JP2002211153A - Original plate of heat-sensitive lithographic printing plate and plate making/printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an original plate of a heat-sensitive lithographic printing plate with improved sensitivity so that a printing plate can be made by simple abroad-the-printing machine processing and a lithographic printing plate forms a high-quality image without a smear in a nonimage, by not increasing a laser exposure as well as a printing plate making/printing method. SOLUTION: The original plate of the heat-sensitive lithographic printing plate comprises a thermal recording layer containing (A) a polymer compound with a functional group which generates a sulfonic acid by heat as represented by the described formulae (1) -L-SO2-O-R', (2) -L-SO2-SO2-R2 and (3), (B) an organic amine compound and (C) a photothermal conversion substance, if desired, formed on a support with a hydrophilic surface. In the formulae (1), (2) and (3), L is a polyvalent organic group, composed of a non-metallic atom, which is required for connecting the functional group to a polymer skeleton.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a direct heat-sensitive lithographic printing plate. More specifically, the present invention relates to a lithographic printing plate precursor capable of recording an image by scanning exposure based on a digital signal and capable of making a plate by simple on-press processing, and a plate making and printing method thereof.

[0002]

2. Description of the Related Art In general, a lithographic printing plate comprises an oleophilic image area for receiving ink during a printing process and a hydrophilic non-image area for receiving fountain solution. As such a lithographic printing plate, a PS plate in which a lipophilic photosensitive resin layer is provided on a hydrophilic support has been widely used. As a plate making method, usually, after exposing through an original such as a lith film, a non-image portion is dissolved and removed with a developing solution, and a desired printing plate is obtained by this method.

[0003] The plate making process in the conventional PS plate requires an operation of dissolving and removing a non-image portion after exposure, and it is necessary to eliminate or simplify such additional wet processing. This is one problem that has been desired to be improved over the prior art. In particular, in recent years, the disposal of the waste liquid discharged by wet processing has become a major concern of the entire industry due to consideration for the global environment, and the demand for improvement in this aspect has been further increased.

[0004] As one of the simple plate making methods responding to this demand, an image heat-sensitive recording layer is used which enables non-image portions of a printing plate precursor to be removed in a normal printing process. A method of developing the above and obtaining a final printing plate has been proposed. The lithographic printing plate making method by such a method is called an on-press development method. Specific examples of the method include a method of using an image heat-sensitive recording layer that is soluble in a fountain solution or an ink solvent, and a method of performing mechanical removal by contact with an impression cylinder or a blanket cylinder in a printing press. However, in the conventional on-press developing method of an image recording method using ultraviolet light or visible light, even after exposure, the image heat-sensitive recording layer is not fixed,
For example, it is necessary to take a time-consuming method, such as storing the original plate completely in a light-shielded state or under constant temperature conditions until the original plate is mounted on a printing press.

On the other hand, another trend in this field in recent years is that digitization techniques for electronically processing, storing, and outputting image information using a computer have become widespread. Technology,
Various new image output systems have come into practical use. Along with this, a computer / computer for manufacturing a printing plate directly without carrying a lithographic film by carrying digitized image information on highly convergent radiation such as laser light and scanning and exposing the original with this light. Attention has been focused on to-plate technology. Accordingly, obtaining a printing plate precursor suitable for this purpose has become an important technical problem. Therefore, simplification, dry processing, and non-processing of plate making operations are more and more desired than ever in view of both the above-mentioned environmental aspects and adaptation to digitalization.

Recently, as a method of manufacturing a printing plate by scanning exposure, which is easy to incorporate into digital technology, semiconductor lasers,
Since high-power solid-state lasers such as YAG lasers have become available at low cost, plate-making methods using these lasers as image recording means have become particularly promising. In the conventional plate making method, image recording is performed by giving imagewise exposure of the photosensitive original plate at low to medium illuminance and changing the imagewise physical properties of the original plate surface by a photochemical reaction. In the method using density exposure, a large amount of light energy is intensively applied to an exposure area during an instantaneous exposure time, and the light energy is efficiently converted to heat energy, and the heat causes chemical change, phase change,
A thermal change such as a change in form or structure is caused, and the change is used for image recording. That is, image information is input by light energy such as laser light, while image recording is recorded by a reaction by heat energy. Normally, a recording method using heat generated by such high power density exposure is called heat mode recording, and changing light energy to heat energy is called photothermal conversion.

A great advantage of the plate making method using the heat mode recording means is that the plate making method is not sensitive to light having a normal illuminance level such as room illumination, and that an image recorded by high illuminance exposure does not require fixing. . In other words, if a heat mode photosensitive material is used for image recording, it is safe against room light before exposure, and it is not essential to fix an image after exposure. Therefore, for example, if a plate-making process using an image heat-sensitive recording layer that is insolubilized or solubilized by heat mode exposure and the exposed image heat-sensitive recording layer is imagewise removed to form a printing plate is performed by an on-press development method, development ( Removal of non-image areas) is performed for some time after image exposure, even if exposed to room ambient light.
A printing system in which images are not affected can be realized. Therefore, the use of heat mode recording is expected to make it possible to obtain a lithographic printing plate precursor that is desirable for an on-press development system.

For example, Japanese Patent Application Laid-Open No. 10-282672 describes a heat-sensitive lithographic master having a recording layer containing a hydrophobic polymer compound whose side chain changes to hydrophilic by heat. This polymer was characterized in that the polymer changed to hydrophilic by heating was developed on a printing press with a dampening solution, so that no special developing treatment was required. However, this master has the property that the generated heat diffuses to the substrate and the heat near the surface of the substrate is unlikely to rise. As a result, the film was not completely removed during on-press development and remained as a residual film, and sometimes stained during printing. Therefore, in order to completely remove the recording layer of the heating section, it is necessary to use a laser with an increased exposure amount, which causes problems such as an increase in output of an exposure apparatus and an increase in recording energy.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to overcome the above-mentioned disadvantages of the prior art, to make a plate by a simple processing on a printing press, and to increase the laser exposure amount and the like. Another object of the present invention is to provide a heat-sensitive lithographic printing plate having improved sensitivity for producing a lithographic printing plate capable of obtaining a high-quality image free from stains on non-images, and a method of making and printing the same.

[0010]

The present inventor has solved the above-mentioned problem by including an organic amine compound in a heat-sensitive recording layer containing a polymer compound having a functional group capable of generating sulfonic acid upon heating. As a result, the solubility of the heat-sensitive recording layer in a hydrophilic liquid (fountain solution or the like) in the heating section is increased, and the sensitivity of the heat-sensitive recording layer is improved. Thus, the present invention has been completed. That is, the heat-sensitive lithographic printing plate precursor according to the invention is provided on a support having a hydrophilic surface,
It is characterized by comprising (A) a polymer compound having a functional group capable of generating sulfonic acid upon heating, and (B) a thermosensitive recording layer containing an organic amine compound. More specifically, the functional group that generates sulfonic acid by heating in the compound (A) having a functional group that generates sulfonic acid by heating is represented by the following general formulas (1) to (3). In a preferred embodiment, at least one of the functional groups is used. Formula _{(1) -L-SO 2 -O} -R 1 Formula _{(2) -L-SO 2 -SO} 2 -R 2

[0011]

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(Where L is a general formula (1), a general formula (2)
Or a polyvalent organic group comprising a nonmetallic atom necessary for linking the functional group represented by the general formula (3) to the polymer skeleton; R ¹ represents an aryl group, an alkyl group or a cyclic imide group; ² and R ³ represent an aryl group or an alkyl group;
⁴ represents an aryl group, an alkyl group or -SO ₂ -R ^5,
R ⁵ represents an aryl group or an alkyl group. Here, by using (C) a light-to-heat conversion material in the thermosensitive recording layer, recording by infrared laser exposure becomes possible. Further, in the plate making and printing method for a heat-sensitive lithographic printing plate precursor according to claim 4 of the present invention, the (A) polymer compound having a functional group capable of generating sulfonic acid upon heating;
A heat-sensitive lithographic printing plate precursor having a heat-sensitive recording layer containing an organic amine compound and (C) a light-to-heat conversion agent is image-exposed by a laser beam, and is directly attached to a printing machine for printing or after being attached to a printing machine. It is characterized by exposing with a laser beam on a printing press and printing as it is.

In the present invention, the mechanism by which the solubility of the heat-sensitive recording layer in the heating section is improved is not clear, but the sulfonic acid generated from the component (A) by heating and the organic amine (B) form a salt. This is because the hydrophilicity of the generated sulfonic acid-containing polymer is increased, and even near the substrate interface where the generation of sulfonic acid is insufficient, the formation of the organic amine salt functions effectively and the solubility is improved. It is conceivable that the generation of a residual film near the substrate interface is effectively suppressed.

[0014]

Embodiments of the present invention will be described below in detail. The heat-sensitive lithographic printing plate precursor of the present invention is:
JP-A-10-2826 on a support having a hydrophilic surface
72. A heat-sensitive recording layer containing (A) a polymer compound having a functional group capable of generating sulfonic acid upon heating (hereinafter referred to as a sulfonic acid-generating polymer compound) and (B) an organic amine compound. This is characterized in that, in the heat-sensitive recording layer, sulfonic acid is generated by heat generated by infrared laser irradiation or heating by a thermal head or the like, so that this portion is highly hydrophilized, and a fountain solution is printed on a printing machine. And the like, it can be easily dissolved or dispersed and removed by a hydrophilic printing liquid, and a good positive image can be obtained without a developing step.

Hereinafter, the constitution of the heat-sensitive lithographic printing plate precursor according to the present invention will be sequentially described. (Thermal recording layer) [(A) Polymer compound having functional group capable of generating sulfonic acid upon heating (sulfonic acid-generating polymer compound)]
The sulfonic acid-generating polymer compound used in the heat-sensitive recording layer of the present invention is not particularly limited as long as it has a functional group that generates sulfonic acid by heating, and a functional group that generates sulfonic acid is included in the main chain. It may have it or may have it in the side chain, but from the viewpoint of synthesis suitability, a polymer compound having a functional group represented by the above general formula (1) to general formula (3) in the side chain is preferable. .

Hereinafter, the polymer compound having at least one of the functional groups represented by the general formulas (1), (2) and (3) in the present invention will be described more specifically.

When R ^{1 to} R ⁵ represent an aryl group or a substituted aryl group, the aryl group includes a carbocyclic aryl group and a heterocyclic (hetero) aryl group. As the carbocyclic aryl group, those having 6 to 19 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group and a pyrenyl group are used. Examples of the heterocyclic aryl group include a pyridyl group, a furyl group, and other quinolyl groups in which a benzene ring is fused, a benzofuryl group, a thioxanthone group, and a carbazole group. Things are used. When R ^{1 to} R ⁵ represent an alkyl group or a substituted alkyl group, the alkyl group may be a linear, branched or cyclic carbon atom such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a cyclohexyl group. 1
To 25 are used.

When R ^{1 to} R ⁵ are a substituted aryl group, a substituted heteroaryl group, or a substituted alkyl group, examples of the substituent include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; a fluorine atom; Atom, halogen atom such as bromine atom, trifluoromethyl group, halogen-substituted alkyl group such as trichloromethyl group, methoxycarbonyl group, ethoxycarbonyl group, t-butyloxycarbonyl group, p-chlorophenyloxycarbonyl group, etc. An alkoxycarbonyl group or an aryloxycarbonyl group having 2 to 15 carbon atoms; a hydroxyl group; an acyloxy group such as an acetyloxy group, a benzoyloxy group or a p-diphenylaminobenzoyloxy group; a carbonate group such as a t-butyloxycarbonyloxy group; t-butyloxycarbonyl Ether groups such as tyloxy group and 2-pyranyloxy group; substituted and unsubstituted amino groups such as amino group, dimethylamino group, diphenylamino group, morpholino group and acetylamino group; thioether groups such as methylthio group and phenylthio group; vinyl An alkenyl group such as a group or styryl group; a nitro group; a cyano group; an acyl group such as a formyl group, an acetyl group or a benzoyl group; an aryl group such as a phenyl group or a naphthyl group; be able to. When R ^{1 to} R ⁵ are a substituted aryl group or a substituted heteroaryl group, alkyl groups such as a methyl group and an ethyl group can be used as the substituent in addition to the above.

When R ¹ represents a cyclic imide group, cyclic imides such as succinimide, phthalimide, cyclohexanedicarboxylic imide, norbornenedicarboxylic imide and the like having 4 to 20 carbon atoms can be used. .

In the general formula (1), R ¹ represents an aryl group substituted with an electron-withdrawing group such as halogen, cyano or nitro, or an alkyl substituted with an electron-withdrawing group such as halogen, cyano or nitro. Group, a secondary or tertiary branched alkyl group, a cyclic alkyl group, and a cyclic imide are preferable, and a secondary alkyl group represented by the following general formula (4) in that both sensitivity and stability over time can be achieved. Is more preferred.

[0021]

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R ⁶ and R ⁷ are substituted or unsubstituted alkyl,
Represents a substituted or unsubstituted aryl group; and R ⁶ , R ⁷
May form a ring with the secondary carbon atom (CH) to which it is attached. When R ⁶ and R ⁷ represent a substituted or unsubstituted alkyl group, examples of the alkyl group include a linear, branched, or cyclic alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a cyclohexyl group. And those having 1 to 25 carbon atoms are preferably used. When R ⁶ and R ⁷ represent a substituted or unsubstituted aryl group, the aryl group includes a carbocyclic aryl group and a heterocyclic aryl group. As the carbocyclic aryl group, those having 6 to 19 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group and a pyrenyl group are used. Examples of the heterocyclic aryl group include those having 3 to 20 carbon atoms and 1 to 5 heteroatoms such as a pyridyl group, a furyl group, and a quinolyl group, a benzofuryl group, a thioxanthone group, and a carbazole group in which a benzene ring is fused. Is used.

When R ⁶ and R ⁷ are a substituted alkyl group or a substituted aryl group, examples of the substituent include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group, a fluorine atom, a chlorine atom and a bromine atom. A halogen atom, a trifluoromethyl group, a halogen-substituted alkyl group such as a trichloromethyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a t-butyloxycarbonyl group, a p-chlorophenyloxycarbonyl or the like having 2 to 15 carbon atoms.
A hydroxyl group; an acyloxy group such as acetyloxy, benzoyloxy, p-diphenylaminobenzoyloxy; a carbonate group such as a t-butyloxycarbonyloxy group; a t-butyloxycarbonylmethyloxy group A substituted or unsubstituted amino group such as an amino group, a dimethylamino group, a diphenylamino group, a morpholino group, or an acetylamino group; a thioether group such as a methylthio group or a phenylthio group; a vinyl group; Alkenyl groups such as steryl group; nitro group; cyano group; acyl groups such as formyl group, acetyl group and benzoyl group; aryl groups such as phenyl group and naphthyl group; heteroaryl groups such as pyridyl group. Can . When R ⁶ and R ⁷ are a substituted aryl group, an alkyl group such as a methyl group or an ethyl group can be used as the substituent in addition to those described above.

As the above R ⁶ and R ⁷ , a substituted or unsubstituted alkyl group is preferable from the viewpoint of excellent storage stability of the light-sensitive material, and an alkoxy group, a carbonyl group,
A secondary alkyl group substituted with an electron-withdrawing group such as an alkoxycarbonyl group, a cyano group, or a halogen group, or a secondary alkyl group such as a cyclohexyl group or a norbornyl group is particularly preferable. As a physical property value, a compound in which the chemical shift of secondary methine hydrogen in proton NMR is lower than 4.4 ppm in deuterated chloroform is preferable, and a compound which is lower in magnetic field than 4.6 ppm is more preferable. Thus, 2 substituted with an electron-withdrawing group
It is considered that the higher alkyl group is particularly preferable because the carbocation, which is considered to be generated as an intermediate during the thermal decomposition reaction, is destabilized by the electron-withdrawing group and the decomposition is suppressed. Specifically, as the structure of —CHR ⁶ R ^7, a structure represented by the following formula is particularly preferable.

[0025]

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In the general formulas (2) and (3), particularly preferred as R ^{2 to} R ⁵ are:
An aryl group substituted with an electron-withdrawing group such as halogen, cyano or nitro; an alkyl group substituted with an electron-withdrawing group such as halogen, cyano or nitro; and a secondary or tertiary branched alkyl group. .

A polyvalent linking group consisting of a nonmetallic atom represented by L means 1 to 60 carbon atoms, 0 to 10 carbon atoms.
Up to nitrogen atoms, 0 to 50 oxygen atoms, 1
From 100 to 100 hydrogen atoms and 0 to 20 sulfur atoms. More specific linking groups include those constituted by combining the following structural units.

[0028]

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When the polyvalent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group;
To 16 aryl groups, hydroxyl groups, carboxyl groups,
An acyloxy group having 1 to 6 carbon atoms such as a sulfonamide group, an N-sulfonylamide group, an acetoxy group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, and a halogen such as chlorine and bromine. An atom, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, a cyano group, and a carbonate group such as t-butyl carbonate can be used.

Specific examples of the monomer suitably used for synthesizing the high molecular compound having a functional group represented by the general formula (1) to the general formula (3) in the side chain according to the present invention [monomer (1)
To monomer (56)] are shown below.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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In the present invention, a polymer compound obtained by subjecting at least one of the monomers having functional groups represented by the general formulas (1) to (3) to radical polymerization is preferably used. I do. As such a polymer compound, a homopolymer using only one of the monomers having a functional group represented by the general formulas (1) to (3) may be used. Copolymers used or copolymers of these monomers with other monomers may be used. In the present invention, a polymer compound more preferably used is a copolymer obtained by radical polymerization of the above-mentioned monomer and another known monomer.

Other monomers used in the copolymer include, for example, acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride Known monomers such as acid and maleic imide are also included. Other monomers include glycidyl methacrylate, N-methylol methacrylamide, omega- (trimethoxysilyl)
It is also possible to copolymerize monomers having crosslinking reactivity such as propyl methacrylate and 2-isocyanate ethyl acrylate.

Specific examples of the acrylates 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, Examples thereof include tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, and 2- (hydroxyphenylcarbonyloxy) ethyl acrylate.

Specific examples of 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, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenyl Carbonyloxy) 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,
Methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, dimethoxystyrene,
Chlorostyrene, dichlorostyrene, bromostyrene,
Examples thereof include iodostyrene, fluorostyrene, carboxystyrene, and the like.

Of these other monomers, those particularly preferably used are acrylates, methacrylates, acrylamides, methacrylamides, vinyl esters, styrenes, acrylates having not more than 20 carbon atoms. Acids, methacrylic acid, and acrylonitrile. General formulas (1) to (3) used for the synthesis of the copolymer
Is preferably 5 to 99% by weight, more preferably 10 to 9% by weight.
5% by weight.

Hereinafter, specific examples of the high molecular compound having the functional group represented by the general formula (1) to the general formula (3) in the side chain [the high molecular compound (1) to the high molecular compound (28)] are shown. In addition,
The number in the following formula or the molar composition of the polymer compound is shown.

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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Further, the compounds represented by the general formulas (1) to (1) used in the present invention:
The weight average molecular weight of the polymer compound having at least one of the functional groups represented by (3) is preferably 200
0 or more, more preferably in the range of 5000 to 300,000, the number average molecular weight is preferably 800 or more,
More preferably, it is in the range of 1,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably in the range of 1.1 to 10. These polymer compounds may be any of a random polymer, a block polymer, a graft polymer and the like, but are preferably a random polymer.

Examples of the solvent used for synthesizing the sulfonic acid generating polymer compound used in the present invention include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, and ethylene glycol. Glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene,
Examples include ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more. As the radical polymerization initiator used for synthesizing the sulfonic acid generating polymer compound used in the present invention, known compounds such as an azo initiator and a peroxide initiator can be used.

The sulfonic acid-generating polymer compound (A) used in the present invention may be used alone or as a mixture. These sulfonic acid-generating polymer compounds are used in an amount of 50 to 99% by weight, preferably 60 to 90% by weight of the total solids of the heat-sensitive recording layer.
Can be used in proportions by weight. If the amount is less than 50% by weight, the printed image becomes unclear. If the addition amount exceeds 90% by weight, it becomes impossible to form an image sufficiently by laser exposure.

[(B) Organic amine compound] The organic amine compound used in the heat-sensitive recording layer of the present invention includes an organic amine compound represented by the following general formula (5).

[0060]

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In the general formula (5), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an organic group, and R ⁸ , R ⁹ and R ¹⁰
Cannot be hydrogen atoms at the same time. Examples of the organic group for R ⁸ , R ⁹ and R ¹⁰ include a substituted or unsubstituted alkyl group, aryl group, aralkyl group, and heterocyclic group.

The alkyl group represented by R ⁸ , R ⁹ and R ¹⁰ preferably has 1 to 12 carbon atoms, and may be linear or branched and has a cyclic structure. And a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and the like. Further, the alkyl group may have a substituent, as the substituent, a substituted or unsubstituted alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a hydroxyl group, a cyano group, In addition to a carbonyl group, a carboxyl group, and a halogen atom, examples thereof include a group represented by the following general formula (6), and may further include an ester bond, an ether bond, and a thioether bond.

[0063]

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(R ¹² and R ¹³ each independently represent a hydrogen atom or an organic group having the same meaning as R ⁸ , R ⁹ and R ¹⁰ ;
¹¹ represents a substituted or unsubstituted alkylene group or aralkylene group. The alkylene group represented by R ¹¹ is preferably one having 2 to 12 carbon atoms, and may have a substituent. Specifically, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, cyclohexylene, methylene, ethylene, etc. and cyclohexylene And a group in combination with a group. These alkylene groups may further have a substituent, such as a substituted or unsubstituted alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group,
An aralkyloxy group, a hydroxyl group, a cyano group, a carbonyl group, a carboxyl group, a halogen atom, and the like, an alkyl group having 1 to 6 carbon atoms, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, The alkoxy group preferably has 1 to 6 carbon atoms in the alkyl portion, the aryloxy group preferably has 6 to 12 carbon atoms in the alkyl portion, and the aralkyloxy group has 7 to 6 carbon atoms in the alkyl portion.
Twelve are preferred, and specific examples of the halogen atom include a chlorine atom.

The alkylene group may have an oxycarbonyl group, an oxy group, a thio group or the like, and may have an ester bond, an ether bond, a thioether bond, or may have a repeating structure. When a repeating structure is included, the number of carbon atoms per repeating structure is 2 to 6
Is preferred. _{Specifically, -CH 2 CH 2 -O-CH} 2 C
_{H 2 -, - CH 2 CH} (CH 3) -O-CH 2 CH (C
_{H 3) -, - CH 2} CH 2 -C (O) -O-CH 2 CH 2 -
_{O-C (O) -CH 2} CH 2 -, - CH 2 CH 2 - (O-C
_{H 2 CH 2) n -,} - CH 2 CH (CH 3) - (O-CH 2
_{CH (CH 3)) n -} , - CH 2 CH 2 -C (O) -O-
_{(CH 2 CH 2 -O) n} -C (O) -CH 2 CH 2 - has the like, polyoxyethylene groups, structures containing polyoxypropylene groups. In this case, n = 2 to 30 is preferable.

The aralkylene group represented by R ¹¹ preferably has 7 to 12 carbon atoms, and specific examples include a xylylene group. The aralkylene group may further have a substituent, and examples of the substituent include those similar to the alkylene group. Further, like the alkylene group, an aralkylene group is an ester bond,
It may contain an ether bond or a thioether bond. )

Specific examples of the substituted alkyl group represented by R ⁸ , R ⁹ and R ¹⁰ include a hydroxyethyl group, a hydroxypropyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, a cyanoethyl group, a carboxymethyl group, and a carboxymethyl group. Ethyl group, hydroxyethoxyethyl group, methoxyethoxyethyl group, hydroxyethoxycarbonylethyl group, N, N-dimethylaminoethyl group,
Examples thereof include an N, N-dihydroxyethylaminoethyl group, a polyoxyethylene group having a repeating number of 2 or more, preferably 2 to 10, having a terminal hydroxy group or an alkoxy group, and a polyoxypropylene group.

The aryl group represented by R ⁸ , R ⁹ and R ¹⁰ preferably has 6 to 12 carbon atoms, and specific examples include a phenyl group and a naphthyl group. These may have a substituent, and specific examples of the substituent include those similar to the substituents of the above-mentioned substituted alkyl group.

The aralkyl group represented by R ⁸ , R ⁹ and R ¹⁰ preferably has 7 to 12 carbon atoms, and specific examples include a benzyl group and a phenethyl group. These may have a substituent, and specific examples of the substituent include those similar to the substituents of the above-mentioned substituted alkyl group.

Examples of the heterocyclic group represented by R ⁸ , R ⁹ and R ¹⁰ include a pyridyl group. These may have a substituent, and specific examples of the substituent include those similar to the substituents of the above-mentioned substituted alkyl group. Further, two or three of R ⁸ , R ⁹ , and R ¹⁰
One is linked, for example, morpholino group, thiomorpholino group, piperidino group, piperazinyl group, pyrrolidinyl group,
A heterocyclic group such as a pyridinyl group may be formed.

Specific examples of (B) the organic amine compound include ethylamine, isopropylamine, n-butylamine, benzylamine, monoethanolamine, monoisopropanolamine, aniline, ethylenediamine,
Primary amines such as xylylenediamine, diethylamine, diisopropylamine, di-n-butylamine, dibenzylamine, diethanolamine, diisopropanolamine, morpholine, pyrrolidine, piperidine, N-
Methylaniline, N-hydroxyethylaniline, N-
(2-hydroxypropyl) aniline, N-hydroxyethoxyethylaniline, diphenylamine, benzylmethylamine, benzylhydroxyethylamine, benzyl (2-hydroxypropyl) amine, benzylhydroxyethoxyethylamine, N, N'-diphenylethylenediamine, N, N '-Dibenzylethylenediamine, N, N'-dimethylethylenediamine, N, N'-
Dimethylxylylenediamine, N, N'-dihydroxyethylethylenediamine, N, N'-dihydroxyethylxylylenediamine, N, N'-dihydroxyethoxyethylethylenediamine, N, N'-dihydroxyethoxyethylxylylenediamine, N, N '-Di (2-
2 such as hydroxypropyl) ethylenediamine, N, N'-di (2-hydroxypropyl) xylylenediamine;
Secondary amines, trimethylamine, triethylamine, triisopropylamine, tri-n-butylamine, triphenylamine, triethanolamine, triisopropanolamine, N-methylmorpholine, N-methylpyrrolidine, N, N'-dimethylpiperidine, N-phenyl Morpholine, N-phenylpyrrolidine, N, N'-diphenylpiperidine, N-benzylmorpholine, N-benzylpyrrolidine, N, N'-dibenzylpiperidine, N
-Hydroxyethylmorpholine, N-hydroxyethylpyrrolidine, N, N'-dihydroxyethylpiperidine, N-hydroxyethoxyethylmorpholine, N-hydroxyethoxyethylpyrrolidine, N, N'-dihydroxyethoxyethylpiperidine, N- (2-hydroxy Propyl) morpholine, N- (2-hydroxypropyl) pyrrolidine, N, N′-di (2-hydroxypropyl) piperidine, N, N-dimethylaniline, N, N-
Dihydroxyethylaniline, N, N-di (2-hydroxypropyl) aniline,

N, N-di (hydroxyethoxyethyl)
Aniline, benzyldimethylamine, benzyldi (hydroxyethyl) amine, benzyldi (2-hydroxypropyl) amine, benzyldi (hydroxyethoxyethyl) amine, methyldiphenylamine, hydroxyethyldiphenylamine, (2-hydroxypropyl) diphenylamine, (hydroxyethoxyethyl) Diphenylamine, methyldibenzylamine, hydroxyethyldibenzylamine, (2-hydroxypropyl) dibenzylamine, (hydroxyethoxyethyl) dibenzylamine, pyridine, 2-hydroxyethylpyridine,
N, N, N ', N'-tetramethylethylenediamine,
N, N, N ', N'-tetramethylxylylenediamine, N, N, N', N'-tetrahydroxyethylethylenediamine, N, N, N ', N'-tetrahydroxyethylxylylenediamine, N, N N, N ', N'-tetrahydroxyethoxyethylethylenediamine, N,
N, N ′, N′-tetrahydroxyethoxyethylxylylenediamine, N, N, N ′, N′-tetra (2-hydroxypropyl) ethylenediamine, N, N, N ′,
Tertiary amines such as N'-tetra (2-hydroxypropyl) xylylenediamine, triethylenediamine,
Examples include amino acids such as glycine and alanine and derivatives thereof, but are not limited thereto.

The organic amine compound used in the present invention preferably has a hydrophilic group, and is preferably a tertiary amine, from the viewpoint of improving developability and stability over time. Those containing one amine function are preferred. The amount of the organic amine compound used in the present invention is 3 to 50% by weight, preferably 5 to 30% by weight, more preferably 8 to 20% by weight of the total solids of the heat-sensitive recording layer.

[(C) Light-to-Heat Conversion Material] The heat-sensitive lithographic printing plate precursor according to the present invention preferably contains a light-to-heat conversion material. Any substance that can convert light into heat by absorbing light can be used, for example, carbon black, carbon graphite, pigment, phthalocyanine pigment, iron powder,
Examples thereof include graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, and chromium sulfide. Particularly preferred are dyes, pigments, or metals that effectively absorb infrared light 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 azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, and dyes such as metal thiolate complexes. Preferred dyes include, for example, JP-A-58-125246.
JP-A-59-84356, JP-A-59-2028
29, JP-A-60-78787, JP-A-58-173696, and JP-A-5-173696.
Methine dyes described in JP-A-8-181690 and JP-A-58-194595;
JP-A-58-224793, JP-A-59-481
No. 87, JP-A-59-73996, JP-A-60-52
No. 940, JP-A-60-63744 and the like, naphthoquinone dyes described in JP-A-58-112792 and the like, British Patent 434
No. 875, and the like.

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. Further, as another preferable example of the dye, a near-infrared absorbing dye described as formulas (I) and (II) in U.S. Pat. No. 4,756,993 can be exemplified. 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
When it is less than m, the dispersion is not preferred in terms of stability in the coating solution for the photosensitive layer, and when it exceeds 10 μm, it is not preferred in terms of uniformity of the image heat-sensitive recording layer. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

These dyes or pigments are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 30% by weight based on the total solids of the heat-sensitive recording layer.
% By weight, particularly preferably 1 to 20% by weight for dyes, and particularly preferably 5 to 25% by weight for pigments. If the amount of the pigment or the dye is less than 0.01% by weight, the sensitivity is lowered.

[Other Components] In the heat-sensitive recording layer of the present invention, various compounds may be added, if necessary, in addition to the above three components. For example, a dye having a large absorption in the visible light region can be used as a colorant for an image.
Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green B
G, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, Crystal Violet (CI
42555), methyl violet (CI4253)
5), ethyl violet, rhodamine B (CI145
170B), malachite green (CI42000),
Methylene blue (CI52015), etc.
The dyes described in JP-A-293247 can be exemplified. These dyes are preferably added because they fade after laser exposure and are easy to distinguish between image areas and non-image areas. The amount of addition was 0.01% of the total solids of the heat-sensitive recording layer.
-10% by weight.

The heat-sensitive recording layer of the present invention has a structure described in JP-A-62-25 in order to increase the stability under printing conditions.
Non-ionic surfactants described in JP-A-1740 and JP-A-3-208514, and JP-A-59-1
An amphoteric surfactant as described in JP-A-21044 and JP-A-4-13149 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, alkylpoaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-
Hydroxyethyl imidazolinium betaine and N-tetradecyl-N, N-betaine type (for example, trade name Amogen K, manufactured by Dai-ichi Kogyo Co., Ltd.) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the heat-sensitive recording layer is preferably from 0.05 to 15% by weight, and more preferably from 0.1 to 5% by weight.

The heat-sensitive recording layer of the present invention may further comprise
A plasticizer is added to impart flexibility and the like to the coating film.
For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate,
For example, oligomers and polymers of tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid are used.

In addition to these, epoxy compounds, vinyl ethers, phenol compounds having a hydroxymethyl group and phenol compounds having an alkoxymethyl group described in Japanese Patent Application No. 7-18120 may be added. Further, another polymer compound may be added to improve the strength of the coating film.

The lithographic printing plate precursor according to the present invention can be usually produced by dissolving the above-mentioned components in a solvent and coating the 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, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene,
Water and the like can be mentioned, but it is 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. The coating amount (solid content) on the support obtained after coating and drying is 0.1 to 5.0.
preferably g / m ^2, more preferably 0.3 to 3.0 g / m ^2, more preferably 0.4 to 2.0 g / m ^2. Within this range, both developability and printing durability are compatible. 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.

The heat-sensitive recording layer in the present invention may contain a surfactant for improving coating properties, for example, JP-A-62-170.
For example, a fluorine-based surfactant described in JP-A-950-950 can be added. The amount of these additives is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the solid content of the heat-sensitive recording layer.

(Support having hydrophilic surface) The support having a hydrophilic surface used in the present invention may be a support having a hydrophilic surface, a support having a hydrophilic surface, or a support having a hydrophilic surface. And those provided with a hydrophilic layer on a support.

The support used in the lithographic printing plate precursor according to the present invention is a dimensionally stable plate-like material. Paper, metal plates (eg, aluminum, zinc, copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, Polypropylene, polycarbonate, polyvinyl acetal, etc.),
Examples include paper on which metal is laminated or vapor-deposited, plastic film, or the like. As the support used in the lithographic printing plate precursor of the present invention,
(A) Aluminum plate or (b) polyester film is preferred. Hereinafter, these preferred supports and their hydrophilic treatment will be described.

[A-1. Aluminum Plate (Support Substrate)] As the support used in the lithographic printing plate precursor according to the present invention, a polyester film or an aluminum plate is preferable as described above. Is particularly preferred. 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 the foreign element in the alloy is at most 10% by weight or less. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.1 mm to 0.4 mm.
It is 2 mm to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove rolling oil on the surface. The surface roughening treatment of the surface of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can be used.

The surface roughening by the above-mentioned method is performed when the center line surface roughness (Ha) of the surface of the aluminum plate is 0.3-1.
It is preferable that the coating be performed within a range of 0 μm. The roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide or sodium hydroxide as required, and further neutralized, and then anodized to enhance abrasion resistance if desired. Processing is performed.
As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used, and generally, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The anodizing treatment conditions vary depending on the electrolyte to be used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are appropriate. The amount of the anodic oxide film is 1.0 to 5.0 g / m ² , particularly 1.5 to 4.0 g / m ² .
g / m ² is preferable, and if it is less than 1.0 g / m ² , the printing durability is insufficient or the non-image area of the lithographic printing plate is easily scratched. The so-called "scratch stain" to which ink adheres easily occurs. [A-2. Hydrophilization treatment of aluminum plate] By subjecting the aluminum surface subjected to the anodic oxidation treatment as described above to the hydrophilic treatment, a support having the surface hydrophilized can be obtained. As the hydrophilic treatment used here,
U.S. Pat. Nos. 2,714,066 and 3,181,4
No. 61, No. 3,280,734 and No. 3,902,
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in US Pat. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, Tokuboku Sho 36
Potassium fluoride zirconate disclosed in U.S. Pat. No. 2,220,632 and polyvinyl as disclosed in U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689,272. For example, a method of treating with phosphonic acid is used.

[B-1. Non-conductive support (support substrate)] When a non-conductive substrate such as polyester is used for the substrate of the present invention, an antistatic layer is provided on the heat-sensitive recording layer side or on the opposite side or on both sides of the substrate. Is preferred. When the antistatic layer is provided between the support and the hydrophilic layer, it also contributes to the adhesion to the hydrophilic layer. As the antistatic layer, a polymer layer in which metal oxide fine particles and a matting agent are dispersed can be used.

As the material of the metal oxide particles used for the antistatic layer, SiO ₂ , ZnO, TiO ₂ , SnO ₂ ,
Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₃ , V ₂ O
₅ and their composite oxides, and / or metal oxides further containing different atoms in these metal oxides. These may be used alone or as a mixture. As the metal oxide, SiO ₂ , ZnO, Sn
O ₂ , Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ and MgO are preferred. As an example containing a small amount of heteroatoms, ZnO
l or In, SnO ₂ doped with Sb, Nb or a halogen element, and In ₂ O ₃ with a hetero atom such as Sn in an amount of 30 mol% or less, preferably 10 mol% or less. it can. The metal oxide particles
It is preferable that the antistatic layer contains 10 to 90% by weight. The average particle diameter of the metal oxide particles is preferably in the range of 0.001 to 0.5 μm. Here, the average particle diameter is a value including not only the primary particle diameter of the metal oxide particles but also the particle diameter of the higher-order structure.

The matting agent that can be used in the antistatic layer is preferably an inorganic or organic particle having an average particle size of 0.5 to 20 μm, more preferably an average particle size of 1.0 to 15 μm. Is mentioned. As inorganic particles,
Examples thereof include metal oxides such as silicon oxide, aluminum oxide, titanium oxide, and zinc oxide, and metal salts such as calcium carbonate, barium sulfate, barium titanate, and strontium titanate. Examples of the organic particles include cross-linked particles of polymethyl methacrylate, polystyrene, polyolefin, and a copolymer thereof. The matting agent is preferably contained in the antistatic layer in a range of 1 to 30% by weight. Examples of the polymer that can be used for the antistatic layer include, for example, gelatin, proteins such as casein, carboxymethyl cellulose, hydroxyethyl cellulose, acetyl cellulose, diacetyl cellulose, cellulose compounds such as triacetyl cellulose, dextran, agar, sodium alginate, and starch derivatives. Such as saccharides, polyvinyl alcohol, polyvinyl acetate, polyacrylate, polymethacrylate, polystyrene,
Examples include synthetic polymers such as polyacrylamide, polyvinylpyrrolidone, polyester, polyvinyl chloride, polyacrylic acid, and polymethacrylic acid. The polymer is preferably contained in the antistatic layer in the range of 10 to 90% by weight.

[Hydrophilic layer] As a method for making the surface of the support hydrophilic, other than the above-mentioned method of hydrophilizing the surface of the aluminum support, a method of providing a hydrophilic layer on various support substrates is available. is there. Examples of the hydrophilic layer that can be provided on the support include, for example, an organic hydrophilic matrix obtained by crosslinking or pseudo-crosslinking an organic hydrophilic polymer, and hydrolysis of polyalkoxysilane, titanate, zirconate, or aluminate. And a thin film of a metal or a metal compound having a hydrophilic surface or an inorganic hydrophilic matrix obtained by a sol-gel conversion comprising a condensation reaction.

[Organic hydrophilic matrix] The crosslinking reaction used to form the organic hydrophilic matrix of the hydrophilic layer of the present invention can be the formation of a covalent bond by heat or light, or the formation of an ionic bond by a polyvalent metal salt. is there. As the organic hydrophilic polymer used in the present invention, a polymer having a functional group that can be used for a crosslinking reaction is preferable. Preferred functional groups include, for example, -OH, -SH, -N
_{H 2, -NH -, - CO} -NH 2, -CO-NH -, - O
-CO-NH-, -NH-CO-NH-, -CO-O
^{H, -CO-O -, -CO} -O -, - CS-OH, -C
O-SH, -CS-SH, -SO 3 H, -SO
₂ (O ⁻ ), —PO ₃ H ₂ , —PO (O ⁻ ) ₂ , —SO ₂ —N
_{H 2, -SO 2 -NH -,} - CH = CH 2, -CH = CH
-, - CO-C (CH 3) = CH 2, -CO-CH = CH
_{2, -CO-CH 2 -CO -} , - CO-O-CO-, and functional group, and the like shown below.

[0098]

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Among these functional groups, a hydroxyl group, an amino group, a carboxyl group and an epoxy group are particularly preferred.

Such organic hydrophilic polymers include:
Known water-soluble binders can be used, for example, polyvinyl alcohol (polyvinyl acetate having a saponification degree of 60% or more), modified polyvinyl alcohol such as carboxy-modified polyvinyl alcohol, starch and derivatives thereof, carboxymethyl cellulose and salts thereof, Cellulose derivatives such as hydroxyethyl cellulose,
Casein, gelatin, gum arabic, polyvinylpyrrolidone, vinyl acetate-crotonic acid copolymer and its salt, styrene-maleic acid copolymer and its salt, polyacrylic acid and its salt, polymethacrylic acid and its salt, polyethylene glycol, Polyethyleneimine, polyvinylphosphonic acid and its salt, polystyrenesulfonic acid and its salt, poly (methacryloyloxypropanesulfonic acid) and its salt, polyvinylsulfonic acid and its salt, poly (methacryloyloxyethyltrimethylammonium chloride), polyhydroxy Examples include ethyl methacrylate, polyhydroxyethyl acrylate, and polyacrylamide. These polymers may be copolymers as long as hydrophilicity is not impaired, and may be used alone or in combination of two or more. The amount used is from 20% by weight to 9% by weight based on the total solid weight of the hydrophilic layer.
It is 9% by weight, preferably 25% to 95% by weight, more preferably 30% to 90% by weight.

In the present invention, the organic hydrophilic polymer can be crosslinked with a known crosslinking agent. Known crosslinking agents include polyfunctional isocyanate compounds, polyfunctional epoxy compounds, polyfunctional amine compounds, polyol compounds, polyfunctional carboxyl compounds, aldehyde compounds,
Polyfunctional (meth) acrylic compound, polyfunctional vinyl compound,
Polyfunctional mercapto compounds, polyvalent metal salt compounds, polyalkoxysilane compounds and their hydrolysates, polyalkoxytitanium compounds and their hydrolysates, polyalkoxyaluminum compounds and their hydrolysates, polymethylol compounds, polyalkoxymethyl compounds, etc. It is also possible to add a known reaction catalyst to promote the reaction. The amount used is 1% by weight to 50% by weight, preferably 3% by weight to 40% by weight, more preferably 5% by weight to 35% by weight, based on the total solid content in the coating solution of the hydrophilic layer. .

[Inorganic hydrophilic matrix]

The system capable of sol-gel conversion which can be used for forming the inorganic hydrophilic matrix of the hydrophilic layer of the present invention has a network-like structure in which a bonding group derived from a polyvalent element is linked via an oxygen atom. At the same time, the polyvalent metal also has unbonded hydroxyl groups and alkoxy groups, and is a polymer having a resin-like structure in which these are mixed, and in a stage where there are many alkoxy groups and hydroxyl groups, it is in a sol state. In some cases, the network-like resin structure becomes strong as the ether bonding proceeds. In addition, it also has a function of modifying the surface of the solid fine particles by binding a part of the hydroxyl groups to the solid fine particles and changing the degree of hydrophilicity. The polyvalent bonding element of the compound having a hydroxyl group or an alkoxy group that undergoes sol-gel conversion is aluminum, silicon, titanium, zirconium, or the like, and any of these can be used in the present invention. A sol-gel conversion system using a siloxane bond will be described. aluminum,
The sol-gel conversion using titanium and zirconium can be performed by substituting silicon for each element described below.

That is, particularly preferably used are:
This is a system containing a silane compound having at least one silanol group and capable of sol-gel conversion. Hereinafter, a system utilizing the sol-gel conversion will be further described. The inorganic hydrophilic matrix formed by the sol-gel conversion is preferably a resin having a siloxane bond and a silanol group, and is coated with a coating solution that is a sol system containing a silane compound having at least one silanol group. During the drying and aging, the hydrolytic condensation of the silanol groups proceeds to form the structure of the siloxane skeleton, which is formed by the progress of gelation. Further, in the matrix of this gel structure, for the purpose of improving physical properties such as film strength and flexibility, improving coating properties, adjusting hydrophilicity, etc.
It is also possible to add the above-mentioned organic hydrophilic polymer and crosslinking agent. The siloxane resin that forms the gel structure is
The silane compound represented by the following general formula (I) and having at least one silanol group is obtained by hydrolysis of the silane compound represented by the following general formula (II), and is not necessarily the silane compound represented by the general formula (II) It is not necessary to use the partial hydrolyzate alone. In general, the silane compound may be composed of an oligomer partially hydrolyzed, or may be a mixed composition of the silane compound and its oligomer.

[0105]

Embedded image

The siloxane resin represented by the general formula (I) is
It is formed by sol-gel conversion of at least one compound of the silane compounds represented by the following general formula (II), wherein at least one of R ^{01 to} R ^{03 in} the general formula (I) represents a hydroxyl group, and Represents an organic residue selected from the symbols R ⁰ and Y in the general formula (II).

Formula (II) (R ⁰ ) _n Si (Y) _4-n

In the general formula (II), R ⁰ represents a hydroxyl group, a hydrocarbon group or a heterocyclic group. Y represents a hydrogen atom, a halogen atom (representing a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), —OR ¹ , —OCOR ^2, or —N (R ³ )
(R ⁴⁾ represents the (R ^1, R ² each represents a hydrocarbon group,
R ³ and R ⁴ may be the same or different and represent a hydrogen atom or a hydrocarbon group), and n represents 0, 1, 2 or 3.

The hydrocarbon group or heterocyclic group represented by R ^{0 in} the general formula (II) is, for example, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (for example, methyl group , Ethyl group, propyl group, butyl group, pentyl group,
A hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and the like; the groups substituted by these groups include a halogen atom (a chlorine atom, a fluorine atom, a bromine atom), a hydroxy group, a thiol group, and a carboxy group. Group, sulfo group, cyano group, epoxy group, -OR 'group (R' is a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group,
Hexyl, octyl, decyl, propenyl, butenyl, hexenyl, octenyl, 2-hydroxyethyl, 3-chloropropyl, 2-cyanoethyl, N, N-dimethylaminoethyl, 1-bromoethyl Group, 2- (2-methoxyethyl) oxyethyl group, 2
-Methoxycarbonylethyl group, 3-carboxypropyl group, benzyl group, etc.), -OCOR "group (R"
Represents the same content as R ′), —COOR ″
Group, -COR "group, -N (R"")(R"") group (R""
Represents the same content as a hydrogen atom or the aforementioned R ′, and may be the same or different), —NHCONHR ″ group, —
NHCOOR "group -Si (R") 3 group, -CONH
R ′ ″ group, —NHCOR ″ group and the like. (These substituents may be substituted plurally in the alkyl group),

An optionally substituted linear or branched alkenyl group having 2 to 12 carbon atoms (for example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, dodecenyl group, etc. And the groups substituted with these groups include those having the same contents as the groups substituted with the above-mentioned alkyl groups), having 7 to 14 carbon atoms.
Optionally substituted aralkyl groups (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, etc .; Groups having the same content as the group to be mentioned, or may be substituted plurally),

An optionally substituted alicyclic group having 5 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl, 2
-Cyclohexylethyl group, 2-cyclopentylethyl group, norbornyl group, adamantyl group and the like, the group substituted with these groups include those having the same contents as the substituents of the alkyl group, and those substituted with a plurality of May be substituted), an aryl group having 6 to 12 carbon atoms which may be substituted (for example,
A phenyl group, a naphthyl group, and examples of the substituent include those having the same contents as the group substituted with the alkyl group, and a plurality of the groups may be substituted), or a nitrogen atom, an oxygen atom,
A condensable heterocyclic group containing at least one atom selected from sulfur atoms (for example, the heterocyclic ring includes a pyran ring, a furan ring, a thiophene ring, a morpholine ring, a pyrrole ring, a thiazole ring, and an oxazole And a ring, a pyridine ring, a piperidine ring, a pyrrolidone ring, a benzothiazole ring, a benzoxazole ring, a quinoline ring, a tetrahydrofuran ring, etc., which may contain a substituent. The same content may be mentioned, or a plurality of the same may be substituted).

In the general formula (II), -OR ¹ group of Y, -OC
As a substituent of the OR ² group or the —N (R ³ ) (R ⁴ ) group,
For example, it represents the following substituents. —OR ¹ group includes R ¹
Is an aliphatic group having 1 to 10 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, pentyl group, octyl group, nonyl group, decyl group, propenyl group) , Butenyl, heptenyl, hexenyl, octenyl, decenyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, 2- (methoxyethyloxo) ethyl, 1- (N, N -Diethylamino) ethyl group, 2-methoxypropyl group, 2-cyanoethyl group, 3-methyloxapropyl group, 2-chloroethyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, chlorocyclohexyl group, methoxycyclohexyl group, benzyl group, Phenethyl group, dimethoxybenzyl group, methylbenzyl group, bromobenzyl It represents a group and the like).

In the —OCOR ² group, R ² is an aliphatic group having the same contents as R ¹ or an aromatic group having 6 to 12 carbon atoms which may be substituted (the aromatic group is the aryl group in the above R). And the same as those exemplified for the group).
In the —N (R ³ ) (R ⁴ ) group, R ³ and R ⁴ may be the same or different from each other, and each may be a hydrogen atom or an optionally substituted aliphatic group having 1 to 10 carbon atoms ( For example, those having the same contents as those of R ¹ in the above-mentioned —OR ¹ group can be mentioned). More preferably, the total number of carbon atoms of R ³ and R ⁴ 16
It is within the number. Specific examples of the silane compound represented by the general formula (II) include the following, but are not limited thereto.

Tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propylsilane, tetra-t-butoxysilane, tetra-n-butoxysilane, dimethoxydiethoxysilane, methyltrichlorosilane , Methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriiso Propoxysilane, ethyltri-t-butoxysilane, n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane,
n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltri-t-butoxysilane, n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n
-Hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane, n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n -Decyltriisopropoxysilane, n-decyltri-t-butoxysilane, n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane, phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltrisilane -Butoxysilane, dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyl Dibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane,

Triethoxyhydrosilane, tribromohydrosilane, trimethoxyhydrosilane, isopropoxyhydrosilane, tri-t-butoxyhydrosilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, Vinyl tri-t-butoxysilane, trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxip Pills trimethoxysilane, gamma
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane Γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltri-t-butoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Aminopropyltriisopropoxysilane, γ-aminopropyltri-t-butoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane Γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. Is mentioned.

Along with the silane compound represented by the general formula (II) used for forming the inorganic hydrophilic matrix of the hydrophilic layer of the present invention, the silane compound binds to the resin during the sol-gel conversion of Ti, Zn, Sn, Zr, Al, etc. And a metal compound capable of forming a film. Examples of the metal compound used include Ti (OR ⁵ ) ₄ (R ⁵ is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc.), Ti
Cl4, Ti (CH ₃ COCHCOCH ₃ ) ₂ (O
R ⁵ ) ₂ , Zn (OR ⁵ ) ₂ , Zn (CH ₃ COCHCOC
H ₃ ) ₂ , Sn (OR ⁵ ) ₄ , Sn (CH ₃ COCHCOC)
_{H 3) 4, Sn (OCOR} 5) 4, SnCl 4, Zr (OR
⁵ ) ₄ , Zr (CH ₃ COCHCOCH ₃ ) ₄ , Al (O
R ⁵ ) ₃ and Al (CH ₃ COCHCOCH ₃ ) ₃ .

Further, in order to promote the hydrolysis and polycondensation reaction of the silane compound represented by the general formula (II), and the metal compound used in combination, it is preferable to use an acidic catalyst or a basic catalyst in combination. As the catalyst, an acid or basic compound used as it is or in a state of being dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst or a basic catalyst, respectively) is used. The concentration at that time is not particularly limited, but when the concentration is high, hydrolysis /
The polycondensation rate tends to increase. However, when a basic catalyst having a high concentration is used, a precipitate may be generated in the sol solution.

The type of the acidic catalyst or the basic catalyst is not particularly limited. Specific examples of the acidic catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, and hydrogen peroxide. Examples of basic catalysts include ammonia, such as carboxylic acids such as carbonic acid, formic acid and acetic acid, substituted carboxylic acids in which R of the structural formula represented by RCOOH is substituted with another element or a substituent, and sulfonic acids such as benzenesulfonic acid. Examples include ammoniacal bases such as water and amines such as ethylamine and aniline.

For further details of the above-mentioned sol-gel method, refer to Saio Sakuhana, “Sol-gel Method Science”, Agne Shofusha Co., Ltd.
(1988), Takashi Hirashima, "Functional thin film production technology by the latest sol-gel method" General Technology Center (published) (1992)
It is described in detail in written documents such as year).

In the hydrophilic layer of the organic or inorganic hydrophilic matrix according to the present invention, in addition to the above, control of the degree of hydrophilicity, improvement of the physical strength of the hydrophilic layer, and mutual Various compounds can be added, such as improvement in dispersibility, improvement in coating properties, and improvement in printability. For example, plasticizers, pigments, dyes, surfactants, hydrophilic particles and the like can be mentioned.

The hydrophilic particles are not particularly limited, but preferably include silica, alumina, titanium oxide, magnesium oxide, magnesium carbonate, calcium alginate and the like. These can be used for promoting hydrophilicity, strengthening a film, and the like. More preferably, it is silica, alumina, titanium oxide or a mixture thereof. In a preferred embodiment, the hydrophilic layer of the organic or inorganic hydrophilic matrix of the present invention particularly contains metal oxide particles such as silica, alumina, and titanium oxide.

Silica has many hydroxyl groups on the surface, and the inside constitutes a siloxane bond (—Si—O—Si—). In the present invention, silica that can be preferably used is ultrafine silica particles having a particle diameter of 1 to 100 nm, also referred to as colloidal silica, dispersed in water or a polar solvent. Specifically, it is described in "Applied Technology of High Purity Silica", Vol. 3, supervised by Yoshitoshi Kaga and Ei Hayashi, CMC Corporation (1991).

Alumina which can be preferably used is alumina hydrate (boehmite) having a colloidal size of 5 to 200 nm, and an anion (for example, a halogen atom such as a fluorine ion or a chlorine ion) in water. Ions, carboxylate anions such as acetate ions, etc.) as a stabilizer. The titanium oxide that can be preferably used has an average primary particle size of 50 to 5
Anatase-type or rutile-type titanium oxide having a thickness of 00 nm is dispersed in water or a polar solvent using a dispersant, if necessary.

In the present invention, the hydrophilic particles which can be preferably used have an average primary particle size of 1 to 5000 nm.
And more preferably 10 to 1000 nm.
In the hydrophilic layer of the present invention, these hydrophilic particles may be used alone or in combination of two or more. The amount used is based on the total solid weight of the hydrophilic layer.
It is 5% to 90% by weight, preferably 10% to 70% by weight, more preferably 20% to 60% by weight.

The hydrophilic layer of the organic or inorganic hydrophilic matrix used in the present invention may be formed by dissolving or dispersing in a suitable solvent such as water or a polar solvent such as methanol or ethanol alone or a mixed solvent thereof. Is applied, dried and cured on the photothermal conversion layer. Its coating weight in weight after drying is suitably from 0.1-5 g / m ^2, preferably from 0.3 to 3 g / m ^2, more preferably 0.5 to 2 g /
m ² . The coating weight of the hydrophilic layer after drying is 0.1 g.
/ M ² is too low, the retention of hydrophilic liquids such as fountain solution and retention, undesired results such as a decrease in film strength are given,
If it is too high, the film becomes brittle, giving undesired results such as reduced printing durability.

[Thin Film of Metal or Metal Compound Having Hydrophilic Surface] The thin film of metal or metal compound having a hydrophilic surface used in the hydrophilic layer of the present invention is not particularly limited as long as it has surface hydrophilicity. Not available, for example, for aluminum, chromium, manganese, tin, tellurium, titanium, iron, cobalt, nickel, indium, bismuth, zirconium, zinc, lead, vanadium, silicon, copper, silver metal and alloys and their respective metals Metal oxides, metal carbides, metal nitrides, metal borides, metal sulfides, and metal halides. Substantially, the surface of the thin film of the metal and the metal compound is in a highly oxidized state, and works advantageously in terms of hydrophilicity. Therefore, a thin film of a metal oxide such as indium tin oxide, tungsten oxide, manganese oxide, silicon oxide, titanium oxide, aluminum oxide, and zirconium oxide can be suitably used as the hydrophilic layer of the present invention.

For forming a thin film of a metal or a metal compound having a hydrophilic surface used in the hydrophilic layer of the present invention, a PVD method such as a vacuum evaporation method, a sputtering method, and an ion plating method may be used.
Method D (physical vapor deposition) or CVD (chemical vapor deposition) is used as appropriate. For example, in a vacuum evaporation method, resistance heating, high-period induction heating, electron beam heating, or the like can be used as a heating method. In addition, oxygen, nitrogen, or the like may be introduced as a reactive gas, or reactive vapor deposition using means such as ozone addition or ion assist may be used.

When the sputtering method is used, the target material
Use pure metal or the desired metal compound
When using pure metal, oxygen or
Nitrogen and the like are introduced. DC power supply,
A pulse DC power supply or a high-frequency power supply can be used.

Prior to the formation of a thin film by the above method, degassing of the substrate by heating the substrate or vacuum glow treatment on the surface of the heat-sensitive layer may be performed to improve the adhesion to the heat-sensitive layer. For example, in vacuum glow processing, 1 to 10 mt
A high frequency is applied to the base under a pressure of about orr to form a glow discharge, and the substrate can be processed by the generated plasma. Further, the effect can be improved by increasing the applied voltage or introducing a reactive gas such as oxygen or nitrogen.

The thickness of the metal or metal compound thin film having a hydrophilic surface used in the hydrophilic layer of the present invention is 10 nm to 3 nm.
000 nm is preferred. More preferably, 20 to 150
0 nm. If the thickness is too small, unfavorable results such as a decrease in retention of a hydrophilic liquid such as a fountain solution and a decrease in film strength are given. If the thickness is too large, it takes time to form a thin film, which is not preferable in terms of production suitability.

The support used in the present invention has a maximum roughness depth (R) on the back surface of the support from the viewpoint of preventing blocking.
t) is preferably at least 1.2 μm, and furthermore, the dynamic friction when the back surface of the support (that is, the back surface of the lithographic printing plate precursor of the present invention) slides on the surface of the lithographic printing plate precursor of the present invention. Preferably, the coefficient (μk) is 2.6 or less.

The thickness of the support used in the present invention is about 0.05 mm to about 0.6 mm, preferably 0.1 mm to 0.6 mm.
mm to 0.4 mm, particularly preferably 0.15 mm to 0.4 mm.
3 mm.

[Other Layers of Lithographic Printing Plate Precursor] [Undercoat Layer] The lithographic printing plate precursor of the invention has a heat-sensitive recording layer of the invention provided on a support having a hydrophilic surface. An undercoat layer can be provided between them according to the above. Various organic compounds are used as the undercoat layer component,
For example, carboxymethylcellulose, dextrin,
Gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid which may have a substituent Organic phosphonic acids such as acids, phenylphosphoric acid optionally having a substituent, naphthylphosphoric acid, organic phosphoric acid such as alkylphosphoric acid and glycerophosphoric acid, phenylphosphinic acid optionally having a substituent, naphthylphosphinic acid, Selected from organic phosphinic acids such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxy group such as hydrochloride of triethanolamine. You may use it.

The undercoat layer can be provided by the following method. That is, a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof is coated on a support, dried, and provided. A method in which a support is immersed in a solution obtained by dissolving the above organic compound in an organic solvent or a mixed solvent thereof to adsorb the compound, and then washed with water or the like and dried to form an organic undercoat layer. . In the former method, 0.005 of the above organic compound is used.
Solutions having a concentration of 〜１０10% by weight can be applied in various ways.
In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight, the immersion temperature is 20 to 90 ° C, preferably 25 to 50 ° C, and the immersion time is It is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute.
The solution used for this is ammonia, triethylamine,
The pH can be adjusted to a range of 1 to 12 with a basic substance such as potassium hydroxide or an acidic substance such as hydrochloric acid or phosphoric acid. The coating amount of the undercoat layer is suitably from ² to 200 mg / m ² , and preferably from 5 to 100 mg / m ² .

(Image Recording Step) The image recording of the heat-sensitive lithographic printing plate precursor according to the present invention can be performed, for example, by directly performing image-wise thermal recording with a thermal recording head or the like, or by using a wavelength of 700 to 1200.
Solid-state lasers or semiconductor lasers emitting infrared light of nm, high-intensity flash light such as xenon discharge lamps, and light-heat conversion type exposure such as infrared lamp exposure can also be used. In the present invention, it is particularly preferable to use laser light, and the laser light energy used for image recording is absorbed by the photothermal conversion material (C) contained in the heat-sensitive lithographic printing plate precursor according to the present invention, and the thermal energy is used. The heat-generated lithographic printing plate precursor is heated in an image-like manner by the heat generated thereby, and image recording is performed.
The laser used in the present invention is not particularly limited as long as it provides an exposure amount necessary to generate heat sufficient for image recording on the heat-sensitive lithographic printing plate precursor.
gas lasers such as r lasers, carbon dioxide lasers,
A solid-state laser such as a YAG laser and a semiconductor laser can be used. Usually, a laser having an output of 50 mW class or more is required. Semiconductor lasers and semiconductor-excited solid-state lasers (such as YAG lasers) are preferably used in terms of practicality such as maintainability and price.
The recording wavelength of these lasers is in the infrared wavelength range, and an oscillation wavelength of 700 nm to 1200 nm is often used. Exposure can also be performed using an imaging device described in JP-A-6-186750. In the present invention, at the time of laser irradiation, a heating process can be performed between the laser irradiation step and the printing step for the purpose of reducing the laser energy required for recording. Preferred conditions for the heat treatment are 80 ° C to 15 ° C.
10 seconds to 5 minutes in the range of 0 ° C. This image recording step can also be performed after the lithographic printing plate precursor has been mounted on a printing press. In that case, as described later, printing can be performed as it is after image recording.

(Printing Step) The heat-sensitive lithographic printing plate precursor according to the present invention is prepared by mounting a printing plate precursor on which an image has been recorded into a printing machine without any further processing, and performing normal lithographic printing using dampening solution and ink. Or JP-B-49-26844, JP-B-49-27124, JP-B-49-27125, JP-A-53-36307, and JP-A-53-36.
No. 308, JP-B-61-52867, JP-A-58-2114844, and JP-A-53-27803.
JP, JP-A-53-29807, JP-A-54-29807
146110, JP-A-57-212274, JP-A-58-37069, JP-A-54-10
It is possible to perform simple lithographic printing using an emulsion ink described in JP-A-6305 and the like without using dampening water.

When the printing original plate on which the image was recorded was mounted on a printing press without further processing and printing was started, sulfonic acid was generated in the exposed portion (heating portion) of the heat-sensitive recording layer. The heat-sensitive recording layer in the exposed portion (heating portion) is dissolved or dispersed and removed (on-press development) by the hydrophilic liquid such as dampening solution supplied above, and the hydrophilic surface is exposed in that portion. A hydrophilic liquid such as a fountain solution adheres to the exposed hydrophilic surface, and the ink is deposited on a heat-sensitive recording layer in a non-exposed portion (non-heated portion) to start printing. When performing normal lithographic printing using a dampening solution and ink, in order to efficiently dissolve or disperse the heat-sensitive recording layer of the above-mentioned exposed portion (heating portion) from the plate surface, apply dampening solution to the plate surface in advance. After the supply, the ink is preferably supplied.

[Emulsion Ink] The emulsion ink which can be used in the present invention is an emulsion ink obtained by adding a hydrophilic component to an oil-based ink component, and is a W / O (water in oil) type. O / W
(Oil in water) type. Further, the emulsion ink used in the present invention maintains a stable emulsified state in an ink fountain of a printing press when applied to printing in a storage state in an ink can and receives a shear (shear force) during printing. At the time when the inking system is transferred to the inking roller, the emulsification is broken and the hydrophilic component is separated and supplied onto the plate surface. On the plate surface, the hydrophilic component adheres to the non-image area to form a liquid film, thereby preventing the oil-based ink component from adhering. On the other hand, the oil-based ink component adheres to the image area. Any emulsion ink having such a function can be used in the present invention without any particular limitation. Further, in order for the emulsion ink used in the present invention to exhibit the above function, it is more preferable to use a printing machine equipped with a cooling mechanism in the inking system.

The proportion of the oily ink component and the hydrophilic component in the emulsion ink of the present invention is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, based on 100 parts by weight of the oily ink component. Preferably, 20 to
100 parts by weight. As the oily ink component of the emulsion ink of the present invention, vegetable oil, synthetic resin varnish or natural resin varnish, or a synthetic varnish thereof,
An ordinary oil-based ink comprising a high-boiling petroleum solvent, a pigment, and other additives (such as a friction resistance improver, an ink dryer, and a drying inhibitor) can be used.

As the hydrophilic component of the emulsion ink that can be used in the present invention, water and / or polyhydric alcohols can be used. As polyhydric alcohols, for example, glycerin, diglycerin, ethylene glycol,
Examples thereof include diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, sorbitol, butanediol, and pentanediol. Among them, glycerin, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol can be preferably used. The polyhydric alcohol may be used singly, or two or more kinds may be used as a mixture. Further, the polyhydric alcohol may be used as a mixture with water. The preferred content of the polyhydric alcohol in the hydrophilic component is 30 to 10
The content is preferably 0% by weight, more preferably 50 to 100% by weight. In addition to the above, additives can be used as the hydrophilic component for the purpose of improving emulsion stability, improving flow characteristics, improving hydrophilicity, suppressing evaporation of the hydrophilic component, and the like. For example, monohydric alcohols such as methanol and ethanol, monoethanolamine,
Amino alcohols such as diethanolamine, nonionic, anionic, cationic and betaine known surfactants, oxycarboxylic acids such as glycolic acid, lactic acid and citric acid, polyvinylpyrrolidone, polyacrylic acid, gum arabic and carboxymethylcellulose And inorganic acids and salts such as phosphoric acid, silicic acid, nitric acid, and salts thereof.

Further, the heat-sensitive lithographic printing plate precursor of the present invention comprises:
As described in Japanese Patent No. 2938398, after mounting on a printing press cylinder, an image is recorded by a laser mounted on the printing press, and then, on-press development and printing can be performed in the same manner as described above. It is possible. Further, the heat-sensitive lithographic printing plate precursor of the present invention is obtained by dissolving the heat-sensitive recording layer of an exposed portion (heating portion) by using water or an appropriate aqueous solution (for example, fountain solution) with the printing original plate on which an image is recorded. After dispersion removal (development), printing can be performed in the same manner as described above.

[0142]

[Examples 1 to 13]

(Preparation of support) Thickness 180 with corona treatment on both sides
The following coating solution was applied to both surfaces of a polyethylene terephthalate having a thickness of μm and dried by heating (180 ° C., 30 seconds) to form an antistatic layer having a dry film thickness of 0.2 g / m 2. (Antistatic layer coating solution) Acrylic resin aqueous dispersion (Julima ET-410, solid content 20% by weight, manufactured by Nippon Pure Chemical Co., Ltd.) 20 g tin oxide-antimony oxide aqueous dispersion (average particle size: 0. 1 μm, 17% by weight) 30 g ・ Polyoxyethylene nonylphenyl ether (Nonipol 100, manufactured by Sanyo Chemical Industries, Ltd.) 0.6 g ・ Alkyl diphenyl ether disulfonate sodium salt aqueous solution (Sandet BL, concentration: 40% by weight, Sanyo Chemical Industries ( 0.6g-Melamine compound 0.2g (Sumitec Resin M-3, active ingredient concentration 80% by weight, manufactured by Sumitomo Chemical Co., Ltd.)-20% silica gel aqueous dispersion 17g (Snowtex C (Nissan) (Manufactured by Chemical Industry Co., Ltd., average particle size: about 10 nm) 42.4 g of water

Next, the following coating solution was applied to one side of the above polyethylene terephthalate, and dried by heating (100
C. for 10 minutes) to form a hydrophilic layer having a dry weight of 5 g / m ² . (Hydrophilic layer coating liquid) 8 g of aqueous dispersion of titanium oxide 20% / polyvinyl alcohol 10% (titanium oxide (manufactured by Wako Pure Chemical Industries, Ltd., rutile type, average particle diameter 200 nm)) / PVA117 (manufactured by Kuraray Co., Ltd.) = 2/1 weight ratio)-8 g of methanol silica (Nissan Chemical: colloid consisting of a methanol solution containing 30% by weight of silica particles of 10 nm to 20 nm)-Sol-gel preparation liquid (the following composition) 4.7 g-Polyoxy Ethylene nonyl phenyl ether (Nonipol 100, manufactured by Sanyo Chemical Industries, Ltd.) 0.025 g ・ water 15 g ・ methanol 5 g

(Preparation of sol-gel preparation liquid) A liquid having the following composition was aged at room temperature for 1 hour to prepare a sol-gel preparation liquid. -8.5 g of tetraethoxysilane-1.8 g of methanol-15.0 g of water-0.015 g of phosphoric acid

(Formation of Thermosensitive Recording Layer) Then, the following thermosensitive recording layer coating solution was applied on the hydrophilic layer of the polyethylene terephthalate support and dried (at 100 ° C. for 2 minutes) to obtain a dry coating weight. A heat-sensitive recording layer of 0.6 g / m ² was formed to obtain each lithographic printing plate precursor. (Coating solution for heat-sensitive recording layer) Sulfonic acid-generating polymer compound in Table 1 (average molecular weight: about 30,000) 1.0 g Organic amine compound in Table 1 (amount described in Table 1) Infrared absorber A (described below) Structure) 0.2 g ・ Dye in which the counter ion of Victoria Pure Blue BOH is converted to 1-naphthalene-sulfonic acid 0.05 g ・ Fluorinated surfactant (MegaFac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0 .02 g ・ Methyl ethyl ketone 15 g ・ Propylene glycol monomethyl ether 4 g ・ Methyl alcohol 7 g ・ Dimethylformamide 1 g

[0146]

Embedded image

[0147]

[Table 1]

(Preparation of Lithographic Printing Plate) (Laser Exposure) A 40 W trend setter of CREO (40 W 8
Using a 30 nm semiconductor laser mounted plate setter), exposure was performed at an energy of 200 mJ / cm ² to record an image.

(Printing evaluation) Next, the lithographic printing plate precursor on which the image was recorded was attached to a cylinder of a printing machine SOR-M manufactured by Heidelberg without any processing, and after supplying dampening water, ink was supplied. Further, paper was supplied and printing was performed (fountain solution used: 1% by volume of EU-3 (manufactured by Fuji Photo Film Co., Ltd.) and 1% by volume of isopropanol.
Aqueous solution with 0% by volume added, ink used: GEOS-
G ink (manufactured by Dainippon Ink and Chemicals, Inc.) However, the heat-sensitive recording layer in the non-image area (exposed area) was promptly removed from the plate surface on the printing press, and there was no stain on the non-image area. As a result, 20,000 good prints having no problem in printing durability were obtained.

(Comparative Example 1) A lithographic printing plate precursor was obtained in the same manner as in Example 9 except that no organic amine compound was added to the heat-sensitive recording layer. Next, image recording was performed in the same manner as in Example 9, the image was mounted on a printing machine, and printing was performed.
Although the upper part of the heat-sensitive recording layer in the non-image part (exposed part) was quickly removed, the heat-sensitive recording layer near the hydrophilic layer interface was not completely removed, and the non-image part of the printed matter was stained. ,
Good prints were not obtained.

Example 14 Printing was carried out in the same manner as in Example 9 except that printing was performed using an emulsion ink having the following composition without using fountain solution. The heat-sensitive recording layer of the exposed portion) was promptly removed from the plate surface on the printing press, and 20,000 sheets of good printed matter without stain on the non-image portion were obtained.

(Emulsion Ink Composition 1) [Preparation of Emulsion Ink] (1) Preparation of Varnish (Hereinafter, parts are by weight.) Varnish A: Maleated petroleum resin (Neopolymer 120: Nippon Oil Co., Ltd.) 47 parts Spindle oil 53 parts Gel varnish B: Rosin-modified phenolic resin (Tamanol 354: manufactured by Arakawa Chemical Industries, Ltd.) 34 parts Machine oil 31 parts Spindle oil 31 parts Aluminum stearate 4 parts Varnish C: Gilsonite 25 parts Machine oil 75 parts

(2) Preparation of oil-based ink component: Carbon black 14 parts Calcium carbonate (Shirashina DD: manufactured by Shiraishi Industry Co., Ltd.) 5 parts Varnish A 27 parts Gel varnish B 7 parts Varnish C 11 parts Linseed oil 4 parts Machine Oil 6 parts Spindle oil 24 parts Cyanine blue 1 part (3) Preparation of hydrophilic component: Purified water 5 parts Ethylene glycol 25 parts Propylene glycol 35 parts Glycerin 34 parts Surfactants (polyoxyethylene alkyl phenyl ether, Liponox NCE: 1 part 100 parts by weight of the oil-based ink component (2) and 70 parts by weight of the hydrophilic component (3) were stirred and mixed to prepare a W / O emulsion ink.

(Example 15) A lithographic printing plate precursor was obtained in the same manner as in Example 9, except that an undercoated aluminum substrate formed as described below was used as a support. Next, when image recording and printing were performed in the same manner as in Example 9, the heat-sensitive recording layer in the non-image area (exposed area) was promptly removed from the printing plate on the printing press, and 20,000 non-image areas were printed. And a good printed matter free of dirt was obtained.

(Preparation of aluminum substrate) 0.01% by weight of copper and 0.1% by weight of titanium were added to 99.5% by weight of aluminum.
03% by weight, 0.3% by weight of iron, 0.1% by weight of silicon
Contain JISA1050 aluminum material thickness 0.2
The surface of a 4 mm rolled plate is grained using a 400-mesh aqueous suspension of pumicestone (manufactured by Kyoritsu Ceramics Co., Ltd.) and a rotating nylon brush (6,10-nylon), and then thoroughly washed with water. did. This was immersed in a 15% by weight aqueous sodium hydroxide solution (containing 4.5% by weight of aluminum), etched so that the amount of aluminum dissolved was 5 g / m ² , and washed with running water. Further, it is neutralized with 1% by weight nitric acid, and then, in a 0.7% by weight nitric acid aqueous solution (containing 0.5% by weight of aluminum), a rectangular wave having a voltage of 10.5 volts at the anode and a voltage of 9.3 volts at the cathode. Using an alternating waveform voltage (current ratio r = 0.90, current waveform described in Example of Japanese Patent Publication No. 58-5796), 160 clones /
Electrolytic surface-roughening treatment was performed with a dm ² anode charge. After washing with water, the substrate was immersed in a 10% by weight aqueous solution of sodium hydroxide at 35 ° C., etched so that the amount of aluminum dissolved was 1 g / m ² , and then washed with water. Next, it was immersed in a 30% by weight aqueous sulfuric acid solution at 50 ° C., desmutted, and washed with water. Further, a porous anodic oxide film forming treatment was performed in a 20% by weight aqueous sulfuric acid solution (containing 0.8% by weight of aluminum) at 35 ° C. using a direct current. That is, the current density is 13 A /
Electrolysis was performed at dm ² , and the anodic oxide film weight was adjusted to 2.7 g / m ² by adjusting the electrolysis time. After washing the support with water, 7
It was immersed in a 0.2% by weight aqueous solution of sodium silicate at 0 ° C. for 30 seconds, washed with water and dried. The aluminum substrate obtained as described above had a reflection density of 0.30 measured with a Macbeth RD920 reflection densitometer and a center line average roughness Ra.
Was 0.58 μm.

(Preparation of Undercoat Layer) The following undercoat layer coating solution was coated on the aluminum support and dried by heating (1).
00 ° C, 1 minute) to obtain a dry coating amount of 0.05 g
/ M ² undercoat layer. (Coating solution for undercoat layer) ・ Arabic gum 1g ・ Water 1000g

Example 16 A lithographic printing plate precursor was obtained in the same manner as in Example 9 except that the formation of the hydrophilic layer was changed as follows. Next, when image recording and printing were performed in the same manner as in Example 9, the heat-sensitive recording layer in the non-image portion (exposed portion) was promptly removed from the printing plate on a printing press.
20,000 sheets of good printed matter without stain on the non-image area were obtained. (Formation of hydrophilic layer) On the antistatic layer, a batch type sputtering film forming apparatus (CFS-10-EP7 manufactured by Shibaura Eletech Co., Ltd.)
Using 0), a silicon oxide film was formed to a thickness of 20 nm under the following conditions to form a hydrophilic layer. Target material: silicon oxide Atmosphere: argon Film formation pressure: 5 mtorr Power: RF1 kW (power supply is JRF- manufactured by JEOL Ltd.)
3000)

Before the film formation, the surface of the antistatic layer was glow-treated under the following conditions. Atmosphere: argon Processing pressure: 5.0 mtorr Power: Rf3 kW (Power supply is JRF manufactured by JEOL Ltd.
-3000) Time: 2.5 minutes

[0159]

According to the heat-sensitive lithographic printing plate precursor of the present invention, an image can be recorded with high sensitivity by heating or heat generated by light-to-heat conversion. It is possible to provide a lithographic printing plate in which the generation of a residual film in a portion is suppressed, and a good printed matter without stain is obtained.
Further, according to the plate making / printing method using the heat-sensitive lithographic printing plate, the lithographic printing plate after recording does not require a special developing process, and can perform high-quality printing.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AB03 AC08 AD03 BH03 CB41 CC11 CC20 FA10 2H084 AA14 AA38 BB02 BB13 CC05 CC12 2H096 AA06 BA20 EA04 EA23 2H114 AA04 AA14 AA22 AA24 BA01 FA10 DA32 DA52 DA53

Claims (4)

[Claims] 1. A method according to claim 1, wherein (A) is provided on a support having a hydrophilic surface.
A lithographic printing plate precursor comprising a heat-sensitive recording layer containing a polymer compound having a functional group capable of generating sulfonic acid upon heating and (B) an organic amine compound. 2. The functional group which generates sulfonic acid by heating is at least one of functional groups represented by the general formula (1), the general formula (2) or the general formula (3). The lithographic printing plate precursor as claimed in claim 1. General formula (1) -L-SO ₂ -OR ¹ General formula (2) -L-SO ₂ -SO ₂ -R ² (In the formula, L represents a polyvalent organic group comprising a nonmetallic atom necessary for connecting the functional group represented by the general formula (1), (2) or (3) to the polymer skeleton. , R ¹ represents an aryl group, an alkyl group or a cyclic imide group,
R ^2, R ³ represents an aryl group or an alkyl group, R ⁴ represents an aryl group, an alkyl group or -SO ₂ -R ^5, R ⁵ represents an aryl group or an alkyl group. ) 3. The lithographic printing plate precursor according to claim 1, wherein the heat-sensitive recording layer further contains (C) a light-to-heat conversion material. 4. The heat-sensitive lithographic printing plate precursor according to claim 3 is image-exposed by a laser beam and is directly mounted on a printing machine for printing, or is mounted on the printing machine, and then is irradiated with the laser beam on the printing machine. A method of making and printing a heat-sensitive lithographic printing plate precursor characterized by exposing and printing as it is.