts, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, homopolymers and copolymers of hydroxypropyl acrylate, homopolymers of hydroxybutyl methacrylate Polymers and copolymers, homopolymers and copolymers of hydroxybutyl acrylate Polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, hydrolyzed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, acrylamide homopolymers and copolymers having a degree of hydrolysis of 60% by mass or more, preferably 80% by mass or more , Methacrylamide homopolymers and polymers, N-methylolacrylamide homopolymers and copolymers, polyvinylpyrrolidone, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. Is mentioned.

  The binder polymer preferably has a weight average molecular weight of 5000 or more, more preferably 10,000 to 300,000, and a number average molecular weight of 1,000 or more, preferably 2000 to 250,000. More preferred. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1.1 to 10.

  The binder polymer may be either a random polymer or a block polymer, but is preferably a random polymer. Moreover, a binder polymer may be used independently or may be used in mixture of 2 or more types.

The binder polymer can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These may be used alone or in combination of two or more.
As the radical polymerization initiator used for synthesizing the binder polymer, known compounds such as an azo initiator and a peroxide initiator can be used.

<Surfactant>
In the present invention, it is preferable to use a surfactant in the image recording layer in order to promote on-press developability at the start of printing and to improve the coated surface state. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants. Surfactant may be used independently and may be used in combination of 2 or more type.

  The nonionic surfactant used for this invention is not specifically limited, A conventionally well-known thing can be used. For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol Fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, Polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N N- bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid ester, trialkylamine oxide, polyethylene glycol, copolymers of polyethylene glycol and polypropylene glycol.

The anionic surfactant used in the present invention is not particularly limited, and conventionally known anionic surfactants can be used. For example, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinate esters, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy poly Oxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, fatty acid alkyl esters Sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alcohol Ruphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / maleic anhydride Examples thereof include partial saponification products of polymers, partial saponification products of olefin / maleic anhydride copolymers, and naphthalene sulfonate formalin condensates.

The cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
The amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines.

  Of the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.

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

Surfactant can be used individually or in combination of 2 or more types.
The content of the surfactant is preferably 0.001 to 10% by mass and more preferably 0.01 to 7% by mass with respect to the total solid content of the image recording layer.

<Colorant>
In the present invention, various compounds other than these may be added as necessary. For example, a dye having a large absorption in the visible light region can be used as an image colorant. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientated chemistry) Manufactured by Kogyo Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI522015), etc. And dyes described in No. 293247. In addition, pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide can also be suitably used.

  These colorants are preferably added since it is easy to distinguish an image area from a non-image area after image formation. The addition amount is 0.01 to 10% by mass with respect to the total solid content of the image recording material.

<Bakeout agent>
In the image recording layer of the present invention, a compound that changes color by an acid or a radical can be added to produce a printout image. As such a compound, for example, various dyes such as diphenylmethane, triphenylmethane, thiazine, oxazine, xanthene, anthraquinone, iminoquinone, azo, and azomethine are effectively used.

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

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

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

<Polymerization inhibitor>
A small amount of a thermal polymerization inhibitor is preferably added to the image recording layer of the present invention in order to prevent unnecessary thermal polymerization of the radical polymerizable compound during the production or storage of the image recording layer.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t- (Butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt are preferred.
The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the image recording layer.

<Higher fatty acid derivatives, etc.>
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the image recording layer of the present invention, and the surface of the image recording layer is dried during the coating process. It may be unevenly distributed. The amount of the higher fatty acid derivative added is preferably about 0.1 to about 10% by mass with respect to the total solid content of the image recording layer.

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

<Inorganic fine particles>
The image recording layer of the present invention may contain inorganic fine particles for the purpose of improving the strength of the cured film in the image area and improving the on-press developability of the non-image area.
As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate or a mixture thereof can be preferably mentioned. Even if they are not photothermally convertible, they can be used for strengthening the film, enhancing interfacial adhesion by surface roughening, and the like.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 to 3 μm. Within the above range, it is possible to form a non-image portion having excellent hydrophilicity that is stably dispersed in the image recording layer, sufficiently retains the film strength of the image recording layer, and hardly causes stains during printing.
The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the image recording layer.

<Low molecular hydrophilic compound>
The image recording layer of the present invention may contain a hydrophilic low molecular weight compound for improving on-press developability. Examples of the hydrophilic low-molecular compound include water-soluble organic compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like, and ether or ester derivatives thereof, glycerin, Polyhydroxys such as pentaerythritol, organic amines such as triethanolamine and diethanolamine monoethanolamine and salts thereof, organic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid and salts thereof, organic phosphonic acids such as phenylphosphonic acid and the like Examples thereof include organic carboxylic acids such as salts thereof, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid and amino acids, and salts thereof.

(Formation of image recording layer)
In the present invention, several modes can be used as a method for incorporating the above-mentioned image recording layer constituents into the image recording layer. One is, for example, an embodiment in which the constituent components are dissolved and applied in an appropriate solvent as described in JP-A-2002-287334, and the other is, for example, JP-A-2001-277740, As described in Japanese Patent Application Laid-Open No. 2001-277742, it is an embodiment (microcapsule type image recording layer) in which the constituent components of the image recording layer are encapsulated in microcapsules and contained in the image recording layer. Further, in the microcapsule type image recording layer, the constituent component can be contained outside the microcapsule. In the microcapsule type image recording layer, it is preferable that the hydrophobic constituent component is encapsulated in the microcapsule and the hydrophilic constituent component is contained outside the microcapsule. In order to obtain better on-press developability, the image recording layer is preferably a microcapsule type image recording layer.

  As a method of microencapsulating the above-mentioned image recording layer constituent components, known methods can be applied. For example, as a method for producing microcapsules, a method using coacervation found in U.S. Pat. Nos. 2,800,547 and 2,800,498, U.S. Pat. No. 3,287,154, JP-B-38-19574, 42-446 by the interfacial polymerization method, US Pat. No. 3,418,250, US Pat. No. 3,660,304 by polymer precipitation method, US Pat. No. 3,796,669, isocyanate polyol A method using a wall material, a method using an isocyanate wall material found in US Pat. No. 3,914,511, and a urea-formaldehyde system found in US Pat. Nos. 4,001,140, 4,087,376 and 4,089,802. Or urea formaldehyde-resorcino A method using a wall forming material, a method using a wall material such as melamine-formaldehyde resin and hydroxycellulose, as shown in US Pat. No. 4,025,445, and Japanese Patent Publication Nos. 36-9163 and 51-9079. In situ method using monomer polymerization, spray drying method found in British Patent No. 930422, US Pat. No. 3,111,407, electrolytic dispersion cooling method seen in British Patent Nos. 952807 and 967074, etc. However, it is not limited to these.

  A preferable microcapsule wall used in the present invention has a three-dimensional cross-linking and has a property of swelling with a solvent. From such a viewpoint, the wall material of the microcapsule is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, and a mixture thereof, and particularly preferably polyurea and polyurethane. Further, a compound having a crosslinkable functional group such as an ethylenically unsaturated bond capable of introducing the binder polymer may be introduced into the microcapsule wall.

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

The image recording layer of the present invention is applied by preparing a coating solution by dispersing or dissolving the necessary components described above in a solvent. 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, toluene, water and the like. However, the present invention is not limited to this. These solvents are used alone or in combination. The solid content concentration of the coating solution is preferably 1 to 50% by mass.
The image recording layer of the present invention can also be formed by preparing a plurality of coating solutions in which the same or different components are dispersed or dissolved in the same or different solvents, and repeatedly applying and drying a plurality of times.

Further, the coating amount (solid content) of the image recording layer on the support obtained after coating and drying varies depending on the use, but generally 0.3 to 3.0 g / m ² is preferable. Within this range, good sensitivity and good film characteristics of the image recording layer can be obtained.
Various methods can be used as a coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

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

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

  The thickness of the support is preferably from 0.1 to 0.6 mm, more preferably from 0.15 to 0.4 mm, and even more preferably from 0.2 to 0.3 mm.

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

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

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

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

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

The support preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the image recording layer, good printing durability and good stain resistance can be obtained.
The color density of the support is preferably 0.15 to 0.65 as the reflection density value. Within this range, good image formability by preventing halation during image exposure and good plate inspection after development can be obtained.

[Back coat layer]
After the surface treatment is performed on the support or after the undercoat layer is formed, a back coat can be provided on the back surface of the support, if necessary.
Examples of the back coat include hydrolysis and polycondensation of organic polymer compounds described in JP-A-5-45885, organometallic compounds or inorganic metal compounds described in JP-A-6-35174. A coating layer made of a metal oxide obtained in this manner is preferred. Among them, it is inexpensive to use a silicon alkoxy compound such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) _4. It is preferable in terms of easy availability.

[Undercoat layer]
In the planographic printing plate precursor of the invention used in the planographic printing method of the invention, an undercoat layer can be provided between the image recording layer and the support, if necessary. Since the undercoat layer functions as a heat insulating layer, heat generated by exposure with an infrared laser is not diffused to the support and can be used efficiently, so that there is an advantage that high sensitivity can be achieved. In addition, in the unexposed area, the image recording layer is easily peeled off from the support, so that the on-press developability is improved.
As the undercoat layer, specifically, a silane coupling agent having an ethylenic double bond reactive group capable of addition polymerization described in JP-A-10-282679, an ethylenic double bond reaction Preferable examples include a phosphorus compound having a group.
The coating amount (solid content) of the undercoat layer is preferably from 0.1-100 mg / m ^2, and more preferably 3 to 30 mg / m ^2.

[Protective layer]
In the lithographic printing plate precursor of the present invention used in the lithographic printing method of the present invention, image recording is performed as necessary to prevent the occurrence of scratches in the image recording layer, to block oxygen, and to prevent ablation during high-illuminance laser exposure. A protective layer can be provided on the layer.
In the present invention, the exposure is usually performed in the atmosphere, but the protective layer is an image of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that inhibit the image forming reaction caused by exposure in the image recording layer. This prevents the recording layer from being mixed, and prevents the image formation reaction from being hindered by exposure in the air. Therefore, the properties desired for the protective layer are low permeability of low-molecular compounds such as oxygen, furthermore, good transparency of light used for exposure, excellent adhesion to the image recording layer, and It is preferable that it can be easily removed in an on-press development process after exposure. Various studies have been made on protective layers having such characteristics, and are described in detail, for example, in US Pat. No. 3,458,311 and JP-A-55-49729.

  Examples of the material used for the protective layer include water-soluble polymer compounds that are relatively excellent in crystallinity. Specific examples include water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, and polyacrylic acid. Among these, when polyvinyl alcohol (PVA) is used as a main component, the best results are obtained for basic characteristics such as oxygen barrier properties and development removability. The polyvinyl alcohol may be partially substituted with an ester, ether or acetal as long as it contains an unsubstituted vinyl alcohol unit for providing the oxygen barrier property and water solubility necessary for the protective layer, and a part of the other You may have a copolymerization component.

  As specific examples of polyvinyl alcohol, those having a hydrolysis degree of 71 to 100 mol% and a polymerization degree of 300 to 2400 are preferably mentioned. Specifically, for example, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA- HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613, and L-8 are mentioned.

The components of the protective layer (selection of PVA, use of additives, etc.), coating amount, etc. are appropriately selected in consideration of fogging properties, adhesion, scratch resistance, etc. in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of PVA (that is, the higher the content of unsubstituted vinyl alcohol units in the protective layer), the higher the film thickness, the higher the oxygen barrier property, which is preferable in terms of sensitivity. . Further, in order to prevent unnecessary polymerization reaction during production and storage, unnecessary fogging during image exposure, image line thickening, and the like, it is preferable that the oxygen permeability is not excessively high. Accordingly, the oxygen permeability A at 25 ° C. and 1 atm is preferably 0.2 ≦ A ≦ 20 (cc / m ² · day).

As another composition of the protective layer, glycerin, dipropylene glycol and the like can be added in an amount corresponding to several mass% with respect to the water-soluble polymer compound, and flexibility can be imparted. Anionic surfactants such as sodium acid salts; amphoteric surfactants such as alkylaminocarboxylates and alkylaminodicarboxylates; nonionic surfactants such as polyoxyethylene alkylphenyl ethers based on (co) polymers Mass% can be added.
The thickness of the protective layer is suitably from 0.1 to 5 μm, particularly preferably from 0.2 to 2 μm.

  In addition, adhesion to the image area, scratch resistance, and the like are extremely important in handling the lithographic printing plate precursor. That is, when a protective layer that is hydrophilic because it contains a water-soluble polymer compound is laminated on an image recording layer that is oleophilic, the protective layer is easily peeled off due to insufficient adhesion, and polymerization is inhibited by oxygen at the peeled portion. It may cause defects such as poor film hardening due to.

  On the other hand, various proposals have been made to improve the adhesion between the image recording layer and the protective layer. For example, JP-A-49-70702 and British Patent Application No. 1303578 disclose an acrylic emulsion, a water-insoluble vinylpyrrolidone-vinyl acetate copolymer, etc. in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesiveness can be obtained by mixing 20 to 60% by mass and laminating on an image recording layer. Any of these known techniques can be used in the present invention. The method for applying the protective layer is described in detail, for example, in US Pat. No. 3,458,311 and JP-A-55-49729.

  Furthermore, other functions can be imparted to the protective layer. For example, by adding a colorant (for example, a water-soluble dye) that is excellent in the transparency of infrared rays used for exposure and that can efficiently absorb light of other wavelengths, safe light is not caused. Suitability can be improved.

〔exposure〕
In the planographic printing method of the present invention, the above-described planographic printing plate precursor of the present invention is exposed imagewise with an infrared laser.
Although the infrared laser used for this invention is not specifically limited, The solid laser and semiconductor laser which radiate | emit infrared rays with a wavelength of 760-1200 nm are mentioned suitably. The output of the infrared laser is preferably 100 mW or more. In order to shorten the exposure time, it is preferable to use a multi-beam laser device.
The exposure time per pixel is preferably within 20 μsec. Moreover, it is preferable that irradiation energy amount is 10-300 mJ / cm < ² >.

[Printing method]
In the lithographic printing method of the present invention, as described above, after exposing the lithographic printing plate precursor of the present invention imagewise with an infrared laser, an oil-based ink and an aqueous component are supplied without any development processing steps. Print.
Specifically, after exposing the lithographic printing plate precursor with an infrared laser, mounting it on a printing machine without passing through the development process, printing the lithographic printing plate precursor on the printing machine, Examples include a method of printing with an infrared laser and printing without going through a development process.

After exposing the lithographic printing plate precursor imagewise with an infrared laser and supplying it with an aqueous component and oil-based ink without passing through a development process such as a wet development process, in the exposed part of the image recording layer, The image recording layer cured by exposure forms an oil-based ink receiving portion having an oleophilic surface. On the other hand, in the unexposed area, the uncured image recording layer is dissolved or dispersed and removed by the supplied aqueous component and / or oil-based ink, and a hydrophilic surface is exposed in that area.
As a result, the aqueous component adheres to the exposed hydrophilic surface, and the oil-based ink is deposited on the image recording layer in the exposed area, and printing is started. Here, the water-based component or the oil-based ink may be supplied to the printing plate first, but the oil-based ink is first used to prevent the water-based component from being contaminated by the image recording layer in the unexposed area. It is preferable to supply. As the aqueous component and oil-based ink, a dampening water and printing ink for ordinary lithographic printing are used.
In this way, the lithographic printing plate precursor is subjected to on-press development on an offset printing machine and used as it is for printing a large number of sheets.

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

<Synthesis of Graft Polymer (A-1) with Hydrophilic Segment as Graft Chain>
(Synthesis of hydrophilic macromer)
30 g of acrylamide and 3.8 g of 3-mercaptopropionic acid are dissolved in 70 g of ethanol, the temperature is raised to 60 ° C. in a nitrogen atmosphere, and 300 mg of a thermal polymerizable initiator 2,2′-azobisisobutyronitrile (AIBN) is added. For 6 hours. After the reaction, the white precipitate was filtered and sufficiently washed to obtain 30.8 g of a terminal carboxylic acid prepolymer (carboxylic acid value 0.78 meq / g, weight average molecular weight 1.3 × 10 ³ ).
20 g of the obtained prepolymer was dissolved in 62 g of N, N-dimethylacetamide, and 6.71 g of glycidyl methacrylate, 504 mg of N, N-dimethyldodecylamine (catalyst) and 62.4 mg of hydroquinone (polymerization inhibitor) were added at 130 ° C. The reaction was continued for 6 hours. After the reaction, it was put into acetone, the polymer was precipitated, and washed well to obtain 23.4 g of terminal methacrylate acrylamide macromonomer. (Weight average molecular weight: 1.4 × 10 ³ ). ¹ H-NMR (D ₂ O) 6.12, 5.70 ppm The presence of a methacryloyl group olefin peak and a decrease in the carboxylic acid value (0.023 meq / g) confirmed that a polymerizable group could be introduced at the terminal. did. The glass transition temperature of the hydrophilic macromer was measured by a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc. and found to be 160 ° C.

(Synthesis of graft polymer)
15 g of N, N-dimethylacetamide amide is placed in a flask and heated to 60 ° C. under a nitrogen atmosphere. A solution of N, N-dimethylacetamide amide in 15 g was added dropwise over 2 hours. After completion of dropping, heating was continued for 6 hours. The product was precipitated and washed well to obtain 14.5 g of a graft polymer (A-1) having a hydrophobic segment as a graft chain. The weight average molecular weight is shown in Table 1.

<Synthesis of graft polymer (A-2 to 5) having hydrophilic segment as graft chain>
Graft polymers (A-2) to (A-5) were synthesized in the same manner as the synthesis of graft polymer (A-1) except that the hydrophobic monomer (methyl methacrylate) in the above synthesis example was changed as shown in Table 1. Obtained. The weight average molecular weight is shown in Table 1.

<Synthesis of graft polymer (B-1) having hydrophilic segment as graft chain>
(Synthesis of hydrophilic macromer)
After dissolving 40 g of N, N-dimethylacrylamide and 3.8 g of 3-mercaptopropionic acid in 95 g of ethanol, the temperature was raised to 60 ° C. in a nitrogen atmosphere, and the thermal polymerizable initiator 2,2′-azobisisobutyronitrile ( AIBN) 300 mg was added and reacted for 6 hours. After the reaction, the white precipitate was filtered and sufficiently washed to obtain 38.5 g of a terminal carboxylic acid prepolymer (carboxylic acid value 0.75 meq / g, weight average molecular weight 1.25 × 10 ³ ).
20 g of the obtained prepolymer was dissolved in 62 g of N, N-dimethylacetamide, and 6.71 g of glycidyl methacrylate, 504 mg of N, N-dimethyldodecylamine (catalyst) and 62.4 mg of hydroquinone (polymerization inhibitor) were added at 130 ° C. The reaction was continued for 6 hours. After the reaction, it was put into acetone, the polymer was precipitated, and washed well to obtain 23.4 g of terminal methacrylate acrylamide macromonomer. (Weight average molecular weight: 1.33 × 10 ³ ). ¹ H-NMR (D ₂ O) 6.12, 5.70 ppm The presence of a methacryloyl group olefin peak and a decrease in the carboxylic acid value (0.019 meq / g) confirmed that a polymerizable group could be introduced at the terminal. did. The glass transition temperature of the hydrophilic macromer was measured with a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc. and found to be 90 ° C.

(Synthesis of graft polymer)
15 g of N, N-dimethylacetamide amide is placed in a flask and heated to 60 ° C. under a nitrogen atmosphere. A solution of N, N-dimethylacetamide amide in 15 g was added dropwise over 2 hours. After completion of dropping, heating was continued for 6 hours. The product was precipitated and washed well to obtain 14.5 g of a graft polymer (B-1) having a hydrophobic segment as a graft chain (weight average molecular weight 1.0 × 10 ⁵ ).

<Synthesis of graft polymer (B-2 to 5) having hydrophilic segment as graft chain>
Graft polymers (B-2) to (B-5) in the same manner as the synthesis of graft polymer (B-1) except that the hydrophobic monomer (methyl methacrylate) in the above synthesis example was changed as shown in Table 2.
Got. The weight average molecular weight is shown in Table 2.

<Synthesis of Graft Polymer (C-1) for Comparison>
Take 53 g of 1-methoxy-2-propanol in a flask, raise the temperature to 60 ° C. in a nitrogen atmosphere, then 22 g of methyl methacrylate, 30 g of polyoxyethylene monomethacrylate (Nippon Yushi Co., Ltd., Bremer PME1000), start of thermal polymerization A solution prepared by dissolving 250 mg of the agent 2,2′-azobisisobutyronitrile in 53 g of 1-methoxy-2-propanol was added dropwise over 2 hours. After completion of dropping, heating was continued for 6 hours. The product was precipitated and washed well to obtain 45 g of a comparative graft polymer (C-1) (weight average molecular weight 1.3 × 10 ⁵ ).

<Production of support>
In order to remove rolling oil on the surface of an aluminum plate (material JIS A1050) having a thickness of 0.3 mm, a degreasing treatment was performed at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution, and then the hair diameter was 0.3 mm. The surface of the aluminum plate was grained using 3 bundle-planted nylon brushes and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and washed thoroughly with water. This plate was etched by being immersed in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds, washed with water, further immersed in 20% nitric acid at 60 ° C. for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .

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

Next, in a 0.5% by mass aqueous solution of hydrochloric acid (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C., the above nitric acid was used under the condition of an electric quantity of 50 C / dm ² when the aluminum plate was an anode. An electrochemical surface roughening treatment was performed in the same manner as in electrolysis, and then water washing by spraying was performed. The plate was provided with a direct current anodized film of 15% sulfuric acid (containing 0.5% by weight of aluminum ions) as an electrolyte and a current density of 15 A / dm ² and 2.5 g / m ² , washed with water, dried, Then, it was treated with a 2.5% by mass aqueous solution of sodium silicate at 30 ° C. for 10 seconds. The centerline average roughness (Ra) of this substrate was measured using a needle having a diameter of 2 μm and found to be 0.51 μm.

[Examples 1 to 10, Comparative Example 1]
<Preparation of lithographic printing plate precursor>
An image recording layer coating solution (1) having the following composition was bar-coated on the support, followed by oven drying at 100 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 1.0 g / m ^2. The lithographic printing plate precursors 1 to 10 and the comparative lithographic printing plate precursor 1 ′ were obtained.

Image recording layer coating solution (1)
・ The following infrared absorber (1) 0.05 g
・ The following polymerization initiator (1) 0.2 g
・ 0.5 g of graft polymer listed in Table 3
・ Polymerizable compound 1.0g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)
・ Victoria Pure Blue Naphthalenesulfonate 0.02g
・ 0.1 g of the following fluorosurfactant (1)
・ Methyl ethyl ketone 18.0g

<Exposure and printing>
The obtained lithographic printing plate precursor was exposed to a Trend setter 3244VX manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser under the conditions of an output of 9 W, an outer drum rotating speed of 210 rpm, and a resolution of 2400 dpi. The exposure image includes a thin line chart. The exposed exposed original plate was attached to a cylinder of a printing machine SOR-M manufactured by Heidelberg without developing. Dampening water (EU-3 (Effect manufactured by Fuji Photo Film Co., Ltd.) / Water / isopropyl alcohol = 1/89/10 (volume ratio)) and TRANS-G (N) black ink (Dainippon Ink Chemical Co., Ltd.) After supplying dampening water and ink, printing was performed at a printing speed of 6000 sheets per hour.

<Evaluation>
In general, in the case of a negative lithographic printing plate precursor, when the exposure amount is small, the degree of cure of the image recording layer (photosensitive layer) is low, and when the amount of exposure is large, the degree of cure is high. When the image recording layer has a too low degree of curing, the printing durability of the lithographic printing plate becomes low, and the reproducibility of small dots and fine lines becomes poor. On the other hand, when the degree of cure of the image recording layer is high, the printing durability is high, and the reproducibility of small dots and fine lines is good.
In this example, as shown below, the negative lithographic printing plate precursors 1 to 10 and 1 ′ obtained above were evaluated for printing durability and fine line reproducibility under the same exposure conditions described above. It was used as an index of sensitivity of the lithographic printing plate precursor. That is, it can be said that the sensitivity of the lithographic printing plate precursor is higher as the number of printed sheets in printing durability is higher and the fine line width in fine line reproducibility is thinner.

(1) On-machine developability After starting printing as described above, after printing 100 sheets, the number of printing papers required until a print with no ink stains on the non-image area on the printing paper was counted. The number of developed images. The smaller the number, the higher the on-press developability.

(2) Fine line reproducibility As described above, after 100 sheets were printed and it was confirmed that a printed matter free from ink stains in the non-image area was obtained, 500 sheets were continuously printed. A thin line chart (10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 60, 80, 100 and 200 μm fine line exposed charts) of a total of 600 printed sheets with a 25X magnifier The fine line reproducibility was evaluated based on the fine line width that was observed and reproduced with ink without interruption. The results are shown in Table 3.

(3) Printing durability After printing for fine line reproducibility evaluation as described above, printing was further continued. As the number of printed sheets was increased, the image recording layer was gradually worn out and the ink acceptability was lowered, so that the ink density in the printing paper was lowered. Printing durability was evaluated by the number of printed sheets when the ink density (reflection density) was reduced by 0.1 from the start of printing. The results are shown in Table 3.

  From the above results, in the comparative example using C-1 having a polyethylene oxide chain (Tg = −45 ° C.) having a low glass transition temperature as a graft chain, the on-press developability is good, but the fine line reproducibility and resistance The lithographic printing plate precursor according to the present invention using a graft polymer having a hydrophilic segment graft chain having a high glass transition temperature, in addition to having an insufficient on-press developability, not only has good on-press developability. It can be seen that fine line reproducibility and printing durability are also excellent. Therefore, it can be said that the lithographic printing plate precursor of the present invention is excellent in sensitivity.

[Examples 11 to 15, Comparative Example 2]
An image recording layer coating solution (2) having the following composition was bar-coated on the same support used in Example 1, and then oven-dried at 70 ° C. for 60 seconds to obtain a dry coating amount of 0.8 g / m ^2. The lithographic printing plate precursors 11 to 15 and the comparative lithographic printing plate precursor 2 ′ were obtained.

Image recording layer coating solution (2)
・ Water 8g
・ Propylene glycol monomethyl ether 10g
・ Methyl ethyl ketone 2g
・ The following infrared absorber (2) 0.03 g
-0.1 g of graft polymer described in Table 4
・ The following microcapsules (1) (in terms of solid content) 1 g
・ 0.1 g of the above polymerization initiator (1)
・ 0.02 g of the above fluorosurfactant (1)

(Synthesis of microcapsule (1))
As an oil phase component, trimethylolpropane and xylene diisocyanate adduct (manufactured by Mitsui Takeda Chemical Co., Ltd., Takenate D-110N) 10 g, pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., SR444) 3.5 g, 1-g of 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., ODB), and Pionein A-41C (manufactured by Takemoto Yushi Co., Ltd., Na dodecylbenzene sulfonate) Salt) 0.1 g was dissolved in 17 g of ethyl acetate. As an aqueous phase component, 40 g of a 4% by mass aqueous solution of PVA-205 was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12000 rpm using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 3 hours. The microcapsule solution thus obtained was diluted with distilled water so that the solid content concentration became 20% by mass. The average particle size was 0.3 μm.

  The lithographic printing plate precursor thus obtained was exposed, printed and evaluated in the same manner as in Example 1. The results are shown in Table 4.

From the above results, even in a lithographic printing plate precursor using microcapsules for the image recording layer, the lithographic printing plate precursor of the present invention is more thin than Comparative Example 2 using C-1 having a polyethylene oxide chain as a graft chain. It can be seen that reproducibility and printing durability are excellent.

<Synthesis of Graft Polymer (A′-1) Using Hydrophobic Segment as Graft Chain>
[Synthesis of hydrophobic macromers]
After dissolving 42 g of methyl methacrylate and 3.8 g of 3-mercaptopropionic acid in 84 g of methyl ethyl ketone, the temperature was raised to 60 ° C. in a nitrogen atmosphere, and 300 mg of a thermal polymerizable initiator 2,2-azobisisobutyronitrile (AIBN) was added. For 6 hours. After the reaction, it was poured into water, the polymer was precipitated, filtered, and sufficiently washed with water to obtain 43.5 g of a terminal carboxylic acid prepolymer (carboxylic acid value 0.75 meq / g, weight average molecular weight 1. 8 × 10 ³ ).
20 g of the obtained prepolymer was dissolved in 62 g of N, N-dimethylacetamide, and 6.71 g of glycidyl methacrylate, 504 mg of N, N-dimethyldodecylamine (catalyst) and 62.4 mg of hydroquinone (polymerization inhibitor) were added at 130 ° C. The reaction was continued for 6 hours. After the reaction, it was poured into water to precipitate the polymer, and washed well to obtain 23.4 g of terminal methacrylate methyl methacrylate macromonomer. (Weight average molecular weight: 1.8 × 10 ³ ). ^{From 1} H-NMR (CDCl ₃ ) 6.12, 5.70 ppm methacryloyl group olefin peak and a decrease in carboxylic acid value (0.043 meq / g), it was confirmed that a polymerizable group could be introduced at the terminal.

[Synthesis of Graft Polymer (A′-1)]
Take 15 g of 1-methoxy-2-propanol in a flask and raise the temperature to 60 ° C. under a nitrogen atmosphere. A solution dissolved in 15 g of 1-methoxy-2-propanol was added dropwise over 2 hours. After completion of dropping, heating was continued for 6 hours. The product was precipitated and washed well to obtain 14.5 g of a graft polymer (A′-1) having a hydrophobic segment as a graft chain (weight average molecular weight 1.30 × 10 ⁵ ).

<Synthesis of Graft Polymer (A′-2 to 5) with Hydrophobic Segment as Graft Chain>
A hydrophobic macromer was synthesized in the same manner as the synthesis of the graft polymer (A′-1) except that the hydrophilic monomer (methacrylamide) used in the synthesis of the graft polymer (A′-1) was changed as shown in Table 5. Graft polymers (A′-2) to (A′-5) were obtained by copolymerizing with hydrophilic monomers. The weight average molecular weight is shown in Table 5.

<Synthesis of Graft Polymer (B′-1) Using Hydrophobic Segment as Graft Chain>
[Synthesis of hydrophobic macromers]
After dissolving 44 g of styrene and 3.8 g of 3-mercaptopropionic acid in 88 g of methyl ethyl ketone, the temperature was raised to 60 ° C. in a nitrogen atmosphere, and 300 mg of a thermal polymerizable initiator 2,2′-azobisisobutyronitrile (AIBN) was added. For 6 hours. After the reaction, it was poured into water, the polymer was precipitated, filtered, and sufficiently washed with water to obtain 43.5 g of a terminal carboxylic acid prepolymer (carboxylic acid value 0.76 meq / g, weight average molecular weight 1. 9 × 10 ³ ).
20 g of the obtained prepolymer was dissolved in 62 g of N, N-dimethylacetamide, and 6.71 g of glycidyl methacrylate, 504 mg of N, N-dimethyldodecylamine (catalyst) and 62.4 mg of hydroquinone (polymerization inhibitor) were added at 130 ° C. The reaction was continued for 6 hours. After the reaction, it was poured into water to precipitate the polymer and washed well to obtain 23.4 g of terminal methacrylate styrene macromonomer. (Weight average molecular weight: 1.8 × 10 ³ ). ^{From 1} H-NMR (CDCl ₃ ) 6.12, 5.70 ppm methacryloyl group olefin peak and a decrease in carboxylic acid value (0.041 meq / g), it was confirmed that a polymerizable group could be introduced at the terminal.

(Synthesis of graft polymer)
15 g of 1-methoxy-2-propanol was placed in a flask, heated to 60 ° C. under a nitrogen atmosphere, 10 g of the above-mentioned terminal methacrylate styrene macromonomer, 5 g of methacrylamide, thermal polymerizable initiator 2,2′-azobisisobutyrate. A solution of 150 mg of nitrile dissolved in 15 g of 1-methoxy-2-propanol was added dropwise over 2 hours. After completion of dropping, heating was continued for 6 hours. The product was precipitated and washed well to obtain 14.5 g of a graft polymer (B′-1) having a hydrophobic segment as a graft chain (weight average molecular weight 1.2 × 10 ⁵ ).

<Synthesis of Graft Polymer (B′-2 to 5) with Hydrophobic Segment as Graft Chain>
The same method as the synthesis of the graft polymer (B′-1) except that the hydrophilic monomer shown in Table 6 was used instead of the hydrophilic monomer (methacrylamide) used in the synthesis of the graft polymer (B′-1). Graft polymers (B′-2) to (B′-5) were obtained. The weight average molecular weight is shown in Table 6.

<Synthesis of Comparative Graft Polymer (C′-1)>
Take 53 g of 1-methoxy-2-propanol in a flask, raise the temperature to 60 ° C. under a nitrogen atmosphere, 22 g of the above methyl methacrylate, 30 g of polyoxyethylene monomethacrylate (Nippon Yushi Co., Ltd., Bremer PME1000), thermopolymerizable. A solution of 250 mg of initiator 2,2-azobisisobutyronitrile dissolved in 53 g of 1-methoxy-2-propanol was added dropwise over 2 hours. After completion of dropping, heating was continued for 6 hours. The reaction solution was precipitated and washed well to obtain 45 g of a comparative graft polymer (C′-1) (weight average molecular weight 1.3 × 10 ⁵ ).

<Production of support>
In order to remove rolling oil on the surface of an aluminum plate (material JIS A1050) having a thickness of 0.3 mm, a degreasing treatment was performed at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution, and then the hair diameter was 0.3 mm. The surface of the aluminum plate was grained using 3 bundle-planted nylon brushes and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and washed thoroughly with water. This plate was etched by being immersed in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washed with water, further immersed in 20 mass% nitric acid at 60 ° C for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .

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

Next, in a 0.5% by mass aqueous solution of hydrochloric acid (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C., the above nitric acid was used under the condition of an electric quantity of 50 C / dm ² when the aluminum plate was an anode. An electrochemical surface roughening treatment was performed in the same manner as in electrolysis, and then water washing by spraying was performed. This plate was provided with a direct current anodized film of 2.5 g / m ² at a current density of 15 A / dm ² using 15% by mass sulfuric acid (containing 0.5% by mass of aluminum ions) as an electrolytic solution, then washed with water and dried. Furthermore, it processed at 30 degreeC for 10 second with 2.5 mass% sodium silicate aqueous solution. The centerline average roughness (Ra) of this substrate was measured using a needle having a diameter of 2 μm and found to be 0.51 μm.

(Examples 16 to 25, Comparative Example 3)
<Preparation of lithographic printing plate precursor>
An image recording layer coating solution (3) having the following composition was bar-coated on the above support, followed by oven drying at 100 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 1.0 g / m ^2. The lithographic printing plate precursors 16 to 25 and the comparative lithographic printing plate precursor 3 ′ were obtained.

Image recording layer coating solution (3)
・ 0.05g of the above infrared absorber (1)
・ 0.2 g of the above polymerization initiator (1)
・ 0.5 g of graft polymer listed in Table 7
・ Polymerizable compound 1.0g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)
・ Victoria Pure Blue Naphthalenesulfonate 0.02g
・ 0.1 g of the above-mentioned fluorosurfactant (1)
・ Methyl ethyl ketone 18.0g

Each lithographic printing plate precursor thus obtained was exposed, printed and evaluated in the same manner as in Example 1. The results are shown in Table 7.

  From the above results, Comparative Example 3 using (C′-1) having hydrophilic polyoxyethylene as a graft chain has good on-press developability but insufficient thin line reproducibility and printing durability. On the other hand, the lithographic printing plate precursor according to the present invention not only has excellent on-press developability but also excellent thin line reproducibility and printing durability. Since the lithographic printing plate precursor of the present invention is excellent in fine line reproducibility and printing durability, it can be said that it is excellent in sensitivity as described above.

(Examples 26 to 30)
An image recording layer coating solution (4) having the following composition was bar-coated on the support, followed by oven drying at 70 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 0.8 g / m ^2. The lithographic printing plate precursors 26 to 30 and the comparative lithographic printing plate precursor 4 ′ were obtained.

Image recording layer coating solution (4)
・ Water 8.0g
・ Propylene glycol monomethyl ether 10.0g
・ Methyl ethyl ketone 2.0g
・ The above infrared absorber (2) 0.03 g
-0.1g of graft polymers listed in Table 8
・ 1.0 g of the above microcapsules (1) (in terms of solid content)
・ 0.1 g of the above polymerization initiator (1)
・ 0.02 g of the above fluorosurfactant (1)
・ Polymerizable compound 1.0g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)

  The obtained lithographic printing plate precursor was exposed and printed in the same manner as in Example 16, and evaluated in the same manner as in Example 16. The results are shown in Table 8.

  The above results show that even when microcapsules encapsulating a polymerizable compound are used, the lithographic printing plate precursor of the present invention not only has excellent on-press developability but also excellent fine line reproducibility and printing durability. It shows that.

Claims (5)

  A lithographic printing plate precursor comprising an infrared absorbing agent and a graft polymer having a hydrophilic segment graft chain on a support, and having an image recording layer removable by printing ink and / or fountain solution, The hydrophilic segment is at least selected from an amide group-containing monomer, an acid group-containing monomer, an alkali metal salt of an acid group-containing monomer, a quaternary ammonium salt-containing monomer, and a hydroxyl group-containing monomer. A lithographic printing plate precursor comprising a polymer containing at least 50 mol% of one monomer unit.   A lithographic printing plate precursor having an image recording layer containing an infrared absorbent and a graft polymer having a hydrophilic main chain and a hydrophobic segment graft chain on a support.   The lithographic printing plate precursor as claimed in claim 1 or 2, wherein the image recording layer comprises a polymerization initiator and a polymerizable compound.   3. The lithographic printing plate precursor as claimed in claim 2, wherein the image recording layer is removable with printing ink and / or fountain solution.   The lithographic printing plate precursor according to claim 1 or 2 is mounted on a printing press and imagewise exposed with an infrared laser, or imagewise exposed with an infrared laser and then mounted on a printing press, and the lithographic plate A lithographic printing method in which an oil-based ink and an aqueous component are supplied to a printing plate precursor to remove an infrared unexposed portion of the image recording layer and print.