JP2001232960A - Original plate for lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an original plate for a lithographic printing plate capable of direct platemaking from digital data by recording by using scanning exposure, that is, a laser exposure method in a short time to manufacture the lithographic printing plate having improved image degree and adhesive properties of an image part without necessity of a special treatment such as wet development, rubbing or the like after image exposure. SOLUTION: The original plate for the lithographic printing plate comprises a hydrophilic heat insulation layer and a layer containing a hydrophilic polymer compound changing at a side chain to a hydrophobic property by a heat, sequentially arranged on a support in this order. In this case, the heat insulation layer contains a hydrophilic polymer compound having a crosslinking structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate precursor, and more particularly to a lithographic printing plate capable of directly making a plate by operating a laser or the like based on a digital signal and requiring no additional wet processing. For the original plate.

[0002]

2. Description of the Related Art In general, a lithographic printing plate comprises an oleophilic image area which receives ink during a printing process, and a hydrophilic non-image area which receives fountain solution. Conventionally, as a lithographic printing plate precursor used for manufacturing such a lithographic printing plate,
PS provided with a lipophilic photosensitive resin layer on a hydrophilic support
Plates are widely used, and as a plate-making method, usually, a mask is exposed through a lithographic film, and then a non-image portion is dissolved and removed with a developing solution to obtain a desired printing plate.

In recent years, digitization techniques for electronically processing, storing, and outputting image information using a computer have become widespread. Then, various new image output systems corresponding to such digitizing technology have come into practical use. As a result, computer-to-plate technology that scans actinic radiation having high directivity such as laser light according to digitized image information and directly manufactures a printing plate without passing through a lithographic film has been desired. Obtaining a printing plate precursor adapted to this is one of the important technical issues.

On the other hand, in the production of a printing plate using a conventional PS plate, a process of dissolving and removing a non-image portion after exposure is indispensable, and usually, the developed printing plate is washed with washing water. Further, a post-treatment step of treating with a rinse solution containing a surfactant, gum arabic, and a desensitizing solution containing a starch derivative was also required. The fact that such additional wet processing is essential is another problem that has been desired to be improved over the prior art. Particularly in recent years, consideration for the global environment has become a major concern of the entire industry. The simplification of processing, dry processing, and no-processing are more and more desired than ever before, from the viewpoint of both the environmental aspect and the rationalization of the process accompanying the aforementioned digitization. I have.

As a method of manufacturing a printing plate by scanning exposure, a method using a high energy density actinic radiation such as an electron beam or a high output laser is proposed in addition to a method using a highly sensitive photosensitive material. Have been. Recently, high-power solid-state lasers such as semiconductor lasers and YAG lasers have become available at low cost. In particular, computer-to-plate systems using these lasers have become promising. . A feature of the high energy density exposure system is that various developments can be used, which are different from the photoreaction used in the photosensitive material system using low to medium energy density exposure. Specifically, in addition to chemical changes,
Structural changes such as phase changes and morphological changes can be used. Usually, such a recording method using high energy density exposure is called heat mode recording. In high energy density exposure systems,
In many cases, the light energy absorbed by the light-sensitive material is converted into heat, and it is believed that the generated heat causes the desired development. A major advantage of the heat mode recording method is that it can potentially simplify the processing, dry the processing, and eliminate the processing. This is due to the fact that the phenomenon used for image recording of heat mode light sensitive materials is exposure to light of normal intensity,
This is based on the fact that the fixation of the image after exposure is not necessary since it does not substantially occur at a normal environmental temperature.

[0006] A preferred method for producing a lithographic printing plate based on heat mode recording is to expose an original plate comprising a hydrophilic layer and an lipophilic layer to heat mode exposure and remove only one of the layers in an image-like manner. There has been proposed a method of expressing hydrophilicity / hydrophobicity in a shape. This method provides a printing plate precursor exhibiting relatively good printing performance in addition to the possibility of scanning exposure and the non-processing / dry processing method.

[0007] As an example of such a lithographic printing plate precursor, a film obtained by using a sulfonated film of polyolefins as a plate material and changing the hydrophilicity of the surface by thermal writing to eliminate the need for development processing Can be formed as described in JP-A-5-77574 and JP-A-4-1251.
No. 89, U.S. Pat. No. 5,187,047 and JP-A-62-195646. In these systems, sulfone groups on the surface of the photosensitive material are desulfonated by thermal writing to form an image. U.S. Pat. No. 4,081,572 discloses a method of forming an image by dehydrating and cyclizing a polymer having a carboxylic acid by heat or laser. These are all examples of so-called polarity-converting negative type printing plates in which a hydrophilic film is converted to hydrophobic by exposure before exposure, and a feature thereof is that development processing is not required.

[0008]

However, in the above-mentioned prior art, since the thermal reactivity of the plate material is poor, the sensitivity is low, and much time is required for image formation. Further, since the hydrophilic and hydrophobic discrimination is low, only a photosensitive material having insufficient hydrophilicity or low image strength can be produced. That is, these conventional techniques do not provide a photosensitive material that is satisfactory in terms of image strength and image portion adhesion. Accordingly, an object of the present invention is to perform scanning exposure in a short time, that is, by performing recording using a laser exposure method, it is possible to directly make a plate from digital data, and to perform special development such as wet development processing or rubbing after image exposure. It is an object of the present invention to provide a technique capable of manufacturing a lithographic printing plate which requires no processing and has improved image strength and adhesion of an image portion.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the problems of the prior art, and as a result, the temperature near the aluminum substrate did not rise due to thermal diffusion by the aluminum substrate. When the amount of laser exposure is increased, the temperature near the substrate rises to some extent, but the temperature near the surface is too high, and the main chain of the polymer in the image forming layer is decomposed. Therefore, it was determined that the image intensity was weakened. Therefore, by providing a heat-insulating hydrophilic layer as an intermediate layer between the aluminum substrate and the image forming layer, for a lithographic printing plate having sufficient image strength and image portion adhesion without increasing the exposure amount. The present inventors have found that an original plate can be obtained, and have reached the present invention. That is, the present invention is as follows. (1) A lithographic printing plate having, in this order, a hydrophilic heat insulating layer and a layer containing a hydrophilic polymer compound whose side chain changes to hydrophobic by heat (hereinafter, also referred to as an image forming layer) on a support. Original version. (2) The lithographic printing plate precursor as described in (1) above, wherein the hydrophilic heat-insulating layer contains a hydrophilic polymer compound having a crosslinked structure.

The lithographic printing plate precursor of the present invention can be directly subjected to plate making by scanning exposure of an image with a laser beam such as infrared light, and requires no special processing such as wet development processing or rubbing after image exposure. Plates can be made, and after image exposure, they can be directly mounted on a printing press and printed. The lithographic printing plate precursor according to the invention is provided with a hydrophilic heat-insulating layer or a hydrophilic cross-linking heat-insulating layer as an intermediate layer between the support and the image forming layer, thereby making the vicinity of the support hydrophilic and simultaneously forming the intermediate layer. The layer has a heat insulating effect and can suppress heat diffusion to the support. That is, the heat polarity conversion (hydrophilicity → hydrophobicity) of the image forming layer proceeds efficiently without increasing the exposure amount by introducing the heat insulating intermediate layer. As a result, a lithographic printing plate precursor with significantly improved image strength and adhesion can be provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The lithographic printing plate precursor of the present invention has a case where a hydrophilic heat-insulating layer containing a hydrophilic polymer compound is formed on a support,
A hydrophilic crosslinked heat-insulating layer containing a hydrophilic polymer compound having a crosslinked structure may be formed on various supports.
First, the hydrophilic heat-insulating layer used in the present invention is a layer containing the following hydrophilic polymer compound.

[Hydrophilic high molecular compound] The hydrophilicity of the hydrophilic high molecular compound used in the present invention means water-soluble (it means completely soluble in water), pseudo-water-soluble (it means amphiphilic). Macros include those that dissolve in water but micros contain insoluble portions) and those that have water swelling properties (meaning those that swell in water but do not dissolve). That is, it includes polymers that adsorb or absorb water under ordinary use conditions, and polymers that dissolve or swell in water. As it applies to the above definition, -COOR a (1) side _{chain, -COOM, -SOR, -SO 2 R} ,
_{-SO 3 R, -SOM, -SO 2} M, -SO 3 M, -O
H, -NR ¹ R ² (where R represents a hydrogen atom, an alkyl group or an aryl group, M represents a metal atom, and R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group. And (2) a hydrophilic polymer compound having an alkylene oxide group in the molecule, and a known natural polymer compound having these functional groups or synthetic. High molecular compounds can be used.

(1) -COOR, -COOM,-
_{SOR, -SO 2 R, -SO 3} R, -SOM, -SO
_{2 M, -SO 3 M, -OH} , -NR 1 R 2 ( wherein, R represents a hydrogen atom, an alkyl group or an aryl group, M represents a metal atom, R ^1, R ² are each independently, Examples of the synthetic polymer compound as a hydrophilic polymer compound having a functional group selected from a hydrogen atom, an alkyl group, and an aryl group include the following compounds. Carboxylate-based copolymer, N-vinylcarboxylic acid amide-based copolymer, sulfonate-based copolymer, vinylpyrrolidone-based copolymer, polyvinyl alcohol, aqueous urethane resin, water-soluble polyester, hydroxyethyl (meth) Acrylate-based polymers, poly (vinyl methyl ether-co-maleic anhydride), polyethylene glycol di (meth) acrylate-based crosslinked polymers, polypropylene glycol di (meth) acrylate-based crosslinked polymers, and the like. -COOR or -C on the side chain
As the carboxylate copolymer having OOM, from the viewpoint of water absorption and durability, it is derived into a carboxyl group or a carboxyl group such as a carboxylate, a carboxylate, a carboxylic amide, a carboxylic imide, or a carboxylic anhydride. A saponification reaction product of a carboxylic acid copolymer containing, as a monomer component, an α, β-unsaturated compound having one or two functional groups which can be used in a molecule.

Specific examples of the α, β-unsaturated compound include:
Acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylic amides, methacrylic amides, maleic anhydride, maleic acid, maleic amides, maleic imides, itaconic acid, crotonic acid, fumaric acid Acid, mesaconic acid and the like. 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, 2-hydroxyethyl acrylate, 2
-Hydroxypropyl acrylate, 5-hydroxypentyl 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, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenylcarbonyloxy)
Ethyl acrylate and the like can be mentioned.

Specific examples of the methacrylates 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, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate , Trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate,
Hydroxyphenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate,
Examples include tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, and 2- (hydroxyphenylcarbonyloxy) ethyl methacrylate.

Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide,
Hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl)
Acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-
N-phenylacrylamide, N-hydroxyethyl-
N-methylacrylamide and the like can be mentioned.

Specific examples of maleic amides include maleic amide, N-methylmaleamide, N-ethylmaleamide, N-propylmaleamide, N-butylmaleamide, N-benzylmaleic acid Amide, N-hydroxyethylmaleamide,
N-phenylmaleamide, N-tolylmaleamide, N- (hydroxyphenyl) maleamide, N- (sulfamoylphenyl) maleamide, N- (phenylsulfonyl) maleamide, N
-(Tolylsulfonyl) maleamide, N, N-dimethylmaleamide, N-methyl-N-phenylmaleamide, N-hydroxyethyl-N'-methylmaleamide and the like. Specific examples of maleic imides include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide,
N-benzylmaleimide, N-hydroxyethylmaleimide, N-phenylmaleimide, N
-Tolylmaleic acid imide, N- (hydroxyphenyl) maleic acid imide, N- (sulfamoylphenyl) maleic acid imide, N- (phenylsulfonyl) maleic acid imide, N- (tolylsulfonyl) maleic acid imide and the like. Can be

The carboxylate copolymer used in the present invention may be a homopolymer of the above α, β-unsaturated compound, or may be copolymerizable as long as it exhibits the hydrophilicity required for the present invention. It may be a copolymer with other monomers. Examples of other copolymerizable monomer components include known monomers such as ethylene, propylene, isobutylene, 1-butylene, diisobutylene, methyl vinyl ether, acrylonitrile, vinyl esters, and styrenes.

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, ethoxy methyl styrene, acetoxy methyl styrene, methoxy styrene, dimethoxy styrene , Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

When combined with other monomers, α, β containing a carboxyl group or a group convertible thereto
The unsaturated compound is usually 10 mol% of the total monomer components
More preferably, it is at least 40 mol%. Α, β containing a carboxyl group or a group convertible thereto
-A polymer containing an unsaturated compound as a monomer can be produced by a known method. For example, Polymer Chemistry, Vol. 7, p. 142 (1950). That is, these carboxylate-based copolymers may be any of a random polymer, a block polymer, a graft polymer, and the like, but are preferably a random polymer, and are appropriately selected depending on the polymerization method. It is synthesized by radical polymerization using a polymerization initiator such as oxides, peroxides such as benzoyl peroxide, persulfates such as ammonium persulfate, and azo compounds such as azobisisobutyronitrile. Polymerization methods include solution polymerization,
Emulsion polymerization, suspension polymerization and the like are required.

These carboxylate salts are preferably used as solvents for synthesizing a copolymer, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, and the like.
Methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether,
-Methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide,
N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide,
Water and the like. These solvents are used alone or in combination of two or more. The degree of polymerization of these carboxylate copolymers is not particularly limited.

The above-described polymer or copolymer preferably undergoes a saponification reaction in the presence of an alkali catalyst. As the solvent used for the saponification reaction, water, alcohol, and an aqueous alcohol solution are preferable. As a catalyst used for the saponification reaction, a known alkali catalyst is used.
Particularly, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferable. The saponification reaction is achieved by dissolving or dispersing the polymer or the copolymer in the above-mentioned solvent, adding an alkali catalyst thereto, and stirring at 20 to 80 ° C for 1 to 10 hours. Further, the saponification reaction product of the present invention includes:
The salt can be arbitrarily changed by a known method. Commonly used salt-forming substances include sodium hydroxide, potassium hydroxide, ammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monoethanolamine. , Diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine, N,
Examples include N-dimethylisopropanolamine, cyclohexylamine, benzylamine, aniline, pyridine and the like. Also, polyvalent metal salts of alkaline earth metal salts such as magnesium and calcium can be added in the form of a mixed salt with the above-mentioned salts.

Specific examples of the carboxylate copolymer include a saponification reaction product of an acrylic acid polymer, a methacrylic acid polymer, a methyl acrylate polymer, and a saponification reaction product of a methacrylamide copolymer. And saponification reaction products of acrylic acid / methacrylic acid copolymer, maleic acid / styrene copolymer, methyl acrylate / vinyl acetate copolymer, and the like. The N-vinylcarboxylic acid amide-based copolymer is an N-vinyl carboxylic acid amide-based copolymer represented by the following general formula (1).
It means a copolymer having vinylcarboxylic amide (hereinafter abbreviated as NVA) as an essential repeating unit (hereinafter abbreviated as an NVA-based copolymer).

The N-vinylcarboxylic acid amide-based copolymer means a copolymer containing N-vinylcarboxylic acid amide represented by the following general formula (1) as an essential repeating unit.

[0025]

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In the formula, R ¹ is a hydrogen atom or a group having 1 to 4 carbon atoms.
R ² represents a hydrogen atom or a methyl group or a phenyl group; R ³ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms.

Specific examples of NVA include N-vinylformamide, N-vinylpropionamide, N-vinylbenzoamide, N-methyl-N-vinylbenzoamide, N-phenyl-N-vinylacetamide, -Phenyl-N-vinylbenzoic acid amide and the like,
The present invention is not limited to these examples.

The N-vinylcarboxylic acid amide-based copolymer preferably used in the present invention is, from the viewpoint of water absorption and durability, a carboxyl group, a carboxylate, a carboxylic amide, a carboxylic imide, a carboxylic anhydride, or the like. It is preferable to contain, as a copolymerized unit, an α, β-unsaturated compound having one or two carboxyl groups or a functional group which can be derived into a carboxyl group in the molecule. Specific examples of the α, β-unsaturated compound include acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides, methacrylamides, maleic anhydride,
Maleic acid, maleic amides, maleic imides, itaconic acid, crotonic acid, fumaric acid, mesaconic acid, and the like. Specific examples of acrylic esters, methacrylic esters, acrylamides, methacrylamides, maleic amides, and maleic imides include the compounds described above.

The NVA-based copolymer preferably used in the present invention can further contain other copolymerizable monomers as copolymerized units as long as the hydrophilicity required for the present invention is exhibited. Examples of other copolymerizable monomer components include ethylene, propylene, isobutylene, 1
-Butylene, diisobutylene, methyl vinyl ether,
Known monomers such as acrylonitrile, vinyl esters, styrenes and the like can be mentioned. Specific examples of vinyl esters and styrenes include the compounds described above. The NVA-based copolymer is usually prepared by radical polymerization. These NVA-based copolymers are random polymers,
Any of a block polymer, a graft polymer and the like may be used, but a random polymer is preferable, and it can be produced by a known method. For example, polymer chemistry,
7, 142 (1950). That is, these carboxylate-based copolymers may be any of a random polymer, a block polymer, a graft polymer, and the like, but are preferably a random polymer, and are appropriately selected depending on the polymerization method. It is synthesized by radical polymerization using a polymerization initiator such as oxides, peroxides such as benzoyl peroxide, persulfates such as ammonium persulfate, and azo compounds such as azobisisobutyronitrile. As the polymerization method, solution polymerization, emulsion polymerization, suspension polymerization and the like are required.

Examples of solvents used for synthesizing these NVA-based copolymers include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy Ethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2
-Propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like.
These solvents are used alone or in combination of two or more. The degree of polymerization of these NVA-based copolymers is not particularly limited. Specific examples of the NVA-based copolymer include:
The following polymers may be mentioned. Poly (N-vinylacetamide), N-vinylacetamide / (meth) acrylic acid copolymer and partially or completely neutralized product thereof ("partially or completely neutralized product" refers to carboxylic acid, sulfone in the copolymer) A part of or all of the hydrogen ions in a polymerizable functional group such as acid or phosphoric acid is replaced by an alkali metal salt such as sodium or potassium, or a metal earth chloride such as calcium or barium), N-vinyl Acetamide / crotonic acid copolymer and partially or completely neutralized product thereof, N
-Vinylacetamide / maleic acid copolymer and its partially or completely neutralized product, N-vinylacetamide / fumaric acid copolymer and its partially or completely neutralized product, N-vinylacetamide / citraconic acid copolymer and its portion Or a completely neutralized product, an N-vinylacetamide / cinnamic acid copolymer and a partially or completely neutralized product thereof, an N-vinylacetamide / vinylsulfonic acid copolymer and a partially or completely neutralized product thereof, N-vinylacetamide / Maleic anhydride copolymer and partially or completely neutralized product thereof, N-vinylacetamide / itaconic acid copolymer and partially or completely neutralized product thereof, N-vinylacetamide / aconitic acid copolymer and partially or completely thereof Neutralized product, N-vinylacetamide / 3-butenoic acid copolymer and a part thereof Fully neutralized product, N-vinylacetamide / 4-pentenoic acid copolymer and its partially or completely neutralized product, N-vinylacetamide / allylsulfonic acid copolymer and its partially or completely neutralized product, N-vinylacetamide / Methallyl sulfonic acid copolymer and partially or completely neutralized product thereof, N-vinylacetamide /
Allyl phosphoric acid copolymer and its partially or completely neutralized product, N-vinylacetamide / carboxyethyl acrylate copolymer and its partially or completely neutralized product, N-
Vinyl acetamide / 2-acryloylethyl phosphoric acid copolymer and partially or completely neutralized product thereof, N-vinyl acetamide / 3-acryloyl propyl phosphoric acid copolymer and partially or completely neutralized product thereof, N-vinyl acetamide / 8-methacryloyloctyl phosphate copolymer and its partially or completely neutralized product, N-vinylacetamide / 2
-Acrylamide-n-propanesulfonic acid copolymer and partially or completely neutralized product thereof, N-vinylacetamide / 2-acrylamide-n-octanesulfonic acid copolymer and partially or completely neutralized product thereof, N-vinylacetamide / 2-acrylamide-2-methylpropanesulfonic acid copolymer and partially or completely neutralized products thereof.

The sulfonate-based copolymer having —SO ₃ R and —SO ₃ M in the side chain can be derived into a sulfonate or a sulfonate such as a sulfonamide or a sulfonate in the molecule. A copolymer containing an unsaturated compound having a functional group as a monomer component, or a saponified reaction product of the copolymer may be used. Specific examples of such unsaturated compounds include the following compounds.

[0032]

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Homopolymers using only one of these monomers may be used, but copolymers using two or more of these monomers or other monomers as long as they exhibit the hydrophilicity required for the present invention can be used. A copolymer with a monomer may be used. Examples of other copolymerizable monomer components include ethylene, propylene, isobutylene, 1-butylene, diisobutylene, methyl vinyl ether, acrylonitrile, acrylic esters, methacrylic esters, acrylamides, methacrylamides, and vinyl esters. And known monomers such as styrenes. Specific examples of acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, and styrenes are as described above.

The polymer containing a sulfonate or an unsaturated compound containing a group which can be converted into the sulfonate as a monomer is usually prepared by radical polymerization. These sulfonate-based copolymers may be any of a random polymer, a block polymer, a graft polymer and the like, but are preferably a random polymer, and can be produced by a known method. For example, Polymer Chemistry, Vol. 7, p. 142 (1950). That is, these carboxylate-based copolymers may be any of a random polymer, a block polymer, a graft polymer, and the like, but are preferably a random polymer, and are appropriately selected depending on the polymerization method. It is synthesized by radical polymerization using a polymerization initiator such as oxides, peroxides such as benzoyl peroxide, persulfates such as ammonium persulfate, and azo compounds such as azobisisobutyronitrile.
As the polymerization method, solution polymerization, emulsion polymerization, suspension polymerization and the like are required.

Solvents used for synthesizing these sulfonate-based copolymers include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, -Methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-
Examples include dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more. The degree of polymerization of these sulfonate copolymers is not particularly limited.

The copolymer described above preferably undergoes a saponification reaction in the presence of an alkali catalyst. As the solvent used for the saponification reaction, water, alcohol, and an aqueous alcohol solution are preferable. As the catalyst used in the saponification reaction, a known alkali catalyst is used, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is particularly preferable. The saponification reaction is achieved by dissolving or dispersing the polymer or the copolymer in the above-mentioned solvent, adding an alkali catalyst thereto and stirring at 20 to 80 ° C for 1 to 24 hours.

The salt of the saponification reaction product of the present invention can be arbitrarily changed by a known method. Commonly used salt-forming substances include sodium hydroxide, potassium hydroxide, ammonium hydroxide, monomethylamine,
Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monoethanolamine, diethanolamine,
Triethanolamine, monoisopropanolamine,
Diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine, N, N-dimethylisopropanolamine, cyclohexylamine,
Benzylamine, aniline, pyridine and the like can be mentioned. Also, polyvalent metal salts of alkaline earth metal salts such as magnesium and calcium can be added in the form of a mixed salt with the above-mentioned salts.

Specific examples of the sulfonate-based copolymer include the following polymers.

[0039]

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Among the above-mentioned hydrophilic high molecular compounds, polymers having a hydrophilic property preferable for sufficiently exhibiting the effects of the present invention are carboxylate copolymers, NVA copolymers, and the like.
Sulfonate-based copolymers and polyvinyl alcohols are more preferred, and carboxylate-based copolymers, NVA-based copolymers, and sulfonate-based copolymers are more preferred.

Preferred among the carboxylate copolymers are polymers or copolymers of acrylic acid and methacrylic acid, α-olefins, and copolymers of vinyl compounds and maleic anhydride, more preferably. Is a saponification reaction product of a vinyl ester and a (meth) acrylic acid ester copolymer (in the following description, (meth) acrylic acid means acrylic acid for methacrylic acid). In the copolymer, the (meth) acrylate component preferably accounts for 20 to 80 mol% of the copolymer,
Further, the content is more preferably 30 to 70 mol% in order to achieve both the water absorption and the mechanical strength of the hydrophilic intermediate layer. Also,
Preferred among the NVA-based copolymers are copolymers of NVA and carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride. Is preferably at least 10 mol%, more preferably at least 40 mol%.

Further, as the sulfonic acid salt-based copolymer, styrene sulfonic acid salt, styrene sulfonic acid ester polymer, copolymer or styrene sulfonic acid salt or styrene sulfonic acid ester and (meth) acrylic acid, (meth) acrylic acid, ) Copolymers with acrylic esters, vinyl esters and / or maleic anhydride, or saponification products of these polymers and copolymers. From the viewpoints of water absorption and durability, the amount of the styrene sulfonate or styrene sulfonic acid ester unit is preferably 20 mol% or more, more preferably 50 mol%, of all the monomers.

Further, -COOR, -CO
_{OM, -SOR, -SO 2 R,} -SO 3 R, -SOM,
Examples of natural polymer compounds as hydrophilic polymer compounds having a functional group selected from —SO ₂ M, —SO ₃ M, —OH, and —NR ¹ R ² include starch-styrenesulfonic acid-based graft polymers, starch- Examples include a vinyl sulfonic acid-based graft polymer, a starch-acrylamide-based graft polymer, a carboxylated methyl cellulose, a cellulose-styrene sulfonic acid-based graft polymer, and a carboxymethyl cellulose-based cross-linked product.

The hydrophilic polymer compound (2) having an alkylene oxide group in the molecule used in the present invention is not particularly limited as long as it has an alkylene oxide group in a main chain or a side chain. For example, polyethylene oxide, poly (ethylene oxide-co-propylene oxide) and the like can be mentioned, and as the natural polymer compound, starch-acrylonitrile-based graft polymer hydrolyzate, starch-acrylic acid-based graft polymer, Methylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, cellulose xanthate, cellulose-acrylonitrile-based graft polymer, hyaluronic acid, agarose, collagen, milk casein, acid casein, rennet casein, ammonia casein, casein Casein, borax casein, glue, gelatin, gluten, soy protein, alginate, ammonium alginate, potassium alginate, sodium alginate, arabia gum, tragacanth gum, karaya gum, guar gum, locust bean gum, Irish moss, soy lecithin, pectic acid , Starch, carboxylated starch, agar, dextrin, mannan and the like. The hydrophilic intermediate layer in the present invention may contain, as necessary, the following compounds as constituent components other than the above-mentioned hydrophilic polymer compound as long as the effects of the present invention are not impaired.

In the hydrophilic heat insulating layer of the lithographic printing plate precursor according to the present invention, JP-A-62-251740 and JP-A-3-208514 are used in order to enhance stability under printing conditions.
Non-ionic surfactants described in JP-A-59-121044, JP-A-4-13149.
An amphoteric surfactant such as that described in JP-A No. 2-211 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene nonyl phenyl ether, and the like. Specific examples of the amphoteric surfactant include:
Alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine type (for example, trade name Amogen K, Daiichi Kogyo Co., Ltd.) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the total solids of the hydrophilic layer is 0.0%.
It is preferably from 5 to 15% by weight, more preferably from 0.1 to 5% by weight.
% By weight.

The hydrophilic heat-insulating layer of the lithographic printing plate precursor according to the present invention can be usually produced by dissolving the above-mentioned components in a solvent and applying the resulting solution on a suitable support. As the solvent used herein, 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 Ethane, methyl lactate, ethyl lactate,
Examples include, but are not limited to, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene, water and the like. .

These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. Various methods can be used as the method of coating, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. In the hydrophilic heat insulating layer of the lithographic printing plate precursor according to the invention, a surfactant for improving coating properties, for example, JP-A-62-17095
No. 0 can be added. The preferred addition amount is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the total solid content of the hydrophilic intermediate layer.

The hydrophilic heat-insulating layer exhibits a function of improving thermal efficiency by exposure, and from this, the coating amount (solid content) on the support obtained after coating and drying is as follows:
Generally preferred 0.1-5 g / m ^2, more preferably ^{0.1g / m 2 ~2g / m 2} , more preferably 0.
² to 1.5 g / m ² . The coating amount is 0.1 g / m ²
If it is less than 5 g, the effect of improving the thermal efficiency becomes insufficient and 5 g / m
^{Even if} it exceeds ² , the effect is not improved, and the printing durability is rather deteriorated.

[Hydrophilic high molecular compound having crosslinked structure]
The layer containing a hydrophilic polymer compound having a crosslinked structure (hydrophilic crosslinked heat insulating layer) of the lithographic printing plate precursor according to the invention is not particularly limited as long as it has an extremely lower thermal conductivity than aluminum. And those mainly composed of organic polymers are preferably used. The silica and the organic polymer used for the hydrophilic cross-linked heat-insulating layer of the lithographic printing plate precursor according to the present invention have a thermal conductivity of about 180 times that of aluminum and 1100, respectively.
~ 1600 times lower.

As the hydrophilic cross-linked heat insulating layer of the lithographic printing plate precursor according to the invention, any of conventionally known cross-linked hydrophilic layers can be used. For example, 1) International Publication WO98 / 4
No. 0212, a hydrophilic layer composed of a crosslinked polymer containing a metal colloid, 2) Japanese Patent Publication No. 2592225, a hydrophilic layer composed of a condensate of an organic hydrophilic polymer and a silane coupling agent, 3) JP-A-10-6468 And a hydrophilic layer composed of a crosslinked organic polymer described in JP-A-10-58636.

Hereinafter, each of the hydrophilic crosslinked heat insulating layers will be described. First, 1) a hydrophilic layer composed of a crosslinked polymer containing a metal colloid will be described. Examples of the metal colloid include colloids such as hydroxysilane, hydroxyaluminum, hydroxytitanium, and hydroxyzircon. These metal colloids can be formed by crosslinking with a crosslinking agent such as di, tri, tetraalkoxysilane or titanate, or aluminate. A method for producing a metal colloid is described in, for example, US Pat.
5, can be manufactured according to US2574902 and the like. Among these, a particularly useful metal colloid is colloidal silica, and the crosslinking agent is aminopropyltriethoxysilane. The amount of metal colloid used is in the range from 100 to 5000%, especially preferably in the range from 500 to 1500%, based on the amount of crosslinking agent.

Next, 2) a hydrophilic cross-linked heat-insulating layer composed of a condensate of an organic hydrophilic polymer and a silane coupling agent will be described. Hydrophilic polymers having free reactive groups including, for example, hydroxyl, carboxyl, hydroxyethyl, hydroxy-propyl, amino, aminoethyl, aminopropyl, carboxymethyl, etc., can be used, for example, hydrophilic organotitanium reagents, aluminoformyl acetate, dimethylol Preferably, it is cast from an aqueous composition which includes a suitable crosslinker or modifier, including urea, melamine, aldehyde, hydrolyzed tetraalkyl orthosilicate, and the like.

Suitable polymers for the hydrophilic crosslinked thermal barrier are gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and their Na salts, cellulose acetate, sodium alginate, vinyl acetate
Maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and their salts, polymethacrylic acids and their salts, hydroxy-ethylene polymers, polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, and It can be selected from the group consisting of hydrolyzed polyvinyl acetate having a degree of degradation of at least 60% by weight, preferably at least 80% by weight.

For example, polyvinyl alcohol as disclosed in US Pat. No. 3,476,937 or at least 6
The hydrophilic cross-linking heat-insulating layer containing polyvinyl acetate hydrolyzed to the extent of 0% by weight and hardened with tetraalkyl orthosilicate, for example, tetraethyl orthosilicate or tetramethyl orthosilicate, is used for the lithographic printing of the present invention. The use of a plate precursor is particularly preferable because excellent lith printability is produced.

Yet another suitable hydrophilic crosslinked thermal barrier is EP
No. 9112227.5. The hydrophilic layer disclosed in this EP-application comprises a hardening reaction product of a copolymer containing an amine or amide function with at least one free hydrogen (eg an amino-modified dextran) and an aldehyde. According to the lithographic printing plate precursor according to the invention, the hydrophilic crosslinked thermal insulation layer can contain additional materials such as, for example, plasticizers, pigments, dyes and the like. The hydrophilic cross-linked thermal insulation layer can also include a particulate material such as, for example, TiO ₂ or colloidal silica to increase the strength and / or hydrophilicity of the layer.

Next, 3) a hydrophilic cross-linked heat insulating layer made of a cross-linked organic polymer will be described. The crosslinked organic polymer referred to in the present invention is a polymer composed of carbon-carbon bonds, as a side chain, a carboxyl group, an amino group, a phosphate group, a sulfonic acid group, or a salt, a hydroxyl group, an amide group, One or more hydrophilic functional groups such as polyoxyethylene groups and the like, or a networked polymer containing a plurality thereof, or a carbon atom, one of carbon-carbon bonds is at least one or more of oxygen, nitrogen, sulfur, and phosphorus. One kind of a hydrophilic functional group such as a carboxyl group, an amino group, a phosphoric acid group, a sulfonic acid group, or a salt thereof, a hydroxyl group, an amide group, or a polyoxyethylene group in a polymer or a side chain thereof linked by a hetero atom A meshed polymer containing a plurality of the above, specifically, poly (meth)
Acrylate type, polyoxyalkylene type, polyurethane type, epoxy ring-opening addition polymerization type, poly (meth) acrylic acid type, poly (meth) acrylamide type, polyester type, polyamide type, polyamine type, polyvinyl type, polysaccharide type or the like A polymer such as a composite system can be exemplified.

Among them, a hydroxyl group, a cal is a xyl group or its alkali metal salt, an amino group or its hydrogen halide, a sulfonic acid group or its amine, an alkali metal salt, an alkaline earth metal salt, an amide group Those having any one of these or a combination thereof and those having a polyoxyethylene group overlapped with a part of the hydrophilic functional group and the main chain segment are preferable because of high hydrophilicity. In addition, those having a urethane bond or a urea bond in the main chain or side chain of the hydrophilic binder polymer are more preferable because not only the hydrophilicity but also the printing durability of the non-image area are improved.

The binder polymer may contain various other components described below, if necessary. Specific examples of the three-dimensionally crosslinked hydrophilic binder polymer are shown below. As the hydrophilic binder polymer, (meth) acrylic acid or its alkali, amine salt, itaconic acid or its alkali, amine salt, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N
-Monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, 3-vinylpropionic acid or its alkali, amine salt, vinylsulfonic acid or its alkali, amine salt, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol Mono (meth) acrylate, 2-acrylamide-2-
Methylpropanesulfonic acid, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate,
Hydroxyl group such as allylamine or its mineral acid salt, carboxyl group or its salt, sulfonic acid group or its salt,
A hydrophilic homo- or copolymer is synthesized using at least one of phosphoric acid or a salt thereof, a hydrophilic monomer having a hydrophilic group such as an amide group, an amino group, and an ether group.

The hydrophilic binder polymer having a functional group such as a hydroxyl group, a carboxyl group, an amino group or a salt thereof, and an epoxy group in the hydrophilic polymer utilizes these functional groups to form a vinyl group, an allyl group, ) An unsaturated group-containing polymer having an addition polymerizable double bond such as an acryl group or a ring-forming group such as a cinnamoyl group, a cinnamylidene group, a cyanosinnamylidene group or a p-phenylenediacrylate group is obtained. If necessary, a monofunctional or polyfunctional monomer copolymerizable with the unsaturated group, a polymerization initiator described below, and other components described below are added, and the mixture is dissolved in an appropriate solvent to adjust a dope. This is coated on the above-mentioned support and subjected to three-dimensional crosslinking after drying or also as drying.

The hydrophilic binder polymer containing active hydrogen such as hydroxyl group, amino group and carboxyl group is
The isocyanate compound or the blocked polyisocyanate compound and other components described below are added to the above-mentioned solvent containing no active hydrogen, a dope is prepared, coated on a support, and dried or reacted with drying for three-dimensional crosslinking. A monomer having a glycidyl group such as glycidyl (meth) acrylate and a carboxyl group such as (meth) acrylic acid can be used in combination as a copolymer component of the hydrophilic binder polymer. The hydrophilic binder polymer having a glycidyl group is used as a crosslinking agent such as α, ω-alkane or alkenedicarboxylic acid such as 1,2-ethanedicarboxylic acid and adipic acid, 1,2,3-propanetricarboxylic acid, trimellitic acid and the like. Polycarboxylic acid, 1,2-ethanediamine, diethylenediamine, diethylenetriamine, polyamine compounds such as α, ω-bis- (3-aminopropyl) -polyethylene glycol ether, ethylene glycol, propylene glycol, diethylene glycol, tetraethylene glycol, etc. Using a polyhydroxy compound such as oligoalkylene or polyalkylene glycol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, three-dimensional crosslinking can be performed by utilizing a ring opening reaction with these.

The hydrophilic binder polymer having a carboxyl group or an amino group may be used as a crosslinking agent such as ethylene or propylene glycol diglycidyl ether, polyethylene or polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether,
Three-dimensional crosslinking can be performed by using an epoxy ring-opening reaction using a polyepoxy compound such as 1,6-hexanediol diglycidyl ether or trimethylolpropane triglycidyl ether.

When the hydrophilic binder polymer is a polysaccharide such as a cellulose derivative, polyvinyl alcohol or a partially saponified product thereof, a glycidol homo or copolymer, or a hydrophilic binder polymer based on these, the hydroxyl groups contained therein are used to make use of the above-mentioned hydroxyl groups. Introducing a functional group capable of performing a cross-linking reaction of the above, it is possible to provide a three-dimensional cross-linked structure by the method described above.

In the above description, the hydrophilic binder polymer is (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, 2-hydroxyethyl (meth) acrylate, ( (Meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth)
Acrylamide, allylamine or its hydrohalide salt, 3-vinylpropionic acid or its alkali metal salt and amine salt, vinylsulfonic acid or its alkali metal salt and amine salt, 2-sulfoethylene (meth) acrylate, polyoxyethylene glycol Mono (meth) acrylate, 2-acrylamide-2-
Methylpropanesulfonic acid, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate,
At least one selected from hydrophilic monomers having a hydrophilic group such as a carboxyl group, a sulfonic acid group, a phosphoric acid, an amino group or a salt thereof, a hydroxyl group, an amide group and an ether group, such as allylamine or a hydrohalide thereof; And a three-dimensionally crosslinked hydrophilic binder polymer composed of polyoxymethylene glycol or polyoxyethylene glycol by the method described above.

The thickness of the hydrophilic cross-linked heat insulating layer of the lithographic printing plate precursor according to the present invention exhibits a function of improving the thermal efficiency by exposure. The coating amount (solid content) is generally 0.1 to 5
g / m ² , and more preferably 0.1 g / m ² to
2 g / m ^2, more preferably from 0.2 to 1.5 g / m ^2. When the coating amount is less than 0.1 g / m ² , the effect of improving the thermal efficiency is insufficient, and even when the coating amount is more than 5 g / m ² , no improvement in the effect is observed, and the printing durability is rather deteriorated. Absent.

Next, the image of the lithographic printing plate precursor according to the present invention, which contains the hydrophilic high molecular compound whose side chain changes to hydrophobic by heat, which is provided on the above-mentioned hydrophilic heat-insulating layer or hydrophilic cross-linking heat-insulating layer. The formation layer will be described. The hydrophilic polymer compound used as the image forming layer of the present invention is not particularly limited as long as it is a polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylate group that cause decarboxylation by heat. However, it is preferably at least one selected from the group represented by the following general formulas (2) and (3).

[0066]

Embedded image

(Wherein X is selected from the group consisting of elements of Groups 4 to 6, oxides, sulfides, selenides and tellurides, P represents a polymer main chain, and -L- Represents a divalent linking group, R ⁴ and R ⁵ each represent a monovalent group which may be the same or different, and M is any one selected from the group consisting of alkali metals, alkaline earth metals and onium Represents.)

R^Four, R^FiveAs monovalent non-gold containing hydrogen
Group is used, and a preferable example is a halogen atom.
(-F, -Br, -Cl, -I), a hydroxyl group,
Alkyl group, alkoxy group, aryloxy group, mercap
G, alkylthio, arylthio, alkyldithio
O group, aryldithio group, amino group, N-alkylamido
Group, N, N-diarylamino group, N-alkyl-N
-Arylamino group, acyloxy group, carbamoylo
Xy group, N-alkylcarbamoyloxy group, N-ali
Carbamoyloxy group, N, N-dialkylcarba
Moyloxy group, N, N-diarylcarbamoyloxy
S group, N-alkyl-N-arylcarbamoyloxy
Group, alkylsulfoxy group, arylsulfoxy group,
Silthio group, acylamino group, N-alkyl acylamido
Group, N-arylacylamino group, ureido group, N '
-Alkyl ureido group, N ', N'-dialkyl urea
Group, N'-arylureido group, N ', N'-diali
Ureido group, N'-alkyl-N'-aryluree
Id group, N-alkyl ureido group, N-aryl ureide
Group, N'-alkyl-N-alkylureido group, N '
-Alkyl-N-arylureido group, N ', N'-di
Alkyl-N-alkylureido group, N ', N'-dia
Alkyl-N-arylureido group, N'-aryl-N
-Alkyl ureido group, N'-aryl-N-aryl
Ureido group, N ', N'-diaryl-N-alkyl
RAID group, N ', N'-diaryl-N-aryluree
Id group, N'-alkyl-N'-aryl-N-alkyl
Luureido group, N'-alkyl-N'-aryl-N-
Arylureido group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, N-alkyl-N-
Alkoxycarbonylamino group, N-alkyl-NA
Reyloxycarbonylamino group, N-aryl-NA
Lucoxycarbonylamino group, N-aryl-N-ali
-Carbonyloxyamino group, formyl group, acyl group,
Carboxyl group, alkoxycarbonyl group, aryloxy
Sicarbonyl group, carbamoyl group, N-alkylcarba
Moyl group, N, N-dialkylcarbamoyl group, N-A
Reel carbamoyl group, N, N-diarylcarbamoy
Group, N-alkyl-N-arylcarbamoyl group,
Rukylsulfinyl group, arylsulfinyl group,
Killsulfonyl group, arylsulfonyl group, sulfo group
(-SO_ThreeH) and its conjugated base group (hereinafter, sulfonato
Group), alkoxysulfonyl group, aryloxys
Ruphonyl group, sulfinamoyl group, N-alkyl sulf
Inamoyl group, N, N-dialkylsulfinamoyl
Group, N-arylsulfinamoyl group, N, N-diali
Sulfinamoyl group, N-alkyl-N-aryl
Sulfinamoyl group, sulfamoyl group, N-alkyl
Sulfamoyl group, N, N-dialkylsulfamoyl
Group, N-arylsulfamoyl group, N, N-diary
Rusulfamoyl group, N-alkyl-N-arylsul
Famoyl group, phosphono group (-PO_ThreeH_Two) And both
Role base group (hereinafter referred to as phosphonate group), dialkyl
A phosphono group (-PO_Three(alkyl) _Two), Diarylphosph
Ono group (-PO_Three(aryl)_Two), Alkyl aryl phospho
No group (-PO_Three(alkyl) (aryl)), monoalkylphospho
No group (-PO_ThreeH (alkyl)) and its conjugated base group (hereinafter, referred to as H (alkyl))
Alkylphosphonato group), monoarylphosphine
Ono group (-PO_ThreeH (aryl)) and its conjugate base group (hereinafter
Hereinafter referred to as an arylphosphonato group),
Group (-OPO_ThreeH_Two) And its conjugated base group (hereinafter referred to as phos
Phonatooxy group), dialkylphosphonooxy
Group (-OPO_Three(alkyl)_Two), Diarylphosphono
Xy group (-OPO_Three(aryl)_Two), Alkyl aryl phosph
Onoxy group (-OPO_Three(alkyl) (aryl)), monoalkyl
Ruphosphonooxy group (-OPO_ThreeH (alkyl)) and its
Conjugated base group (hereinafter referred to as alkylphosphonatooxy group)
), Monoarylphosphonooxy group (-OPO_ThreeH
(aryl)) and its conjugated base group (hereinafter arylphospho)
Natoxy group), cyano group, nitro group, aryl
Group, alkenyl group and alkynyl group.

Specific examples of preferable alkyl groups include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms which may have a substituent. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
Dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group,
Examples thereof include a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among these, straight-chain having 1 to 12 carbon atoms, branched having 3 to 12 carbon atoms,
Further, a cyclic alkyl group having 5 to 10 carbon atoms is more preferable.

Examples of the substituent of the substituted alkyl group
Is preferably a monovalent non-metallic atomic group other than hydrogen.
Examples include halogen atoms (-F, -Br, -Cl,
-I), hydroxyl group, alkoxy group, aryloxy
Group, mercapto group, alkylthio group, arylthio group,
Alkyldithio group, aryldithio group, amino group, N-
Alkylamino group, N, N-diarylamino group, N-
Alkyl-N-arylamino group, acyloxy group,
Rubamoyloxy group, N-alkylcarbamoyloxy
Group, N-arylcarbamoyloxy group, N, N-dia
Alkylcarbamoyloxy group, N, N-diarylcar
Bamoyloxy group, N-alkyl-N-arylcarba
Moyloxy group, alkyl sulfoxy group, aryl sulf
Oxy, acylthio, acylamino, N-alkyl
Luacylamino group, N-arylacylamino group, urea
Id group, N'-alkylureido group, N ', N'-dia
Alkyl ureido group, N'-aryl ureido group, N ',
N'-diarylureido group, N'-alkyl-N'-
Arylureido group, N-alkylureido group, NA
Reelureido group, N'-alkyl-N-alkyluree
An id group, an N'-alkyl-N-arylureido group,
An N ′, N′-dialkyl-N-alkylureido group,
An N ′, N′-dialkyl-N-arylureido group,
N'-aryl-N-alkylureido group, N'-ali
-N-arylureido group, N ', N'-diary
Ru-N-alkylureido group, N ', N'-diaryl
-N-arylureido group, N'-alkyl-N'-a
Reel-N-alkylureido group, N'-alkyl-
N'-aryl-N-arylureido group, alkoxy
Carbonylamino 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, alkoxy
Cicarbonyl group, aryloxycarbonyl group, carbamo
Yl group, N-alkylcarbamoyl group, N, N-dial
A kill carbamoyl group, an N-aryl carbamoyl group,
N, N-diarylcarbamoyl group, N-alkyl-N
-An arylcarbamoyl group, an alkylsulfinyl group,
Arylsulfinyl group, alkylsulfonyl group, ant
Sulfonyl group, sulfo group (—SO_ThreeH) and both
Role base group (hereinafter referred to as sulfonato group), alkoxys
Ruphonyl group, aryloxysulfonyl group, sulfinamo
Yl group, N-alkylsulfinamoyl group, N, N-di
Alkylsulfinamoyl group, N-arylsulfina
Moyl group, N, N-diarylsulfinamoyl group, N
-Alkyl-N-arylsulfinamoyl group, sulf
Amoyl group, N-alkylsulfamoyl group, N, N-
Dialkylsulfamoyl group, N-arylsulfamo
Yl group, N, N-diarylsulfamoyl group, N-A
Alkyl-N-arylsulfamoyl group, phosphono group
(-PO_ThreeH_Two) And its conjugated base group (hereinafter referred to as phosphona
A dialkylphosphono group (—PO_Three(alky
l)_Two), A diarylphosphono group (—PO_Three(aryl)_Two),
Alkylarylphosphono group (-PO_Three(alkyl) (ary
l)), monoalkylphosphono group (-PO_ThreeH (alkyl))
And its conjugated base group (hereinafter referred to as alkylphosphonate group)
), Monoarylphosphono group (-PO_ThreeH (ary
l)) and its conjugated base group (hereinafter, arylphosphonate)
Group), a phosphonooxy group (-OPO_ThreeH_Two)as well as
Its conjugated base group (hereinafter referred to as phosphonatoxy group)
), A dialkylphosphonooxy group (-OPO_Three(alky
l)_Two), Diarylphosphonooxy group (—OPO_Three(ary
l) _Two), An alkylarylphosphonooxy group (—OP
O_Three(alkyl) (aryl)), monoalkylphosphonooxy group
(-OPO_ThreeH (alkyl)) and its conjugate base group (hereinafter a
Alkylphosphonatooxy group)
Sulfonooxy group (-OPO_ThreeH (aryl)) and its conjugate
A base group (hereinafter referred to as an arylphosphonatooxy group)
), Cyano group, nitro group, aryl group, alkenyl
And alkynyl groups.

In these substituents, specific examples of the alkyl group include the aforementioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and mesityl groups. , Cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl, benzoyloxyphenyl, methylthiophenyl, phenylthiophenyl A methylaminophenyl group, a dimethylaminophenyl group, an acetylaminophenyl group, a carboxyphenyl group, a methoxycarbonylphenyl group, an ethoxyphenylcarbonyl group,
Examples thereof include a phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, and a phosphonatophenyl group. Examples of the alkenyl group include a vinyl group, 1
-Propenyl group, 1-butenyl group, cinnamyl group, 2-
Examples thereof include a chloro-1-ethenyl group, and examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.
Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above-described alkyl and aryl groups. Of these substituents, still more preferred are a halogen atom (-F, -Br, -Cl, -I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, an N, N- Dialkylamino 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, sulfonato group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N
An arylsulfamoyl group, a phosphono group, a phosphonate group, a dialkylphosphono group, a diarylphosphono group, a monoalkylphosphono group, an alkylphosphonato group, a monoarylphosphono group, an arylphosphonato group, a phosphonooxy group, Examples include a phosphonatoxy group, an aryl group, and an alkenyl group.

On the other hand, examples of the alkylene group in the substituted alkyl group include those obtained by removing any one of the above hydrogen atoms on the alkyl group having 1 to 20 carbon atoms to obtain a divalent organic residue. And preferably a straight-chain alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms and a cyclic alkylene group having 5 to 10 carbon atoms. Preferred specific examples of the substituted alkyl group obtained by combining the substituent with an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, and allyl. Oxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy Rubonirubuchiru group, chlorophenoxy carbonyl methyl group, a carbamoylmethyl group, N- methylcarbamoyl ethyl, N, N- dipropylcarbamoylmethyl group, N
-(Methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl 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, tolylphosphonohexyl 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.

Examples of the aryl group include a group in which one to three benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Phenyl group, naphthyl group, anthryl group,
Phenanthryl group, indenyl group, acenaphthenyl group,
Examples thereof include a fluorenyl group and the like, and among these, a phenyl group and a naphthyl group are more preferable. The aryl group includes a heterocyclic (hetero) aryl group in addition to the carbocyclic aryl group. Examples of the heterocyclic aryl group include a pyridyl group, a furyl group, and other quinolyl, benzofuryl, thioxanthone, and carbazole groups each having 3 to 20 carbon atoms and 1 to 5 heteroatoms such as a benzene ring condensed. Used.

As the substituted aryl group, those having a monovalent nonmetallic atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups,
In addition, there can be mentioned those described above as the substituent in the substituted alkyl group. Preferred specific examples of such a substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, and a trifluoromethylphenyl group. ,
Hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinophenyl, acetyloxyphenyl, benzoyl Oxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxy Carbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N (Methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N- Dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenyl Phosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpro Nirufeniru group, 2-propynyl phenyl group, 2-butynyl phenyl group, and a 3-butynylphenyl group.

Preferred examples of -X- include -O- and -S
-, - Se -, - NR 3 -, - CO -, - SO -, - S
O ₂ — and —PO— are represented. Among them, -CO from the viewpoint of heat reactive -, - SO -, - SO 2 - is particularly preferred.
Specific examples of preferred R ^6, which may be different and the same as R ⁴ and R ^5, R ⁴ and R ⁵ You can choose from specific examples.

The divalent linking group represented by L includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100 And up to 20 hydrogen atoms and 0 to 20 sulfur atoms. More specific examples of the linking group include those constituted by combining the following structural units.

[0077]

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M is not particularly limited as long as it is a cation, but is preferably a monovalent to tetravalent metal cation or an ammonium salt represented by the following formula (4).

[0079]

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(R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each represent a monovalent group which may be the same or different.)

The metal cations of 1-4 represented by M include Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Fr ⁺ , B
e ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ra ²⁺ , Cu
^{+, Cu 2 +, Ag +} , Zn 2+, Al 3+, Fe 2+, Fe 3+,
Co ²⁺ , Ni ²⁺ , Ti ⁴⁺ and Zr ⁴⁺ can be mentioned. More preferably, Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , C
Examples include s ⁺ , Fr ⁺ , Cu ⁺ , and Ag ⁺ .

In the ammonium ion represented by the general formula (4), specific examples of the groups represented by R ^{7 to} R ¹⁰ include the same groups as those represented by R ^{4 to} R ^6. Can be Specific examples of the ammonium ion represented by the general formula (4) include the following.

[0083]

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The polymer main chain represented by P is selected from at least one of the partial structure groups represented by the following general formula.

[0085]

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The polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylic acid group in the present invention may be a homopolymer of only one kind or a copolymer of two or more kinds. As the monomer used in the synthesis of the polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylate group in the present invention, those exemplified in the following specific examples are preferable.

[0087]

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[0088]

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[0089]

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The polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylate group in the present invention may be a copolymer of the above-mentioned monomer and another monomer. As other monomers used, for example, acrylates, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide and the like Known monomers are also included. By copolymerizing such monomers, various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity, and stability can be improved.

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, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl acrylate, furfuryl acrylate, Examples include tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenylcarbonyloxy) ethyl acrylate, and the like.

Specific examples of the methacrylates 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, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate,
Benzyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (Hydroxyphenylcarbonyloxy) ethyl methacrylate and the like.

Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide,
Hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl)
Acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-
N-phenylacrylamide, N-hydroxyethyl-
N-methylacrylamide and the like can be mentioned.

Specific examples of methacrylamides include methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-propyl methacrylamide, N-butyl methacrylamide, N-benzyl methacrylamide, N-hydroxyethyl methacryl Amide,
N-phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N
-(Tolylsulfonyl) methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide 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, ethoxy methyl styrene, acetoxy methyl styrene, methoxy styrene, dimethoxy styrene , Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

The proportion of these other monomers used in the synthesis of the copolymer must be sufficient to improve various physical properties. The function of the monomer containing is insufficient. Therefore, the preferable total ratio of the other monomers is preferably 80% by weight or less, and more preferably 50% by weight or less.

Hereinafter, specific examples of the polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylic acid group which cause decarboxylation by heat in the present invention are shown below.

[0098]

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[0099]

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[0100]

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[0101]

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In the image forming layer of the lithographic printing plate of the present invention, JP-A-6
Nonionic surfactants as described in JP-A-2-251740 and JP-A-3-208514, and amphoteric as described in JP-A-59-121044 and JP-A-4-13149. Surfactants can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene nonyl phenyl ether, and the like. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N- Betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the total solids of the image forming material is 0.05 to 15%.
% By weight, more preferably 0.1 to 5% by weight.

Further, a plasticizer may be added to the image forming layer of the lithographic printing plate of the present invention, if necessary, in order to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers of acrylic acid or methacrylic acid And a polymer.

The image-forming layer of the lithographic printing plate of the present invention can be usually produced by dissolving the above-mentioned components in a solvent and coating the resulting solution on a suitable intermediate layer. As the solvent used here, 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,
Dimethoxyethane, methyl lactate, ethyl lactate, N, N-
Dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone,
Examples include toluene and water, but are not limited thereto. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. Coating amount (solid content) on the intermediate layer obtained after coating and drying
Is generally preferably 0.5 to 5.0 g / m ² . Various methods can be used as the method of coating, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

In the image forming layer of the lithographic printing plate of the present invention,
Surfactants for improving coatability, for example,
A fluorine-based surfactant as described in JP-A-170950 can be added. A preferable addition amount is 0.1 to the total solid content of the image recording layer of the lithographic printing plate precursor.
The content is preferably from 01 to 1% by weight, more preferably from 0.05 to 0.5% by weight.

[Light-to-heat converting agent] When the lithographic printing plate precursor of the present invention is used to form an image by laser exposure, at least one of the hydrophilic heat-insulating layer or the hydrophilic cross-linking heat-insulating layer, the image-forming layer and the interlayers A light-to-heat conversion agent. As the photothermal conversion agent, any substance that can convert light into heat by absorbing light such as ultraviolet light, visible light, infrared light, and white light can be used.Examples include carbon black, carbon graphite, pigments, phthalocyanine pigments, and metal powders. ,
Metal compound powder and the like can be mentioned. Particularly preferred are dyes, pigments, metal powders, and metal compound powders that effectively absorb infrared rays having a wavelength of 760 nm to 1200 nm.

As the dye, commercially available dyes and known dyes described in literatures (for example, “Dye Handbook” edited by The Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, and metal thiolate complexes.

Preferred dyes include, for example, those described in
Cyanine dyes described in JP-A-8-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, etc .;
No. 96, JP-A-58-181690, JP-A-58-1
No. 94595, etc., methine dyes described in
8-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996,
Naphthoquinone dyes described in JP-A-60-52940 and JP-A-60-63744;
Squarylium dyes described in No. 12792, etc.,
Cyanine dyes described in British Patent 434,875 and the like can be mentioned.

Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924 is also preferable. And JP-A-57-142645 (U.S. Pat. No. 4,327,169).
Nos. 8-220143, 59-41363 and 59-
No. 84248, No. 59-84249, No. 59-146
Nos. 063 and 59-146061; cyanine dyes described in JP-A-59-216146; pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475; Fairness 5-135
Nos. 14 and 5-19702 are also preferably used.

Examples of other preferred dyes include those represented by formulas (I) and (I) described in US Pat. No. 4,756,993.
Mention may be made of near-infrared absorbing dyes described under I). Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.

The pigment used in the present invention includes
Commercial Pigment and Color Index (CI) Handbook,
"Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" CMC Publishing, 1984)
Can be used. The types of pigments include black pigment, yellow pigment, orange pigment, brown pigment,
Red pigment, purple pigment, blue pigment, green pigment, fluorescent pigment,
Metal powder pigments and other polymer-bound dyes can be used.
Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments And quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like. Preferred among these pigments is carbon black.

These pigments may be used without surface treatment, or may be used after surface treatment. Examples of the surface treatment include a method of surface coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface. Conceivable. The above surface treatment methods are described in “Properties and Applications of Metallic Soap” (Koshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). I have.

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm. Pigment particle size 0.01μ
If it is less than m, the dispersion is not preferred in terms of stability in the coating solution for the recording layer, and if it exceeds 10 μm, it is not preferred in terms of the uniformity of the recording layer. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Dispersers include ultrasonic dispersers, sand mills, attritors, pearl mills, super mills,
Examples include a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, see “Latest Pigment Application Technology”
(CMC Publishing, 1986).

Next, the metal powder or the metal compound powder will be described. Specifically, the metal compound is a compound such as a metal, a metal oxide, a metal nitride, a metal sulfide, and a metal carbide. As the metal, Mg, Al, Si, Ti,
V, Cr, Mn, Fe, Co, Ni, Cu, Zn, G
a, Ge, Y, Zr, Nb, Mo, Tc, Ru, Pd,
Ag, Cd, In, Sn, Sb, Hf, Ta, W, R
e, Os, Ir, Pt, Au, Pb and the like. Among them, those which particularly easily cause an exothermic reaction such as an oxidation reaction by thermal energy are preferable.
1, Si, Ti, V, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Y, Zr, Mo, Ag, In, Sn, and W are preferable. In addition, Fe, Co, N have high absorption efficiency of radiation and large heat energy of self-heating reaction.
i, Cr, Ti, and Zr are preferred.

[0115] In addition to these metals alone, they may be composed of two or more components, or may be composed of metals and metal oxides, nitrides, sulfides, carbides and the like. The metal itself has a higher self-heating reaction heat energy such as oxidation, but its handling in the air is complicated, and there is a risk of spontaneous ignition when it comes into contact with the air. Therefore, several n from the surface
The thickness of m is preferably covered with an oxide, nitride, sulfide, carbide or the like. Further, these may be particles or a thin film such as a vapor-deposited film, but when used in combination with an organic substance, particles are preferable. The size of the particles is 10 μm or less, preferably 0.005 to 5 μm, more preferably 0.1 μm.
01 to 3 μm. If it is less than 0.01 μm, it is difficult to disperse the particles, and if it is more than 10 μm, the resolution of the printed matter deteriorates.

Among the above-mentioned metal fine powders of the present invention, iron powder is preferred. Any of iron powders is preferable, and among them, an iron alloy powder containing α-Fe as a main component is preferable. These powders contain Al, Si, S, S
c, Ca, Ti, V, Cr, Cu, Y, Mo, Rh, P
d, Ag, Sn, Sb, Te, Ba, Ta, W, Re,
Au, Hg, Pb, Bi, La, Ce, Pr, Nd,
It may contain atoms such as P, Co, Mn, Zn, Ni, Sr, and B. In particular, Al, Si, Ca, Y, Ba,
At least one of La, Nd, Co, Ni, and B is α-F
It is preferable to contain other than e, and it is more preferable to contain at least one of Co, Y, and Al. The content of Co is preferably from 0 atomic% to 40 atomic% with respect to Fe,
More preferably, it is 15 atomic% or more and 35% or less, and more preferably 20 atomic% or more and 35 atoms or less. The content of Y is preferably from 1.5 to 12 at%, more preferably from 3 to 10 at%, and still more preferably from 4 to 9 at%. Al is preferably 1.5 atomic% or more and 12 atomic% or less, and more preferably 3 atomic% or less.
It is at least 10 at% and more preferably at least 4 at% and at most 9 at%. The iron alloy fine powder may contain a small amount of hydroxide or oxide. Specifically, JP-B-44-14090, JP-B-45-18372, JP-B-47-22062, JP-B-47-22513,
JP-B-46-28466, JP-B-46-38755
No., JP-B-47-4286, JP-B-47-12422
No., JP-B-47-17284, JP-B-47-1850
No. 9, JP-B-47-18573, JP-B-39-103
07, Japanese Patent Publication No. 46-39639, U.S. Pat.
No. 6215, No. 3031341, No. 3100194
Nos. 3,242,005 and 3,389,014.

These light-to-heat conversion materials are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 50% by weight, based on the total solids of the layer to be contained.
It can be used in an amount of 10% by weight, particularly preferably 0.5 to 10% by weight for dyes, and particularly preferably 3.1 to 10% by weight for pigments. If the amount of the pigment or dye added is less than 0.01% by weight, the sensitivity becomes low,
If the amount exceeds the weight percentage, stains occur in the non-image area during printing. When the light-to-heat conversion material is used, the concentration of the layer material to be contained is at least 0.3, preferably 0.5, more preferably 1.1, in terms of the optical density (OD) at the exposure wavelength.
Must be 0 or greater. However, the OD at this time is a value when the layer material composition to be contained is applied to a transparent support and measured by transmission.

[Support] In the support of the lithographic printing plate precursor used in the invention, a hydrophilic heat insulating layer containing a hydrophilic polymer compound is formed as an intermediate layer provided on the support. The case is not particularly limited as long as its surface is hydrophilic in the following specific examples. When a hydrophilic crosslinked heat-insulating layer containing a hydrophilic polymer compound having a crosslinked structure is formed as an intermediate layer provided on the support, the surface properties of the support are not particularly limited.

The support of the lithographic printing plate precursor requires the above considerations, but is not particularly limited as long as it is a dimensionally stable plate. For example, paper, plastic (eg, polyethylene, polypropylene) , Polystyrene, etc.)
Paper, 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 film on which the above-mentioned metal is laminated or vapor-deposited.

As the support of the present invention, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of foreign elements in the alloy is at most 10% by weight
It is as follows. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.1 mm to 0.4 mm.
It is 2 mm to 0.3 mm.

In the above-mentioned support, in the case of a support having a metal surface, particularly an aluminum surface, a graining treatment, a dipping treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or It is preferable that a surface treatment such as an anodic oxidation treatment has been performed. Also,
As described in U.S. Pat. No. 2,714,066, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate is disclosed in U.S. Pat.
As described in Japanese Patent No. 461, an aluminum plate which has been subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is also preferably used. The anodic oxidation treatment is, for example, an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or oxalic acid, an organic acid such as sulfamic acid, or an aqueous or non-aqueous solution of a salt thereof alone or in combination of two or more. This is carried out by flowing a current in an electrolytic solution using an aluminum plate as an anode.

As the graining method, any of mechanical, chemical and electrochemical methods is effective. Examples of the mechanical method include a ball polishing method, a blast polishing method, and a brush polishing method in which an aqueous dispersion slurry of an abrasive such as pumice is rubbed with a nylon brush, and the chemical method is disclosed in JP-A-54-31187. A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in the official gazette is suitable, and as an electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid or a combination thereof is used. Is preferred. Among such surface-roughening methods, a surface-roughening method combining mechanical surface-roughening and electrochemical surface-roughening as described in JP-A-55-137993 is particularly preferred. Is preferred because of its strong adhesion to the support. The graining by the method as described above is such that the center line surface roughness (Ha) of the surface of the aluminum plate is 0.3 to 1.0 μm.
It is preferable that the application is performed in such a range as follows. The aluminum plate thus grained is washed with water and chemically etched as required.

The etching solution is usually selected from aqueous solutions of bases or acids that dissolve aluminum. In this case, a film different from aluminum derived from the etchant component must not be formed on the etched surface. Preferred examples of the etching agent include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate as basic substances; and sulfuric acid and persulfuric acid as acidic substances. , Phosphoric acid, hydrochloric acid, and salts thereof. Metals having a lower ionization tendency than aluminum, such as salts of zinc, chromium, cobalt, nickel, and copper, are not preferable because they form unnecessary films on the etched surface. In these etching agents, the dissolution rate of the aluminum or alloy to be used is set at a immersion time of 1 at the setting of the use concentration and temperature.
Most preferably from minute per 0.3 g / m ² from being carried out so as to become 40 g / m ^2, but no problem even well below or above this.

The etching is carried out by immersing the aluminum plate in the above-mentioned etching solution or by applying the etching solution to the aluminum plate.
The treatment is preferably performed so as to be in the range of 10 to 10 g / m ² . As the etching agent, it is desirable to use an aqueous solution of a base because of its high etching rate. In this case, since a smut is generated, a normal desmutting process is performed. The acid used for desmut treatment is
Nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid and the like are used. These etchants, use concentration, in the setting of temperature, most preferably the rate of dissolution of aluminum or alloy used is performed as consisting of immersion time 1 minute per 0.3 g / m ² to 40 g / m ² It may be higher or lower than this.

The etched aluminum plate is
Washed and anodized as needed. The anodic oxidation can be performed by a method conventionally used in this field. Specifically, sulfuric acid, phosphoric acid, chromic acid, oxalic acid,
An anodic oxide film can be formed on the surface of an aluminum support by applying a direct current or an alternating current to aluminum in an aqueous solution or a non-aqueous solution of sulfamic acid, benzenesulfonic acid, or a combination of two or more of these.

The anodizing treatment conditions cannot be generally determined because they vary depending on the electrolytic solution to be used.
° C, current density 0.5-60 amps / dm ² , voltage 1-10
0V and an electrolysis time of 30 seconds to 50 minutes are appropriate. Among these anodizing treatments, in particular, British Patent No. 1,4
Anodizing at high current density in sulfuric acid as described in U.S. Pat.
The method of anodizing phosphoric acid as an electrolytic bath described in US Pat. No. 661 is preferable.

In the present invention, in the case of a support having a surface of the above-mentioned metal, particularly aluminum, graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, Alternatively, after a surface treatment such as an anodizing treatment is performed, the surface of the support is subjected to a hydrophilic treatment as necessary. The hydrophilizing treatment of the surface of the support is not particularly limited, and examples thereof include a silicate treatment, a polyvinylphosphonic acid treatment, a sol-gel treatment, and a tamol treatment described below.

Hereinafter, the silicate processing will be described.
In the silicate treatment, the surface of the support is subjected to a hydrophilic treatment using an aqueous solution of an alkali metal silicate. For the hydrophilization treatment with the alkali metal silicate, various conventionally known methods can be adopted, but the amount of the alkali metal silicate deposited on the aluminum support surface is reduced to Si.
The amount of atoms is 0.1 to 8 mg / m ² , preferably 0.1 to 8 mg / m ² .
5-6 mg / m ² , more preferably 0.5-4 mg / m ²
m ² . If the attached amount is less than 0.1 mg / m ^{2 in} terms of the amount of Si atoms, the contamination performance is poor and the intended purpose cannot be achieved. Further, when a developer containing no alkali metal silicate is used in the developer, it is not possible to prevent whitening of a non-image portion during development and generation of scum and sludge during development. Further, the amount of adhesion is 8 mg
If it exceeds / m ² , the printing durability is poor and the intended purpose cannot be achieved.

In the present invention, the amount of the alkali metal silicate adhering to the surface of the support is determined by an X-ray fluorescence spectrometer (XRF; X-ray Fluorescence Science S).
spectrometer) and S
It is measured as the amount of i atoms (Simg / m ² ). A standard sample for preparing a calibration curve was prepared by applying a sodium silicate aqueous solution containing a known amount of Si atoms to a 30 mmφ on a support.
After uniformly dripping in the area of, dried. Although there is no particular limitation on the model of the X-ray fluorescence spectrometer, RIX30 manufactured by Rigaku Denki Kogyo
Using the sample No. 00, the amount of Si atoms was measured from the peak height of the Si-Kα spectrum under the following conditions.

Apparatus: RIX3000 manufactured by Rigaku Denki Kogyo KK X-ray tube: Rh Measurement spectrum: Si-Kα Tube voltage: 50 kV Tube current: 50 mA Slit: COARSE Spectral crystal: RX4 Detector: F-PC Analysis area: 30 mmφ Peak position (2θ): 144.75 deg. Background (2θ): 140.70 deg. , 146.85 deg. Integration time: 80 seconds / sample

In this hydrophilization treatment, the alkali metal silicate contains 0.001 to 30% by weight, preferably 0.01 to 10% by weight.
Wt.%, Particularly preferably 0.1 to 5 wt%, of an alkali metal silicate aqueous solution having a pH of 10 to 13 at 25 ° C. By immersing for 0.5 to 120 seconds, preferably for 2 to 30 seconds, processing conditions such as alkali metal silicate concentration, processing temperature, and processing time are appropriately selected so that the attached amount of Si atoms becomes the above specific amount. It can be preferably performed. In performing this hydrophilization treatment, if the pH of the aqueous solution of the alkali metal silicate is lower than 10, the solution gels, and if the pH is higher than 13.0, the anodic oxide film is dissolved.

As the alkali metal silicate used in the hydrophilization treatment of the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. In the hydrophilization treatment of the present invention, if necessary, a hydroxide can be blended to adjust the pH of the aqueous solution of the alkali metal silicate to a high value. As the hydroxide, sodium hydroxide,
Potassium hydroxide, lithium hydroxide and the like can be mentioned. If necessary, an alkaline earth metal salt or a Group IVB metal salt may be added to the aqueous alkali metal silicate solution. Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and sulfates, hydrochlorides, phosphates, acetates, oxalates, and the like of these alkaline earth metals. And water-soluble salts such as borate. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide,
Zirconium oxychloride, zirconium tetrachloride and the like can be mentioned. Alkaline earth metal salt or IVB
Group metal salts can be used alone or in combination of two or more. The preferred use amount range of these metal salts is 0.1.
01 to 10% by weight, and a more preferred range is 0.0
5 to 5.0% by weight.

In the present invention, the support subjected to the hydrophilization treatment can be treated with an acidic aqueous solution, if necessary. Examples of the acidic aqueous solution include aqueous solutions of sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, phosphoric acid, and the like. In addition, the acidic aqueous solution treatment converts the support subjected to the hydrophilization treatment to an aqueous solution having an acid concentration of 0.001 to 10% by weight, preferably 0.01 to 1% by weight, at a temperature of 15 to 70 ° C. The immersion is preferably performed at 25 to 50 ° C. for 0.5 to 120 seconds, preferably for 2 to 30 seconds. By this acidic aqueous solution treatment, adjustment can be made to reduce the amount of the alkali metal silicate attached to the support by the hydrophilic treatment.

Next, the polyvinyl phosphonic acid treatment will be described. The polyvinyl phosphonic acid treatment is a treatment in which the surface of the support is hydrophilized with an aqueous solution of polyvinyl phosphonic acid. The aqueous solution used for the polyvinyl phosphonic acid aqueous solution treatment has a concentration of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.2 to 2.5% by weight, and a temperature of 10 ° C. To 70 ° C., preferably 30 to 60 ° C., and 0.5 seconds to 4
It is appropriate to carry out by immersion for 0 second, more preferably for 1 to 20 seconds.

When the concentration of the aqueous solution of polyvinyl phosphonic acid is 0.
When the concentration is less than 01% by weight, the amount of polyvinylphosphonic acid adsorbed to the anodic oxide film described later decreases, and sufficient printing durability cannot be obtained. On the other hand, when the concentration is higher than 10% by weight, the amount of adsorption of polyvinylphosphonic acid increases. It becomes too much, and the payment stain deteriorates. On the other hand, if the treatment temperature is lower than 10 ° C., the amount of polyvinyl phosphonic acid adsorbed on the anodic oxide film decreases, and sufficient printing durability cannot be obtained. It is too much and the dirt on payment deteriorates. Furthermore, the immersion time is 0.5
If the time is shorter than 2 seconds, the amount of adsorption of polyvinylphosphonic acid to the anodic oxide film decreases, and sufficient printing durability cannot be obtained. Will deteriorate. The pH of the aqueous polyvinyl phosphonic acid solution is preferably 1.5 or less.

Next, the sol-gel treatment will be described. The sol-gel treatment is a treatment in which a sol solution or a liquid composition described in JP-A-9-269593 is applied to the surface of a support and then air-dried or heat-dried. As a result, the inorganic polymer comprising the metal-oxygen-metal bond is gelled and simultaneously covalently bonds with the support surface. Drying is performed to evaporate the solvent, residual water and optionally the catalyst,
The step can be omitted depending on the purpose of use of the treated support. In order to increase the adhesion between the inorganic polymer portion in the liquid composition according to this method and the surface of the metal to be treated, a temperature can be positively applied. The drying step in this case is
It can be continuously carried out even after evaporation of the solvent, water and the like. The maximum temperature during drying and, optionally, subsequent heating is preferably in such a range that the functional groups implanted on the metal surface do not decompose. Accordingly, the drying temperature conditions that can be used are room temperature to 200 ° C, preferably room temperature to 150 ° C, and more preferably room temperature to 120 ° C. Drying time is generally 30 seconds to
It is 30 minutes, preferably 45 seconds to 10 minutes, more preferably 1 minute to 3 minutes. The application method of the liquid composition (organic silicone compound or its solution or sol solution) used in the present invention includes brush coating, dip coating, atomizing, spin coating, doctor blade coating, and the like.
Various types can also be used, and are determined in consideration of the shape of the support surface, the required thickness of the processed film, and the like. When the support is a metal plate, when treating the metal surface, it is preferable that the surface is a clean surface free of oils and the like, except when it is significantly contaminated by oils and the like. Can be used as is. If necessary, the metal surface may be roughened by mechanically roughening or electrolytic deposition, electrolytic etching, or the like. In addition, those in which a natural oxide film is formed on the metal surface or those whose surface is positively oxidized by anodic oxidation, contact oxidation or the like can be suitably used. Of course, an oxide film different from the base metal may be provided on the surface by thermal spraying, coating, CVD, or the like.

[0137] If necessary, a back may be provided on the back of the support.
A light coat is provided. As such a back coat
Organic polymer compounds described in JP-A-5-45885 and
Or inorganic or organic compounds described in JP-A-6-35174
Metals obtained by hydrolysis and polycondensation of metal compounds
An oxide coating layer is preferably used. these
Among the coating layers, Si (OCH_Three)_Four , Si (OC_Two H_Five)_Four , S
i (OC_Three H₇) _Four , Si (OC_Four H₉)_Four Such as silicon al
Koxy compounds are inexpensive and readily available, and gold obtained from them
A coating layer of a metal oxide is particularly preferable because of its excellent hydrophilicity.

As described above, the lithographic printing plate precursor of the present invention can be prepared. The lithographic printing plate precursor is exposed imagewise with a solid-state laser or semiconductor laser that emits infrared light having a wavelength of 760 nm to 1200 nm, or is thermally (imagewise heated by a thermal head or the like) to form an image. In the case where the heat insulating layer (intermediate layer) is a non-crosslinked hydrophilic heat insulating layer, the lower part of the hydrophilic heat insulating layer also dissolves in dampening water and the like in the image area, and the image strength and adhesion are reduced. However, by laser irradiation,
In the image forming layer, for example, radicals are generated as intermediates after the carboxylic acid-generating polymer is decarboxylated, and this can react with the hydrophilic polymer of the underlying hydrophilic heat-insulating layer to prevent dissolution. , Image strength and adhesion can be improved.

In the present invention, it is not necessary to perform a dissolution treatment, and it becomes possible to mount a printing plate on a printing machine immediately after laser irradiation and perform printing, and perform a heat treatment between the laser irradiation step and the printing step. It became unnecessary. The planographic printing plate obtained by such a process is used for printing a large number of sheets by using an offset printing machine or the like. When the lithographic printing plate precursor of the invention is subjected to thermal recording using a thermal head or the like, the above-mentioned infrared absorbing agent may not be contained in the image forming layer. The thermal head used in this case is not particularly limited, but may be a simple and compact thermal printer such as a word processor or a thermal facsimile.

[0140]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. Synthesis Example 1 [Synthesis of hydrophilic polymer compound (P-1)] A mixture of 60 g of vinyl acetate and 40 g of methyl acrylate and 0.5 g of benzoyl peroxide as a polymerization initiator, and partially saponified polyvinyl as a dispersion stabilizer It was dispersed in 300 ml of water containing 3 g of alcohol and 10 g of NaCl. The dispersion was stirred at 65 ° C. for 6 hours to perform suspension polymerization. The methyl acrylate component of the obtained copolymer is N
The result of identification from the MR spectrum was 48 mol%.
The intrinsic viscosity in a benzene solution at 30 ° C. was 2.10. Next, 8.6 g of the copolymer was added to 200 g.
Methanol and 10 g of water and 40 ml of 5N NaOH
, And suspended by stirring.
After the saponification reaction was performed for 1 hour, the temperature was raised to 65 ° C., and the saponification reaction was further performed for 5 hours. The obtained saponification reaction product was sufficiently washed with methanol and freeze-dried.
The saponification degree was 98.3 mol%, and as a result of measurement of an infrared absorption spectrum, a strong absorption attributed to a -COO- group was confirmed at 1570 cm ^-1 .

Synthesis Example 2 [Hydrophilic polymer compound (P-2)
Synthesis of vinyl acetate 60 g and methyl p-styrenesulfonate 90
g of benzoyl peroxide as a polymerization initiator
Was added to a dispersion stabilizer containing 300 g of water containing 3 g of partially saponified polyvinyl alcohol and 10 g of NaCl.
l. The dispersion was stirred at 65 ° C. for 6 hours to perform suspension polymerization. The methyl p-styrenesulfonate component of the obtained copolymer was identified by NMR spectrum to be 45 mol%. The intrinsic viscosity in a benzene solution at 30 ° C. was 2.10. Next, 10.5 g of the copolymer was added to a saponification reaction solution consisting of 200 g of methanol, 10 g of water and 40 ml of 5N NaOH, and the suspension was stirred and suspended. Was heated to 65 ° C., and a saponification reaction was further performed for 5 hours. The obtained saponification reaction product was sufficiently washed with methanol and freeze-dried. Degree of saponification is 97.9 mol%
And as a result of the measurement of the infrared absorption spectrum, 1150c
strong absorption attributed to the -SO ₃ H group was observed at m ^-1.

Synthesis Example 3 [Hydrophilic polymer compound (P-3)
Synthesis of polyacrylic acid (molecular weight: 25,000, manufactured by Wako Pure Chemical Industries)
0 g is dissolved in dimethylacetamide to give 2-methacryloyloxyethyl isocyanate (hereinafter abbreviated as MOI).
5.5 g and 0.1 g of dibutyltin dilaurate were added and 3
Reacted for hours. Then, 80 equivalent% of carboxyl groups were partially neutralized with sodium hydroxide, acetone was added to precipitate the polymer, and the polymer was washed and purified well to obtain a hydrophilic polymer (P-
3) was obtained.

[Preparation of hydrophilic heat insulating layer [A-1]] Thickness
Trim 0.30mm aluminum plate (material 1050)
After cleaning and degreasing with chloroethylene, use a nylon brush
Surface using 400 mesh pumicestone-water suspension
Was grained and washed well with water. Place this plate at 45 ° C
Etch for 5 seconds in 5% aqueous sodium hydroxide
After washing with water, immerse in 2% nitric acid for 20 seconds
I washed. At this time, the etching amount of the grained surface is about 3 g.
/ M ^TwoMet. Next, use this plate with 7% sulfuric acid as electrolyte
Current density 15A / dm^Two3g / m^TwoDC anodized film
And then washed with water and dried. In addition, the processed
The following solution [A-1] was applied to a luminium plate,
Aluminum plate coated with hydrophilic layer after drying at 2 ℃ for 2 minutes
[A-1] was obtained. Weight after drying is 0.5 g / m^TwoIn
Was.

Solution [A-1] Hydrophilic polymer compound (P-1) 1.0 g Megafac F-177 0.06 g (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) Methyl alcohol 5 5.0 g Purified water 5.0 g

[Preparation of Hydrophilic Heat Insulating Layer [A-2]] The following solution [A-2] was applied to the treated aluminum plate.
After drying at 100 ° C. for 2 minutes, an aluminum plate [A-2] coated with a hydrophilic layer was obtained. Weight after drying is 0.6 g / m
^{Was 2} .

Solution [A-2] Hydrophilic polymer compound (P-2) 1.0 g Megafac F-177 0.06 g (manufactured by Dainippon Ink and Chemicals, Inc., fluorine-based surfactant) Methyl alcohol 5 0.0g Purified water 5.0g Infrared absorbing dye (specific dye A) 0.08g

[0147]

Embedded image

[Preparation of hydrophilic heat insulating layer [A-3]] The aluminum plate coated with the hydrophilic layer by applying the following solution [A-3] to the treated aluminum plate and drying at 100 ° C. for 2 minutes. [A-3] was obtained. 0.8g after drying
/ M ² .

Solution [A-3] Hydrophilic polymer compound (P-3) 1.0 g Megafac F-177 0.06 g (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) Methyl alcohol 5 0.0g Purified water 5.0g Infrared absorbing dye (specific dye A) 0.08g

The following solution [A-4] was applied to the treated aluminum plate, dried at 100 ° C. for 2 minutes, and exposed to a UV light for 700 counts (Eye rotary printer,
(I Graphic Co., Ltd.) to obtain a crosslinked hydrophilic layer [A-4]. The weight after drying was 1.0 g / m ² .

Solution [A-4] Hydrophilic polymer compound (P-3) 1.0 g Water-soluble triazine initiator A 0.1 g Methyl alcohol 10.0 g Purified water 10.0 g

[0152]

Embedded image

[Preparation of hydrophilic cross-linked heat insulating layer [A-5]]
The following solution [A-5] was applied to an aluminum plate treated in the same manner as in [A-4], and dried at 100 ° C for 1 minute.
The crosslinked hydrophilic layer [A-5] was obtained by exposing the entire surface to 700 counts (Eye Rotary Printer, manufactured by Eye Graphic Co., Ltd.) with UV light. 1.0 g after drying
/ M ² .

Solution [A-5] Hydrophilic polymer compound (P-3) 1.0 g Infrared absorbing dye (specific dye 1) 0.1 g Water-soluble triazine initiator A 0.1 g Methyl alcohol 10.0 g Purified water 10 0.0g

[Preparation of hydrophilic cross-linked heat insulating layer [A-6]] A 200 μm thick PET obtained by corona-treating the following solution [A-6]
It was applied on top and dried at 100 ° C. for 10 minutes to obtain a crosslinked hydrophilic layer [A-6]. 0.9 after drying
g / m ² .

Solution [A-6] Colloidal silica 200 g (Snowtex R503, 20 wt% aqueous dispersion, manufactured by Nissan Chemical Industries, Ltd.) Aminopropyltriethoxysilane 5 g

[Preparation of hydrophilic cross-linked heat insulating layer [A-7]] 50 g of titanium oxide (manufactured by Titanium Industry, particle size: 0.3 μm), polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.)
Of 10% aqueous solution and 240 g of water together with glass beads by a paint shaker (manufactured by Toyo Seiki Co., Ltd.).
Dispersed for minutes. Further, 110 g of a 20% (water / ethanol 1/1 weight ratio) solution of tetraethoxysilane hydrolyzed in advance and 200 g of colloidal silica (Snowtex R503, 20 wt% aqueous dispersion, manufactured by Nissan Chemical Industries, Ltd.) were added thereto. After dispersion for 3 minutes, the glass beads were separated by filtration to obtain a dispersion. Next, this was corona treated 2
It was applied on a PET having a thickness of 00 μm and dried at 100 ° C. for 10 minutes to obtain a crosslinked hydrophilic layer [A-7]. The weight after drying was 1.1 g / m ² .

[Preparation of hydrophilic cross-linked heat-insulating layer [A-8]]
The replacement of titanium oxide in the hydrophilic cross-linked heat insulating layer [A-7]
The parent cross-linked in the same manner except that the following Fe particles were used instead.
An aqueous layer was obtained. Weight after drying is 1.2 g / m ^TwoSo
Was. Fe: Co: Al: Y ratio in the ferromagnetic iron alloy powder
100: 20: 5: 5, and the particle size is 0.1
μ, minor diameter 0.02μ and specific surface area 60m^Two/ G
use.

(Examples 1 to 15) [Preparation of Image Forming Layer] Preparation of Image Forming Layer Coating Solution The image forming layer was prepared by changing the types of the polymer compound having a carboxylic acid group and the photothermal conversion agent as shown in Table 1. A coating solution was prepared. This coating solution was applied on the surface of the above-mentioned hydrophilic heat-insulating layer or hydrophilic cross-linking heat-insulating layer [A-1] to [A-7] as shown in Table 1, respectively.
After drying for 3 minutes, heat-sensitive lithographic printing plates [B-1] to [B-1]
5]. The weight after drying was 1.0 g / m ² .

(Coating liquid) Polymer compound having a carboxylic acid group (see Table 1) 4.0 g Light-to-heat converting agent (see Table 1) 0.4 g Megafac F-177 0.06 g (Dainippon Ink Chemical Industry Co., Ltd. ), Fluorine-based surfactant) methyl ethyl ketone 20.0 g methyl alcohol 7.0 g

(Types of photothermal conversion agent) (1) Specific dye A (the following structure) (2) CB: carbon black (MHI black, # 5)
257M) Mikuni Shigyo Co., Ltd.

[0162]

Embedded image

(Comparative Examples 1 to 5) Except that the heat insulating layer of the above example was not provided and the film thickness of the heat insulating layer was changed, the same operation as in the above example was carried out to obtain a lithographic printing plate precursor [C-1]. ] ~
[C-5] was obtained.

[0164]

[Table 1]

(Evaluation of Printing Performance) The lithographic printing original plates [B-1] to [B-15] and [C-1] to [C-5] were subjected to plate printing using an infrared semiconductor laser emitting infrared light having a wavelength of 830 nm. Laser power: 400 mW, scanning speed: 3.0
Exposure was performed at m / s. After the exposure, printing was performed by a Heidel KOR-D machine without developing. The printing fountain solution conditions at this time are shown below. Fountain solution: pH 8.8 (water 84.7%, isopropanol (IPA) 10%, triethylamine 5%, concentrated hydrochloric acid 0.1%).
At this time, it was evaluated whether or not the ink was sufficiently deposited on the image portion of the printed matter. As for the inking property at the time of printing, the inking property at the time of printing 1000 sheets and at the time of printing 20,000 sheets was observed. The results are shown in Table 2.

[0166]

[Table 2]

(Examples 16 to 30) [Preparation of image forming layer] Preparation of coating solution for image forming layer Coating of image forming layer by changing the types of the polymer compound having a carboxyl group and the photothermal conversion agent as shown in Table 3 A liquid was prepared. As shown in Table 3, this coating solution was applied to the above-mentioned hydrophilic heat-insulating layer or hydrophilic cross-linked heat-insulating layer [A-1] to [A-1], respectively.
-7] and dried at 80 ° C. for 3 minutes to obtain heat-sensitive lithographic printing plates [B-16] to [B-30]. The weight after drying was 1.0 g / m ² .

(Coating liquid) Polymer compound having a carboxyl group (see Table 3) 4.0 g Light-to-heat conversion agent (see Table 1) 0.4 g Megafac F-177 0.06 g (Dainippon Ink Chemical Industry Co., Ltd.) Manufactured, fluorine-based surfactant) methyl ethyl ketone 20.0 g methyl alcohol 7.0 g

(Types of photothermal conversion agent) (1) Specific dye A (the following structure) (2) CB: carbon black (MHI black, # 5)
257M) Mikuni Dye Co., Ltd.

[0170]

Embedded image

(Comparative Examples 6 to 10) Except that the heat insulating layer of the above example was not provided, and the thickness of the heat insulating layer was changed, the same operation as in the above example was carried out to obtain a lithographic printing plate precursor [C-6]. ] ~
[C-10] was obtained.

[0172]

[Table 3]

(Evaluation of Printing Performance) The obtained lithographic printing original plates [B-16] to [B-30], [C-6] to [C-1]
0] using an infrared semiconductor laser emitting infrared light having a wavelength of 830 nm, plate laser power: 400 mW, scanning speed:
Exposure was performed at 3.0 m / s. After exposure, without developing
Printed on a Heidel KOR-D machine. At this time, distilled water was used as a printing dampening solution. At this time, it was evaluated whether or not the ink was sufficiently deposited on the image portion of the printed matter. As for the inking property at the time of printing, the inking property at the time of printing 1000 sheets and at the time of printing 20,000 sheets was observed. Table 4 shows the results.

[0174]

[Table 4]

As is clear from Tables 2 and 4, the lithographic printing plate precursors of the examples according to the present invention were all
The inking property of the image area at the time of printing was good even at 20,000 sheets, and a good printed matter with no stain on the non-image area was obtained, and satisfactory results were obtained. The lithographic printing plate precursor was unsatisfactory even when the inking property was 1,000 sheets.

[0176]

As described above, the lithographic printing plate precursor according to the present invention comprises a hydrophilic heat-insulating layer or a hydrophilic cross-linked heat-insulating layer as an intermediate layer between a support and an image forming layer. At the same time, the vicinity of the support is made hydrophilic, and at the same time, the intermediate layer has a heat insulating effect, so that heat diffusion to the support can be suppressed. That is, the thermal polarity conversion (hydrophilicity → hydrophobicity) of the image forming layer without increasing the exposure amount by introducing the heat insulating intermediate layer.
Progresses efficiently. As a result, it is possible to provide a lithographic printing plate precursor having significantly improved image strength and adhesion. Further, the lithographic printing plate precursor of the present invention can be directly made by scanning exposure of an image with laser light such as infrared light, and does not require any special processing such as wet development processing or rubbing after image exposure. After the image exposure, the plate can be directly mounted on a printing press and printed.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 2H025 AA13 AA14 AB03 AC08 AD01 BH03 CB41 CB42 CB51 DA35 DA40 FA10 2H096 AA06 BA01 CA01 EA04 EA23 2H114 AA04 AA22 AA24 AA30 BA01 BA10 DA03 DA04 DA08 DA10 DA33 DA46 DA33 DA46 DA50 DA51 DA52 DA53 DA56 DA60 DA61 EA01 EA02 EA08

Claims (2)

[Claims] 1. A lithographic printing plate precursor comprising, in this order, a hydrophilic heat insulating layer and a layer containing a hydrophilic polymer compound whose side chain changes to hydrophobic by heat on a support. 2. The method according to claim 1, wherein the hydrophilic heat-insulating layer contains a hydrophilic polymer compound having a crosslinked structure.
The lithographic printing plate precursor described in.