JP2002254842A - Original plate for lithographic printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an original plate for lithographic printing which is capable of printing by being attached directly to a printing press without any process after exposure and improved in plate wear, and further hardly susceptible to stain. SOLUTION: The original plate for lithographic printing is provide on a substrate with a hydrophilic image forming layer, containing a hydrophobic precursor as well as an organic and inorganic composite while becoming hydrophobic by heat and containing a photothermal converting agent in the image forming layer or a layer neighbored to the same. In this case, the organic and inorganic composite can be obtained by hydrolizing and polycondensation under the presence of both a metal complex compound and an organic hydrophilic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a hydrophilic image forming layer on a support, and can record an image by infrared scanning exposure based on a digital signal. The present invention relates to a lithographic printing original plate that can be directly mounted on a printing press for printing.

[0002]

2. Description of the Related Art A computer-to-printer for producing a printing plate by laser beam scanning exposure based on a digital signal.
Numerous studies have been made on plate (CTP) systems. In order to further streamline the process and solve the problem of waste liquid treatment, a development-free lithographic printing plate that can be mounted on a printing machine and printed without exposure processing after exposure has been studied. For example, the Journal of the Printing Society of Japan,
No. 36, pp. 148-163 (1999)
Various methods are described for P printing plates.

One promising method is to use a heat-sensitive lithographic printing original plate having a hydrophilic layer (image forming layer) in which hydrophobic polymer fine particles are dispersed in a matrix such as a crosslinked hydrophilic resin. When heat is applied to the hydrophilic layer, the hydrophobic polymer particles fuse and coalesce, and the surface of the hydrophilic layer is converted into a hydrophobic image area. The surface composed of the hydrophobic image area and the hydrophilic non-image area of the hydrophilic resin matrix obtained in this manner is completely lithographic printing using a fountain solution without any treatment such as liquid development. It is known that it can be used as a printing plate.

[0004] A heat-sensitive lithographic printing original plate using microcapsules containing a hydrophobic substance instead of the hydrophobic polymer fine particles is also known. In this case, when heat is applied to the hydrophilic layer, the microcapsules are broken, and the contained hydrophobic substance oozes out to convert the hydrophilic layer into a hydrophobic image area.

[0005] For example, Research Disclos in January 1992
ure NO.33303 and Japanese Patent No. 2938397, a hydrophilic layer in which thermoplastic polymer fine particles are contained in a matrix obtained by crosslinking a hydrophilic binder such as polyvinyl alcohol with hydrolyzed tetraalkyl orthosilicate is used as a support. The heat-sensitive lithographic printing plate provided above is described.

Further, Japanese Patent Application Laid-Open Nos. 7-1849 and 7-18
No. 50, No. 10-6468 and No. 11-70756
No. 1 describes a heat-sensitive lithographic printing plate having a hydrophilic layer in which microcapsules encapsulating a lipophilic component are encapsulated in a cross-linked hydrophilic binder polymer. It is stated that there is.

[0007]

However, in these prior arts, the difficulty in printing or the printing durability was still insufficient. It is an object of the present invention to solve this problem. That is, it is an object of the present invention to provide a lithographic printing plate which can be directly mounted on a printing machine for printing after exposure without any processing, has improved printing durability, and is excellent in stain resistance.

Another object is to provide a lithographic printing plate which can be mounted directly on a printing press after exposure without any processing and can be used for printing, has improved printing durability, and has excellent stain resistance. To provide.

[0009]

Means for Solving the Problems The present inventor has found that the above object can be achieved by the following constitution. That is, the present invention is as follows.

[0010] 1. On a support, having a hydrophilic image forming layer which becomes hydrophobic by heat containing a hydrophobizing precursor and an organic-inorganic composite, and containing a photothermal conversion agent in the image forming layer or a layer adjacent thereto. A lithographic printing plate precursor, wherein the organic-inorganic composite is obtained by hydrolysis and polycondensation under conditions in which a metal complex compound and an organic hydrophilic resin coexist. Original plate for printing.

2. 2. The lithographic printing original plate as described in 1 above, wherein the organic hydrophilic resin has a crosslinkable group comprising a metal complex compound residue.

3. (1) The ratio of the organic hydrophilic resin when the organic-inorganic composite is formed is less than 50% of the total amount of the metal complex compound and the organic hydrophilic resin.
Or a lithographic printing plate as described in 2 above.

The present invention is based on the discovery of the results of a detailed study of an organic-inorganic composite used in an image forming layer of a lithographic printing plate. That is, conventionally, Japanese Patent No. 2938
As described in No. 397 or the like, a hydrophilic resin (organic-inorganic composite) crosslinked by reacting a previously hydrolyzed metal complex compound with a hydrophilic resin has been produced. However, the present inventor has proposed that the production of the organic-inorganic composite is carried out by a method in which hydrolysis and polycondensation are carried out under the condition that the metal complex compound and the organic hydrophilic resin coexist, so that the organic component and the inorganic component are uniform. It has been found that an organic-inorganic composite film can be formed by an interaction such as a chemical bond or a hydrogen bond in a proper state, and as a result, the film strength is improved and the printing durability is increased.

When an organic hydrophilic resin having a metal complex compound residue as a crosslinking group is used, a strong organic-inorganic composite having high hydrophilicity and a chemical bond is formed.
It has also been found that stain resistance and printing durability can be further improved. Furthermore, the ratio of the organic hydrophilic resin of the organic-inorganic composite is 50%.
It has also been found that when the content is less than the above, the ratio of the inorganic component having a high hydrophilicity is increased, and the stain resistance is remarkably improved. At the same time, the film strength is increased due to the increase of the hard inorganic component, and the printing durability can be improved.

[0015]

Embodiments of the present invention will be described below in detail. In the present invention,% means mass% unless otherwise specified.

The lithographic printing plate of the present invention has an image forming layer on a support. Further, a layer structure having a water-soluble protective layer on the image forming layer may be used. Further, a heat insulating layer may be provided as a lower layer of the image forming layer. Accordingly, the layer adjacent to the image forming layer in the present invention means a water-soluble protective layer or a heat insulating layer.

[Image-forming layer] The hydrophobizing precursor used in the image-forming layer of the present invention is a fine particle capable of converting a hydrophilic image-forming layer to hydrophobic when heat is applied thereto.
For example, thermoplastic polymer fine particles, thermosetting polymer fine particles, polymer fine particles having a thermoreactive functional group, microcapsules containing a hydrophobic substance, and the like, dispersed in the hydrophilic image forming layer can be used. These are particles capable of converting a hydrophilic image forming layer to hydrophobic, when heat is applied, the polymer particles melt or react and coalesce, or the microcapsules are broken and the hydrophobic substance oozes out. These fine particles can be used alone or in combination of two or more in the image forming layer.

The thermoplastic polymer fine particles suitable for the present invention include Research Disclosure No. 33, January 1992.
303, JP-A-9-12387, 9-131
No. 850, No. 9-171249, No. 9-17
Suitable examples include thermoplastic polymer fine particles described in 1250 and EP931647. Specific examples of the polymer constituting such polymer fine particles include homopolymers of monomers such as ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, and vinyl carbazole. Copolymers or mixtures thereof can be mentioned. Among them, polystyrene and polymethyl methacrylate are more preferable.

Examples of the thermosetting polymer suitable for the thermosetting polymer fine particles of the present invention include a resin having a phenol skeleton and a urea-based resin (for example, a urea derivative such as urea or methoxymethylated urea is converted into a resin by using an aldehyde such as formaldehyde). Melamine-based resin (for example,
Melamine or a derivative thereof obtained by resinification with an aldehyde such as formaldehyde), alkyd resin, unsaturated polyester resin, polyurethane resin, epoxy resin and the like.

Suitable resins having a phenol skeleton include, for example, phenol resins obtained by resinifying phenol, cresol and the like with aldehydes such as formaldehyde, hydroxystyrene resins, and phenol skeletons such as N- (p-hydroxyphenyl) methacrylamide. A methacrylamide or acrylamide resin having
A methacrylate or acrylate resin having a phenol skeleton such as -hydroxyphenyl methacrylate; Among them, particularly preferred are a resin having a phenol skeleton, a melamine resin, a urea resin and an epoxy resin.

The average particle size of the thermosetting polymer fine particles used in the present invention is preferably 0.01 μm to 2.0 μm.
As a method for synthesizing such fine particles, these compounds are dissolved in a water-insoluble organic solvent, mixed and emulsified with an aqueous solution containing a dispersing agent, and further heated to form fine particles while removing the organic solvent. There is a method of solidifying. In addition, fine particles may be formed when the thermosetting polymer is synthesized. However, it is not limited to these methods.

As the heat-reactive functional group of the polymer fine particles having a heat-reactive functional group used in the present invention, an ethylenically unsaturated group which undergoes a polymerization reaction (for example, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.) A functional group having an active hydrogen atom which is an isocyanate group or a block body thereof for performing an addition reaction and a reaction partner thereof (for example,
Amino group, hydroxyl group, carboxyl group, etc.), an epoxy group which also performs an addition reaction and its reaction partner, an amino group, a carboxyl group or a hydroxyl group, a carboxyl group and a hydroxyl group or an amino group which perform a condensation reaction, a ring-opening addition reaction And an amino group or a hydroxyl group. However, a functional group that performs any reaction may be used as long as a chemical bond is formed.

The polymer fine particles having a thermoreactive functional group used in the image forming layer of the present invention include acryloyl groups,
Examples thereof include a methacryloyl group, a vinyl group, an allyl group, an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, an acid anhydride, and those having a group protecting them. The introduction of these functional groups into the polymer particles may be performed at the time of polymerization, or may be performed using a polymer reaction after polymerization.

When introduced during the polymerization, it is preferable to carry out emulsion polymerization or suspension polymerization of the monomer having these functional groups. Specific examples of the monomer having such a functional group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, glycidyl methacrylate, glycidyl acrylate, 2-
Block isocyanate with isocyanate ethyl methacrylate or its alcohol, block isocyanate with 2-isocyanate ethyl acrylate or its alcohol, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, Examples include, but are not limited to, acrylic acid, methacrylic acid, maleic anhydride, bifunctional acrylate, bifunctional methacrylate, and the like. Examples of the monomer having no heat-reactive functional group copolymerizable with these monomers include, for example, styrene, alkyl acrylate, alkyl methacrylate, acrylonitrile, and vinyl acetate. It is not limited to these as long as it has no monomer.

The polymer reaction used when the heat-reactive functional group is introduced after the polymerization is, for example, WO96-34.
316 publication.

The solidification temperature of these polymer particles having a thermoreactive functional group is preferably 70 ° C. or higher, and more preferably 100 ° C. or higher in view of the stability over time. The average particle size of the polymer fine particles is preferably from 0.01 to 20 μm, more preferably from 0.05 to 2.0 μm, and most preferably from 0.1 to 1.0 μm. Within this range, good resolution and stability over time can be obtained.

The addition amount of the polymer fine particles having a reactive functional group is preferably at least 20%, more preferably at least 40% of the solid content of the image forming layer.

The microcapsules used in the present invention are:
Contains a hydrophobic substance. As the hydrophobic substance, a compound having a thermoreactive functional group is preferable. Examples of such a heat-reactive functional group include the same functional groups as those used in the polymer fine particles having the heat-reactive functional group.

As the compound having a polymerizable unsaturated group,
At least one ethylenically unsaturated bond such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group;
And preferably two or more compounds. Such a compound group is widely known in the industrial field, and in the present invention, these can be used without particular limitation. These are, in chemical form, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures or copolymers thereof.

Examples include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids and fatty acids. Esters with aliphatic polyhydric alcohols and amides of unsaturated carboxylic acids with aliphatic polyhydric amines.

An addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxide; and Also, a dehydration condensation product with a monofunctional or polyfunctional carboxylic acid is preferably used.

Also, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and a halogen group Also preferred are substitution products of unsaturated carboxylic acid esters or amides having a leaving substituent such as thiol or tosyloxy groups with monofunctional or polyfunctional alcohols, amines and thiols. Another preferred example is a compound in which the above unsaturated carboxylic acid is replaced with unsaturated phosphonic acid or chloromethylstyrene.

Specific examples of the polymerizable compound which is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate,
3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloyloxypropyl) ether, trimethylolethane Triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate,
Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate,
Examples thereof include sorbitol pentaacrylate, sorbitol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, and polyester acrylate oligomer.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloyloxy-2 Hydroxypropoxy) phenyl]
Examples include dimethylmethane and bis- [p- (methacryloyloxyethoxy) phenyl] dimethylmethane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
Examples thereof include 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.

As the crotonic acid ester, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like can be mentioned. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include, for example, JP-B-46-27926, JP-B-51-47334,
Aliphatic alcohol esters described in JP-A-57-196231, JP-A-59-5240 and JP-A-59-196231
Examples thereof include those having an aromatic skeleton described in JP-A-5241 and JP-A-2-226149 and those containing an amino group described in JP-A-1-165613.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples thereof include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylamide. Examples of other preferred amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

A urethane-based addition-polymerizable compound produced by an addition reaction between an isocyanate and a hydroxyl group is also suitable.
JP-A-8-41708 discloses a polyisocyanate compound having two or more isocyanate groups in one molecule and an unsaturated monomer having a hydroxyl group represented by the following formula (I) added to one molecule. Urethane compounds containing at least two polymerizable unsaturated groups are exemplified.

Formula (I) CH ₂ ＣC (R ¹ ) COOCH ₂ CH (R ² ) OH

(Where R ¹ and R ² are H or CH
_{Shows 3} . )

Also, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, and JP-B-58-4804.
9860, JP-B-56-17654, JP-B-62-
Urethane compounds having an ethylene oxide skeleton described in JP-A-39417 and JP-B-62-39418 are also preferable.

Further, radical polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277563, JP-A-63-260909, and JP-A-1-105238 are preferable. It can be mentioned as.

Other preferred examples include JP-A-48-64183, JP-B-49-43191 and JP-A-49-43191.
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-2-30490 can be exemplified. Also, JP-B-46-43946, JP-B-1-40
Specific unsaturated compounds described in JP-A Nos. 337 and 1-40336 and vinylphosphonic acid-based compounds described in JP-A-2-25493 can also be mentioned as preferable examples. In some cases, compounds containing a perfluoroalkyl group described in JP-A-61-22048 are also preferably used. In addition, Journal of the Adhesion Society of Japan, Volume 20, 7
No., pages 300 to 308 (1984) as photocurable monomers and oligomers can also be suitably used.

Preferred epoxy compounds include glycerin polyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene diglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, bisphenols and polyphenols or hydrogenated products thereof. And polyglycidyl ether.

Preferred isocyanate compounds include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, xylylene diisocyanate, naphthalene diisocyanate, cyclohexane phenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, or alcohols such as alcohols. Alternatively, a compound blocked with an amine can be mentioned.

Suitable amine compounds include ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, propylenediamine, polyethyleneimine and the like.

Suitable compounds having a hydroxyl group include compounds having a terminal methylol group, polyhydric alcohols such as pentaerythritol, and bisphenols and polyphenols.

Preferred compounds having a carboxyl group include aromatic polycarboxylic acids such as pyromellitic acid, trimellitic acid and phthalic acid, and aliphatic polycarboxylic acids such as adipic acid.

Suitable acid anhydrides include pyromellitic anhydride, benzophenonetetracarboxylic anhydride and the like.

A preferred copolymer of the ethylenically unsaturated compound is a copolymer of allyl methacrylate. For example, an allyl methacrylate / methacrylic acid copolymer, an allyl methacrylate / ethyl methacrylate copolymer, an allyl methacrylate / butyl methacrylate copolymer, and the like can be given.

As a method for microencapsulation, a known method can be applied. For example, as a method for producing microcapsules, US Pat.
U.S. Pat. No. 3,287,154, U.S. Pat. No. 3,287,154.
No. 38-19574, JP-B-42-446, JP-B-42-711, a method by precipitation of a polymer shown in U.S. Pat. Nos. 3,418,250 and 3,660,304, U.S. Pat. No. 3,796,669. U.S. Pat. No. 3,914,511, U.S. Pat. No. 4,087,376, U.S. Pat. No. 4,089,802, a method using an isocyanate polyol wall material as disclosed in U.S. Pat.
Method using resorcinol-based wall forming material, US Pat.
No. 025445, a method using a wall material such as melamine-formaldehyde resin and hydroxycellulose, Japanese Patent Publication Nos. 36-9163 and 51-9079, an in situ method by monomer polymerization, and British Patent 930.
No. 422, U.S. Pat. No. 3,111,407, Spray drying method, British Patent Nos. 952807, 96707
No. 4, but not limited thereto.

The preferred microcapsule wall used in the present invention has three-dimensional crosslinking and has a property of swelling by a solvent. From such a viewpoint, the wall material of the microcapsule is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, and a mixture thereof, and particularly preferably polyurea and polyurethane. A compound having a thermoreactive functional group may be introduced into the microcapsule wall.

The average particle size of the above microcapsules is
0.01 to 20 μm is preferable, and 0.05 to
2.0 μm is more preferred, and 0.10 to 1.0 μm is particularly preferred. Within this range, good resolution and stability over time can be obtained.

In such microcapsules, the capsules may or may not be combined by heat. In short, of the microcapsule inclusions, those that oozed out of the capsule surface or outside the microcapsules during application, or those that penetrated the microcapsule wall,
A chemical reaction may be caused by heat. It may react with the added hydrophilic resin or the added low molecular compound. The microcapsules may be reacted with each other by providing two or more types of microcapsules with functional groups that react with each other with different functional groups. Therefore, it is preferable from the viewpoint of image formation that the microcapsules are melted and united by heat.
Not required.

The amount of the microcapsules added to the image forming layer is preferably 10 to 60%, more preferably 15 to 40% in terms of solid content. Within this range, good sensitivity and printing durability can be obtained.

When the microcapsules are added to the image forming layer, a solvent capable of dissolving the inclusions and swelling the wall material can be added to the microcapsule dispersion medium. Such a solvent promotes the diffusion of the encapsulated compound having a thermoreactive functional group out of the microcapsules.
Such a solvent depends on the microcapsule dispersion medium, the material, wall thickness, and inclusions of the microcapsule wall, but can be easily selected from many commercially available solvents. For example, in the case of water-dispersible microcapsules composed of crosslinked polyurea and polyurethane walls, alcohols,
Preferred are ethers, acetals, esters, ketones, polyhydric alcohols, amides, amines, fatty acids and the like.

Specific compounds include methanol, ethanol, tertiary butanol, n-propanol, tetrahydrofuran, methyl lactate, ethyl lactate, methyl ethyl ketone, propylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, and γ-butyl lactone. , N, N-dimethylformamide, N, N-dimethylacetamide, etc., but are not limited thereto. In addition, these solvents
Two or more kinds may be used.

Solvents which do not dissolve in the microcapsule dispersion but can be dissolved by mixing the above solvents can also be used. The amount of addition is determined by the combination of materials. If the amount is less than the appropriate value, image formation becomes insufficient, and if the amount is too large, the stability of the dispersion is deteriorated. Normal,
The effective range is 5 to 95% of the coating solution,
９０90%, more preferably 15-85%.

Since the polymer fine particles or microcapsules having a heat-reactive functional group are used in the image forming layer of the present invention, a compound for initiating or promoting these reactions may be added as necessary. . Examples of the compound that initiates or promotes the reaction include compounds that generate radicals or cations by heat, and include, for example, lophine dimers, trihalomethyl compounds, peroxides, azo compounds, diazonium salts, and diphenyliodonium salts. Onium salts, acylphosphines, imidosulfonates and the like. These compounds can be added in the range of 1 to 20% of the solid content of the image forming layer. Preferably it is in the range of 3 to 10%. Within this range, a favorable reaction initiation or acceleration effect can be obtained without impairing the on-press developability.

Examples of the metal complex compound for forming the organic-inorganic composite of the present invention include metal halides, metal oxyacid salts, metal organic acid salts, metal chelate compounds and metal alkoxide compounds. Especially metal chelate compounds,
Metal alkoxide compounds are preferred.

Examples of the central metal of the metal complex compound include atoms in the second to sixth periods of the periodic table.
Among them, metals and semiconductor elements in the third to fifth periods are preferable. Al, Si, Mg of the third period metal, Ca, Ti, Mn, Fe, Co, Ni, Cu, Z of the fourth period metal
Particularly preferred are n, Ge, and the fifth-period metals Zr, In, and Sn.

Examples of the ligand of the metal complex compound include monodentate ligands to hexadentate ligands, and specific examples include halogen atoms, alkoxy groups, β-diketones such as acetylacetone, and methyl acetoacetate. Hydroxycarboxylic acids or salts thereof such as lactic acid, salicylic acid and tartaric acid; hydroxycarboxylic acid esters such as methyl tartrate; keto alcohols such as 4-hydroxy-4-methyl-2-pentanone; amino alcohols such as triethanolamine. , Malonic acid diethyl ester,
Examples thereof include enol active hydrogen compounds such as methylolmelamine.

Specific compounds include tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propyloxysilane, tetra-t-butoxysilane and tetra-n-butoxysilane. Silane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrit
-Butoxysilane, n-propyltrimethoxysilane,
n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltri-t-butoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n -Hexyltri-t-butoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltrit-butoxysilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxy Silane, n-
Octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane,

Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane, dimethoxydiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyl Methyldimethoxysilane, phenylmethyldiethoxysilane, triethoxyhydrosilane, trimethoxyhydrosilane, isopropoxyhydrosilane, tri-t-butoxyhydrosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane, Trifluoropropyltrimethoxysilane,
Trifluoropropyltriethoxysilane,

Trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane , Γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldi Ethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-
Methacryloxypropyltri-t-butoxysilane, γ
-Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltrit-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,

Tetraethyl titanate, tetra-iso
-Propyl titanate, tetra-n-butyl titanate, tetra-2-ethylhexyl titanate, tetrastearyl titanate, di-iso-propoxy-bis (acetylacetone) titanate, di-n-butoxy-
Bis (triethanolamine) titanate, dihydroxy-bis (lactic acid) titanate,

Tetraethyl zirconate, tetra-is
o-propyl zirconate, tetra-n-butyl zirconate, tetra-2-ethylhexyl zirconate, zirconium acetate, ammonium zirconium carbonate, tetraacetylacetonato zirconate

Triethyl aluminate, tri-iso-
Examples thereof include propyl aluminate, tri-n-butyl aluminate, tri-2-ethylhexyl aluminate, ethyl acetoacetate aluminum diisopropylate, and aluminum tris (ethyl acetoacetate).

The organic hydrophilic resin for forming the organic-inorganic composite of the present invention may be any organic hydrophilic polymer or copolymer capable of cross-linking with a metal complex compound or interacting with hydrogen bonds or the like. . Specific examples include vinyl alcohol, acrylamide, methylol acrylamide,
Methylol methacrylamide, acrylacetamide,
Homopolymer and copolymer of N, N-dimethylacrylamide, 1-vinyl-2-pyrrolidinone, 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate Merged or maleic anhydride /
And vinyl methyl ether copolymer.

In addition to the above, particularly preferred organic hydrophilic resins include the organic hydrophilic resins having the above-mentioned metal complex compound residues as crosslinking groups. It is preferable as it can form a strong organic-inorganic composite having high hydrophilicity and improve printing durability. Among them, a hydrophilic resin having a silicon alkoxide residue is preferable. More specifically, there may be mentioned hydrophilic resins having structural units represented by the following general formulas (II) and (III).

[0073]

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(Where R ¹ , R ² and R ³ each represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, R ⁴ represents an alkoxy group or an acyloxy group having 1 to 40 carbon atoms, and k represents
Is an integer of 0 to 2, m is an integer of 0 to 3, and k + m is less than or equal to 3, X represents a monovalent metal or a hydrogen atom, Y is -NHCOCH _3, -CONH _2, -CON
_{(CH 3) 2, -COCH 3} , -OH, -CO 2 M, -OC
Represents of H ₃ or 2-pyrrolidone-1-yl group, M represents a hydrogen or a metal ion, n represents an integer of 1-8. )

Specific examples of the organic hydrophilic resin having the structural units of the general formulas (II) and (III) are shown below, but are not limited thereto.

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The production of the organic-inorganic composite of the present invention is characterized in that hydrolysis and polycondensation are carried out under the condition that the metal complex compound and the organic hydrophilic resin coexist. As a result, the organic component and the inorganic component can be uniformly dispersed, and high hydrophilicity, high film strength, and high printing durability can be obtained.

Further, in order to form a highly hydrophilic organic-inorganic composite, the metal complex compound and the organic hydrophilic resin are used in such a ratio that the organic hydrophilic resin is less than 50%. When the ratio of the organic hydrophilic resin exceeds 50%, the hydrophilicity and the film strength are reduced, and the stain resistance and the printing durability are reduced. Further, in the present invention, two or more kinds of organic hydrophilic resins may be mixed and used.

In the production of the organic-inorganic composite, it is preferable to use an acidic catalyst or a basic catalyst in combination to promote the hydrolysis and the polycondensation reaction.

As the catalyst, an acid or a basic compound may be 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). The concentration at that time is not particularly limited, but when the concentration is high, the rate of hydrolysis and polycondensation tends to increase. However, if a concentrated basic catalyst is used, a precipitate may be formed in the sol solution,
The concentration of the basic catalyst is desirably 1 N (concentration conversion in an aqueous solution) or less.

The type of the acidic catalyst or the basic catalyst is not particularly limited, but when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element which hardly remains in the coating film after drying is preferable. Specifically, acidic catalysts are represented by hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, and their RCOOH. Examples of basic catalysts include carboxylic acids such as substituted carboxylic acids in which R in the structural formula is substituted by other elements or substituents, sulfonic acids such as benzenesulfonic acid, and ammonia bases such as aqueous ammonia and amines such as ethylamine and aniline. Can be

In the production of the organic-inorganic composite of the present invention, the metal complex compound and the organic hydrophilic resin are dissolved in a solvent such as ethanol, and the above catalyst is added.
Hydrolysis and polycondensation proceed by stirring for a time to obtain an organic-inorganic composite sol solution. The sol solution is used together with other materials for the image forming layer such as polymer fine particles to prepare a coating solution, which is applied to form an image forming layer.

As described above, the image forming layer using the organic-inorganic composite of the present invention utilizes the sol-gel method.
For further details of the sol-gel method, see Sakuhana Saio, "Science of the Sol-Gel Method", Agne Shofusha Co., Ltd. (published by 1988), and Hirashima Tsuyoshi, "Functional thin film forming technology by the latest sol-gel method. This is described in detail in books such as the General Technology Center (published) (1992).

In the image forming layer of the lithographic printing plate of the present invention, in addition to the hydrophobizing precursor and the organic-inorganic composite, a photothermal converting agent which absorbs light and generates heat, inorganic fine particles, a surfactant, a coloring agent Agents, control of the degree of hydrophilicity, improvement of physical strength of the image forming layer, improvement of dispersibility of the constituents of the layers, improvement of coating properties, improvement of printability, workability of plate making Various objective compounds can be added for convenience. These will be described below.

As the photothermal conversion agent, metals, oxides, nitrides or sulfides of metals, pigments and dyes are preferred.
As the metal and the metal compound, A1, Si, Ti,
V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y,
Zr, Mo, Ag, Au, Pt, Pd, Rh, In, S
A metal selected from metals or metal compounds selected from the metals consisting of n and W, which can be formed into particles and dispersed in the organic-inorganic composite of the image forming layer can be used.

In particular, metal fine particles of iron, silver, platinum, gold and palladium are preferable. In addition, TiOx (x = 1.0-
2.0), SiOx (x = 0.6-2.0), AlOx
(X = 1.0-2.0), metal azide compounds such as azide of copper, silver and tin are also preferable.

Each of the above metal oxides, nitrides and sulfides can be obtained by a known production method. Also,
Many are commercially available under names such as titanium black, iron black, molybdenum red, emerald green, cadmium red, cobalt blue, dark blue, and ultramarine.

The pigment used in the image forming layer of the invention is
In addition to the above-mentioned metal compounds and metals, non-metal single particles such as carbon black, graphite (graphite) and bone charcoal (bone black) and various organic and inorganic pigments can also be contained in the image forming layer as photothermal conversion fine particles. it can.
Further, a light-to-heat conversion dye which is not in the form of particles can be added to the image forming layer.

The dye contained as a photothermal converting agent in the image forming layer has a light absorption region in the spectral wavelength range of the irradiation light, and is a solid particulate pigment which can be dispersed in an organic-inorganic composite; It is a dye that has a light absorption range in the spectral wavelength region and is dyeable to the organic-inorganic composite, or a non-dyeable and molecularly dispersible dye. Preferred solid particulate, dyeable and molecularly disperse dyes are IR (infrared) absorbers, specifically polymethine dyes, cyanine dyes, squarylium dyes, pyrylium dyes, diimmonium dyes, phthalocyanine compounds, triaryls It is a dye selected from methane dyes and metal dithiolenes. Of these, polymethine dyes, cyanine dyes, squarylium dyes, pyrylium dyes, diimmonium dyes, and phthalocyanine compounds are more preferable. Among them, polymethine dyes, cyanine dyes, and phthalocyanine compounds are most preferable from the viewpoint of synthesis suitability. The dye described above may be a water-soluble dye having a water-soluble group in the molecule. Preferred water-soluble groups of the water-soluble dye include a sulfonic acid group,
Carboxyl groups and phosphonic acid groups can be mentioned.

Specific examples of the dye (infrared ray absorbing agent) used as the photothermal converting agent contained in the image forming layer are shown below, but are not limited thereto.

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The light-to-heat converting agent may be contained in the image forming layer by adding the light-to-heat converting agent to the coating solution for the image forming layer, or may be made to be contained in the hydrophobizing precursor.
That is, the hydrophobic polymer fine particles can be contained in the polymer fine particles by being added to the oil phase at the time of production. Alternatively, it can be used together with a hydrophobic substance included in a microcapsule. In these cases, the above-described light-to-heat conversion agent may be used, but it is preferable to use a lipophilic light-to-heat conversion agent having good affinity for a hydrophobic polymer or a hydrophobic substance. Examples of such a lipophilic light-to-heat conversion agent are shown below, but are not limited thereto.

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The content of the light-to-heat converting agent contained in the image forming layer may be an amount sufficient for the hydrophobizing precursor to hydrophobize the image forming layer by the heat generated by the light absorption of the light-to-heat converting agent. , 2 to 50% of the solid components.

In the image forming layer of the present invention, inorganic fine particles may be added.
Preferable examples include magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate and mixtures thereof, and these are used for strengthening the film or strengthening the interfacial adhesion by roughening the surface even if it is not light-heat converting. be able to.

The average particle size of the inorganic fine particles is 5 nm to 10 μm
Is more preferable, and more preferably 10 nm to 1 μm. When the particle diameter is within this range, both the polymer fine particles and the metal fine particles of the photothermal conversion agent are stably dispersed in the organic-inorganic composite,
It is possible to form a non-image portion having sufficient hydrophilicity, which has a sufficient film strength of the image forming layer and is less likely to cause printing stains and which has excellent hydrophilicity. Such inorganic fine particles can be easily obtained as a commercial product such as a colloidal silica dispersion.

The content of the inorganic fine particles in the image forming layer is preferably from 1.0 to 70%, more preferably from 5.0 to 50% of the total solid content of the image forming layer.

The surfactants used in the image forming layer include, in addition to nonionic and anionic surfactants, cationic surfactants and fluorine-containing surfactants described in JP-A-2-195356. And JP-A-59
And amphoteric surfactants described in JP-A-1221044 and JP-A-4-13149. The amount of the surfactant added is 0.05 to 1 of the solid content of the image forming layer.
5% is preferable, and 0.1 to 5% is more preferable.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and polyoxyethylene nonylphenyl. Polyoxyethylene alkylaryl ethers such as ethers, polyoxyethylene / polyoxypropylene block copolymers, and aliphatic groups having 5 to 24 carbon atoms are ether-bonded to the terminal hydroxyl groups of the polyoxyethylene / polyoxypropylene block copolymer. Complex polyoxyalkylene alkyl ethers, also complex polyoxyalkylene alkyl aryl ethers having alkyl-substituted aryl groups ether-bonded, sorby Emissions monolaurate, sorbitan monostearate, sorbitan tristearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan fatty acid esters such as sorbitan trioleate,
Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan triolate and the like. Can be

Specific examples of anionic surfactants include alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, alkylnaphthalenesulfonic acids, alkylnaphthalenesulfonic acids or condensation type of naphthalenesulfonic acid and formaldehyde, and those having 9 carbon atoms. To 26-26 aliphatic sulfonic acids, alkylbenzene sulfonic acids, polyoxyethylene-containing sulfuric acid such as lauryl polyoxyethylene sulfate, cetyl polyoxyethylene sulfonic acid, oleyl polyoxyethylene phosphonic acid, and polyoxyethylene-containing phosphoric acid.

Specific examples of the cationic surfactant include laurylamine acetate, lauryltrimethylammonium chloride, distearyldimethylammonium chloride, and alkylbenzyldimethylammonium chloride.

Specific examples of the fluorinated surfactant include perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl trimethylammonium salt, perfluoroalkyl betaine, perfluoroalkyl alcohol and perfluoroalkyl sulfonamide. And ethylene oxide adducts.

Specific examples of the amphoteric surfactant include alkylcarboxybetaines, alkylaminocarboxylic acids, alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethyl. Examples include imidazolinium betaine and N-tetradecyl-N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.).

The image forming layer according to the present invention may contain
In order to make it easy to distinguish between the image area and the non-image area, a dye having a large absorption in the visible light region can be used as a colorant for the image. Specifically, Oil Yellow # 10
1, oil yellow # 103, oil pink # 312,
Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black B
S, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI
42000), methylene blue (CI52015) and the like.
And dyes described in JP-A-62-293247. Further, pigments such as phthalocyanine pigments, azo pigments, and titanium oxide can also be suitably used. The amount of addition is 0.01 to 10% based on the total solid content of the image forming layer.

[Heat insulation layer] The lithographic printing plate of the present invention includes:
Although not essential, it is preferable to provide a heat insulating layer as a lower layer of the image forming layer. Hereinafter, the heat insulating layer will be described.

The heat insulating layer provided as a lower layer of the image forming layer has a low thermal conductivity and has a function of suppressing heat diffusion to the support. Further, the heat insulating layer may contain a photothermal conversion agent. In this case, heat is generated by light irradiation, which contributes to improvement of the heat fusion sensitivity.

The heat insulating layer contains an organic or inorganic resin as a main component. Organic or inorganic resin
It can be widely selected from hydrophilic or hydrophobic ones.

For example, hydrophobic resins include polyethylene, polypropylene, polyester, polyamide, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl butyral resin, nitrocellulose, polyacrylate, polymethacrylate, polycarbonate, polyurethane, polystyrene, and the like. Vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, vinyl chloride-acrylate copolymer, vinylidene chloride-acrylonitrile copolymer, etc. No.

In the present invention, as the resin having hydrophobicity, a resin composed of an aqueous emulsion can be used. The aqueous emulsion is a hydrophobic polymer suspension aqueous solution in which particles comprising fine polymer particles and, if necessary, a protective agent for stabilizing the dispersion of the particles are dispersed in water. Specific examples of the aqueous emulsion used include vinyl polymer latex (polyacrylate, vinyl acetate, ethylene-vinyl acetate, etc.) and conjugated diene polymer latex (methyl methacrylate-
Butadiene-based, styrene-butadiene-based, acrylonitrile-butadiene-based, chloroprene-based, etc.) and polyurethane resins.

Examples of the hydrophilic resin include polyvinyl alcohol (PVA), modified PVA such as carboxy-modified PVA, starch and derivatives thereof, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, and alginic acid. Ammonium,
Polyacrylic acid, polyacrylate, polyethylene oxide, water-soluble urethane resin, water-soluble polyester resin, polyhydroxyethyl acrylate, polyethylene glycol diacrylate polymer, N-vinyl carboxylic acid amide polymer, casein, gelatin, polyvinyl pyrrolidone, acetic acid And water-soluble resins such as vinyl-crotonic acid copolymer and styrene-maleic acid copolymer.

Further, the resin having hydrophilicity is cross-linked,
It is preferable to use it after curing. Such cross-linking agents include glyoxal, melamine formaldehyde resin,
Aldehydes such as urea formaldehyde resin, methylol compounds such as N-methylol urea, N-methylol melamine, methylolated polyamide resin, active vinyl compounds such as divinyl sulfone and bis (β-hydroxyethyl sulfonic acid), epichlorohydrin and polyethylene glycol Glycidyl ether, adducts of polyamide / polyamine / epichlorohydrin, epoxy compounds such as polyamide epichlorohydrin resin, ester compounds such as monochloroacetate and thioglycolate, polyacrylic acid, methyl vinyl ether / maleic acid copolymer And inorganic crosslinkers such as salts of boric acid, boric acid, titanyl sulfate, Cu, Al, Sn, V, and Cr; and modified polyamide polyimide resins. In addition, a crosslinking catalyst such as ammonium chloride, a silane coupling agent and a titanate coupling agent can be used in combination.

Further, as the inorganic polymer, an inorganic matrix formed by sol-gel conversion is preferable. A system capable of sol-gel conversion that can be preferably applied to the present invention includes:
The bonding group bonded to the polyvalent element forms a network-like structure via the oxygen atom, and at the same time, the polyvalent metal also has an unbonded hydroxyl group or an alkoxy group, and has a resin-like structure in which these are mixed. It is a molecular body and is in a sol state when there are many alkoxy groups and hydroxyl groups, and the network-like resin structure becomes strong as dehydration condensation proceeds.

Further, in addition to the property of changing the degree of hydrophilicity of the resin structure, a function of modifying the surface of the solid fine particles by binding a part of hydroxyl groups to the solid fine particles and changing the degree of hydrophilicity is also provided. I have. The polyvalent bonding element of the compound having a hydroxyl group or an alkoxy group that performs sol-gel conversion is aluminum, silicon, titanium, zirconium, or the like,
All of these can be used in the present invention.

From the viewpoint of adhesiveness to the image forming layer, among these resins, hydrophilic resins are particularly preferred.

When a light-to-heat conversion agent is contained in the heat insulating layer,
As the light-to-heat conversion agent, the same substance as the light-to-heat conversion agent used in the above-described image forming layer can be used. The content of the photothermal conversion agent contained in the heat insulating layer can be selected widely from 2 to 95% of the solid components.

In the heat-insulating layer, in addition to the above-mentioned resin and light-to-heat converting agent, the physical strength of the heat-insulating layer, the dispersibility of the components constituting the layer, the applicability, the image forming layer Various kinds of substances such as inorganic fine particles and surfactants can be added for the purpose of improving the adhesiveness with the adhesive. As such a substance, the same substances as described above that can be added to the image forming layer can be exemplified, and the added amount thereof can be used in the same range as described for the image forming layer.

[Water-soluble protective layer] Since the surface of the lithographic printing original plate of the present invention is hydrophilic, the water-soluble protective layer is used when the original plate is transported or stored in a product form, or handled before use. At this time, the film is susceptible to hydrophobicity due to the influence of the environment atmosphere, temperature and humidity, or mechanical damage or dirt. Therefore, to prevent this, the lithographic printing plate of the present invention is preferably provided with a water-soluble surface protective layer containing a water-soluble polymer as a main component, but the surface protective layer is not essential to the present invention. .

Since this water-soluble protective layer is dissolved in dampening water at the initial stage of printing and is washed away, it is not necessary to take extra steps for removal, and it does not hinder printing. Less than,
The components contained in the water-soluble protective layer will be described.

The water-soluble polymer contained in the water-soluble protective layer functions as a binder for the water-soluble layer. Examples of the water-soluble polymer include a polymer having sufficient groups such as a hydroxyl group, a carboxyl group, and a basic nitrogen-containing group.

Specifically, polyvinyl alcohol (PV
A), modified PVA such as carboxy-modified PVA, gum arabic, water-soluble soybean polysaccharide, polyacrylamide, copolymer of acrylamide, polyacrylic acid, acrylic acid copolymer, vinyl methyl ether / maleic anhydride copolymer, Vinyl acetate / maleic anhydride copolymer, styrene /
Maleic anhydride copolymer, roasted dextrin, oxygen-decomposed dextrin, enzyme-decomposed etherified dextrin, starch and derivatives thereof, carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, casein, gelatin, polyvinylpyrrolidone, acetic acid Vinyl-crotonic acid copolymer, styrene-maleic acid copolymer, alginic acid and its alkali metal salt, alkaline earth metal salt or ammonium salt, polyacrylic acid, poly (ethylene oxide), water-soluble urethane resin, water-soluble polyester Resin, polyhydroxyethyl acrylate, polyethylene glycol, polypropylene glycol, N-vinyl carboxylic acid amide polymer, and the like. Among them,
Polyvinyl alcohol (PVA), carboxy-modified PV
It is preferred to use modified PVA such as A, gum arabic, polyacrylamide, polyacrylic acid, acrylic acid copolymer, polyvinylpyrrolidone, alginic acid and alkali metal salts thereof. In the present invention, two or more of the above water-soluble resins may be used in combination.

The content of the water-soluble resin in the coating solution is 3
~ 25% is suitable, and a preferred range is 10-25%.

The water-soluble protective layer may contain various surfactants as other components. Surfactants that can be used include anionic or nonionic surfactants. Specific examples thereof include the same surfactants as those used in the image forming layer described above.
The amount of the surfactant to be added is preferably 0.01 to 1%, more preferably 0.01%, based on the total solid content of the water-soluble layer.
5 to 0.5%.

In addition to the above components, if necessary, lower polyhydric alcohols such as glycerin, ethylene glycol and triethylene glycol can be used as wetting agents.
The amount of these wetting agents used is 0.1 to 5.0 in the surface protective layer.
% Is appropriate, and a preferable range is 0.5 to 3%.
The amount is 0%. In addition to the above, a preservative or the like can be added to the coating solution for the surface protective layer of the lithographic printing plate of the present invention. For example, benzoic acid and its derivatives, phenol, formalin, sodium dehydroacetate etc.
It can be added in the range of 5 to 2.0%. Further, an antifoaming agent can be added to the coating solution. Preferred antifoaming agents include an organosilicone compound, the amount of which is 0.0001.
The range of about to 0.1% is preferable.

Further, a light-to-heat converting agent can be added to the water-soluble protective layer. In this case, the sensitivity of thermal fusion by light irradiation of the image forming layer is further increased, so that preferable results are obtained. As the light-to-heat converting agent, the light-to-heat converting agents described for the image forming layer can be used in the same addition amount range.

[Coating] The above-mentioned image forming layer, heat insulating layer and protective layer were prepared by mixing the respective constituent components and applying a prepared coating solution to a support by using any of the conventionally known coating methods. Coating and drying to form a coating layer.

As the coating method, various known methods can be used. For example, bar coating, spin coating, spray coating, curtain coating, dip coating,
Examples include air knife application, blade application, roll application, and the like.

The coating amount (solid content) of the image forming layer obtained after coating and drying varies depending on the application, but for a general lithographic printing plate precursor, it is preferably 0.1 to 30 g / m ² , and 0.1 to 30 g / m ² . 3-10 g / m < ² > is more preferable.

The coating amount (solid content) of the heat-insulating layer also varies depending on the constitution, but in the case of a general lithographic printing plate precursor,
0.1 to 10 g / m ² is preferred, and 0.3 to 5 g / m ² is more preferred. Protective layer coating amount (solid content) also varies depending on the configuration, As for the original plate for general lithographic printing plate is preferably ^{0.1~5g / m 2, 0.2~3g / m} 2
Is more preferred. The coating is usually performed in the order of a heat insulating layer, an image forming layer and a protective layer.

[Support] A dimensionally stable plate is used for the support. As the support that can be used in the present invention, paper, plastic (for example, polyethylene,
Paper, metal plate (eg, aluminum, zinc, copper, nickel, stainless steel, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, acetic acid) laminated with polypropylene, polystyrene, etc. Cellulose butyrate,
Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or vapor-deposited.

Preferred supports are polyester film, aluminum, or SUS which is hardly corroded on a printing plate.
It is a steel plate, and among them, an aluminum plate having good dimensional stability and relatively low cost is preferable.

Preferred 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 foreign elements in the alloy is at most 10% 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 support used in the present invention is about 0.05 mm to 0.6 mm, preferably 0.1 mm to 0.4 mm, particularly preferably 0.15 m
m 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 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 chemically roughening the surface. Is selectively dissolved. 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. The chemical method is described in JP-A-54-31187.
The method of immersion in a saturated aqueous solution of an aluminum salt of a mineral acid as described in Japanese Patent Application Laid-Open Publication No. H10-157, 1988 is suitable. Further, as an electrochemical surface roughening method, there is a method of carrying out an alternating current or a direct current in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Also, an electrolytic surface roughening method using a mixed acid as disclosed in JP-A-54-63902 can be used.

Among such surface roughening methods, a surface roughening method combining mechanical surface roughening and electrochemical surface roughening as described in JP-A-55-137993 is particularly preferred.
Preferably, the adhesiveness of the oil-sensitive image to the support is strong, and the center line surface roughness (Ra) of the surface of the aluminum plate is 0.3.
It is preferable that the surface is roughened in a range of about 1.0 μm.

The roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide or sodium hydroxide, if necessary, and further subjected to a neutralization treatment. Is anodized.

As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes forming a porous oxide film can be used. Generally, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. Can be 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 thus cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80%, the solution temperature is 5 to 70 ° C., and the current density is 5 to 70%. 60A / dm ² , voltage 1-100V, electrolysis time 10
A range of seconds to 5 minutes is appropriate.

The amount of the formed oxide film is 1.0 to 5.0.
g / m ^2, it is particularly preferably 1.5 to 4.0 g / m ^2. If the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability will be insufficient or the film will be easily scratched.

Among these anodic oxidation treatments, in particular, the method of anodic oxidation at high current density in sulfuric acid described in British Patent No. 1,412,768 and US Pat. No. 3,511,661. The method of anodizing using phosphoric acid as an electrolytic bath described in above is preferable.

When the heat insulating layer is a resin having hydrophobicity, it is desirable to make the surface of the support hydrophobic. The surface of the support is made hydrophobic by applying an undercoat liquid containing, for example, a silane coupling agent or, in some cases, a titanium coupling agent. The silane coupling agent is mainly represented by the general formula (RO) ₃ SiR ′ (R, R ′ is an alkyl group or a substituted alkyl group), and the RO group is hydrolyzed to an OH group to form an OH group and an ether bond to the support surface. Combine
The R 'groups provide a hydrophobic surface for receiving the ink.

Examples of silane coupling agents include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxy. Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Ureidopropyltriethoxysilane, β-aminoethyl-β-aminopropyldimethoxysilane, and the like.

In order to ensure adhesion to the image forming layer, the plastic support is subjected to a corona charging treatment by a known method before coating.

[Plate Making and Printing] The lithographic printing plate of the present invention forms an image by heat. Specifically, direct image-like recording using a thermal recording head or the like, scanning exposure using an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, or infrared lamp exposure is used.
Exposure with a solid-state high-output infrared laser such as a semiconductor laser or a YAG laser that emits 0-nm infrared light is preferable.

The original plate for lithographic printing of the present invention can be irradiated with a laser having a laser output of 0.1 to 300 W. When a pulse laser is used, it is preferable to irradiate a laser having a peak output of 1000 W, preferably 2000 W. In this case, the exposure amount is preferably in the range of 0.1 to 10 J / cm ² , more preferably in the range of 0.3 to 1 J / cm ² , before the surface exposure intensity is modulated in the print image. preferable.

When the support is transparent, exposure can be performed through the support from the back side of the support.

The lithographic printing plate precursor of the present invention, which has been image-exposed, can be mounted on a printing press without any further processing, and can be printed by an ordinary procedure using ink and fountain solution. Further, after these lithographic printing original plates are mounted on a printing press cylinder, they can be exposed by a laser mounted on the printing press, and can be printed as they are using ink and fountain solution in a usual procedure.

[0151]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis of Polymer Fine Particle (1)) Allyl methacrylate 7.5 g, butyl methacrylate 7.5
g, and 200 ml of an aqueous solution of polyoxyethylene nonylphenyl ether (concentration: 9.84 × 10 ⁻³ mol / l) are mixed, and the system is replaced with nitrogen gas while stirring at 250 rpm. After the solution was brought to 25 ° C., cerium (I
V) Add 10 ml of an aqueous ammonium salt solution (concentration 0.984 × 10 ⁻³ mol / l). At this time, an aqueous ammonium nitrate solution (concentration: 58.8 × 10 ⁻³ mol / l) was added, and p
Adjust H to 1.3-1.4. It was then stirred for 8 hours. The solid content concentration of the polymer fine particle dispersion obtained by emulsion polymerization in this way was 9.5%, and the average particle size was 0.4 μm.

(Synthesis of Polymer Fine Particles (2)) Emulsion polymerization was carried out in the same manner as in Synthesis Example (1) above, except that styrene (10 g) was used instead of allyl methacrylate and butyl methacrylate in the synthesis of polymer fine particles (1).
The solid content concentration of the thus-obtained polystyrene fine particle dispersion was 9.0%, and the average particle size was 0.3 μm.

(Preparation of microcapsule (1)) As an oil phase component, 40 g of xylene diisocyanate, 10 g of trimethylolpropane diacrylate, a copolymer of allyl methacrylate and butyl methacrylate (molar ratio: 7 /
3) 10 g of pionin A41C (anionic surfactant manufactured by Takemoto Yushi Co., Ltd.) was dissolved in 60 g of ethyl acetate. As an aqueous phase component, 120 g of a 4% aqueous solution of polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd.) was prepared. The oil phase component and the aqueous phase component were emulsified at 10,000 rpm using a homogenizer. Thereafter, 40 g of water was added, and the mixture was stirred at room temperature for 30 minutes and further at 40 ° C. for 3 hours. The microcapsule solution thus obtained had a solid content of 20% and an average particle size of 0.5 μm.

<Production Example of Aluminum Support> 99.5
% Aluminum, 0.01% copper and 0.03% titanium
%, 0.3% iron and 0.1% silicon
105 rolled aluminum plate with a thickness of 0.24 mm,
The surface was grained using a 400-mesh aqueous suspension of bamistone (manufactured by Kyoritsu Ceramics Co., Ltd.) and a rotating nylon brush (6,10-nylon), and then thoroughly washed with water. Next, 70 ° C. in a 10% aqueous sodium hydroxide solution.
And then rinsed with running water. Further, it was neutralized with a 20% nitric acid aqueous solution and washed with water. The obtained aluminum plate was placed in a 1.0% aqueous nitric acid solution (containing 0.5% of aluminum nitrate) in an anode voltage of 12.7 volts and the ratio of the amount of electricity at the cathode to the amount of electricity at the anode was 0.9.
The electrolytic surface roughening treatment was performed using a current having a rectangular wave alternating waveform under the condition of an anode charge of 160 clones / dm ² . The surface roughness of the obtained substrate was 0.6 μm (Ra display).

Subsequent to this treatment, the substrate was immersed in a 1% aqueous solution of sodium hydroxide at 40 ° C. for 30 seconds, etched, and washed with water. Next, it was immersed in a 30% aqueous sulfuric acid solution at 55 ° C. for 1 minute. Furthermore, using a direct current in a 20% aqueous solution of sulfuric acid (containing 0.8% of aluminum) at 35 ° C.,
The anodic oxidation treatment was performed such that the mass of the anodic oxide film became 2.5 g / dm ² . This was washed with water and dried to prepare a support.

Examples 1 to 7 A coating solution of an aqueous image forming layer having the following composition was prepared, and the amount of the dried coating was 3.0 g / m 2 on a anodic aluminum oxide support obtained in the above Production Example using a bar coater. ^The coating was performed so as to be ^2, and then dried in an oven at 100 ° C. for 3 minutes.

(Coating Solution of Image Forming Layer) 20% aqueous solution of colloidal silica dispersion 150 g Organic-inorganic composite sol 94 g Polymer fine particles (1) (10% aqueous dispersion) 400 g Light-to-heat converting agent (IR-10 described in this specification) ) 10g water 374g

[0159] The organic-inorganic composite sol solution used here was
A solution having the following composition was prepared and aged at room temperature for 2 hours.

(Composition of Organic-Inorganic Composite Sol Solution) Tetramethoxysilane 150 g Organic hydrophilic resin (see Table 1) 70 g Ethanol 300 g 0.1 mol / L nitric acid aqueous solution 45 g

Table 1 shows the results of measuring the contact angle of water droplets on the surface of the printing plate thus obtained. All exhibited extended wetting and were very hydrophilic surfaces.

[0162]

[Table 1]

The original plate for lithographic printing was subjected to an external drum rotation speed of 100 rpm by a trend setter 3244 VFS manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser.
Plate surface energy 200mJ / cm ² , resolution 2400d
Exposure was performed under the conditions of pi to form an image area on the surface of the exposed portion. The surface of the exposed portion of the printing plate changed to a highly hydrophobic surface (see the measured value of the contact angle of the exposed portion water droplet in Table 1). After that, it was used for printing without development processing.

For printing, a printing machine SO manufactured by Heidelberg Company was used.
A 1% by volume aqueous solution of EU-3 (manufactured by Fuji Photo Film Co., Ltd.) was used as a dampening solution, and GEOS (N) black manufactured by Dainippon Ink and Chemicals, Inc. was used as an ink. As a printing procedure, first, roll-up (run-in operation) was performed 10 times with dampening water, and then ink was supplied to start printing. As a result, in any printing plate,
High-quality printed matter was obtained without printing stains from the start of printing until 20,000 sheets.

Comparative Examples 1-2 A lithographic printing plate was prepared in the same manner as in Example 1 except that the type, amount of addition and hydrolysis method of the organic hydrophilic resin used in Example 1 were changed as shown in Table 2. Then, image exposure and subsequent printing were performed (here, hydrolysis method A is an organic-inorganic composite sol liquid production method in which tetramethoxysilane and an organic hydrophilic resin are mixed and hydrolyzed with an acid. Method B is
This is a production method in which only a tetramethoxysilane is hydrolyzed with an acid to form a sol solution, and an organic hydrophilic resin is added at the time of preparing an image forming layer coating solution). Table 2 shows the results.

[0166]

[Table 2]

[0167] All the printing plates had good background smearing property, but background wear occurred on less than 10,000 sheets due to abrasion of the non-image area, and good printed matters could not be obtained. In particular, in Comparative Example 1, in addition to abrasion of the non-image area, lack of hydrophilicity and water retention due to a high ratio of the organic hydrophilic resin,
The soil was generated quickly.

Examples 8 to 9 Instead of the polymer particles (1) used in Example 1, the polymer particles (2) were used in Example 8, and the microcapsules (1) were used in Example 9. A lithographic printing original plate was prepared in the same manner as in Example 1, and image exposure and printing were performed. In each case, no print stain was generated on up to 20,000 sheets, and high-quality printed matter was obtained.

Example 10 A corona treatment was applied to the surface of a polyethylene terephthalate film having a thickness of 180 μm, and the surface of the polyethylene terephthalate film was treated as in Example 1
The image forming layer coating solution described above is applied, and dried by heating (100 ° C.,
3 minutes) to form an image forming layer having a dry film thickness of 3.0 g / m ² . Next, laser image exposure and printing evaluation were performed in the same manner as in Example 1. As a result, similar to Example 1, up to 20,000 sheets were not stained by printing, and high quality printed matter was obtained.

Examples 11 to 15 The metal complex compounds shown in Table 3 were used in place of the tetramethoxysilane used in the organic-inorganic composite sol solution of Example 1, and the planographic printing plates were otherwise the same as in Example 1. An original printing plate was prepared, image-exposed, and then printed.

[0171]

[Table 3]

In these lithographic printing original plates,
The non-image part showed high hydrophilicity, and the exposed part showed high hydrophobicity. Further, as in the case of Example 1, print stains did not occur up to 20,000 sheets, and high quality printed matter was obtained.

[0173]

According to the present invention, after exposure, printing can be carried out directly by mounting it on a printing press without performing any processing, and the lithographic printing plate having improved printing durability and excellent stain resistance can be obtained. We can provide original plate.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/11 G03F 7/11 (72) Inventor Sumaki Yamazaki 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fujisha Shin Film Co., Ltd. F-term (reference) 2H025 AA00 AA12 AB03 AC08 AD01 AD03 BH03 CB32 CC20 FA10 2H096 AA00 AA07 AA08 BA16 BA20 EA04 2H114 AA04 AA24 BA01 BA10 DA03 DA04 DA08 DA38 DA39 DA48 DA52 DA53 DA64 DA05 DA60 DA60 EA08

Claims (3)

[Claims] An image forming layer or a layer adjacent thereto is provided with a hydrophilic image forming layer containing a hydrophobizing precursor and an organic-inorganic composite and becoming hydrophobic by heat on a support. A lithographic printing original plate containing a conversion agent, wherein the organic-inorganic composite is obtained by hydrolysis and polycondensation under conditions in which a metal complex compound and an organic hydrophilic resin coexist. A lithographic printing plate characterized by the following. 2. The lithographic printing plate according to claim 1, wherein the organic hydrophilic resin has a crosslinkable group comprising a metal complex compound residue. 3. The method according to claim 1, wherein the ratio of the organic hydrophilic resin when forming the organic-inorganic composite is less than 50% of the total amount of the metal complex compound and the organic hydrophilic resin.
Alternatively, the lithographic printing plate according to claim 2.