JP2001356477A - Method for producing planographic printing plate and planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a planographic printing plate in which a waste leaching solution is easily treated. SOLUTION: The planographic printing plate is produced by successively carrying out a step for bringing a planographic printing original plate with a planographic printing material layer comprising hydrophobic fine particles each having a crosslinkable surface on a hydrophilic substrate into an imagewise crosslinking reaction to chemically bond the hydrophobic fine particles to one another, and a step for removing the chemically unbonded hydrophobic fine particles to form a hydrophilic region comprising the exposed substrate surface and a hydrophobic region comprising the chemically bonded hydrophobic fine particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plate making method for making a lithographic printing plate in which a hydrophilic region and a hydrophobic region are formed in an image.

[0002]

2. Description of the Related Art A method of forming a relief image by tanning development using silver halide as an optical sensor is already known. Various publications (eg, TH James, The Theory of the Photograph)
ic Process, 4th edition, pages 326-327, 1977). A method of making a printing plate by tanning a silver halide photosensitive material is described in British Patent 726.
No. 543, No. 988744, No. 10884512, No. 1112393, No. 1318213, No. 15470
Nos. 40, 1547350, 1567844, 1571155, 1590058, 20400
No. 60, U.S. Pat. Nos. 3,620,737 and 3,669,018
And No. 4,115,118. In plate making of a printing plate by tanning development, a silver halide photosensitive material provided with a silver halide gelatin emulsion layer on a support having a hydrophilic surface is image-exposed, and the gelatin in the portion where the silver image is formed by tanning development is obtained. To cure. Thereafter, it is immersed in warm water, and the unhardened gelatin of the silver halide emulsion layer is washed off (washed off) to form a lipophilic relief image on a hydrophilic plate surface. The lithographic printing plate thus produced by tanning development has a problem that the gelatin in the image area is swollen by the dampening water, and the ink receptivity and printing durability are reduced.

As methods for improving the ink receptivity, that is, the lipophilicity of gelatin, a method of adding a lipophilic substance to a silver halide gelatin emulsion layer and a method of providing a lipophilic overcoat layer have been proposed (UK). Patent 15678
Nos. 44, 1571155 and 1590058, and JP-A-4-324866).
Even if the lipophilicity is improved by these methods, it is necessary to further improve the printing durability. As a means for improving printing durability, it has been proposed to use a water-soluble copolymer having a nucleophilic group (eg, primary amino group, thiourea group, thiol group) instead of gelatin (Japanese Patent Application Laid-Open No. HEI 9-163572). Nos. 5-289228 and 10-3170). However, in such a method, it is difficult to achieve both the receptivity of the image portion and the removability of the non-image portion, and poor ink receptivity of small spots and contamination of the non-image portion occur, so that a good printed matter can be obtained. It was difficult.

[0004]

An object of the present invention is to provide a lithographic printing plate having good ink receptivity and printing durability. Another object of the present invention is to provide a method for making a lithographic printing plate, in which the waste liquid of the eluate can be easily treated.

[0005]

The object of the present invention has been attained by the following (1) to (9) lithographic printing plate making methods and the following (10) lithographic printing plate. (1) A lithographic printing original plate having a lithographic printing material layer composed of hydrophobic fine particles having a crosslinkable surface on a hydrophilic support is subjected to an imagewise crosslinking reaction to chemically bond the hydrophobic fine particles to each other. And removing the hydrophobic fine particles that have not been chemically bonded to form a hydrophilic region composed of the exposed support surface and a hydrophobic region composed of the chemically bonded hydrophobic fine particles. A method of making lithographic printing plates in order.

(2) The lithographic printing material layer or a photosensitive layer provided adjacent to the lithographic printing material layer contains silver halide, and after performing a step of imagewise exposing the lithographic printing original plate, the silver halide is developed using a developing agent. The plate-making method according to (1), wherein an oxidized form of the developer causes the cross-linkable surface of the hydrophobic fine particles to undergo an image-wise cross-linking reaction. (3) The plate making method according to (1), wherein the crosslinkable surface of the hydrophobic fine particles is formed by attaching or bonding the polymer having an amino group to the surface of the hydrophobic fine particles. (4) The crosslinkable surface of the hydrophobic fine particles is formed by attaching or bonding the polymer having an amino group to the surface of the hydrophobic fine particles, and the silver halide is subjected to tanning development using a tanning developer and tanning development The plate-making method according to (2), wherein the polymer having an amino group is crosslinked imagewise by an oxidized form of the drug. (5) The plate making method according to (3), wherein the polymer having an amino group is gelatin. (6) The plate making method according to (5), wherein the hydrophobic fine particles are made of a hydrophobic polymer, and gelatin and the hydrophobic polymer are graft-polymerized.

(7) The plate making method according to (3), wherein the polymer having an amino group is a reaction product of a polymer having a carboxyl group and an alkyleneimine. (8) The plate making method according to (7), wherein the hydrophobic fine particles are made of a hydrophobic polymer, and the polymer having a carboxyl group and the hydrophobic polymer are graft-polymerized. (9) The plate making method according to (4), wherein a tanning developer is added to the lithographic printing material layer, the photosensitive layer or any other layer provided on the lithographic printing original plate. (10) A relief image composed of chemically bonded hydrophobic fine particles is formed on the hydrophilic support, and the chemically bonded hydrophobic fine particles function as hydrophobic regions, and the exposed support is A lithographic printing plate wherein the surface functions as a hydrophilic region.

[0008]

According to the present invention, the hydrophilic fine particles comprising the exposed surface of the support are formed by carrying out an imagewise crosslinking reaction to chemically bond the hydrophobic fine particles to each other, and then removing the hydrophobic fine particles which have not been chemically bonded. And a hydrophobic region formed of hydrophobic fine particles chemically bonded to each other. Hydrophobic fine particles that have not been chemically bonded can be removed without using an eluate. In addition, even when an eluate is used, hydrophobic fine particles that have not been chemically bonded can be removed with a small amount of the eluate. Therefore, in the method of making a lithographic printing plate according to the present invention, waste liquid treatment of the eluate is easy. Hydrophobic fine particles that are chemically bonded are in a good hydrophobic area (ink receiving area)
Function as Further, hydrophobic fine particles chemically bonded have excellent strength and high durability (printing durability). The exposed surface of the hydrophilic support can be used as a favorable hydrophilic region (fountain solution receiving portion). Therefore, according to the present invention, a lithographic printing plate having good ink receptivity and printing durability can be obtained.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Hydrophobic fine particles] The hydrophobic fine particles are preferably formed from a hydrophobic polymer. Latex (synthetic latex) can be used as the hydrophobic polymer fine particles. Examples of latex include
Polyvinyl chloride (PVC) latex, polyvinyl acetate (PVAc) latex, styrene-butadiene resin latex, styrene-butadiene rubber (SBR) latex, vinylpyridine (VP) latex, isoprene rubber (IR) latex, acrylonitrile-butadiene rubber ( NBR) latex, chloroprene rubber (C
R) latex, acrylate latex (AR), butyl rubber latex and polyurethane (U) latex.

The hydrophobic fine particles may have a core / shell structure. Latex of core / shell fine particles comprising a core comprising a polymer having a repeating unit derived from a conjugated diene monomer and a shell derived from an ethylenically unsaturated monomer having one kind of active methylene group (Japanese Patent Application Laid-Open No. 8-208767) Publication) can be particularly preferably used. The shell is preferably formed by polymerizing a carboxylic acid monomer (a carboxyl group-containing vinyl monomer) or a derivative thereof. Examples of carboxylic acid monomers include methacrylic acid (MAA), acrylic acid (AA), itaconic acid (IA), fumaric acid (FA),
Includes maleic acid and crotonic acid. In the presence of an epoxy resin, a carboxylic acid monomer can be subjected to a polymerization reaction to form hydrophobic fine particles. In addition, hydrophobic fine particles can be formed from an acrylic-modified epoxy resin having a carboxyl group in the molecule and having a self-emulsifying property. For the method of synthesizing these hydrophobic fine particles,
These are described in JP-A-5-9431 and JP-A-6-1940.

The hydrophobic fine particles preferably exhibit self-emulsifiability in an alkaline aqueous medium (for example, an aqueous solution of ammonia or amine and are finely and stably dispersed. The hydrophobic fine particles are preferably an acidic aqueous medium or a polar medium. (Eg, alcohols), it is preferable that the hydrophobic fine particles are extremely stably dispersed and do not dissolve.
It is preferably from 1 to 5.0 μm, more preferably from 0.01 to 3.0 μm, further preferably from 0.01 to 1.0 μm, and more preferably from 0.05 to 0.5 μm. Still more preferably, it is most preferably 0.1 to 0.3 μm. The amount of the hydrophobic fine particles is preferably 0.1 to 10 g / m ^2, still preferably 0.1 to 5 g / m ^2, most in the range of 0.1 to 3 g / m ² preferable.

[Crosslinkable Surface] A crosslinkable surface is formed by modifying the surface of the hydrophobic fine particles. The crosslinkable group is
It can be directly introduced as a substituent into a hydrophobic polymer forming hydrophobic fine particles. Further, the crosslinkable group can also be introduced as a substituent into a compound other than the hydrophobic polymer forming the hydrophobic fine particles. The compound for introducing a crosslinkable group is preferably a polymer. The compound having a crosslinkable group is adsorbed or bonded to the surface of the hydrophobic fine particles. It is preferable that the compound having a crosslinkable group and the hydrophobic polymer forming the hydrophobic fine particles are chemically bonded. When the compound having a crosslinkable group is a polymer,
It is particularly preferred that the polymer having a crosslinkable group and the hydrophobic polymer are chemically bonded by graft polymerization. Examples of the crosslinkable group include active methine group, active methylene group, ethylenically unsaturated group, acetylenically unsaturated group, epoxy group, amino group, carboxyl group, sulfo group, hydroxyl group,
Mercapto group, aldehyde group, cyano group, cyanato group,
Includes thiocyanato, isocyanato and isothiocyanato groups. The specific type of the crosslinkable group is determined according to a crosslinking reaction (described later) in plate making of a lithographic printing plate.

When an amino group is used as a crosslinkable group,
Gelatin and a hydrophobic polymer can be chemically bonded by graft polymerization. Latex particles whose surface has been modified with gelatin are disclosed in US Pat. No. 5,952,164.
And JP-A-5948857 and JP-A-5-5-2.
No. 24328. When an amino group is used as a crosslinkable group, a reaction product of a polymer having a carboxyl group and an alkylene imine can be used as a polymer having an amino group. As the alkylene imine, propylene imine is preferable. The polymer having a carboxyl group is preferably reacted with an alkylene imine in a latex state (Japanese Patent Application Laid-Open No. 8-53122).
No. 6). As the polymer having an amino group as a crosslinkable group, a homopolymer obtained by polymerizing a monomer having an amino group may be used. Examples of the monomer having an amino group include N- (3-aminopropyl) methacrylamide, N- (2-aminoethyl) methacrylamide,
Aminoethyl methacrylate, 2-aminoethyl acrylate, 3-aminopropyl acrylate, 3-amino-2-hydroxypropyl methacrylate, allylamine, N, N-dimethylaminoethyl acrylate, N,
N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropylacrylamide, diallylamine and N-methylallylamine.

As the polymer having an amino group as a crosslinkable group, a copolymer obtained by copolymerizing a monomer having an amino group with another monomer may be used. Examples of other monomers include acrylamides (eg, acrylamide, methacrylamide, N-methylacrylamide, N, N-
Dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, acrylamidomethylpropanesulfonic acid), unsaturated fatty acids (eg, acrylic acid, methacrylic acid,
Maleic acid, crotonic acid, itaconic acid), sulfonic acid monomer (eg, sodium p-styrene sulfonate, sodium vinyl sulfonate, sodium allyl sulfonate, sodium methallyl sulfonate), quaternary ammonium salt monomer (eg, p- Vinylbenzyltrimethylammonium chloride, acryloylethyltrimethylammonium chloride), acrylates (eg, methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, methoxyethoxyethyl acrylate, methoxy (polyethylene glycol) acrylate), methacrylates (eg, Methyl methacrylate, ethyl methacrylate, methoxy (polyethylene glycol) methacrylate), and other vinyl monomers (eg, N- Acryloyloxy morpholine, N- vinyl-2-pyrrolidone, styrene, acrylonitrile, vinyl acetate, vinyl benzoate) are included.

When an ethylenically unsaturated group (eg, an allyl group) is used as a crosslinkable group, core / shell particles having latex particles as a core and a polymer having an ethylenically unsaturated group as a shell can be used. . When an active methine group or an active methylene group is used as a crosslinkable group, core / shell particles having a latex particle as a core and a polymer having an active methine group or an active methylene group (a so-called polymer coupler) as a shell can be used. . For polymer couplers, see
No. 98743.

When the hydrophobic fine particles are made of a hydrophobic polymer, it is preferable that the compound having a crosslinkable group and the hydrophobic polymer forming the hydrophobic fine particles are chemically bonded. It is more preferable to graft-polymerize a compound having a crosslinkable group and a hydrophobic polymer, and it is further preferable to graft-polymerize a polymer having a carboxyl group and a hydrophobic polymer. The graft polymerization reaction is preferably performed in a latex state. The graft latex is an N-carbamoylpyridinium sulfobetaine compound (JP-A-64-66162, JP-A-2000-1).
No. 0242) can be prepared by introducing a polymer having a crosslinkable group into the carboxylic acid in the shell portion on the surface of the hydrophobic fine particles. The graft latex prepared by this method is characterized in that it is very stably dispersed in an acidic or alkaline aqueous medium or a polar medium such as an alcohol, and does not dissolve in the medium.

[Crosslinking reaction] The crosslinking reaction is carried out imagewise on the lithographic printing plate precursor. That is, it is necessary to distinguish between a region where a crosslinking reaction occurs (finally a hydrophobic region) and a region where a crosslinking reaction does not occur (finally a hydrophilic region). For this purpose, energy for causing a cross-linking reaction may be applied to the lithographic printing plate precursor in accordance with the image. Light or heat is generally used as energy applied to an image. Therefore, when a photopolymerization initiator or a thermal polymerization initiator is added to a lithographic printing material layer, a crosslinking reaction can be caused in an exposed area or a heated area. A latent image may be formed by applying energy corresponding to the image, and a cross-linking reaction may be caused in the subsequent development process so as to correspond to the image. In the case of a photosensitive material using silver halide, an image is generally formed in two stages: formation of a latent image (image exposure) and development.

Means for causing a crosslinking reaction in the development processing of silver halide are as follows: (1) A polymer having an amino group (eg, gelatin) is crosslinked using an oxidized form of a developing agent which has developed silver halide as a crosslinking agent. (So-called tanning development method), and (2) a method of polymerizing an ethylenically unsaturated group using an oxidized form of a silver halide-developed developer as a polymerization initiator (JP-A Nos. 45-11149 and 64-17).
No. 047) and (3) a method in which an oxidized form of a silver halide-developed developer and an active methine group or an active methylene group are subjected to a coupling reaction.
No. 98743). It is particularly preferable to use the tanning development method (1). Hereinafter, the tanning development method will be mainly described.

[Lithographic Printing Material Layer] The lithographic printing material layer preferably contains a binder in addition to the hydrophobic fine particles having a crosslinkable surface described above. When attaching or bonding a polymer having a crosslinkable group to the surface of hydrophobic fine particles,
It is preferable to use a polymer having the same crosslinkable group as the polymer having a crosslinkable group as the binder. That is, in addition to the hydrophobic fine particles, the binder is preferably bonded by crosslinking. Therefore, when binding gelatin to hydrophobic fine particles, the lithographic printing material layer preferably contains gelatin as a binder. Gelatin may be used in combination with another hydrophilic polymer (eg, polyvinylpyrrolidone, starch, albumin, polyvinyl alcohol, gum arabic, hydroxyethyl cellulose).

The lithographic printing material layer may further contain a compound necessary for causing a crosslinking reaction. When a crosslinking reaction is caused by the tanning development method, a compound necessary for causing the crosslinking reaction is silver halide. Although silver halide can be added to a layer (photosensitive layer) different from the lithographic printing material layer, it is more preferable to add it to the lithographic printing material layer. The coating amount of silver halide is 0.0
It is preferably 1 to 5 g / m ² , more preferably 0.03 to 2 g / m ² , and most preferably 0.10 to 1.5 g / m ² . The thickness of the silver halide emulsion layer is preferably from 0.07 to 13 μm, more preferably from 0.2 to 5 μm.

As silver halide, silver chloride, silver bromide,
Any grain of silver iodide, or silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide can be used. The shape of the silver halide grains is preferably cubic or tetradecahedral, but is not limited to those having a regular crystal form, and may be those having an irregular crystal form or a complex form thereof. Potato-shaped,
Spherical, plate-like and plate-like crystal forms are included. In the case of tabular grains, the grain size is generally at least five times the grain thickness.
There is no particular limitation on the grain size of the silver halide.
Fine particles of 0.01 μm or less can also be used. Meanwhile, 1
Large particles of about 0 μm can also be used. With respect to grain size distribution, monodisperse grains are preferred over polydisperse emulsions.
Monodispersed emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748. The crystal structure of silver halide grains is
It may be uniform or the inside and the outside may have different halogen compositions. It may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining. Further, it may be bonded to a compound other than silver halide. Examples of compounds other than silver halide include silver rhodan and lead oxide.

The silver halide grains may contain salts of other elements. Examples of other elements include copper, thallium, lead, bismuth, cadmium, zinc, chalcogens (eg, sulfur, selenium, tellurium), gold and VI.
Group II noble metals (eg, rhodium, iridium, iron, platinum, palladium) can be mentioned. Salts of these elements can be added during or after the formation of silver halide grains and included in the grains. Specific methods are described in U.S. Patent Nos. 1195432 and 1951933,
No. 2448060, No. 2628167, No. 2950
No. 972, No. 3488709, No. 3737313,
Nos. 3772031 and 4269927, and Research Disclosure (RD), No. 13,
No. 4, No. 13452 (June 1975). By adding an aqueous solution of an iridium compound to the emulsion during the preparation of the silver halide emulsion, iridium ions can be introduced into the silver halide grains. Examples of water-soluble iridium compounds include hexachloroiridium (II
I) acid salts and hexachloroiridium (IV) salts. Similarly, rhodium ions may be introduced into silver halide grains by adding an aqueous solution of a rhodium compound to the emulsion. Examples of the water-soluble rhodium compound include rhodium ammonium chloride, rhodium trichloride and rhodium chloride.

The iridium compound or the rhodium compound may be used by dissolving it in an aqueous solution of a halide for forming silver halide grains. Further, the aqueous solution of the iridium compound or the rhodium compound may be added before the particles are formed, or may be added during the formation of the particles. Further, it may be added during the period from grain formation to chemical sensitization treatment. It is particularly preferred to add while the particles are being formed. The iridium ion or the rhodium ion is preferably used in an amount of 10 ^{-9 to} 10 ^-3 mol, more preferably 10 ^{-7 to} 10 ^-5 mol, per 1 mol of silver halide. Two or more silver halide grains having different halogen compositions, crystal habits and grain sizes can be used in combination. Silver halide is preferably used as an emulsion. Silver halide emulsions are described in Research Disclosure (RD) Magazine, No. 17643 (December 1978), pp. 22-23, "I. Emulsion Production (Emulsion p.
reparation and types) "and No. 18716
(November 1979), page 648.

The silver halide emulsion is usually subjected to chemical sensitization after physical ripening. It is preferable to use silver halide grains having a relatively low fog value. Additives used in such a process are described in Research Disclosure Magazine, No. 1
No. 7643 and the same No. 18716. Regarding chemical sensitizers, 17643 (p. 23) and
No. 18716 (page 648, right column). Known additives other than those described above are also described in the above two Research Disclosures. For example, as for the sensitivity enhancer, 18716 (648
In the right column of the page), for the antifoggant and the stabilizer, N
o. No. 17643 (pages 24 to 25) and no. 18716
(From page 649, right column).

Silver halide emulsions can utilize the inherent sensitivity of silver halide without spectral sensitization. However, usually, the silver halide emulsion is used after spectral sensitization. Silver halide sensitizing dyes known in the photographic art can be used. Examples of sensitizing dyes include cyanine dyes, merocyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Spectral sensitizing dyes are used to adjust the spectral sensitivity of photosensitive materials to different light source wavelengths such as various lasers (eg, semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser, YAG laser) and light emitting diodes. Can also be used. For example, applying a plurality of spectral sensitizing dyes having different spectral wavelengths to silver halide in the same or different photosensitive layers to enable writing on the same photosensitive material using light sources having different wavelengths. Can also. In addition to the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization (supersensitizer) can be added to the emulsion. Good. Spectral sensitizing dyes are described in Research Disclosure Magazine, No.
17643 (December 1978), pp. 23-24, supersensitizers are described in the same publication. 18716 (November 1979
Mon.), p. 649.

In order to improve photographic characteristics, additives such as an antifoggant, a silver development accelerator for promoting silver development, and a stabilizer may be added to the lithographic printing material layer. Examples thereof include mercapto compounds (described in JP-A-59-111636), azoles and azaindenes (described in Research Disclosure No. 17643, pages 24 to 25 (1978)), and carboxylic acids containing nitrogen. And phosphoric acids (described in JP-A-59-168442), cyclic amides (described in JP-A-61-151841), thioethers (described in JP-A-62-151842),
Polyethylene glycol derivatives (JP-A-62-1518)
No. 43), thiol (JP-A-62-15184).
No. 4), acetylene compounds (JP-A-62-87).
957) and sulfonamides (JP-A-62
-178232). As silver development accelerators or antifoggants, aromatic ring (carbon ring or heterocyclic) mercapto compounds (JP-A-6-31)
3967) is particularly preferred. Aromatic heterocyclic mercapto compounds, particularly mercaptotriazole derivatives, are more preferred. The mercapto compound may be added to the lithographic printing plate precursor as a mercapto silver compound (silver salt). The amount of these compounds used is 10 mol / mol silver halide.
^-7 mol to 1 mol.

A tanning developer may be added to the lithographic printing material layer. Known surfactants may be added to the lithographic printing material layer. Any of a nonionic activator, an anionic activator, a cationic activator and a fluorine activator can be used. The surfactant is described in JP-A-2-195356. Sorbitans, polyoxyethylenes and fluorinated surfactants are particularly preferred.

[Hydrophilic support] As the support, paper, synthetic paper, synthetic resin (eg, polyethylene, polypropylene,
Polystyrene) laminated paper, plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate), metal plate (eg, aluminum, aluminum alloy,
Zinc, iron, copper), and paper or plastic film on which these metals are laminated or deposited can be used. Aluminum plates, plastic films, paper and synthetic paper are preferred. Further, a composite sheet in which an aluminum sheet is laminated on a polyethylene terephthalate film is also preferable. Aluminum plates and plastic films are more preferred, and aluminum plates are particularly preferred. When a hydrophobic material such as a plastic film is used, it can be used as a hydrophilic support by providing a hydrophilic undercoat layer (described later).

The case where an aluminum plate is used as a support will be further described. The aluminum support is subjected to a surface treatment such as a surface roughening treatment (graining treatment) or a surface hydrophilic treatment as necessary. The surface roughening treatment may be performed by an electrochemical sanding method (for example, a method of sanding an aluminum plate by passing an electric current in a hydrochloric acid or nitric acid electrolyte) and / or a mechanical sanding method. (For example, a wire brush grain method in which the aluminum surface is scratched with a metal wire, a ball grain method in which the aluminum surface is sanded with a polishing ball and an abrasive, a brush grain in which the surface is sanded with a nylon brush and an abrasive) Method). Next, the grained aluminum plate is chemically etched with acid or alkali. An industrially advantageous method is etching using an alkali. Examples of the alkaline agent include sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of the alkaline solution is preferably in the range of 1 to 50% by weight. The temperature of the alkali treatment is preferably in the range of 20 to 100 ° C. Further, it is preferable to adjust the processing conditions so that the amount of aluminum dissolved is 5 to 20 g / m ² .

Usually, after the alkali etching, the aluminum plate is washed with an acid to remove dirt (smut) remaining on the surface. Preferred acids are nitric acid, sulfuric acid,
Phosphoric acid, chromic acid, hydrofluoric acid and borofluoric acid. The smut removal treatment after the electrochemical graining treatment can be performed by a known method such as a method of contacting with sulfuric acid at a concentration of 15 to 65% by weight at 50 to 90 ° C. The aluminum plate subjected to the surface roughening treatment as described above can be subjected to an anodic oxidation treatment or a chemical conversion treatment, if necessary. The anodic oxidation treatment can be performed by a known method. Specifically, an anodic oxide film is formed on the aluminum surface by passing a direct current or an alternating current through an aluminum plate in an acid solution. Examples of acids include sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid and benzenesulfonic acid. Anodizing conditions vary depending on the electrolyte used. Generally, the concentration of the electrolyte is 1 to 80% by weight, the temperature of the electrolyte is 5 to 70 ° C., and the current density is 0.5%.
To 60 amps / dm ^2, a voltage of ^from 1 to 100v, and electrolysis time is preferably in the range of 10 to 100 seconds. Particularly preferred anodic oxidation methods are a method of performing anodization at a high current density in sulfuric acid and a method of performing anodization using phosphoric acid as an electrolytic bath. After the anodizing treatment, the aluminum plate may be subjected to an alkali metal silicate treatment (for example, a treatment of immersing the aluminum plate in an aqueous solution of sodium silicate). In order to improve the adhesion between the aluminum support and the curable layer and the printing characteristics, an undercoat layer may be provided on the support surface.

[Undercoat layer] The components constituting the undercoat layer include polymers (eg, gelatin, casein, polyvinyl alcohol, ethyl cellulose, phenolic resin, styrene-maleic anhydride resin, polyacrylic acid); amines (eg, monoethanol Amines, diethanolamine, triethanolamine, tripropanolamine) and their hydrochlorides, oxalates or phosphates; monoaminomonocarboxylic acids (eg, aminoacetic acid, alanine); oxyamino acids (eg, serine, threonine, dihydroxyamine) Sulfur-containing amino acids (eg, cysteine, cystine); monoaminodicarboxylic acids (eg, aspartic acid, glutamic acid); diaminomonocarboxylic acids (eg, lysine); amino acids having an aromatic nucleus (eg, p-hydroxy) Phenylglycine, Eniruaranin, anthranyl); aliphatic amino acid (e.g., sulfamic acid,
(Cyclohexylsulfamic acid); and (poly) aminopolyacetic acid (eg, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid,
Hydroxyethylethylenediamineacetic acid, ethylenediaminediacetic acid, cycloethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid). A compound in which some or all of the acid groups of the above compounds have become salts (eg, sodium salt, potassium salt, ammonium salt) can also be used. The above components can be used in combination of two or more.

When a plastic film is used as the support, it is preferable to add hydrophilic fine particles (eg, silica powder) to the hydrophilic undercoat layer instead of sanding the aluminum support.

[Arbitrarily Provided Layer] The layer optionally provided on the lithographic printing plate precursor is preferably a hydrophilic layer, more preferably a layer containing gelatin as a binder, like the lithographic printing material layer. . A tanning developer can be added to the optional hydrophilic layer. To provide a back layer containing a matting agent or an overcoat layer containing a matting agent on the lithographic printing plate precursor for the purpose of reducing the adhesiveness of the front and back surfaces of the lithographic printing plate precursor and preventing adhesion when the lithographic printing plate precursors are stacked. Can be. As the matting agent, inorganic or organic solid particles that can be dispersed in a water-soluble polymer are used. Examples of matting materials include:
Oxides (eg, silicon dioxide), alkaline earth metal salts, natural polymers (eg, starch, cellulose) and synthetic polymers can be mentioned. The particle size of the matting agent is 0.
A range of 5 to 50 μm is preferred. The coating amount of the matting agent is preferably in the range of 0.1 to 1 g / m ² . A fogging inhibitor, a silver development accelerator for accelerating silver development, a stabilizer, or a surfactant may be added to the optional hydrophilic layer.

FIG. 1 is a schematic sectional view of a lithographic printing original plate used in the present invention. As shown in FIG. 1, a lithographic printing material layer (2) and an overcoat layer (3) are provided on a hydrophilic support (1). Lithographic printing material layer (2)
Are silver halide particles (21) and hydrophobic fine particles (22)
And a polymer (23) having an amino group. A polymer (24) having an amino group is bonded to the surface of the hydrophobic fine particles (22). The overcoat layer contains a hydrophilic polymer (31).

[Exposure Step] The image exposure in the tanning development method is performed with light having a wavelength corresponding to the spectral sensitivity of silver halide. The wavelength is generally visible light, near ultraviolet light, or near infrared light, but X-rays or electron beams may be used. Examples of light sources include tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps,
Lamps such as carbon arc lamps, various lasers (eg, semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser, Y
AG laser), a light emitting diode, a cathode ray tube and the like. The exposure amount is generally 0.001 to 10
00 μJ / cm ² , preferably 0.01 to 100 μJ
/ Cm ² . When the support is transparent, exposure can be performed through the support from the back side of the support.

FIG. 2 is a schematic sectional view of a lithographic printing original plate during image exposure. As shown in FIG. 2, when the lithographic printing original plate is irradiated with light (L), a latent image (21a) is formed on the silver halide grains in the exposed portions. In contrast, there is no change in the unexposed portions of the silver halide grains (21).

[Tanning Development Step] The tanning development is performed using a developer. The tanning developer is added to the lithographic printing original plate or the developer. The tanning developer is preferably added to the lithographic printing original plate (lithographic printing material layer, photosensitive layer or any other layer provided on the lithographic printing original plate). The developer is generally an alkaline solution. The pH of the developer is preferably 9 or more. p
Examples of the alkaline substance used for adjusting H include sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, lithium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, and ammonia. As a solvent for the developer, water is preferable. If necessary, an organic solvent may be added to water.
The temperature of the developer is preferably 5 to 40 ° C.,
The temperature is more preferably from 20 to 35 ° C. The development time is preferably from 10 seconds to 10 minutes, and more preferably from 20 seconds to 3 minutes. After the development processing, the lipophilicity of the image area may be enhanced by processing with a liquid containing a mercapto compound (described in JP-A-4-324866).
Further, an acidic treatment or a fixing treatment may be performed.

As the tanning developer, compounds having a benzenediol ring or a benzenetriol ring (eg, pyrogallol, hydroquinone, t-butylhydroquinone, catechol, phenylcatechol, nordihydroguaiaretinic acid, 3,3,3 ', 3'-Tetramethyl-5,6,5', 6'-tetrahydroxyspirobisindane) is used. A polymer containing a repeating unit having a benzenezendiol ring or a benzenetriol ring in a side chain can also be used as a tanning developer. The amount of tanning developer used is 0.0
It is preferably from 1 to 1 mol / mol Ag, and
More preferably, it is 3 to 1 mol Ag. The amount of the tanning developer added to the tanning developer is preferably 10 ^{-5 to} 10 ^-1 mol / l.

In addition to the tanning developer, an auxiliary developer can be used. Examples of auxiliary developing agents include amidole, metol and aminophenol. Metol is particularly preferred. The auxiliary developing agent can be added to the tanning developer or the lithographic printing plate precursor. The amount of the auxiliary developer is 5 to 200 mol% of the amount of the tanning developer.
It is preferred that

FIG. 3 is a schematic sectional view of a lithographic printing original plate in tanning development. As shown in FIG. 3, when the lithographic printing plate precursor after image exposure is immersed in a tanning developer (D), the silver halide particles in the exposed part are developed and the silver image (2) is developed.
1b) is formed. The oxidized product (quinone) of the tanning developer generated during the development crosslinks the exposed amino group-containing polymers (23a and 24a). On the other hand, a polymer having an amino group in an unexposed portion (23)
And 24) have no change.

[Removal Step] The lithographic printing plate precursor having been subjected to tanning development is immersed in an eluent (generally hot water) and rubbed to remove uncrosslinked hydrophobic fine particles in unexposed portions, and crosslink. A relief image composed of hydrophobic fine particles can be formed. The temperature of the hot water is preferably 40 to 70 ° C. The surface of the photosensitive material may be rubbed with a sponge or a brush. The formed relief image can be used as a lithographic printing plate by drying. As post-processing,
Heat treatment, light irradiation treatment, or chemical treatment may be performed.

FIG. 4 is a schematic cross-sectional view of a lithographic printing original plate during elution. As shown in FIG. 4, when the lithographic printing original plate after the tanning development is treated with the eluent (S), the overcoat layer and the unexposed lithographic printing material layer are eluted. The lithographic printing material layer (2a) in the exposed area has a crosslinked amino group-containing polymer (23a and 24a).
It remains on the hydrophilic support (1) to form a relief image. In this way, a lithographic printing plate can be made.

[0043]

[Example 1] [Preparation of aluminum support] A surface of an aluminum plate having a thickness of 0.30 mm was coated with a nylon brush and a pumice stone (4).
(00 mesh) with a water suspension, and then thoroughly washed with water. Next, the film was immersed in a 10% by weight aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds for etching, and then washed with running water. It was neutralized and washed with a 20% by weight aqueous solution of nitric acid, and then washed with water. A sinusoidal alternating current (anode voltage: 12.7 V,
Amount of electricity at anode: 160 coulomb / dm ² )
Electrolytic surface-roughening treatment was performed in a weight% nitric acid aqueous solution. The surface roughness of the obtained plate was 0.6 μm (Ra indication).
Following this treatment, it is immersed in a 30% by weight aqueous sulfuric acid solution,
Desmutting was performed at 55 ° C. for 2 minutes. Next, when the thickness is 2.
Anodizing treatment was performed in a 20% by weight aqueous sulfuric acid solution under a current density of 2 A / dm ² for 2 minutes so that the concentration became 7 g / dm ² . This was washed with water and dried to prepare a support. The produced support was used as a No. 3 sodium silicate (SIO ₂ : 28-
30 wt%, Na ₂ O: 9~10 wt%, Fe: 0.0
(2% by weight or less) in a 2.5% by weight aqueous solution at 70 ° C. for 14 seconds and washed with water.

"Preparation of Gelatin-Grafted Polyurethane Fine Particles" 213 g of an aqueous polyurethane dispersion (Witcobond 236, manufactured by Witco Corp.) having a solid content of 20% by weight and 200 g of distilled water were added to 2 liters of a cooler and a stirrer. Placed in a round bottom three neck flask. 1.1 g of 1- (4-morpholinocarbonyl) -4- (2-sulfoethyl) pyridinium hydroxide was dissolved in 75 g of water and added to the polyurethane dispersion. The reaction was continued for 40 minutes. Gelatin (27.8 g) was dissolved in water (250 g) at 60 ° C., and neutralized to pH 9 with triethylamine. An aqueous gelatin solution was added dropwise to the reaction mixture from the funnel, and the grafting reaction was continued for 30 minutes. Cooled to 40 ° C., filtered and stored cold. Thus, a dispersion of gelatin-grafted polyurethane fine particles was prepared. The polyurethane / gelatin weight ratio is 60
/ 40.

"Preparation of silver halide emulsion" A 5% by weight aqueous solution of gelatin containing sodium chloride at pH 2 was kept at 40 ° C., and an aqueous solution of silver nitrate and pentachloroacolodium (III) were added.
An aqueous solution of sodium chloride and potassium bromide containing ammonium acidate (6.0 × 10 ⁻⁷ mol / mol Ag) was added by a double jet method at a silver potential of 90 mV for 8 minutes, and the core of the silver halide grains was removed. Formed. Next, an aqueous silver nitrate solution, potassium hexachloroiridate (III) (1.5 × 10 ⁻⁵ mol / mol Ag) and potassium hexacyanoferrate (II) (2.0 × 10 ⁻⁵ mol / mol Ag) were added. An aqueous solution of sodium chloride and potassium bromide was added by a double jet method at a silver potential of 90 mV for 10 minutes, and an average grain size of 0.25 μm and silver chloride of 9% were added.
Silver chlorobromide cubic grains containing 0 mol% were prepared. After washing with water and desalting, 22 g of gelatin, 2 ml of 1N aqueous sodium hydroxide solution and 4 m of 10% by weight aqueous sodium chloride solution
The pH was adjusted to 5.8 and pAg 7.4. Next, 5,6-cyclopentane-4-hydroxy-1,
3,3a, 7-Tetrazaindene (1.25 × 10 ⁻³ mol / mol Ag) was added, and chemical sensitization was performed with sodium thiosulfate and chloroauric acid at 60 ° C. for 60 minutes. After completion of the chemical sensitization, the temperature was lowered to 45 ° C., and the mixture was combined with 5,6-cyclopentane-4-hydroxy-1,3,3a, 7-tetrazaindene (1.25 × 10 ⁻³ mol / mol Ag). 5- (2
Sodium mercaptobenzothiazole) sulfonate (1.7 × 10 ⁻⁴ mol / mol Ag).

"Formation of lithographic printing material layer" 50 g of a silver halide emulsion heated at 45 ° C. was added to 100 g of a dispersion of gelatin-grafted polyurethane fine particles, and the mixture was stirred for 20 minutes and adjusted to pH 6.5. And a coating solution was prepared.
A coating solution was applied on the aluminum support to form a lithographic printing material layer. The coated silver amount (equivalent to silver nitrate) is 0.7 g /
m ² , the amount of gelatin applied was 0.4 g / m ² , and the amount of urethane polymer applied was 0.35 g / m ² .

[Formation of Overcoat Layer] A coating aid was added to a 4% by weight aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.), and 0.8 g / m ² of 0.8 g / m ² was formed on the lithographic printing material layer. Coating was carried out in the application amount to form an overcoat layer. Thus, a lithographic printing original plate was produced.

"Preparation of tanning developer" A solution A and a solution B having the following compositions were prepared, and they were mixed immediately before use.

液 Liquid A ───────── ─────────────────────────── Pyrogallol 3.0 g Metol 1.0 g Citric acid 1.0 g Water 500 ml ──────── ────────────────────────────

液 Liquid B ─────────カ リ ウ ム Potassium carbonate 200g Potassium bromide 1.0g Water 500ml ──────────── ────────────────────────

(Image formation) 400 nm using a xenon sensitometer
The printing original for print quality evaluation was brought into close contact with the lithographic printing original plate using the interference filter described above, and image exposure was performed with an emission time of 10 ^-5 seconds. The lithographic printing plate precursor subjected to image exposure was immersed in the above tanning developer at 24 ° C. for 30 seconds. Then
The substrate was washed with warm water of 40 ° C., and washed with running water of an unexposed portion for 15 seconds. The surface of the lithographic printing original plate was lightly rubbed with a sponge to remove the unexposed portion of the lithographic printing material layer together with the overcoat layer, thereby obtaining a clear relief image in the exposed portion. In this way, a lithographic printing plate was prepared in which the relief image in the exposed area was ink-receptive and the aluminum support (hydrophilic) exposed in the unexposed area due to elution had ink repellency. A lithographic printing plate was printed using a lithographic printing machine (SORM, manufactured by Heidelberg). The dampening water is raw water for dampening water (EU-
3, Fuji Photo Film Co., Ltd.) was diluted 100 times with water, and 10% by weight of isopropyl alcohol was used. The ink used was black ink (Gloss Ink, manufactured by Dainippon Ink Co., Ltd.). After the start of printing, a clear printed matter was obtained from the fifth sheet. Good printed matter was stably obtained up to 10,000 sheets.

Example 2 Preparation of Gelatin-Grafted Core / Shell Fine Particles 46 g of a 5% by weight aqueous gelatin solution was kept at 45 ° C., and the core was polybutadiene and the shell was styrene / 2-acetoacetoxyethyl methacrylate (weight ratio = 84/16) 25 g of a latex of core / shell fine particles (core / shell weight ratio = 50/50) composed of a copolymer were added with stirring. Gelatin and microparticles were reacted for 20 minutes. Thus, a dispersion of the gelatin-grafted core / shell fine particles was prepared.

"Formation of Lithographic Printing Material Layer" Example 1 was prepared by adding a dispersion of the gelatin-grafted core / shell fine particles prepared as above.
30 g of the silver halide emulsion used in the above was added, and the pH was 6.5.
To prepare a coating solution. A coating solution was applied on the aluminum support used in Example 1 to form a lithographic printing material layer. The coated silver amount (equivalent to silver nitrate) is 0.7 g /
m ² , the coating amount of gelatin was 0.4 g / m ² , and the coating amount of the core / shell fine particles was 0.50 g / m ² .

[Formation of Overcoat Layer] A coating aid was added to a 4% by weight aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.), and 0.8 g / m ² of 0.8 g / m ² was formed on the lithographic printing material layer. Coating was carried out in the application amount to form an overcoat layer. Thus, a lithographic printing original plate was produced.

(Image formation) 400 nm by xenon sensitometer
The printing original for print quality evaluation was brought into close contact with the lithographic printing original plate using the interference filter described above, and image exposure was performed with an emission time of 10 ^-5 seconds. The lithographic printing plate precursor subjected to image exposure was used in Example 1
Was immersed in the tanning developer used in the above at 24 ° C. for 30 seconds. Next, the substrate was washed with warm water of 40 ° C., and washed with running water of an unexposed portion for 15 seconds. The surface of the lithographic printing original plate was lightly rubbed with a sponge to remove the unexposed portion of the lithographic printing material layer together with the overcoat layer, thereby obtaining a clear relief image in the exposed portion. In this way, a lithographic printing plate was prepared in which the relief image in the exposed area was ink-receptive and the aluminum support (hydrophilic) exposed in the unexposed area due to elution had ink repellency. A lithographic printing plate was printed using a lithographic printing machine (SORM, manufactured by Heidelberg). The dampening solution was prepared by using a dampening solution raw water (EU-3, manufactured by Fuji Photo Film Co., Ltd.) with water.
It was diluted to 0-fold, and 10% by weight of isopropyl alcohol was used. The ink used was black ink (Gloss Ink, manufactured by Dainippon Ink Co., Ltd.). After the start of printing, a clear printed matter was obtained from the eighth sheet. Good printed matter was stably obtained up to 20,000 sheets.

Example 3 "Preparation of Gelatin-Grafted Epoxy Resin Fine Particles" 213 g of core / shell particles of epoxy / acrylic resin (ENO270, manufactured by DIC) having a solid content of 20% by weight and 200 g of distilled water were cooled. Into a 1 liter round bottomed three-necked flask equipped with a dropping funnel and a stirrer.
Heated at 8 ° C. for 30 minutes. After confirming that the temperature became constant, 1- (4-morpholinocarbonyl) -4-
(2-sulfoethyl) pyridinium hydroxide 1.1
g in 75 g of water was added dropwise from a dropping funnel. After the supply was completed, the mixture was heated and stirred at 55 ° C. for 40 minutes. 27.8 g of gelatin was dissolved in 250 g of water at 60 ° C. and adjusted to pH 9 with triethylamine. The reaction mixture was added dropwise to the aqueous gelatin solution, and the graft reaction was continued for 30 minutes. Then, it cooled to 40 degreeC, filtered, and stored cold.

[Formation of Lithographic Printing Material Layer] To 30 g of the prepared fine particle dispersion, 11 g of the silver halide emulsion used in Example 1 was added by heating to 45 ° C., and the pH was adjusted to 6.5. A coating solution was prepared. A coating solution was applied on the aluminum support used in Example 1 to form a lithographic printing material layer. The coated silver amount (equivalent to silver nitrate) was 0.7 g / m ² , the gelatin coated amount was 0.7 g / m ² , and the coated amount of fine particles was 1.30.
g / m ² .

[Formation of overcoat layer] A coating aid was added to a 4% by weight aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.), and 0.8 g / m ² of 0.8 g / m ² was formed on the lithographic printing material layer. Coating was carried out in the application amount to form an overcoat layer. Thus, a lithographic printing original plate was produced.

(Image formation) 400 nm with a xenon sensitometer
The printing original for print quality evaluation was brought into close contact with the lithographic printing original plate using the interference filter described above, and image exposure was performed with an emission time of 10 ^-5 seconds. The lithographic printing plate precursor subjected to image exposure was used in Example 1
Was immersed in the tanning developer used in the above at 24 ° C. for 30 seconds. Next, the substrate was washed with warm water of 40 ° C., and washed with running water of an unexposed portion for 15 seconds. The surface of the lithographic printing original plate was lightly rubbed with a sponge to remove the unexposed portion of the lithographic printing material layer together with the overcoat layer, thereby obtaining a clear relief image in the exposed portion. In this way, a lithographic printing plate was prepared in which the relief image in the exposed area was ink-receptive and the aluminum support (hydrophilic) exposed in the unexposed area due to elution had ink repellency. A lithographic printing plate was printed using a lithographic printing machine (SORM, manufactured by Heidelberg). The dampening solution was prepared by using a dampening solution raw water (EU-3, manufactured by Fuji Photo Film Co., Ltd.) with water.
It was diluted to 0-fold, and 10% by weight of isopropyl alcohol was used. The ink used was black ink (Gloss Ink, manufactured by Dainippon Ink Co., Ltd.). After the start of printing, a clear printed matter was obtained from the eighth sheet. Good printed matter was stably obtained up to 30,000 sheets.

Example 4 "Preparation of propyleneimine surface-modified epoxy resin fine particles" Core / shell particles of epoxy / acrylic resin having a solid content of 20% by weight (ENO270, manufactured by DIC)
16 g and 64 g of distilled water were put into a 200 ml round bottom three-necked flask equipped with a condenser, a dropping funnel and a stirrer, and heated at 55 to 58 ° C for 30 minutes. After confirming that the temperature became constant, an aqueous solution in which 0.28 g of propyleneimine was dissolved in 4.0 g of water was dropped from the dropping funnel. After the supply was completed, the mixture was heated and stirred at 55 ° C. for 2 hours. After standing at room temperature overnight, 70 g of an aqueous citric acid solution having a solid content of 10% by weight was added at room temperature, followed by stirring. The content once aggregated, and after one hour, became a good dispersion again.
After leaving at room temperature for half a day, excess citric acid was removed with an ultrafilter to obtain a dispersion of propyleneimine surface-modified epoxy resin fine particles having a solid content of 5% by weight.

[Formation of Lithographic Printing Material Layer] To 30 g of the prepared fine particle dispersion, 11 g of the silver halide emulsion used in Example 1 was added by heating to 45 ° C., and the pH was adjusted to 6.5. A coating solution was prepared. A coating solution was applied on the aluminum support used in Example 1 to form a lithographic printing material layer. The coated silver amount (equivalent to silver nitrate) was 0.7 g / m ² , the gelatin coated amount was 0.7 g / m ² , and the coated amount of fine particles was 1.30.
g / m ² .

[Formation of Overcoat Layer] A coating aid was added to a 4% by weight aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.), and 0.8 g / m ² of 0.8 g / m ² was formed on the lithographic printing material layer. Coating was carried out in the application amount to form an overcoat layer. Thus, a lithographic printing original plate was produced.

(Image formation) 400 nm by xenon sensitometer
The printing original for print quality evaluation was brought into close contact with the lithographic printing original plate using the interference filter described above, and image exposure was performed with an emission time of 10 ^-5 seconds. The lithographic printing plate precursor subjected to image exposure was used in Example 1
Was immersed in the tanning developer used in the above at 24 ° C. for 30 seconds. Next, the substrate was washed with warm water of 40 ° C., and washed with running water of an unexposed portion for 15 seconds. The surface of the lithographic printing original plate was lightly rubbed with a sponge to remove the unexposed portion of the lithographic printing material layer together with the overcoat layer, thereby obtaining a clear relief image in the exposed portion. In this way, a lithographic printing plate was prepared in which the relief image in the exposed area was ink-receptive and the aluminum support (hydrophilic) exposed in the unexposed area due to elution had ink repellency. A lithographic printing plate was printed using a lithographic printing machine (SORM, manufactured by Heidelberg). The dampening solution was prepared by using a dampening solution raw water (EU-3, manufactured by Fuji Photo Film Co., Ltd.) with water.
It was diluted to 0-fold, and 10% by weight of isopropyl alcohol was used. The ink used was black ink (Gloss Ink, manufactured by Dainippon Ink Co., Ltd.). After the start of printing, a clear printed matter was obtained from the eighth sheet. Good printed matter was stably obtained up to 30,000 sheets.

[Example 5] "Preparation of polyallylamine-grafted epoxy resin fine particles" Core / shell particles of epoxy / acrylic resin (ENO270, manufactured by DIC) 426 having a solid content of 20% by weight
g and 400 g of distilled water in a 2 liter round bottom three-necked flask equipped with a condenser, a dropping funnel and a stirrer,
Heated at 55-58 ° C for 40 minutes. After confirming that the temperature became constant, 110 g of polyallylamine (PAA, manufactured by Nitto Boseki Co., Ltd.) was added to 446 g of water, and a liquid having a solid content of 15% by weight was dropped from the dropping funnel. After the supply was completed, the mixture was heated and stirred at 55 ° C. for 30 minutes. After being left overnight at room temperature, a citric acid aqueous solution 1 having a solid concentration of 10% by weight was added at room temperature.
22 g was added and the mixture was stirred. The content once aggregated, and after one hour, became a good dispersion again. After leaving at room temperature for half a day, excess citric acid was removed with an ultrafilter to obtain a dispersion of polyallylamine-grafted epoxy resin fine particles.

[Formation of lithographic printing material layer] To 30 g of the prepared fine particle dispersion, 11 g of the silver halide emulsion used in Example 1 was added by heating to 45 ° C, and the pH was adjusted to 6.5. A coating solution was prepared. A coating solution was applied on the aluminum support used in Example 1 to form a lithographic printing material layer. The coated silver amount (equivalent to silver nitrate) was 0.7 g / m ² , the gelatin coated amount was 0.7 g / m ² , and the coated amount of fine particles was 1.30.
g / m ² .

[Formation of Overcoat Layer] A coating aid was added to a 4% by weight aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.), and 0.8 g / m ² of 0.8 g / m ² was formed on the lithographic printing material layer. Coating was carried out in the application amount to form an overcoat layer. Thus, a lithographic printing original plate was produced.

(Image formation) 400 nm by xenon sensitometer
The printing original for print quality evaluation was brought into close contact with the lithographic printing original plate using the interference filter described above, and image exposure was performed with an emission time of 10 ^-5 seconds. The lithographic printing plate precursor subjected to image exposure was used in Example 1
Was immersed in the tanning developer used in the above at 24 ° C. for 30 seconds. Next, the substrate was washed with warm water of 40 ° C., and washed with running water of an unexposed portion for 15 seconds. The surface of the lithographic printing original plate was lightly rubbed with a sponge to remove the unexposed portion of the lithographic printing material layer together with the overcoat layer, thereby obtaining a clear relief image in the exposed portion. In this way, a lithographic printing plate was prepared in which the relief image in the exposed area was ink-receptive and the aluminum support (hydrophilic) exposed in the unexposed area due to elution had ink repellency. A lithographic printing plate was printed using a lithographic printing machine (SORM, manufactured by Heidelberg). The dampening solution was prepared by using a dampening solution raw water (EU-3, manufactured by Fuji Photo Film Co., Ltd.) with water.
It was diluted to 0-fold, and 10% by weight of isopropyl alcohol was used. The ink used was black ink (Gloss Ink, manufactured by Dainippon Ink Co., Ltd.). After the start of printing, a clear printed matter was obtained from the eighth sheet. Good printed matter was stably obtained up to 20,000 sheets.

Example 6 “Formation of a lithographic printing material layer” The silver halide emulsion 1 used in Example 1 was added to 47 g of the fine particle dispersion prepared in Example 1.
2 g was added by heating to 45 ° C. and stirred for 20 minutes. 0.9 g of pyrogallol and 0.3 g of methol were dissolved in 5 g of an aqueous citric acid solution having a solid content of 10% by weight, and the resulting solution was added to the above-mentioned mixed solution. The coating solution was prepared by adjusting the pH to 3.5 with an aqueous citric acid solution having a solid content of 10% by weight. A coating solution was applied on the aluminum support used in Example 1 to form a lithographic printing material layer. The coated silver amount (equivalent to silver nitrate) was 0.6 g / m ² , and the gelatin coated amount was 0.6 g / m ² .
g / m ² , the coating amount of pyrogallol is 0.3 g / m ² , the coating amount of metol is 0.1 g / m ² , and the coating amount of fine particles is 0.7
It was 0 g / m ² .

[Formation of Overcoat Layer] A coating aid was added to a 4% by weight aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.), and 0.8 g / m ² of 0.8 g / m ² was formed on the lithographic printing material layer. Coating was carried out in the application amount to form an overcoat layer. Thus, a lithographic printing original plate was produced.

"Preparation of tanning developer" A tanning developer having the following composition was prepared.

タ ン Tanning developer 液カ リ ウ ム Potassium carbonate 100g Potassium bromide 2.5g Water 500ml ─────────── ─────────────────────────

(Image formation) 400 nm using a xenon sensitometer
The printing original for print quality evaluation was brought into close contact with the lithographic printing original plate using the interference filter described above, and image exposure was performed with an emission time of 10 ^-5 seconds. The lithographic printing plate precursor subjected to image exposure was immersed in the above tanning developer at 24 ° C. for 30 seconds. Then
The substrate was washed with warm water of 40 ° C., and washed with running water of an unexposed portion for 15 seconds. The surface of the lithographic printing original plate was lightly rubbed with a sponge to remove the unexposed portion of the lithographic printing material layer together with the overcoat layer, thereby obtaining a clear relief image in the exposed portion. In this way, a lithographic printing plate was prepared in which the relief image in the exposed area was ink-receptive and the aluminum support (hydrophilic) exposed in the unexposed area due to elution had ink repellency. A lithographic printing plate was printed using a lithographic printing machine (SORM, manufactured by Heidelberg). The dampening water is raw water for dampening water (EU-
3, Fuji Photo Film Co., Ltd.) was diluted 100 times with water, and 10% by weight of isopropyl alcohol was used. The ink used was black ink (Gloss Ink, manufactured by Dainippon Ink Co., Ltd.). After the start of printing, a clear printed matter was obtained from the eighth sheet. Good printed matter was stably obtained up to 30,000 sheets.

Example 7 "Formation of lithographic printing material layer" The silver halide emulsion 1 used in Example 1 was added to 47 g of the fine particle dispersion prepared in Example 2.
2 g was added by heating to 45 ° C. and stirred for 20 minutes. 0.9 g of pyrogallol and 0.3 g of methol were dissolved in 5 g of an aqueous citric acid solution having a solid content of 10% by weight, and the resulting solution was added to the above-mentioned mixed solution. The coating solution was prepared by adjusting the pH to 3.5 with an aqueous citric acid solution having a solid content of 10% by weight. A coating solution was applied on the aluminum support used in Example 1 to form a lithographic printing material layer. The coated silver amount (equivalent to silver nitrate) was 0.6 g / m ² , and the gelatin coated amount was 0.6 g / m ² .
g / m ² , the coating amount of pyrogallol is 0.3 g / m ² , the coating amount of metol is 0.1 g / m ² , and the coating amount of fine particles is 0.7
It was 0 g / m ² .

[Formation of overcoat layer] A coating aid was added to a 4% by weight aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.), and 0.8 g / m ² of 0.8 g / m ² was formed on the lithographic printing material layer. Coating was carried out in the application amount to form an overcoat layer. Thus, a lithographic printing original plate was produced.

(Image formation) 400 nm by xenon sensitometer
The printing original for print quality evaluation was brought into close contact with the lithographic printing original plate using the interference filter described above, and image exposure was performed with an emission time of 10 ^-5 seconds. The lithographic printing plate precursor subjected to image exposure was used in Example 6
Was immersed in the tanning developer used in the above at 24 ° C. for 30 seconds. Next, the substrate was washed with warm water of 40 ° C., and washed with running water of an unexposed portion for 15 seconds. The surface of the lithographic printing original plate was lightly rubbed with a sponge to remove the unexposed portion of the lithographic printing material layer together with the overcoat layer, thereby obtaining a clear relief image in the exposed portion. In this way, a lithographic printing plate was prepared in which the relief image in the exposed area was ink-receptive and the aluminum support (hydrophilic) exposed in the unexposed area due to elution had ink repellency. A lithographic printing plate was printed using a lithographic printing machine (SORM, manufactured by Heidelberg). The dampening solution was prepared by using a dampening solution raw water (EU-3, manufactured by Fuji Photo Film Co., Ltd.) with water.
It was diluted to 0-fold, and 10% by weight of isopropyl alcohol was used. The ink used was black ink (Gloss Ink, manufactured by Dainippon Ink Co., Ltd.). After the start of printing, a clear printed matter was obtained from the eighth sheet. Good printed matter was stably obtained up to 30,000 sheets.

Example 8 "Formation of a lithographic printing material layer" The silver halide emulsion 1 used in Example 1 was added to 47 g of the fine particle dispersion prepared in Example 3.
2 g was added by heating to 45 ° C. and stirred for 20 minutes. 0.9 g of pyrogallol and 0.3 g of methol were dissolved in 5 g of an aqueous citric acid solution having a solid content of 10% by weight, and the resulting solution was added to the above-mentioned mixed solution. The coating solution was prepared by adjusting the pH to 3.5 with an aqueous citric acid solution having a solid content of 10% by weight. A coating solution was applied on the aluminum support used in Example 1 to form a lithographic printing material layer. The coated silver amount (equivalent to silver nitrate) was 0.6 g / m ² , and the gelatin coated amount was 0.6 g / m ² .
g / m ² , the coating amount of pyrogallol is 0.3 g / m ² , the coating amount of metol is 0.1 g / m ² , and the coating amount of fine particles is 0.7
It was 0 g / m ² .

[Formation of Overcoat Layer] A coating aid was added to a 4% by weight aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.), and 0.8 g / m ² of 0.8 g / m ² was placed on the lithographic printing material layer. Coating was carried out in the application amount to form an overcoat layer. Thus, a lithographic printing original plate was produced.

(Image formation) 400 nm with a xenon sensitometer
The printing original for print quality evaluation was brought into close contact with the lithographic printing original plate using the interference filter described above, and image exposure was performed with an emission time of 10 ^-5 seconds. The lithographic printing plate precursor subjected to image exposure was used in Example 6
Was immersed in the tanning developer used in the above at 24 ° C. for 30 seconds. Next, the substrate was washed with warm water of 40 ° C., and washed with running water of an unexposed portion for 15 seconds. The surface of the lithographic printing original plate was lightly rubbed with a sponge to remove the unexposed portion of the lithographic printing material layer together with the overcoat layer, thereby obtaining a clear relief image in the exposed portion. In this way, a lithographic printing plate was prepared in which the relief image in the exposed area was ink-receptive and the aluminum support (hydrophilic) exposed in the unexposed area due to elution had ink repellency. A lithographic printing plate was printed using a lithographic printing machine (SORM, manufactured by Heidelberg). The dampening solution was prepared by using a dampening solution raw water (EU-3, manufactured by Fuji Photo Film Co., Ltd.) with water.
It was diluted to 0-fold, and 10% by weight of isopropyl alcohol was used. The ink used was black ink (Gloss Ink, manufactured by Dainippon Ink Co., Ltd.). After the start of printing, a clear printed matter was obtained from the eighth sheet. Good printed matter was stably obtained up to 50,000 sheets.

[Example 9] "Formation of lithographic printing material layer" The silver halide emulsion 1 used in Example 1 was added to 47 g of the fine particle dispersion prepared in Example 4.
2 g was added by heating to 45 ° C. and stirred for 20 minutes. 0.9 g of pyrogallol and 0.3 g of methol were dissolved in 5 g of an aqueous citric acid solution having a solid content of 10% by weight, and the resulting solution was added to the above-mentioned mixed solution. The coating solution was prepared by adjusting the pH to 3.5 with an aqueous citric acid solution having a solid content of 10% by weight. A coating solution was applied on the aluminum support used in Example 1 to form a lithographic printing material layer. The coated silver amount (equivalent to silver nitrate) was 0.6 g / m ² , and the gelatin coated amount was 0.6 g / m ² .
g / m ² , the coating amount of pyrogallol is 0.3 g / m ² , the coating amount of metol is 0.1 g / m ² , and the coating amount of fine particles is 0.7
It was 0 g / m ² .

[Formation of Overcoat Layer] A coating aid was added to a 4% by weight aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.), and 0.8 g / m ² of 0.8 g / m ² was formed on the lithographic printing material layer. Coating was carried out in the application amount to form an overcoat layer. Thus, a lithographic printing original plate was produced.

(Image formation) 400 nm by xenon sensitometer
The printing original for print quality evaluation was brought into close contact with the lithographic printing original plate using the interference filter described above, and image exposure was performed with an emission time of 10 ^-5 seconds. The lithographic printing plate precursor subjected to image exposure was used in Example 6
Was immersed in the tanning developer used in the above at 24 ° C. for 30 seconds. Next, the substrate was washed with warm water of 40 ° C., and washed with running water of an unexposed portion for 15 seconds. The surface of the lithographic printing original plate was lightly rubbed with a sponge to remove the unexposed portion of the lithographic printing material layer together with the overcoat layer, thereby obtaining a clear relief image in the exposed portion. In this way, a lithographic printing plate was prepared in which the relief image in the exposed area was ink-receptive and the aluminum support (hydrophilic) exposed in the unexposed area due to elution had ink repellency. A lithographic printing plate was printed using a lithographic printing machine (SORM, manufactured by Heidelberg). The dampening solution was prepared by using a dampening solution raw water (EU-3, manufactured by Fuji Photo Film Co., Ltd.) with water.
It was diluted to 0-fold, and 10% by weight of isopropyl alcohol was used. The ink used was black ink (Gloss Ink, manufactured by Dainippon Ink Co., Ltd.). After the start of printing, a clear printed matter was obtained from the eighth sheet. Good printed matter was stably obtained up to 50,000 sheets.

Example 10 “Formation of a lithographic printing material layer” The silver halide emulsion 1 used in Example 1 was added to 47 g of the fine particle dispersion prepared in Example 5.
2 g was added by heating to 45 ° C. and stirred for 20 minutes. 0.9 g of pyrogallol and 0.3 g of methol were dissolved in 5 g of an aqueous citric acid solution having a solid content of 10% by weight, and the resulting solution was added to the above-mentioned mixed solution. The coating solution was prepared by adjusting the pH to 3.5 with an aqueous citric acid solution having a solid content of 10% by weight. A coating solution was applied on the aluminum support used in Example 1 to form a lithographic printing material layer. The coated silver amount (equivalent to silver nitrate) was 0.6 g / m ² , and the gelatin coated amount was 0.6 g / m ² .
g / m ² , the coating amount of pyrogallol is 0.3 g / m ² , the coating amount of metol is 0.1 g / m ² , and the coating amount of fine particles is 0.7
It was 0 g / m ² .

[Formation of Overcoat Layer] A coating aid was added to a 4% by weight aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.), and 0.8 g / m ² of 0.8 g / m ² was formed on the lithographic printing material layer. Coating was carried out in the application amount to form an overcoat layer. Thus, a lithographic printing original plate was produced.

(Image formation) 400 nm by xenon sensitometer
The printing original for print quality evaluation was brought into close contact with the lithographic printing original plate using the interference filter described above, and image exposure was performed with an emission time of 10 ^-5 seconds. The lithographic printing plate precursor subjected to image exposure was used in Example 6
Was immersed in the tanning developer used in the above at 24 ° C. for 30 seconds. Next, the substrate was washed with warm water of 40 ° C., and washed with running water of an unexposed portion for 15 seconds. The surface of the lithographic printing original plate was lightly rubbed with a sponge to remove the unexposed portion of the lithographic printing material layer together with the overcoat layer, thereby obtaining a clear relief image in the exposed portion. In this way, a lithographic printing plate was prepared in which the relief image in the exposed area was ink-receptive and the aluminum support (hydrophilic) exposed in the unexposed area due to elution had ink repellency. A lithographic printing plate was printed using a lithographic printing machine (SORM, manufactured by Heidelberg). The dampening solution was prepared by using a dampening solution raw water (EU-3, manufactured by Fuji Photo Film Co., Ltd.) with water.
It was diluted to 0-fold, and 10% by weight of isopropyl alcohol was used. The ink used was black ink (Gloss Ink, manufactured by Dainippon Ink Co., Ltd.). After the start of printing, a clear printed matter was obtained from the eighth sheet. Good printed matter was stably obtained up to 40,000 sheets.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a lithographic printing original plate used in the present invention.

FIG. 2 is a schematic cross-sectional view of a lithographic printing original plate during image exposure.

FIG. 3 is a schematic cross-sectional view of a lithographic printing original plate in tanning development.

FIG. 4 is a schematic cross-sectional view of a lithographic printing plate precursor during elution.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Hydrophilic support 2 Lithographic printing material layer 2a Lithographic printing material layer of an exposed part 21 Silver halide particle 21a Latent image of silver halide particle 21b Silver image 22 Hydrophobic fine particle 23 Polymer having amino group 24 On the surface of hydrophobic fine particle Polymers having bonded amino groups 23a, 24a Polymers having cross-linked amino groups 3 Overcoat layer 31 Hydrophilic polymer D Tanning developer L Light S Eluate

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naonori Makino 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Pref. BA01 BA17 BA20 EA02 GA08

Claims (10)

[Claims] 1. A lithographic printing plate precursor having a lithographic printing material layer composed of hydrophobic fine particles having a crosslinkable surface on a hydrophilic support, is subjected to an imagewise cross-linking reaction to chemically bond the hydrophobic fine particles to each other. Binding; and removing the hydrophobic fine particles that have not been chemically bonded to form a hydrophilic region consisting of the exposed support surface and a hydrophobic region consisting of chemically bonded hydrophobic fine particles. And a method of making a lithographic printing plate in this order. 2. A lithographic printing material layer or a photosensitive layer provided adjacent to the lithographic printing material layer contains silver halide, and after performing a step of imagewise exposing the lithographic printing original plate, developing the silver halide using a developing agent. The plate-making method according to claim 1, wherein the cross-linkable surface of the hydrophobic fine particles is subjected to an image-wise cross-linking reaction with an oxidized form of a developing agent. 3. The plate making method according to claim 1, wherein the crosslinkable surface of the hydrophobic fine particles is formed by attaching or bonding the polymer having an amino group to the surface of the hydrophobic fine particles. 4. A crosslinkable surface of the hydrophobic fine particles is formed by attaching or binding a polymer having an amino group to the surface of the hydrophobic fine particles, and tanning developing silver halide using a tanning developer, The plate-making method according to claim 2, wherein a polymer having an amino group is crosslinked imagewise by an oxidized form of a tanning developer. 5. The plate-making method according to claim 3, wherein the polymer having an amino group is gelatin. 6. The plate making method according to claim 5, wherein the hydrophobic fine particles are made of a hydrophobic polymer, and gelatin and the hydrophobic polymer are graft-polymerized. 7. The plate making method according to claim 3, wherein the polymer having an amino group is a reaction product of a polymer having a carboxyl group and an alkyleneimine. 8. The plate making method according to claim 7, wherein the hydrophobic fine particles are made of a hydrophobic polymer, and the polymer having a carboxyl group and the hydrophobic polymer are graft-polymerized. 9. A lithographic printing material layer comprising: a tanning developer;
The plate making method according to claim 4, wherein the plate is added to a photosensitive layer or any other layer provided on a lithographic printing original plate. 10. A relief image composed of chemically bonded hydrophobic fine particles is formed on a hydrophilic support, and the chemically bonded hydrophobic fine particles function as hydrophobic regions and are exposed. A lithographic printing plate wherein the surface of the support functions as a hydrophilic region.