JP2002019319A - Method for lithographic printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for lithographic printing capable of simply and stably obtaining many printed products without using a dampening water by applying to a thermosensitive lithographic printing plate original plate capable of being platemade by simple on-press treating. SOLUTION: The method for lithographic printing comprises the steps of recording an image on the thermosensitive lithographic printing plate original plate having a recording layer containing a polymer compound having a functional group for generating a sulfonic acid represented by the formula (1), (2) or (3) (wherein L is a polyvalent organic group made of a nonmetallic atom necessary to couple the functional group to a polymer skeleton) by heating and a photothermal conversion substance as desired on a support having a hydrophilic surface, and then printing by using an emulsion ink.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing method using a heat-sensitive lithographic printing plate. More specifically,
An image can be recorded by scanning exposure based on a digital signal, and a lithographic printing plate precursor that can be made by simple on-press processing can be stably obtained in good quality without using dampening solution. It relates to a lithographic printing method.

[0002]

2. Description of the Related Art In general, a lithographic printing plate comprises an oleophilic image area receiving ink during a printing process and a hydrophilic non-image area receiving fountain solution. Such lithographic printing utilizes the property that water and oil-based ink repel each other, so that a lipophilic image area is an ink receiving area and a hydrophilic non-image area is a dampening water receiving area (ink non-receiving area). This is a method in which the difference in the adhesion of ink is caused on the plate surface, the ink is applied only to the image area, and then the ink is transferred to a printing material such as paper and printed. PS plates in which a lipophilic photosensitive resin layer is provided on a support are widely used. As the plate making method, usually, a lithographic printing plate precursor is exposed through an original image such as a lith film, and then the photosensitive layer is left in the image area, and the non-image area is dissolved and removed with a developing solution to remove the aluminum substrate surface. Is applied, and a desired printing plate is obtained by this method.

In the plate making process of the conventional PS plate, a step of dissolving and removing the non-image portion with a developing solution corresponding to the photosensitive layer after exposure is necessary. One of the problems is to eliminate or simplify the method. In particular, in recent years, the disposal of waste liquid discharged from 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 recording layer is used which enables the non-image portion of the printing plate precursor to be removed in a normal printing process. And a method for 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 recording layer soluble in a fountain solution or an ink solvent, and a method of mechanically removing the image recording layer 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, the image recording layer is not fixed even after exposure, so that, for example, the original plate is completely shielded from light until it is mounted on a printing press. Alternatively, it was necessary to take a time-consuming method such as preservation under constant temperature conditions.

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 methods 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 high-density exposure, a large amount of light energy is intensively irradiated onto the exposed area in a very short time, the light energy is efficiently converted to heat energy, and the heat causes a chemical change, phase change, morphological or structural change. A thermal change such as a change 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. Usually, a recording method using heat generated by such high power density exposure is called heat mode recording, and converting 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 fixing of an image after exposure is not essential. Therefore, for example, using an image recording layer that is insolubilized or solubilized by heat mode exposure, if the plate making process of removing the exposed image recording layer imagewise to make a printing plate by an on-press development method, development, that is, Removal of the non-image areas allows for a printing system in which the image is not affected for some time after image exposure, even if exposed to room ambient light. 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.

[0008] As one of the preferred methods for producing a lithographic printing plate based on heat mode recording, a hydrophobic image recording layer is provided on a hydrophilic substrate, and is subjected to heat mode exposure in the form of an image. A method has been proposed in which the dispersibility is changed and, if necessary, the non-image areas are removed by wet development. As an example of such an original plate, for example, Japanese Patent Publication No. 46-279
No. 19 discloses an original plate in which a recording layer having a so-called positive action in which solubility is improved by heat, specifically a recording layer having a specific composition such as a saccharide or a melamine formaldehyde resin, is provided on a hydrophilic support. A method of obtaining a printing plate by performing heat mode recording is disclosed.

However, none of the disclosed recording layers has sufficient heat sensitivity, and thus has insufficient sensitivity to heat mode scanning exposure. In addition, the hydrophobic / hydrophilic discrimination before and after exposure, that is, a small change in solubility was also a practical problem. If discrimination is poor, it is practically difficult to make plate making by the on-press development system.

[0010] WO 98/40212 discloses that
A lithographic printing plate precursor is disclosed, in which a hydrophilic layer composed of a transition metal oxide colloid is provided on a substrate coated with an ink-receiving layer containing a photothermal conversion agent, and can be made without development. I have. This is because the hydrophilic layer composed of the transition metal oxide colloid is ablated (scattered) and removed by the heat generated by the photothermal conversion agent in the exposed portion. However, since the photothermal conversion agent exists on the substrate side, the heat converted from the absorbed light diverges to the substrate side,
Therefore, it cannot be effectively used for ablation of a hydrophilic layer made of a colloid, and has a disadvantage of low sensitivity. In addition, JP-A-55-105560 and WO
No. 94/18005 discloses a lithographic printing plate precursor in which a hydrophilic layer to be ablated in the same manner as described above is provided on a substrate coated with a lipophilic light-to-heat conversion layer. All were low sensitivity for the same reason as above.

[0011] WO 99/19143 and WO 99/19143
JP 19144 discloses a lithographic printing plate precursor in which a photothermal conversion agent is added to a hydrophilic layer composed of an upper colloid for the purpose of improving the disadvantage of low sensitivity of the heat-sensitive lithographic printing plate precursor to be ablated. I have. According to this configuration, although the sensitivity is certainly improved, since the photothermal conversion agent is added to the hydrophilic layer, the film quality of the hydrophilic layer is reduced and the printing durability is reduced, and in some cases, the hydrophilicity of the hydrophilic layer is impaired. This causes another problem that the non-image area is contaminated with ink during printing.

Further, in the heat-sensitive lithographic printing plate precursor having such a configuration, since the hydrophilic layer is removed by ablation, there is a concern that the laser exposure device and the light source may be contaminated by fragments of the scattered hydrophilic layer. These devices need to be equipped with an ablation waste trapping device, which complicates the device and makes it difficult to completely remove contaminants even with the trapping device. Was needed.

Plate making using heat mode image recording
The printing method has the advantage that the printing plate can be made directly without going through the process of passing through the film from under the plate, so that the plate can be made on-press and the wet development operation can be omitted. And has the above-mentioned disadvantages.

On the other hand, as a method of simple lithographic printing without using dampening water, Japanese Patent Publication No. 49-26844 and Japanese Patent Publication No. Sho 4
9-27124, 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
No. 6305 proposes lithographic printing using emulsion ink. These emulsion inks are emulsions of water-containing inks, and since water and ink are separated on the plate surface, water can be supplied from the ink side. It is a feature.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to solve the drawbacks of the conventional heat mode plate making method using laser exposure, and furthermore, to provide a heat-sensitive lithographic printing plate precursor which can be made by simple on-press processing. An object of the present invention is to provide a lithographic printing method capable of easily obtaining a large number of stable prints without using dampening water.

[0016]

As a result of the study, the present inventors have found that a recording layer contains a polymer compound having a functional group capable of generating sulfonic acid by heating, and further, by using an emulsion ink in printing. It has been found that the recording layer in the non-image area (sulfonic acid generating area) can be efficiently removed on a printing press, and the present invention has been completed.

That is, the lithographic printing method of the present invention provides a heat-sensitive lithographic printing plate comprising a support having a hydrophilic surface and a recording layer containing a polymer compound having a functional group capable of generating sulfonic acid upon heating. After the image is recorded on the master plate, water and / or a hydrophilic component containing a polyhydric alcohol as a main component are added to the oil-based ink component, and printing is performed using an emulsion ink obtained by emulsification. . Here, the functional group that generates sulfonic acid by heating is
In a preferred embodiment, at least one selected from functional groups represented by the following general formulas (1), (2) and (3). General formula (1) -L-SO ₂ -OR ¹ General formula (2) -L-SO ₂ -SO ₂ -R ²

[0018]

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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. In the lithographic printing method of the present invention, the recording layer further contains a light-to-heat conversion material, thereby enabling image recording by laser light. That is, by irradiation of laser light,
The photothermal conversion material in the exposed area generates heat, and the recording layer can be removed by sulfonic acid generated in the exposed area after image exposure. By supplying the emulsion ink to the printing plate during printing, hydrophilicity mainly contained in the emulsion ink is obtained. The recording layer in the exposed area is removed by the action of the hydrophilic component to form a non-image area. The non-image area receives the aqueous component, and the recording layer surface in the image area becomes an ink-philic layer, and printing can be performed. Become like

According to the lithographic printing method of the present invention, the recording layer of the heat-sensitive lithographic printing plate precursor to which the method of the present invention is applied is such that the exposed portion of the recording layer is highly hydrophilic by the action of an acid generated by heating. In addition, since an image recording mechanism for solubilizing or dispersing is adopted, the sensitivity is excellent, and there is no scattering of the recording layer due to ablation. Therefore, there is no concern that the optical system is contaminated by the recording layer. Further, the solubilized / dispersible recording layer is easily and completely removed even by a slight hydrophilic component, so that the recording layer does not remain in the non-image portion, and therefore, the non-image portion has no stain. It is possible to easily obtain a printed matter of an image excellent in discrimination.

[0021]

Embodiments of the present invention will be described below in detail. The heat-sensitive lithographic printing plate precursor to which the printing method of the present invention is applied has a recording layer containing a polymer compound having a functional group that generates sulfonic acid by heating, and the heat generated by infrared laser irradiation. Alternatively, sulfonic acid is generated in the exposed (heated) area of the recording layer by heating with a thermal head or the like, and this part is highly hydrophilized, and an emulsion ink, which is a fluid used at the time of printing, is particularly described in detail below. It is characterized in that it is easily dissolved or dispersed and removed by the hydrophilic component, and a good positive image can be obtained without a developing step.

[Emulsion Ink] The emulsion ink used in the present invention is an emulsion ink obtained by adding a hydrophilic component to an oil-based ink component and emulsifying it.
ter in oil) type or O / W (oil in water) type. Further, the emulsion ink used in the present invention, in the ink fountain of the printing machine when applied to printing and printing in an ink can, maintain a stable emulsified state,
At the time of printing, the inking system (ink supply system) is transferred while receiving the share, and when the ink reaches the inking roller, the emulsification is destroyed 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, and the oil-based ink component is prevented from adhering, while 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 of 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 ratio of the oil-based ink component to 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 oil-based ink component. Preferably, 20 to
100 parts by weight. As the oil-based 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 of the present invention, water and / or polyhydric alcohols can be used. Examples of polyhydric alcohols include glycerin, diglycerin, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, sorbitol, butanediol, pentanediol, and the like. Among them, glycerin, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol can be preferably used. The polyhydric alcohol may be used alone, or two or more kinds may be used as a mixture, and may be used as a mixture with water. The preferred content of the polyhydric alcohol in the hydrophilic component of the present invention is 30 to 100.
%, More preferably 50 to 100% by weight. As the hydrophilic component of the present invention, in addition to the above, additives can be used 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, amino alcohols such as monoethanolamine and diethanolamine, known nonionic, anionic, cationic and betaine surfactants, glycolic acid, lactic acid, citric acid, etc. Oxycarboxylic acids, polyvinylpyrrolidone, polyacrylic acid, gum arabic,
Examples include hydrophilic polymers such as carboxymethylcellulose, and inorganic acids and salts such as phosphoric acid, silicic acid, nitric acid, and salts thereof.

[Thermosensitive lithographic printing plate precursor] Next, the lithographic printing plate precursor usable in the present invention will be described. The heat-sensitive lithographic printing plate precursor according to the present invention comprises a polymer having a functional group capable of generating sulfonic acid by heating described in JP-A-10-282672 (hereinafter referred to as sulfone) on a support having a hydrophilic surface. Recording layer containing an acid-generating polymer compound).

1. Recording Layer Components constituting the recording layer of the lithographic printing plate precursor will be described below. [1-a. Polymer Compound Having Functional Group that Generates Sulfonic Acid by Heating (Sulfonic Acid Generating Polymer Compound)] The sulfonic acid generating polymer compound used in the recording layer of the present invention generates sulfonic acid in a molecule by heating. There is no particular limitation as long as it has a functional group, and it may have a functional group that generates sulfonic acid in the main chain or in a side chain. Equation (1),
A polymer compound having a functional group represented by (2) or (3) in a 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, benzofuryl groups, thioxanthone groups, thioxanthone groups, carbazole groups, and the like having 3 to 20 carbon atoms and 1 to 5 heteroatoms. Things are used. When R ^{1 to} R ⁵ represent an alkyl group or a substituted alkyl group, examples of the alkyl group include linear, branched or cyclic carbon atoms such as methyl, ethyl, isopropyl, t-butyl, and cyclohexyl. 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 a methoxy group, an ethoxy group and the like, an alkoxy group having 1 to 10 carbon atoms, a fluorine atom, and a chlorine 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, 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, examples of the cyclic imide include those having 4 to 20 carbon atoms such as succinimide, phthalic imide, cyclohexanedicarboxylic imide and norbornenedicarboxylic imide. .

In the above 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) from the viewpoint of achieving both sensitivity and stability over time. Is more preferred.

[0032]

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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, a quinolyl group in which a benzene ring is fused, a benzofuryl group, a thioxanthone group, and a carbazole group. 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 substituted aryl groups, alkyl groups such as a methyl group and 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 in terms 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 chemical shift of secondary methine hydrogen in proton NMR appears in a lower magnetic field than 4.4 ppm in deuterated chloroform is more preferable, and a compound which appears in a lower 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 a structure of —CHR ⁶ R ^7, a structure represented by the following formula is particularly preferable.

[0036]

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

The 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.

[0039]

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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, and a carbon atom having 6 carbon atoms such as a phenyl group and a naphthyl 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 monomers suitably used for synthesizing the high molecular compound having a functional group represented by the general formula (1) to (3) in the side chain according to the present invention [monomer (1) to monomer (56)] Is shown below.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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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 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 include tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, and 2- (hydroxyphenylcarbonyloxy) ethyl acrylate.

Specific examples of the methacrylates include methyl methacrylate, ethyl methacrylate,
(N- or i-) propyl methacrylate, (n-, i
-, Sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate,
Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate,
Glycidyl methacrylate, benzyl methacrylate,
Methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, 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 the 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, particularly preferably used are acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid esters of C20 or less. Acid and acrylonitrile. The proportion of the monomer having a functional group represented by the general formulas (1) to (3) used in the synthesis of the copolymer is preferably from 5 to 99% by weight, more preferably from 10 to 95% by weight.
% By weight.

Hereinafter, specific examples of the high molecular compound having a 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.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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The weight average molecular weight of the high molecular compound having at least one of the functional groups represented by the general formulas (1) to (3) used in the present invention 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 random polymers.

Examples of the solvent used for synthesizing the sulfonic acid generating polymer compound used in the present invention include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, 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 when 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 used in the present invention may be used alone or in combination. These sulfonic acid-generating polymer compounds can be used in a proportion of 50 to 99% by weight, preferably 70 to 95% by weight of the total solids of the recording layer. If the amount is less than 50% by weight, the printed image becomes unclear. If the addition amount exceeds 95% by weight, image formation by laser exposure cannot be sufficiently performed.

Further, the sulfonic acid-generating polymer compound of the present invention is used together with the acid generator described in Japanese Patent Application No. 9-10755 and the base generator described in Japanese Patent Application No. 9-26877. , Can also be used in combination.

[1-b. Photothermal conversion material] Recording layer of heat-sensitive lithographic printing plate precursor to which lithographic printing method of the present invention can be applied,
Alternatively, by including a photothermal conversion substance in a layer adjacent thereto, image recording by exposure to laser light or the like becomes possible. This is because the light-to-heat conversion material contains the light-to-heat conversion material to generate heat in an exposed portion such as an infrared laser, and the heat is used to record an image. As the photothermal conversion substance, any substance can be used as long as it can absorb light such as ultraviolet rays, visible light rays, infrared rays, and white light rays and can convert it into heat, but a substance that generates heat by absorbing the wavelength of light used for exposure is selected. It is preferable to use them. Specifically, for example, carbon black, carbon graphite, pigment,
Examples include phthalocyanine pigments, iron powder, graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, and chromium sulfide. Particularly preferred is a wavelength of 760 nm to 12 nm.
Dyes, pigments, or metals that effectively absorb 00 nm infrared rays.

As the dye, commercially available dyes and known dyes described in literatures (for example, "Dye Handbook" edited by The Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, and metal thiolate complexes. Preferred dyes include, for example, 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, naphthoquinone dyes described in JP-A-60-63744 and the like, squarylium 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 used. 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
If it is less than m, it is not preferable in terms of stability of the dispersion in the coating solution of the photosensitive layer, and if it exceeds 10 μm, it is not preferable in terms of uniformity of the image recording layer. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. As the disperser, an ultrasonic disperser,
Sand mills, attritors, pearl mills, super mills, ball mills, impellers, dispersers, KD mills, colloid mills, dynatrons, three-roll mills, pressure kneaders and the like can be mentioned. 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 recording layer, particularly preferably 1 to 20% by weight for dyes, and particularly preferably 1 to 20% by weight for pigments. Preferably, it can be used at a ratio of 5 to 25% by weight. If the amount of the pigment or dye is less than 0.01% by weight, the sensitivity is lowered, and if it exceeds 50% by weight, the non-image area is stained during printing.

[1-c. Other Components] In the recording layer of the present invention, in addition to the above two components, various compounds may be added as necessary. 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 BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientation above) Chemical Industry Co., Ltd.)
Victoria Pure Blue, Crystal Violet (C
I42555), 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. It is preferable to add these dyes because they fade after laser exposure and the image area and the non-image area are easily distinguished. The addition amount is 0.01 to 0.01% of the total solid content of the recording layer.
10% by weight.

Further, the recording layer in the present invention is disclosed in Japanese Patent Application Laid-Open No. 62-2517 in order to increase the stability under printing conditions.
Non-ionic surfactants described in JP-A-59-121 and JP-A-3-208514.
Further, an amphoteric surfactant as described in JP-A No. 0444/1992 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 alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N- Betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the recording layer is preferably from 0.05 to 15% by weight, more preferably from 0.1 to 5% by weight.

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

In addition to these, epoxy compounds, vinyl ethers, phenol compounds having a hydroxymethyl group described in JP-A-8-276558, phenol compounds having an alkoxymethyl group, and the like 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, 0.5~3.0g / m} 2 is more preferable. 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 recording layer in the present invention may have a surfactant for improving coating properties, for example, JP-A-62-17095.
No. 0, fluorinated surfactants 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 recording layer.

2. Support having hydrophilic surface The lithographic printing plate precursor according to the present invention comprises the recording layer having a hydrophobic (lipophilic) surface provided on a support having a hydrophilic surface. The support having a hydrophilic surface used in the present invention includes a support having a hydrophilic surface, a support having a hydrophilic surface, or a support having a hydrophilic layer on the support. Etc. are included.

The support used in the lithographic printing plate precursor according to the present invention is a dimensionally stable plate-like material, for example, paper or plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated. 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.

[2-a. Support Substrate (Aluminum Plate)] The support used in the lithographic printing plate precursor according to the invention is preferably a polyester film or an aluminum plate. Among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing 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 0.1 mm.
4 mm, particularly preferably 0.2 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 aluminum plate surface is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening 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 an electrolyte used for anodizing the aluminum plate, various electrolytes forming 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 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.

[2-b. Hydrophilic treatment of aluminum plate]
By subjecting the aluminum surface subjected to the anodic oxidation treatment to the hydrophilic treatment as described above, a support having the surface subjected to the hydrophilic treatment can be obtained. The hydrophilizing treatment used here is disclosed in U.S. Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. Such an alkali metal silicate (for example, sodium silicate aqueous solution) method is available. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated.
In addition, potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat.
No. 868, No. 4,153,461, No. 4,68
For example, a method of treating with polyvinyl phosphonic acid as disclosed in US Pat. No. 9,272 is used.

[2-c. Support Substrate (Nonconductive Support)] When a nonconductive substrate such as polyester is used for the substrate of the present invention, it is preferable to provide an antistatic layer on the recording layer side, on the opposite side, or on both sides of the substrate. preferable. As the antistatic layer, a polymer layer in which metal oxide fine particles and a matting agent are dispersed can be used.

The materials of the metal oxide particles used for the antistatic layer include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ ,
Examples include In ₂ O ₃ , MgO, BaO, MoO ₃ , V ₂ O ₅ , composite oxides thereof, and / or metal oxides further containing different atoms. These may be used alone or as a mixture. As metal oxides, ZnO, SnO ₂ , Al ₂ O ₃ , Ti
O ₂ , In ₂ O ₃ and MgO are preferred. Examples of containing a small amount of heteroatoms include Al, In, and Sn with respect to ZnO.
Sb relative O _2, Nb or a halogen element, an In ₂ O
Examples thereof include those obtained by doping ₃ or more with 30 mol% or less, preferably 10 mol% or less of different atoms such as Sn. The metal oxide particles are present in the antistatic layer
Preferably, it is contained in the range of 90% by weight. The metal oxide particles have an average particle diameter of 0.001 to 0.5.
A range of 5 μm is preferred. Here, the average particle size is
The value includes 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 diameter of 0.5 to 20 μm, more preferably an average particle diameter 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 the range of 1 to 30% by weight. Examples of the polymer that can be used in the antistatic layer include 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 a range of 10 to 90% by weight.

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 to 0.6 mm, preferably about 0.05 mm to 0.6 mm.
1 mm to 0.4 mm, particularly preferably 0.15 mm to
0.3 mm.

[2-d, hydrophilic layer] As a method of making the surface of the support hydrophilic, there is a method of providing a hydrophilic layer on the support, in addition to the method of hydrophilizing the surface of the support. .
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 metal compound having a hydrophilic surface or an inorganic hydrophilic matrix obtained by a sol-gel conversion comprising a condensation reaction.

[2-d-1, Organic hydrophilic matrix]
As a crosslinking reaction used for forming an organic hydrophilic matrix of the hydrophilic layer of the present invention, formation of a covalent bond by heat or light or formation of an ionic bond by a polyvalent metal salt is possible. 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, -NH 2, -NH -,} - CO-NH 2, -CO-N
H-, -O-CO-NH-, -NH-CO-NH-,-
CO-OH, -CO-O-, -CO-O-, -CS-O
H, -CO-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]

Embedded image

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 use amount thereof 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. .

[2-d-2, inorganic hydrophilic matrix]
The system capable of sol-gel conversion that can be used for the formation of the inorganic hydrophilic matrix of the hydrophilic layer of the present invention is such that a bonding group derived from a polyvalent element forms a network structure through an oxygen atom, At the same time, the polyvalent metal also has an unbonded hydroxyl group or an alkoxy group, and is a polymer having a resin-like structure in which these are mixed. As the bonding proceeds, the network-like resin structure becomes stronger. Further, a part of the hydroxyl group is bonded to the solid fine particles to modify the surface of the solid fine particles, and also has a function of changing the degree of hydrophilicity. The polyvalent bonding element of the compound having a hydroxyl group or an alkoxy group that performs sol-gel conversion is aluminum, silicon,
Titanium and zirconium, which can be used in the present invention, are described below. The sol-gel conversion system based on a siloxane bond which is most preferably used will be described below. The sol-gel conversion using aluminum, titanium and zirconium can be carried out 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 drying, aging, the hydrolytic condensation of silanol groups proceeds to form a siloxane skeleton structure, and gelation proceeds to form. In addition, in the matrix of this gel structure, for the purpose of improving physical properties such as film strength and flexibility, improving coatability, 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 a partially hydrolyzed oligomer, or may be a mixed composition of a silane compound and its oligomer.

[0104]

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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, a sulfo group, a cyano group, an epoxy group, -OR ^a group (R ^a is a methyl group, an ethyl group, a propyl group, butyl group, 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 ^b group (R ^b is
Wherein represents a R ^a same content as), - COOR ^b group, -C
OR ^b group, -N (R ^c ) (R ^c ) group (R ^c represents a hydrogen atom or the same content as R ^a, and may be the same or different), -NHCONHR ^b group, -NHCOOR ^b Group,
—Si (R ^b ) ₃ groups, —CONHR ^c groups, and —NHCOR ^b groups. (These substituents may be substituted plurally in the alkyl group),

A linear or branched alkenyl group having 2 to 12 carbon atoms which may be substituted (for example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, dodecenyl group and the like) And the groups substituted with these groups include those having the same contents as the groups substituted with the above-mentioned alkyl groups), having 7-14 carbon atoms.
An aralkyl group which may be substituted (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 Or an aryl group having 6 to 12 carbon atoms which may be substituted (for example,
A phenyl group or a naphthyl group, 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 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 for 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 aforementioned 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 aforementioned —OR ¹ group can be mentioned). More preferably, the total number of carbon atoms of R ³ and R ⁴ is 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 and the like. 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 rate of polycondensation tends to increase. However, when a basic catalyst having a high concentration is used, a precipitate may be formed in the sol solution. Therefore, the degree of the basic catalyst is preferably 1 N (concentration conversion in an aqueous solution) or less.

The type of the acidic catalyst or the basic catalyst is not particularly limited, and 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 sol-gel method, refer to Saio Sakuhana, "Science of Sol-Gel Method", published by Agne Shofusha Co., Ltd.
(1988), Takashi Hirashima, "Technology for preparing functional thin films by the latest sol-gel method", General Technology Center (published) (1992)
It is described in detail in written documents such as year.

[2-d-3, Additive of Organic or Inorganic Hydrophilic Matrix] In the hydrophilic layer of the organic or inorganic hydrophilic matrix of the present invention, in addition to the above, control of the degree of hydrophilicity, Various objective compounds such as an improvement in the physical strength of the hydrophilic layer, an improvement in the dispersibility of the compositions constituting the layer, an improvement in applicability and an improvement in printability can be added.
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 and for strengthening the film. 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”, edited by Yoshitoshi Kaga and Akira Hayashi, Vol. 3, CMC Corporation (1991).

The alumina which can be preferably used is an alumina hydrate (boehmite type) 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 diameter 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 dissolved or dispersed in a suitable solvent such as water or a polar solvent such as methanol or ethanol alone or in a mixed solvent thereof. Is applied, dried and cured on the light-to-heat 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, unfavorable results such as a decrease in the retention of the hydrophilic component of the emulsion ink and a decrease in the film strength are given. Give the result.

[2-d-4, Thin Film of Metal or Metal Compound Having Hydrophilic Surface] As the thin film of metal or metal compound having a hydrophilic surface used in the hydrophilic layer of the present invention, a thin film having surface hydrophilicity is used. If it is not particularly limited, for example, aluminum, chromium, manganese, tin, tellurium,
Titanium, iron, cobalt, nickel, indium, bismuth, zirconium, zinc, lead, vanadium, silicon,
Metals and alloys of copper and silver, and metal oxides, metal carbides, metal nitrides, metal borides, metal sulfides, and metal halides corresponding to the respective metals. 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. For this reason, indium tin oxide, tungsten oxide, manganese oxide,
A thin film of a metal oxide such as 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 for 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, a pure metal or a target metal compound can be used as a target material. When a pure metal is used, oxygen or nitrogen is introduced as a reactive gas. 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-described method, in order to improve the adhesion to the heat-sensitive layer, degassing of the substrate by heating the substrate or vacuum glow treatment on the surface of the heat-sensitive layer may be performed. 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 it is too thin, the retention of dampening water will decrease,
An undesired result such as a decrease in film strength is given. If the thickness is too large, it takes a long time to form a thin film, which is not preferable in terms of production suitability.

[0130] 3. Other Layers of Lithographic Printing Plate Precursor (Undercoat Layer) The lithographic printing plate precursor of the present invention comprises a recording layer of the present invention provided on a support having a hydrophilic surface. A coating layer can be provided. 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 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 an aluminum plate and dried, and a method in which water or methanol, ethanol, methyl ethyl ketone, or the like is used. A method in which an aluminum plate is immersed in a solution in which the above organic compound is dissolved in an organic solvent or a mixed solvent thereof to adsorb the above compound by immersing the aluminum plate, and then washed and dried with water or the like to provide an organic undercoat layer. . In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied by various methods. 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 5 ° C.
0 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The solution used for this is ammonia,
The pH can be adjusted to a range of 1 to 12 with a basic substance such as triethylamine or potassium hydroxide or an acidic substance such as hydrochloric acid or phosphoric acid. The coating amount of the undercoat layer is 2 to
200 mg / m ² is suitable, preferably 5 to 100 mg / m ^2.
mg / m ² .

(Overcoat Layer) In the lithographic printing plate precursor according to the invention, an overcoat layer can be formed on the recording layer as required. The overcoat layer used in the present invention is a layer that is easily removed before printing or at the time of printing, and contains a polymer compound capable of forming a film. Further, the overcoat layer of the present invention may have a light-to-heat conversion function. In this case, a light-to-heat conversion substance can be contained in the overcoat layer.

As a method for providing an overcoat layer,
The coating solution containing the overcoat layer composition may be directly applied and dried on the hydrophilic layer, or the coating solution may be applied on another support and dried, and then applied on the hydrophilic layer. May be provided by pressure bonding (lamination), and the support may be peeled off and provided. The polymer used for the overcoat layer is
It is a known organic or inorganic resin, and a film formed by coating and drying has a film-forming ability. Further, at the time of printing, when it is removed with an emulsion ink, the hydrophilic component of the emulsion ink, particularly water as well as/
Alternatively, it is preferable that the compound be easily dissolved or dispersed in polyhydric alcohols. As such a polymer, it is preferable to use a hydrophilic polymer. Specific examples of such a hydrophilic polymer include polyvinyl acetic acid (having a hydrolysis rate of 65% or more) and polyacryl. Acid and its alkali metal salt or amine salt, polyacrylic acid copolymer and its alkali metal salt or amine salt, polymethacrylic acid and its alkali metal salt or amine salt, polymethacrylic acid copolymer and its alkali metal salt or amine salt,
Polyacrylamide and its copolymer, polyhydroxyethyl acrylate, polyvinylpyrrolidone and its copolymer, polyvinyl methyl ether, polyvinyl methyl ether / maleic anhydride copolymer, poly-2-acrylamide-2-methyl-1-propanesulfone Acid and its alkali metal salt or amine salt, poly-2-acrylamido-2-methyl-1-propanesulfonic acid copolymer and its alkali metal salt or amine salt, gum arabic,
Cellulose derivatives (eg, carboxymethyl cellulose,
(Carboxyethyl cellulose, methyl cellulose, etc.) and modified products thereof, white dextrin, pullulan, enzymatically decomposed etherified dextrin, and the like.
Further, according to the purpose, two or more of these resins can be used in combination.

By adding a light-to-heat conversion substance to the overcoat layer, the sensitivity in heat-sensitive recording can be improved. The photothermal conversion material that can be used here is a photothermal conversion material that can absorb laser light used for image recording and convert it into heat, and various pigments and dyes can be used. When removing with an emulsion ink, it is preferred that it be easily dissolved or dispersed in a hydrophilic component of the emulsion ink, particularly, water and / or a polyhydric alcohol. When an infrared laser is used as the laser light source that is a recording light source, various organic and inorganic materials that absorb light having a laser wavelength used for image recording, such as an infrared absorbing dye, an infrared absorbing pigment, an infrared absorbing metal, and an infrared absorbing metal oxide. Material is available.

[Lithographic printing method] The lithographic printing method of the present invention comprises a lithographic printing plate which is mounted on a printing machine without going through an image recording step of recording an image on a heat-sensitive lithographic printing plate precursor and thereafter a special wet developing step. And printing using an emulsion ink. 1. Image recording step The image recording step of the heat-sensitive lithographic printing plate precursor in the lithographic printing method of the present invention will be described. As an image recording method, for example, a method of directly performing image-wise thermal recording with a thermal recording head or the like, or a direct image-wise exposure with a solid-state laser or semiconductor laser that emits infrared light having a wavelength of 700 to 1200 nm, and photothermal conversion Method of performing thermal recording by using heat, and method of performing thermal recording by using photothermal conversion by irradiating high-intensity flash light such as a xenon discharge lamp or exposure to an infrared lamp through a document such as a squirrel film Can be used. In the present invention, from the viewpoint of being suitable for scanning exposure based on digital signals, it is particularly preferable to use laser light as the writing means, and as an image recording mechanism using laser light, the energy of the irradiated laser light is The light-to-heat conversion material contained in the recording layer of the heat-sensitive lithographic printing plate precursor is absorbed and converted into thermal energy, and the heat generated due to this heats the exposed portion imagewise to record an image. You.

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. A gas laser such as a carbon dioxide laser, a solid laser such as a YAG laser, and a semiconductor laser can be used. Usually the output is 5
A laser of 0 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. Also, Japanese Patent Application Laid-Open No. 6-186750
Exposure can also be performed by using an imaging device described in Japanese Patent Application Laid-Open No. H10-26095. 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 heat treatment conditions are 80
C. to 150.degree. C. for 10 seconds to 5 minutes.

2. Printing stepThe heat-sensitive lithographic printing plate precursor used in the printing method of the present invention is:
The printing plate precursor on which the image has been recorded can be mounted on the printing press without further processing. The printing plate precursor on which the image is recorded is mounted on a printing machine without going through a development process such as a wet development process, and printing is started using the emulsion ink. The recording layer in the exposed area is dissolved or dispersed and removed by the hydrophilic component of the emulsion ink supplied on the plate, and the hydrophilic surface is exposed in that area. The unexposed area is free of sulfonic acid and is present as it is, forming an ink receiving area having a lipophilic surface. By printing with the emulsion ink, the hydrophilic component adheres to the exposed hydrophilic surface (heating area),
The oil-based ink component is deposited on the recording layer in the non-exposed area (non-heated area) and printing is started.

[0138]

[Examples 1 to 10]

(Preparation of Aluminum Substrate) 99.5% by weight of aluminum, 0.01% by weight of copper, 0.03% by weight of titanium,
JI containing 0.3% by weight of iron and 0.1% by weight of silicon
A roll of a 0.24 mm-thick sheet of SA1050 aluminum material was converted to a 400 mesh pumice stone (manufactured by Kyoritsu Ceramics Co., Ltd.).
Weight percent aqueous suspension and a rotating nylon brush (6,10-
(Nylon) and the surface was grained, and then washed well with water. 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. Furthermore, neutralize with 1% by weight nitric acid,
Next, in a 0.7% by weight nitric acid aqueous solution (containing 0.5% by weight of aluminum), a rectangular wave alternating waveform voltage (current ratio r = 0.9) having an anode voltage of 10.5 volts and a cathode voltage of 9.3 volts was used.
0, a current waveform described in Examples of Japanese Patent Publication No. 58-5796), and an electrolytic surface roughening treatment was carried out at an anode electricity amount of 160 clones / dm ² . After washing with water,
It was immersed in a 0% by weight aqueous sodium hydroxide solution, etched so that the amount of aluminum dissolved was 1 g / m ² , and washed with water. Next, it was immersed in a 30% by weight aqueous sulfuric acid solution at 50 ° C., desmutted, and washed with water. In addition, 3
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 5 ° C. using a direct current. That is, electrolysis is performed at a current density of 13 A / dm ² , and the anodic oxide film weight is 2.7 g by adjusting the electrolysis time.
/ M ² . After washing the support, the support was immersed in a 0.2% by weight aqueous solution of sodium silicate at 70 ° C. for 30 seconds.
Washed and dried. The aluminum substrate obtained as described above had a reflection density of 0.30 and a center line average roughness Ra of 0.58 μm as measured by a Macbeth RD920 reflection densitometer.
Met.

(Formation 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 of the thermosensitive layer. (Coating solution for undercoat layer) ・ Arabic gum 1g ・ Water 1000g

(Formation of Recording Layer) Then, the following recording layer coating solution was coated on the undercoating support and dried (at 100 ° C.,
2 minutes) to form a recording layer having a dry coating weight of 0.6 g / m ² , thereby obtaining respective lithographic printing plate precursors.

(Recording layer coating solution) Sulfonic acid generating type polymer compound described in Table 1 1.0 g Polymer binder described in Table 1 (amount described in Table 1) Infrared absorber 0.15 g described in Table 1・ Dye in which the counter ion of Victoria Pure Blue BOH is converted to 1-naphthalene-sulfonic acid 0.05 g ・ Fluorine-based surfactant (Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.06 g ・ Methyl ethyl ketone 10 g・ Propylene glycol monomethyl ether 10g ・ Methyl alcohol 7g

[0142]

[Table 1]

[0143]

Embedded image

(Preparation of planographic printing plate) Image recording process (laser exposure) From the recording layer side of the lithographic printing plate precursor, 40
300mJ / cm using W trend setter (plate setter mounted with 830nm semiconductor laser of 40W)
Exposure was performed with energy of ² , and image recording was performed. 2. Printing Step (Printing Evaluation) Then, the lithographic printing plate precursor on which the image was recorded was directly processed without any processing by a printing machine (Heidelberg SOR).
−M, roller cooling temperature 15 ° C.), and printing was performed using an emulsion ink having the following composition. In each of the above Examples, the recording layer of the laser-exposed portion was promptly placed on a printing machine at the beginning of printing. Good prints were obtained from the plate surface, and all of the non-image areas of 20,000 sheets were free of stains. According to the lithographic printing method of the present invention, it was found that good printed matter was stably obtained irrespective of the types of the sulfonic acid-generating polymer compound, the binder, and the infrared absorber contained in the recording layer.

(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 (White gloss flower 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 10 parts Propylene glycol 55 parts Glycerin 34 parts Surfactants (polyoxyethylene alkyl phenyl ether, Liponox NCE: Lion Oil & Fat Co., Ltd. 1) 100 parts by weight of the oil-based ink component of (2) and 70 parts by weight of the hydrophilic component of (3) were stirred and mixed to prepare a W / O emulsion ink.

[Examples 11 to 20] (Preparation of support) Corona treatment was applied to both surfaces of polyethylene terephthalate (center line average roughness Ra: 0.35 μm) having a thickness of 175 μm, both surfaces of which were subjected to sand blasting. Further, the following coating solution was applied to both surfaces 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 1 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) 4 g of 20% aqueous silica gel dispersion (Snowtex C (manufactured by Nissan Chemical Industries, Ltd., average particle size about 10 nm)) 6 g of sol-gel preparation liquid (the following composition) 6 g of polyoxyethylene nonyl Phenyl ether (Nonipol 100, manufactured by Sanyo Chemical Industries, Ltd.) 0.05 g / water 20 g

(Preparation of Sol-Gel Preparation Solution) A solution having the following composition was aged at room temperature for 1 hour to prepare a sol-gel preparation solution. 11.0 g of tetraethoxysilane. 20.7 g of methanol. 4.5 g of 0.1 N nitric acid. (Preparation of recording layer) The recording used in Examples 1 to 10 on the hydrophilic layer of the polyethylene terephthalate support described above. A recording layer having a dry coating weight of 1.0 g / m ² was formed in the same manner as the material, and a lithographic printing plate precursor (Examples 11 to 20).
For) obtained. (Image Recording / Printing Evaluation) When image recording and printing were performed in the same manner as in Example 1, the recording layer of the laser-exposed portion was promptly printed on a printing machine at the beginning of printing of any lithographic printing plate precursor. As a result, 20,000 good prints without stains on the non-image area were obtained. According to the method of the present invention, it was found that the same effect as that of the aluminum support was obtained even when the non-conductive resin sheet was used as the support.

Examples 21 to 30 Except that the formation of the hydrophilic layer was changed as described below, lithographic printing original plates were obtained in the same manner as in Examples 11 to 20, respectively. Next, when image recording and printing were performed in the same manner as in Example 1, in any planographic printing plate, at the initial stage of printing, the recording layer of the laser exposed portion was promptly removed from the plate surface on a printing press. 20,000 good prints without stains on the non-image area were obtained. (Formation of hydrophilic layer) Then, a batch type sputtering film forming apparatus (CFS-10-EP7 manufactured by Shibaura Eletech Co., Ltd.) is formed on the heat-sensitive layer.
Using 0), a titanium 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 glowed under the following conditions.

Atmosphere: Argon Pressure during processing: 5.0 mtorr Power: Rf 3 kW (Power supply is JRF manufactured by JEOL Ltd.)
-3000) Time: 2.5 minutes

Example 31 The printing was evaluated in the same manner as in Example 17 except that the composition of the emulsion ink was changed as follows. At the beginning of printing, the overcoat layer and the hydrophilic layer in the laser-exposed area were evaluated. Immediately on the printing press, it was removed from the plate surface, and 20,000 sheets of good printed matter without stains on the non-image area were obtained. According to the method of the present invention, stable printing was possible even when the composition of the emulsion ink was changed.

(Emulsion Ink Composition 2) [Preparation of Emulsion Ink] (1) Preparation of Varnish (Hereinafter, parts are by weight.) By the following formulation, gelled by heating at 200 ° C. for 1 hour to prepare gel varnish D Obtained. Rosin-modified phenol resin (Hitanol 270T: manufactured by Hitachi Chemical Co., Ltd.) 42 parts Low viscosity linseed oil polymerization varnish (2 poises) 30 parts Spindle oil 27 parts Ethyl acetoaceto aluminum diisopropylate 1 part (2) Oil-based ink component Preparation: Gel Varnish D 66 parts Phthalocyanine Blue 20 parts Low viscosity linseed oil polymerization varnish (2 poise) 5 parts Polyethylene wax compound 3 parts Cobalt dryer 1 part Spindle oil 5 parts (3) Preparation of hydrophilic component: ethylene glycol 100 parts ( A W / O emulsion ink was prepared by stirring and mixing 100 parts by weight of the oily ink component of the item 2) and 45 parts by weight of the hydrophilic component of the item 3).

Examples 32 to 37 The printing evaluation was carried out in the same manner as in Example 31 except that the hydrophilic component of the emulsion ink was changed to the composition shown in Table 2 below. At the beginning of printing, the overcoat layer and the hydrophilic layer in the laser-exposed area were promptly removed from the plate surface on a printing machine, and 20,000 sheets of good printed matter free of non-image areas were obtained. According to the method of the present invention, it was found that the same effect was obtained even when the composition of the hydrophilic component contained in the emulsion ink was changed.

[0155]

[Table 2]

[Comparative Example 1] Instead of using the above-mentioned emulsion ink at the time of printing, Aqualess Echo Ink LZ (Toyo Ink Mfg. Co., Ltd.), a lithographic printing ink requiring no dampening solution, was used.
The printing evaluation was performed in the same manner as in Example 17 except for using) as a printing ink. As a result, a non-image portion was stained, and a good printed matter could not be obtained.

[0157]

According to the lithographic printing method of the present invention, heating,
Alternatively, the heat generated by the light-to-heat conversion enables image recording with high sensitivity, excellent printability such as printing durability and stain resistance, and a heat-sensitive lithographic printing plate precursor that can be made by simple on-press processing. A stable printed matter can be easily obtained without using a dampening solution.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H084 AA14 AA38 AE05 CC06 2H096 AA06 BA16 BA20 CA03 EA04 EA23 GA02 GA60 2H113 AA02 AA03 BA06 BC01 BC02 DA03 DA04 DA07 DA35 DA42 DA53 DA54 FA44 2H114 AA05 AA04 DA03 DA DA34 DA42 DA52 DA53 EA01 EA03 EA05 EA08 GA01

Claims (3)

[Claims] 1. A heat-sensitive lithographic printing plate precursor comprising a support having a hydrophilic surface and a recording layer containing a polymer compound having a functional group capable of generating sulfonic acid upon heating,
After image recording, a lithographic printing method is characterized in that a hydrophilic component containing water and / or a polyhydric alcohol as a main component is added to an oil-based ink component, and printing is performed using an emulsion ink obtained by emulsification. Method. 2. The functional group which generates sulfonic acid by heating is at least one of functional groups represented by the following general formulas (1), (2) or (3). 2. The lithographic printing method according to 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 recording layer contains a photothermal conversion material,
After image exposure by laser light, the recording layer can be removed by the sulfonic acid generated in the exposed area, and by supplying the emulsion ink to the plate surface during printing,
2. The lithographic printing method according to claim 1, wherein the recording layer in the exposed area is removed by the action of the emulsion ink to form a non-image area.