Planographic printing plate precursor containing metal compounds, and process for producing planographic printing plates

Abstract: A planographic printing plate precursor is provided which includes a substrate having thereon an image recording layer containing a metal compound (I-a) which causes a decarboxylation reaction by heat and releases a polyvalent metal cation, and a hydrophilic polymer (I-b) which has two or more hydrophilic groups within the same molecule and can coordinate with the polyvalent cation. Also provided is a planographic printing plate precursor including a substrate having thereon an image recording layer containing a metal complex compound (II-a) and a hydrophilic polymer (II-b) which can coordinate with a metal generated from the metal complex compound by action of heat and which has two or more hydrophilic groups within the molecule and whose main chains are crosslinked.

Description: BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a planographic printing plate precursor. More specifically, the present invention relates to a planographic printing plate precursor which has excellent sensitivity and can be used to manufacture a planographic printing plate directly by heating by a heating device such as a thermal head or by laser scanning on the basis of digital signals of a computer or the like. In addition, the present invention relates to a planographic printing plate precursor requiring no development processing, and a process for manufacturing a planographic printing plate which enables direct image formation by heat. Description of the Related Art In recent years, owing to the progress in technologies related to solid-state lasers and semiconductor lasers which emit rays in regions ranging from a near infrared region to an infrared region, systems, which use these infrared lasers, have been drawing attention as systems for direct planographic printing plate manufacturing in accordance with digital data of a computer. Processes conventionally known as direct planographic printing plate manufacturing processes in which plates are manufactured from digitized image data without using a lithographic film include (1) an electrophotographic process; (2) a process using a high-sensitivity photopolymer which can be written with a blue-light or green-light-emitting laser of a relatively small output power; (3) a process using a silver salt or a combination of a silver salt and another system; and (4) a process in which heat-cured images are obtained by a post-heating process in the presence of an acid which is generated by heat mode laser exposure and acts as a catalyst. Although these conventional processes are very useful in efficiently realizing the printing process, these conventional processes have not yet reached a completely satisfactory level and present the following problems. First, image formation requires a huge amount of energy and a laser of a high output power because the materials used in the above-mentioned heat mode processes generally have low sensitivity. In addition, the processes are complicated because an additional thermal treatment is necessary after laser irradiation. Secondly, despite their extreme usefulness in efficiently realizing the printing process, in addition to the problem that these processes are complicated or require large-scale equipment, these processes also have the following problems. Namely, these processes include a wet development step in which the recording layer formed on substrate surface is removed image-wise after an exposure step, and include a post-treatment step in which the printing plate which has been subjected to development is washed with water or is treated with a rinsing solution containing a surfactant or with a desensitizing solution containing gum arabic or a starch derivative. Therefore, a need exists for a planographic printing plate precursor which does not require the above-mentioned wet developing treatment and can be used directly for printing after exposure. In view of the foregoing needs, in recent years, planographic printing plate precursors, which do not require complicated wet development processing and can be used directly in printing after exposure, have been developed. As an example of a planographic printing plate precursor which does not require wet development processing, USP 5,258,263 discloses a planographic printing plate having a photosensitive hydrophilic layer whose curing or insolubilization is promoted in exposed regions, and a photosensitive hydrophobic layer, and both layers are laminated on a substrate. This plate, however, is a so-called on-printer development type printing plate whose unexposed regions of the photosensitive layer are removed in a printing process. This plate has the drawback that dampening water and printing ink are contaminated at the time of manufacturing a planographic printing plate. Japanese Patent Application Laid-Open (JP-A) No. 7-186, 562 (EP 652,483) discloses a planographic printing plate precursor containing a polymer, which generates a carboxylic acid by the action of heat and acid, and a dye capable of absorbing infrared rays. This planographic printing plate precursor does not require a development step because the plate precursor by itself is a hydrophobic recording layer which generates an acid by being heated to thereby hydrophilize the heated areas so that images are formed. Hawever, this the planographic printing plate precursor presents a problem in that stains are formed at the time of printing because the hydrophilized regions are not sufficiently hydrophilic. On the other hand, JP-A No. 10-329,443 discloses a planographic printing plate precursor for imaging comprising a substrate having a hydrophilic surface and having thereon a photosensitive layer containing a metal chelate compound as a crosslinking agent. However, the sensitivity of this plate is insufficient, and therefore, an improvement of the sensitivity is required. WO 98/29258 discloses a plate for direct thermal lithography comprising a substrate and recording layer which comprises a hydrophilic binder polymer containing polyvalent metal ions and having residues of nitrogenous, oxygenic, or sulfurized Lewis base and which has oleophilic image areas and hydrophilic nonimage areas, which are printed in a thermal mode, wherein the hydrophilic binder polymer contains in the hydrophilic nonimage area is three dimensionally crosslinked by the interaction between the polyvalent metal ions and the Lewis base residues. FR-A-1 302 109 discloses a method for manufacture of lithographic printing plates having ink accepting image areas, which process comprises a short term irradiation of an original image through a thin thermal sensitive copying sheet obtain a visible reproduction of the original on the copying sheet, which reproduction has a strong radiation absorbing property, and subsequently subjecting the copying sheet to a second short term irradiation in contact with a lithographic printing plate having a hydrophilic surface. Examples of the compositions of the copying sheet are described in the examples of this prior art document, which clearly differ from the image recording layer of the present invention. US-2,764,085 discloses masters for planographic printing comprising a base sheet having a continuous surface and a coating on the base sheet having an insolubilized Werner complex compound distributed throughout the coating, wherein the acido group coordinated with the trivalent nuclear chromium is unsaturated and contains 1-8 carbon atoms. Upon imaging, a hydrophilic ink receptive portion is formed on the surface due to a thermal reaction at a temperature of more than 350°F while in the unreacted portion, the surface remains hydrophilic. In an alternative embodiment, the lithographic printing plate comprises a hydrophilic colloid layer on the base sheet and a coating on said layer containing the insolubilized Werner complex compound wherein acido group coordinated with the trivalent nuclear chromium atom contains less than 8 carbon atoms. WO 99/04974 describes single layer direct write lithographic printing plates comprising a support web coated with a coextensive hydrophilic layer having an outer hydrophilic surface comprising a crosslinked polymer matrix containing a colloid of an oxide or hydroxide of a metal selected from Be, Mg, Al, Si, Gd, Ge, As, In, Sn, Sb, Te, Pb, Bi, transition metal oxides and combinations thereof, and a photothermal conversion material comprising a radiation absorber. This lithographic printing plate becomes ink accepting upon exposure to high intensity radiation. The absorber material present therein may be, among others, a specific indolium salt of 4-methylbenzene sulfonic acid as described on page 7, lines 12-15. WO 99/11457 describes processless, laser imageable lithographic printing plates having a substrate, a porous aluminosilicate hydrophilic layer on the substrate, and a porous thermally reactive imaging layer on the hydrophilic layer. The thermally reactive imaging layer contains a composition which absorbs infrared radiation and contains as essential ingredients an acid catalysed crosslinking resin system, a thermal activated acid generator and an infrared absorbing compound. SUMMARY OF THE INVENTION The first aspect of the present invention is a planographic printing plate precursor comprising a substrate having thereon an image recording layer comprising (a) a metal compound which releases a polyvalent metal cation upon heating selected from (I-a) compounds releasing the polyvalent metal cation under decarboxylation selected from trichloroacetate of Al, Ca and Zn, phenylsulfonylacetate of Al, Ca, Zn and Fe, p-chlorophenylsulfonylacetate of Al and Ca, phenylpropiolate of Al, Ca and Zn, 2,4-dichlorophenylpropriolate of Al and Ca, and metal salts of sulfonylacetic acids of the formula (1) or (2): and (II-a) a metal complex compound; and (b) a hydrophilic polymer whose main chains are crosslinked and which has at least two hydrophilic groups within the molecule and can coordinate with the polyvalent metal cation. The second aspect of the present invention is a process for manufacturing a planographic printing plate comprising the step of exposing a planographic printing plate precursor as defined in the first aspect, wherein the image recording layer further comprises a substance (c) capable of converting light to heat, to infrared laser light so as to form a hydrophobic region on a surface of a planographic printing plate precursor. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is described in detail herein after. The planographic printing plate precursor, which is the first aspect of the present invention, is explained. The task of the present invention is to solve the above-mentioned existent problems and to achieve the following objects. That is, the first object of the present invention is to provide a planographic printing plate precursor which can be used to manufacture a planographic printing plate directly with excellent high sensitivity by heat generated either by a heating device or by a light-to-heat conversion action of laser light according to digital signals of a computer or the like. After studies for the first object, the present inventors have found that the sensitivity of a planographic printing plate precursor can be further improved by use of a metal compound which releases a polyvalent metal cation when heated. Based on this discovery, they have established the first aspect of the present invention. The planographic printing plate precursor of the present invention comprises a substrate having thereon an image recording layer comprising (a) a metal compound which releases a polyvalent metal cation upon heating selected from (I-a) compounds releasing the polyvalent metal cation under decarboxylation selected from trichloroacetate of Al, Ca and Zn, phenylsulfonylacetate of Al, Ca, Zn and Fe, p-chlorophenylsulfonylacetate of Al and Ca, phenylpropiolate of Al, Ca and Zn, 2,4-dichlorophenylpropriolate of Al and Ca, and metal salts of sulfonylacetic acids of the formula (1) or (2): and (II-a) a metal complex compound; and (b) a hydrophilic polymer whose main chains are crosslinked and which has at least two hydrophilic groups within the molecule and can coordinate with the polyvalent metal cation, and other constituents, if necessary. As for processes for manufacturing a planographic printing plate of the present invention, preferable are a process comprising irradiating a planographic printing plate precursor, comprised of a substrate having thereon an image recording layer containing a metal compound (a), which releases a polyvalent cation, a hydrophilic polymer (b), which has two or more hydrophilic groups within the same molecule and can coordinate with the polyvalent metal cation and whose main chains are crosslinked, and a substance (c) capable of converting light to heat, with infrared rays image-wise so that hydrophobic regions are formed on the surface. The planographic printing plate precursor of the present invention enables image formation by a heating device such as a thermal head. Further, the incorporation of a substance (c) capable of converting light to heat into the image recording layer of the planographic printing plate precursor enables image formation also by scanning with a laser such as an infrared laser. According to the planographic printing plate precursor of the present invention, the hydrophilic group, which is contained in a hydrophilic polymer (b) having two or more hydrophilic groups within the molecule and having main chains crosslinked and which can coordinate with the metal generated from the metal compound by the action of heat, undergoes a crosslinking reaction by chelation with the metal released from a metal compound (a). The reacted region becomes a hydrophobic region having affinity for ink. On the otherhand, a region free from the chelation maintains the surface property of the hydrophilic polymer to become a hydrophilic region to which dampening water adheres. Accordingly, a planographic printing plate , which can be used directly in printing without the employment of a development step, is manufactured. Although the mechanism is not clear, it is believed that a metal compound (a) undergoes a crosslinking reaction by chelation with the two hydrophilic groups of a hydrophilic polymer (b), which can coordinate with the metal generated from the metal compound by the action of heat and has two or more hydrophilic groups within the molecule and whose main chains are crosslinked, in such a manner that the crosslinking reaction blocks the hydrophilic groups and the formation of the crosslinked structure deprives the hydrophilicity and water absorptivity of the heated region so that the heated region alone becomes a hydrophobic region. In this case, the incorporation of a substance (c) capable of converting light to heat into the recording layer makes the recording layer writable with light such as an infrared laser. Further, the incorporation of a thermoplastic polymer (d) into the recording layer enhances the hydrophobizing effect by thermal fusion and adhesion of the polymer. Furthermore, in order to strengthen the polarity change from hydrophilicity to hydrophobicity, it is preferable that a metal compound (a) is contained in a thermoplastic polymer (d), particularly in thermally fusible hydrophobic polymer particles as a specific form of the polymer. The polymer having hydrophilic functional groups becomes hydrophobic by the formation of a complex with a polyvalent metal cation. The metal compound releases a metal when heated. According to the present invention, the metal compound present in the recording layer releases a metal when heated so that the metal thus generated undergoes a chelation reaction with the hydrophilic polymer to form a complex and hydrophobizes the polymer. As a result, the heated region alone becomes a hydrophobic region having affinity for ink while the rest of the region is hydrophilic. Therefore, a heat-sensitive recording type development treatment-free plate can be formed directly. Particularly because of the effect of the incorporation of a hydrophilic polymer (b) whose main chains are crosslinked, the planographic printing plate precursor of the present invention can be used in printing directly by skipping the development step. The reaction mechanism of the hydrophobizing reaction by the metal compound is schematically described below. Next, the details of a planographic printing plate precursor of the present invention as well as the details of the process for manufacturing a planographic printing plate are given below. <(I-a) a metal compound which causes a decarboxylation reaction when heated and releases a polyvalent metal cation> In one embodiment, the image recording layer of the planographic printing plate precursor of the present invention uses a metal compound (I-a) which causes a decarboxylation reaction when heated and releases a polyvalent metal cation (hereinafter referred to as a thermal decarboxylation-type metal compound (I-a) upon occasion). When heated, the thermal decarboxylation-type metal compound (I-a) causes a decarboxylation reaction and releases a polyvalent metal cation. As illustrated in the example of reaction, the polyvalent cation forms a complex by causing a reaction replacing the monovalent metal cation of the metal carboxylate contained in the structure of the hydrophilic polymer that is described later. As a result, the hydrophilic polymer loses its hydrophilicity and is converted into a hydrophobic polymer structure. Therefore, when heated such that heat is applied image-wise according to the digital signals of a computer or the like, the above-mentioned reaction proceeds only in the heated area and a latent image in image-wise hydrophobization is formed. As the image recording layer uses as a binder polymer a crosslinked hydrophilic polymer that is described later, the image recording layer surface can maintain hydrophilicity despite its insolubility inherent to the crosslinked structure. Accordingly, the area that is not heated maintains its hydrophilicity and forms a non-image area in a stable manner. On the other hand, the heated area forms a complex in the same way as above and is converted into a hydrophobic area, i.e., an area having affinity for ink, so that an image area can be formed. A three-dimensionally crosslinked hydrophilic polymer is also preferable. As a result, without wet development processing, a planographic printing plate can be formed directly due to the crosslinked hydrophilic polymer. The thermal decarboxylation-type metal compound (I-a) includes aluminum trichloroacetate, calcium trichloroacetate, zinc trichloroacetate, aluminum phenylsulfonylacetate, calcium phenylsulfonylacetate, zinc phenylsulfonylacetate, iron phenylsulfonylacetate, calcium p-chlorophenylsulfonylacetate, aluminum p-chlorophenylsulfonylacetate, aluminum phenylpropiolate, calcium phenylpropiolate, zinc phenylpropiolate, aluminum 2,4-dichlorophenylpropiolate, calcium 2,4-dichlorophenylpropiolate and metal salts of sulfonylacetic acids represented by the following general formula (1) or (2). Preferred examples of the thermal decarboxylation-type metal compounds of the formula (1) or (2) are the compounds (1) to (8) shown in Table 1. Thermal decarboxylation-type metal compounds Structural formulae M n (1) (1) Ca 2 (2) (1) Mg 2 (3) (1) Zn 2 (4) (1) Al 3 (5) (2) Ca 2 (6) (2) Mg 2 (7) (2) Zn 2 (8) (2) Al 3 When using the thermal decarboxylation-type metal compound (I-a), it is uniformly dispersed and contained in the hydrophilic polymer (b) that is described later. In particular, in order to strengthen the conversion from hydrophilicity to hydrophobicity, it is preferable that the thermal decarboxylation-type metal compound is contained in a thermoplastic polymer (d), particularly in thermally fusible hydrophobic polymer particles, described later. The amount to be used of the thermal decarboxylation-type metal compound (I-a) is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 10 parts by weight, based on 1 part by weight of the hydrophilic polymer, described later, in the image recording layer. If the amount to be used is less than 0.01 part by weight, the conversion reaction from hydrophilicity to hydrophobicity may not sufficiently occur, whereas if the amount to be used is more than 100 parts by weight, images may become smudgy because non-image area cannot be fully hydrophilized. <(II-a) a metal complex compound> A metal complex compound (II-a) to be used in the present invention is explained below. Examples of the form of the metal complex compound (II-a) (hereinafter referred to as metal complex (II-a) upon occasion) contained in the image recording layer of the planographic printing plate precursor (hereinafter simply referred to as printing plate precursor upon occasion) of the present invention include metal diketenates (a-1), metal alkoxides(a-2), metal carboxylates(a-3), and so on. Among these compounds, the metal diketenate(a-1) is particularly preferable. Specific examples of the chelate portion (ligand) constituting the metal diketenates (a-1) include 2,4-pentanedionate(acetylacetonate), fluoropentanedionate, 2,2,6,6-tetramethyl-3,5-heptanedionate, benzoylacetonate, tenoyltrifluoroacetonate, 1,3-diphenyl-1,3-propanedionate, methylacetoacetate, ethylacetoacetate, methacryloxyethylacetoacetate, allylacetoacetate, and so on. Examples of the central metal of the metal complex compound (II-a) include the atoms of the second to the sixth periods of the Periodic Table. Among these atoms, metals and semiconductive atoms of the third to the fifth periods are preferable. Al, Si, and Mg of the third period, Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn, and Ge of the fourth period, and Zr, In, and Sn of the fifth period are particularly preferable. Specific examples of the metal diketenate (a-1) include acetylacetonates(pentanedionates), ethylacetoacetates(hexanedionates), propylacetoacetonates(heptanedionates), tetramethylheptanedionates, benzylacetonates, and so on which are coordinated by aluminum, iron(III), manganese, cobalt, nickel, titanium, copper, and zirconium. Among these compounds, iron(III) acetylacetonate, aluminum acetylacetonate, and titanium acetylacetonate are particularly preferable. Specific examples of the metal alkoxides (a-2) include tetra-n-butyl titanate, tetrastearoyl titanate, butyl titanate dimer, aluminum oxide isopropylate, tetra-n-butoxy zirconium, and so on. Specific examples of the metal carboxylates (a-3) include aluminum oxide octoate, aluminum oxide stearate, zirconyl octylate, zirconyl stearate, and so on. Other usable example is a ligand-having compound containing a mixture of the metal diketenates (a-1), the metal carboxylates (a-3), and alkylmetals. Specific examples of this compound include dipropoxy-bis(acetylacetonate)titanium, dipropoxytitanium-bis(ethylacetoacetate), dipropoxytitanium-bis(lactate), tri-n-butoxytitanium monostearate, isopropyltristearoyl titanate, aluminum dibutoxide monomethylacetoacetate, and so on. The amount of the metal complex (II-a) to be used in the present invention is preferably within a range of 5 to 300% by weight, more preferably within a range of 10 to 200% by weight, based on the weight of the hydrophilic polymer (b) which can coordinate with the metal generated from the metal complex compound by the action of heat and has two or more hydrophilic groups within the molecule and whose main chains are crosslinked. If the amount to be used is less than 5% by weight, the images to be formed may be defective because the degree of hydrophobicity is insufficient, whereas if the amount to be used is more than 300% by weight, the excess of the metal complex may adversely affect the image formation. <(b) a crosslinked hydrophilic polymer> Next, the hydrophilic polymer, which is used in the image recording layer of the planographic printing plate precursor according to the second aspect of the present invention, i.e., the hydrophilic polymer (b), having within the molecule two or more groups, and which can coordinate with a metal generated from the metal complex compound by the action of heat and are hydrophilic, and having main chains crosslinked (hereinafter referred to as (b) a crosslinked hydrophilic polymer upon occasion), is explained below. The crosslinked hydrophilic compound (b), which is used in the image recording layer of the planographic printing plate precursor according to the second aspect of the present invention, may include any of the hydrophilic polymers listed below in so far as the main chains of the polymer are crosslinked. Any conventionally known polymer having such a structure can be used. The hydrophilic polymer is a polymer which is comprised of a carbon to carbon bond chain and has as side chains thereto two or more hydrophilic functional groups of one or more kinds selected from a hydroxyl group, carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and salts of these acid groups. An example of the hydrophilic polymer (b) is a hydrophilic polymer having at least one kind of hydrophilic functional group selected from a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and salts of these acid groups. Examples of the hydrophilic polymer include polymeric compounds which are based on polymers such as poly(meth)acrylates, polyoxyalkylenes, polyurethanes, polymers prepared by a ring-opening and addition polymerization of epoxy groups, poly(meth)acrylic acids, poly(meth)acrylamides, polyesters, polyamides, polyamines, polyvinyls, polysaccharides, and a combination of these compounds. Further, the structure of the polymeric compound may contain an amido group, a polyoxyalkylene group, and the like. According to the present invention, for the manufacture of a non-development type planographic printing plate precursor, which does not need the wet development processing intended for removal by dissolution of the non-image area after image recording, a hydrophilic polymer, which has two or more hydrophilic groups within the same molecule and can coordinate with a polyvalent metal cation to be released from the metal complex compound and whose main chains are crosslinked, is used. The crosslinked structure within the molecule enables to maintain sufficient hydrophilicity and to provide tough film properties. Therefore, even if the non-image area of the film is not removed by a developing treatment, plate life is not adversely affected and non-image areas do not become smudgy. Further, even if the the non-image area of film is not removed by a developing treatment, the film is not dissolved in dampening water or printing ink at the time of plate making and therefore the dampening water or printing ink is not contaminated. In particular, since the image recording layer surface is hydrophilic and the recording layer is not impaired by the dampening water for a long period of time and satisfactory excellent plate life is obtained, a hydrophilic polymer having an three-dimensional crosslinling structure in the molecular is even more preferable. As described above, because of the use of a polymer, which has hydrophilic groups and is crosslinked, a non-image area, which is not heated, can exist solidly as the non-image area maintaining hydrophilicity, and the area do not be required to removed by a developing treatment. On the other hand, in the area, which is heated, a polyvalent metal cation released from a metal complex compound causes a crosslinking reaction by a replacement reaction with the monovalent metal cation of the metal carboxylate group constituting the polymer to thereby form a complex. As a result, the hydrophilic group is blocked and the water absorptivity is lost by the formation of the crosslinked structure so that only the area heated by image recording forms a hydrophobic image area. The heated area is similar to the case where a developing treatment is required. Accordingly, since the heated area alone becomes a hydrophobic area having affinity for ink whereas the rest of the area is hydrophilic, a planographic printing plate can be obtained without development processing. The hydrophilic polymers having a three-dimensional crosslinked structure are preferably the hydrophilic polymeric compounds listed as examples or regarded as preferable for the hydrophilic polymeric compound (b), wherein the main chains of the polymeric compounds are crosslinked to form a three-dimensional crosslinked structure wherein network-structure is formed. From the standpoint of crosslinking these polymeric compounds, it is preferable that the polymer contain at least one selected from an amino group, a glycidyl group, a polymerizable unsaturated double bond, a photopolymerizable double bond, and others. More specifically, the polymer is a hydrophilic homopolymer or copolymer synthesized by using at least one hydrophilic monomer selected from hydrophilic monomers such as (meth)acrylic acid, or an alkali or amine salt thereof, itaconic acid, or an alkali or amine salt thereof, 2-hydroxyethyl (meth)acrylate, (meth)acrylamide, N-monomethylol(meth)acrylamide, N-dimethylol(meth)acrylamide, 3-vinylpropionic acid, or an alkali or amine salt thereof, vinylsulfonic acid, or an alkali or amine salt thereof, 2-sulfoethyl (meth)acrylate, polyoxyethylene glycol mono(meth)acrylate, 2-acrylamide-2-methylpropanesulfonic acid, acidphosphoxypolyoxyethylene glycol mono(meth)acrylate, allylamine or a mineral acid salt thereof, which each have at least one of a hydrophilic group such as a hydroxyl group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, an amido group, an amino group, an ether group, or the like. The image recording layer containing the hydrophilic polymer (b) having a crosslinked structure may be formed by the following synthesis process. That is, a hydrophilic polymer having in the molecule thereof at least two functional groups, such as a hydroxyl group, a carboxyl group, an amino group or a salt thereof, an epoxy group, or the like, is used. By utilizing the functional groups, an addition-polymerizable double bond, such as a vinyl group, an allyl group, a (meth)acryl group, or the like, or a ring-forming group, such as a cinnamoyl group, a cinnamylidene group, a cyanocinnamylidene group, a p-phenylene diacrylate group, or the like, is introduced into the polymer so as to obtain an unsaturated bond-containing polymer. If necessary, a monofunctional or multifunctional monomer copolymerizable with the unsaturated bond, a polymerization initiator that is described later, and other components that are described later are added to the unsaturated bond-containing polymer and these substances are dissolved in a suitable solvent to prepare a dope. Optionally adjunctive components are added to the resulting solution and the solution is coated on a substrate that is described later. The coating layer may be three-dimensionally crosslinked while being dried simultaneously or after dried. In this way, the image recording layer containing a hydrophilic polymer having a crosslinked structure can be formed. The method for coating the solution on the substrate can be appropriately selected from the coating methods that are described later. In the case where the hydrophilic polymer is a hydrophilic polymer having an active hydrogen atom such as a hydroxyl group, an amino group, a carboxyl group, or the like, the hydrophilic polymer, an isocyanate compound or a block polyisocyanate compound, and other components that are described later are dissolved in a solvent free from an active hydrogen atom, such as tetrahydrofuran, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, or the like so as to prepare a dope. The dope is coated on a substrate and the coating layer is dried or three-dimensionally crosslinked while being dried simultaneously. In this case, a glycidyl group-containing monomer such as glycidyl (meth)acrylate or a carboxyl group-containing monomer such as (meth)acrylic acid can be used as a copolymerization component of the hydrophilic polymer. In the case where the hydrophilic polymer is a hydrophilic polymer having a glycidyl group, a three-dimensionally crosslinked structure can be formed by utilizing a ring-opening reaction using as a crosslinking agent such compound as an α,ω-alkane- or alkenedicarboxylic acid, e.g., 1,2-ethanedicarboxylic acid and adipic acid, a polycarboxylic acid, e.g., 1,2,3-propanetricarboxylic acid and trimellitic acid, a polyamine compound, e.g., 1,2-ethanediamine, diethylenediamine, diethylenetriamine, and α,ω-bis(3-aminopropyl)-polyethyleneglycol ether, an oligoalkylene- or polyalkyleneglycol, e.g., ethyleneglycol, propyleneglycol, diethyleneglycol, and tetraethyleneglycol, and a polyhydroxy compound, e.g., trimethylol propane, glycerin, pentaerythritol, and sorbitol. In the case where the hydrophilic polymer is a hydrophilic polymer having a carboxyl group or an amino group, a three-dimensional crosslinked structure can be formed by utilizing an epoxy ring-opening reaction using as a crosslinking agent such polyepoxy compound as ethylene- or propyleneglycol diglycidyl ether, polyethylene- or polypropyleneglycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, and the like. In the case where the hydrophilic polymer is a polysaccharide such as a cellulosic derivative, polyvinyl alcohol or a partial saponification product thereof, a glycidol homopolymer or copolymer, or a hydrophilic polymer based on any of these compounds, a three-dimensional crosslinked structure can be formed by the introduction of a functional group capable of the crosslinking reaction according to the above-described method utilizing a hydroxy group contained in the hydrophilic polymer. Among these three-dimensionally crosslinked polymers, a preferred polymer is one obtained by three-dimensionally crosslinking a hydrophilic homopolymer or copolymer synthesized by using at least one hydrophilic monomer selected from hydrophilic monomers such as (meth)acrylic acid, or an alkali metal salt or amine salt thereof, itaconic acid, or an alkali metal salt or amine salt thereof, 2-hydroxyethyl (meth)acrylate, (meth)acrylamide, N-monomethylol(meth)acrylamide, N-dimethylol(meth)acrylamide, an allylamine or a hydrogen halide salt thereof, 3-vinylpropionic acid, or an alkali metal salt or amine salt thereof, vinylsulfonic acid, or an alkali metal salt or amine salt thereof, 2-sulfoethylene (meth)acrylate, polyoxyethylene glycol mono(meth)acrylate, 2-acrylamide-2-methylpropanesulfonic acid, acidphosphoxypolyoxyethylene glycol mono(meth)acrylate, and allylamine or a hydrogen halide acid salt thereof which each have a hydrophilic group such as a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, an amino group or a salt thereof, a hydroxyl group, an amido group, an ether group, or the like, or alternatively, a hydrophilic polymer composed of polyoxymethylene glycol or polyoxyethylene glycol in the same way as above. When combined with the metal compound (I-a) the amount of the hydrophilic polymer (b) to be used in the present invention is preferably 5 to 99% by weight, more preferably 2 to 90% by weight, based on the weight of the total solids of the image recording layer. If the amount to be used is less than 5% by weight, image areas may become smudgy because non-image areas are not sufficiently hydrophilized, whereas if the amount to be used is more than 99% by weight, the conversion reaction from hydrophilicity to hydrophobicity may not sufficiently occur. When combined with the metal complex compound (II-a) the amount to be used of the three-dimensionally crosslinked polymer is preferably within a range of 0.1 to 90% by weight, more preferably within a range of 1 to 60% by weight, based on the weight of the total solids of the image recording layer. If the amount to be used is outside the range, a high level of discrimination (i.e., a large difference of hydrophobic property between exposed area and unexposed area) may not be obtained. Examples of suitable known crosslinked polymers usable as the crosslinked hydrophilic polymer (b) of the present invention include (1) a polymer which forms a hydrophilic layer and is composed of a crosslinked polymer containing metal colloids as described in WO98/40212, and (2) a polymer which forms a hydrophilic layer and is composed of a crosslinked organic polymer as described in JP-A Nos. 10-6,468 and 10-58,636. In particular, a hydrophilic polymer illustrated in (2) a hydrophilic layer composed of a crosslinked organic polymer is preferable for use in the present invention. <(c) a substance capable of converting light to heat> In the present invention, the incorporation of a substance (c) capable of converting light to heat, in addition to the aforementioned two components, into the recording layer of the planographic printing plate precursor makes the recording layer writable with active light such as an infrared laser in addition to writability by heating by a thermal head or the like. Therefore, the incorporation of the substance (c) capable of converting light to heat is preferable. When making the planographic printing plate precursor of the present invention a laser-responsive type of planographic printing plate precursor capable of image formation by irradiation with laser light, it is necessary to use a substance which absorbs the irradiated laser light in a highly efficient manner and converts the laser energy to heat. Any substance, which can absorb light such as ultraviolet light, visible light, infrared light, white light, and the like and can convert the light to heat, can be used as the substance capable of converting light to heat. Examples of the substance include carbon black, carbon graphite, a pigment, a phthalocyanine-based pigment, iron powder, graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, chromium sulfide, and so on. Among these substances, a dye, a pigment, or a metal, which effectively absorbs infrared rays in a wavelength region of 760 to 1200 nm, is preferable. The dyes can be commercially available dyes and known dyes described in, for example, "Handbook of Dyes", edited by Association of Organic Synthesis (Yuki Gosei Kagaku Kyokai)(1970). Specific examples of the dyes include azo dyes, azo dyes in the form of a metal complex salt, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, and dyes in the form of a metal thiolate complex. Among these dyes, preferred examples of the dyes include cyanine dyes described in, e.g., JP-A Nos. 58-125,246; 59-84,356; 59-202,829; and 60-78,787, methine dyes described in, e.g., JP-A Nos. 58-173,696; 58-181,690; and 58-194,595, naphthoquinone dyes described in, e.g., JP-A Nos. 58-112, 793; 58-224,793; 59-48,187; 59-73,996; 60-52,940; and 60-63,744, squalylium dyes described in JP-A No. 58-112,792, and cyanine dyes described in U. K. Patent No. 434,875. Other suitable compounds are a near-infrared absorbing sensitizer described in U. S. Patent No. 5,156,938, a substituted arylbenzo(thio)pyrylium salt described in U. S. Patent No. 3,881,924, a trimethinethiapyrylium salt described in JP-A No. 57-142,645 (U. S. Patent No. 4, 327, 169), pyrylium compounds described in JP-A Nos. 58-,181,051; 58-220,143; 59-41,363; 59-84,248; 59-84,249; 59-146,063; and 59-146,061, a cyanine dye described in JP-A No. 59-216,146, a pentamethinethiopyrylium salt described in U. S. Patent No. 4,283,475, and pyrylium compounds described in Japanese Patent Application Publication (JP-B) Nos. 5-13,514 and 5-19,702. Further examples of preferred dyes are near-infrared absorbing dyes represented by the formula (I) or (II) in U.S. Patent No. 4,756,993. Among these dyes, cyanine dyes, squalylium dyes, pyrylium dyes, and nickel thiolate complexes are more preferable. The pigments suitable for use in the present invention are commercially available pigments and those described in "Color Index (C.I.) Handbook", "Latest Pigment Handbook" (Saishin Ganryo Binran) editied by Japan Association of Pigment Technologies (Nihon Ganryo Gijutsu Kyokai) (1977), "Latest Pigment Application Technologies" (Saishin Ganryo Oyo Gijutsu), CMC, 1986, and "Printing Ink Technologies" (Insatsu Inki Gijutsu) , CMC, 1984. Examples of the pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymers containing chemically combined dyes. Specific examples of the pigments are insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine based pigments, anthraquinone based pigments, perylene and perinone based pigments, thioindigo based pigments, quinacridone based pigments, dioxazine based pigments, isoindolinone based pigments, quinophthalone based pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like. Among these pigments, carbon black is preferable. These pigments may be used without being surface-treated or may be used after being surface-treated. Possible surface treatments include a treatment wherein a resin or a wax is coated on the surface of the pigments, a treatment wherein a surfactant is adhered to the surface of the pigments, and a treatment wherein a reactive substance (e.g., a silane coupling agent, an epoxy compound, or a polyisocyanate) is bound to the surface of the pigments. These surface-treating methods are described in "Properties and Applications of Metal Soaps" (Sachi Shobo Co., Ltd.), "Printing Ink Technologies" (Insatsu Inki Gijutsu), CMC, 1984, and "Latest Pigment Application Technologies" (Saishin Ganryo Oyo Gijutsu), CMC, 1986. The diameter of the pigments is preferably 0.01 to 10 µm, more preferably 0.05 to 1 µm, and most preferably 0.1 to 1 µm. If the diameter is less than 0.1 µm, the dispersion stability of the dispersion in a coating liquid for the image recording layer may be insufficient, whereas, if the diameter is greater than 10 µm, the uniformity of the image recording layer may be impaired. A known dispersing technology employed in the preparation of ink, toners, and the like can also be used for the purpose of dispersing the pigments. Examples of the dispersing machine include an ultrasonic wave dispersing machine, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roller mill, a pressurized kneader, and the like. Details of these dispersing technologies are described in "Latest Pigment Application Technologies" (Saishin Ganryo Oyo Gijutsu), CMC, 1986. When combined with the metal compound (I-a), the amount added of the dye or the pigment is preferably 0.01 to 50% by weight, more preferably 0.1 to 10% by weight, most preferably 0.5 to 10% by weight in the case of the dye, and most preferably 3.1 to 10% by weight in the case of the pigment, based on the weight of the total solids of the image recording layer. If the amount added of the dye or the pigment is less than 0.01% by weight, the sensitivity may decrease, whereas, if the amount is more than 50% by weight, non-image areas may become smudgy at the time of printing. When combined with the metal complex compound (II-a), the amount added of the dye or the pigment is preferably 0.1 to amount added of the dye or the pigment is preferably 0.1 to 30% by weight based on the weight of the total solids of the image recording layer. If the amount added of the dye or the pigment is less than 0.1% by weight, the sensitivity decreases, whereas, if the amount is more than 30% by weight, non-image areas become smudgy at the time of printing. <(d) a thermoplastic polymer> It is preferable that the image recording layers of the planographic printing plate precursors of the present invention further contain a thermoplastic polymer. The addition of the thermoplastic polymer causes thermal fusion and adhesion of the polymer inside the layer so that the hydrophobizing effect is enhanced. The metal compound and metal complex compound is preferably contained in the thermoplastic polymer(d), particularly in a thermally fusible hydrophobic polymer particles. The use of the thermoplastic polymer is effective particularly in manufacture of the planographic printing plate precursor containing the metal complex compound (II-a) requiring no development processing. The use of the thermoplastic polymer is effective also in manufacture of other planographic printing plate precursors requiring development processing because the thermoplastic polymer is useful in enhancing the affinity for ink in the image area. Therefore, the thermoplastic polymer needs to be present uniformly in the layer, and, in this regard, it is preferable to use a thermoplastic polymer in the form of particles (hereinafter referred to as "thermoplastic polymer particles" upon occasion). In addition, in order to upgrade the effect, the glass transition point of the thermoplastic polymer is preferably 10 to 150°C and more preferably 10 to 120°C. If the glass transition point of the thermoplastic polymer is below 10°C, the particles may adhere to each other by fusion and a recording layer having well dispersed particles can not be formed in the process wherein the recording layer is formed by coating a coating liquid containing the polymer particles on a substrate and drying the coating layer, in the case where each particle is not perfectly isolated by a binder resin. On the other hand, if the glass transition point of the thermoplastic polymer is above 150°C, the thermal fusion of the thermoplastic particles is so difficult to occur that the formation of tough images is difficult by a laser having a relatively small output power. Examples of the thermoplastic polymer include hydrophobic polymers such as polyethylene, polyvinyl chloride, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polyvinylidene chloride, polyacrylonitrile, polyvinylcarbazole, and copolymers thereof. Among these polymers, polyethylene is preferable. The molecular weight of the thermoplastic polymer is preferably 5,000 to 1,000,000. The diameter of the particles of the thermoplastic polymer is preferably 0.01 to 50 µm, more preferably 0.05 to 10 µm, and most preferably 0.05 to 2 µm. It is believed that the larger the particle diameter, the smaller the resolution of the produced planographic printing plate will be. On the contrary, if the particle diameter is too small, the image formability tends to become poor because the discrimination between hydrophilicity and hydrophobicity is lessened. From the standpoint of stability, it is preferable to use the fine particles of the thermoplastic polymer in a state of an aqueous dispersion comprising the particles dispersed uniformly in an aqueous coating liquid. Such an aqueous dispersion of polymer particles can be prepared by a method described in U. S. Patent No. 3,476,937. An example of other methods for preparing the aqueous dispersion comprises the steps of dissolving a hydrophobic thermoplastic polymer in an organic solvent not miscible with water, dispersing the resulting solution in water or an aqueous medium, and removing the organic solvent by evaporation. In combination with the metal compound (I-a), the amount added of the thermoplastic polymer is preferably 20 to 65% by weight, more preferably 25 to 55% by weight, and most preferably 30 to 45% by weight based on the weight of the total solids of the image recording layer. In combination with the metal complex compound (II-a), the amount added of the thermoplastic polymer is preferably 1 to 80% by weight, more preferably 5 to 55% by weight, and most preferably 10 to 40% by weight based on the weight of the total solids of the image recording layer. If the amount added of the thermoplastic polymer particles is too small, the expected effect of adding the polymer is insufficient with respect to the enhancement of hydrophobicity of exposed areas. On the other hand, if the amount added of the thermoplastic polymer particles is too large, the hydrophilic layer of unexposed areas is adversely affected to an extent that ink receptivity is created in non-image regions and the non-image areas may become smudgy. According to the image recording layer incorporating particles of the thermoplastic polymer(d), a pattern region which forms an image of the layer is directly heated or the layer is exposed or the layer is exposed while being held in contact with an original containing a pattern region capable of converting light to heat. As a result, in the image recording layer, the thermoplastic polymer particles in the region, which has been heated or exposed image-wise, are softened or melted so that this region alone is solidified after the completion of the heating. In this way, the hydrophobicity of the region is enhanced. <Other components> In the present invention, besides the above-described essential components and preferred components, a variety of known additives can be used if necessary in so far the effect of the present invention is not impaired. For example, a dye, which has a large percentage of absorption in a visible light region, can be used as an image coloring agent Specific examples include Oil Yellow No. 101, Oil Yellow No. 103, Oil Pink No. 312, Oil Green BG, Oil Blue BOS, Oil Blue No. 603, Oil Black BY, Oil Black BS, and Oil Black T-505 (all manufactured by Orient Chemical Industries, Co., Ltd.), Victoria Pure Blue, Crystal Violet(C. I. 42555), Methyl Violet (C. I . 42535), Ethyl Violet (C. I. 42600), Rhodamine B(C. 1. 145170B), Malachite Green(C. I. 42000), Methylene Blue (C. I. 52015), and the like along with dyes described in JP-A No. 62-293,247. It is preferable to add the dyes because these dyes fade after laser exposure and allows easy discernment between image and non-image areas. The amount added of the dye is preferably 0.01 to 10% by weight based on the weight of the total solids of the image recording layer. In addition, in order to increase mechanical strength and porosity of the recording layer, colloidal silica can be incorporated into the recording layer. The colloidal silica to be used has an average particle diameter of, for example, 40 nm or less. More specifically, commercially available colloidal silica having an average diameter of, for example, 20 nm and in the form of an aqueous dispersion can be incorporated directly into the coating liquid for the recording layer. Further, inert particles which have particle diameters larger than those of colloidal silica and are exemplified by, silica produced according to Stoeber, J. Colloid and Interface Sci., vol.26 (1968), 62-69 and alumina particles, titanium dioxide particles, or particles of other heavy metal oxides, having an average particle diameter of at least 100 nm, can also be used in the same way. The incorporation of these fine particles into the recording layer creates uniform and uneven concavities and convexities of microscopic dimensions on the layer surface. These concavities and convexities function as storing sites of dampening water in the background area (non- image region, i.e., hydrophilic region). Further, in order to broaden the latitude of stable printing conditions, the image recording layer may contain a nonionic surfactant as described in JP-A Nos. 62-251,740 and 3-208,514, and an amphoteric surfactant as described in JP-A Nos. 59-121,044 and 4-13,149. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, monoglyceride stearate, and polyoxyethylene nonylphenyl ether. Specific examples of the amphoteric surfactant include alkyldi(aminoethyl)glycine, hydrochloric acid salt of alkylpolyaminoethylglycine, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, and N-tetradecyl-N, N-betaine (e.g., Amogen K (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). The preferred amount added of the nonionic surfactant and the amphoteric surfactant are each 0.05 to 15% by weight, more preferably from 0.1 to 5% by weight, based on the weight of the total solids of the image recording layer. If necessary, in order to impart flexibility to the image recording layer after drying, a plasticizer may be incorporated into the layer. Examples of the plasticizer include polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, and an oligomer or a polymer of acrylic acid or methacrylic acid. In addition to the above-described substances, other substances, such as an epoxy compound, vinyl ethers, and a phenolic compound having a hydroxymethyl group and a phenolic compound having an alkoxymethyl group as described in Japanese Patent Application No. 7-18,120, may also be added. Further, in order to increase the strength of the image recording layer, other polymeric compound may also be added. Normally, the planographic printing plate precursor of the present invention can be manufactured by coating a coating liquid for the image recording layer, which coating liquid is prepared by dissolving or dispersing the above-mentioned components in a solver, on a suitable substrate. Examples of the solvent include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N,N-dimethylacetamide, N,N-dimethylformamide, tetramethylurea, N-methylpyrolidone, dimethyl sulfoxide, sulfolane, γ-butylolactone, toluene, and water. It should be noted, however, that the present invention is not limited to these solvents. These solvents may be used singly or in a combination of two or more. The concentration of the total solid components (constituent components and other components) in the solvent is preferably 1 to 50% by weight. The coated amount (solids) after coating and drying on the substrate is preferably 0.5 g to 5.0 g/m 2 . The coating liquid for image recording layer can be applied by various methods. Examples of the methods include bar coating, rotational coating, spraying, curtain coating, dipping, air-knife coating, blade coating, and roll coating. In order to improve the coatability, the coating liquid for image recording layer of the planographic printing plate precursor of the present invention may contain a surfactant such as a fluorine-based surfactant described in JP-A No. 62-170,950. The preferred amount added of the surfactant is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the weight of the total solids of the image recording layer. <Substrate> A substrate which can be used in the present invention is preferably a dimensionally stable plate. Specific examples of the substrate include paper, paper laminated with a plastic (e.g., polyethylene, polypropylene, and polystyrene), plates of metals such as aluminum, zinc, and copper, films of plastics such as diacetylcellulose, triacetylcellulose, cellulose propionate, cellulose butyrate, cellulose butyrate acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, and paper or plastic films laminated or vapor-deposited with the aforementioned metals. Preferred examples include polyethylene terephthalate films, cellulose acetate films, and paper coated with a polyolefin (e.g., polyethylene). Besides, the substrate can be coated with a first undercoat layer containing, for example, a latex of copoly(vinylidene chloride/methyl methacrylate/itaconic acid) and silica so that the adhesion between a hydrophilic layer contiguous to the undercoat layer and the substrate is improved. The thickness of the substrate is preferably 0.1 to 0.6 mm, more preferably 0.15 to 0.4 mm, and most preferably 0.2 to 0.3 mm. When manufacturing a planographic printing plate which is not of an on-machine development type and does not require development processing, using a crosslinked hydrophilic polymer as in the second aspect, the substrate surface does not need to be hydrophilic. On the other hand, when manufacturing an on-machine developing type planographic printing plate requiring development processing in the first aspect using a non-crosslinked hydrophilic polymer, the substrate surface needs to be hydrophilic. In this regard, it is preferable to use a hydrophilic substrate which has undergone the following hydrophilization treatment. As necessary, the substrate undergoes a surface treatment such as a hydrophilization treatment. In the case of substrate whose surface is aluminum in particular, it is preferable that the surface undergoes a surface treatment such as graining, immersion in an aqueous solution of, for example, sodium silicate, potassium fluorozirconate, or a phosphate, or anodizing. Preferred examples include an aluminum plate treated by a method wherein the aluminum plate after graining is immersed in an aqueous solution of sodium silicate as described in U. S. Patent No. 2, 714, 066, and an aluminum plate treated by a method wherein the aluminum plate after anodizing is immersed in an aqueous solution of an alkali metal silicate as described in U. S. Patent No. 3,181,461. The anodizing is performed, for example, by applying an electric current, using the aluminum plate as an anode, in an electrolyte solution comprising a single, or two or more aqueous or nonaqueous solutions of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, and boric acid, an organic acid such as oxalic acid and sulfamic acid, or a salt thereof. Also, electrodeposition of a silicate as described in U. S. Patent No. 3,658,662 is effective. The purposes of these hydrophilization treatments are to prevent an undesirable reaction between the substrate surface and the image recording layer formed thereon and to increase the adhesion between the image recording layer and the substrate surface, in addition to the hydrophilization of the substrate surface. Prior to the graining of the aluminum plate, it is also possible to carry out a pretreatment to remove any rolling oil from the surface of the aluminum plate or to clean the surface of the aluminum. For the purpose of removing the rolling oil, a method using a solvent such as trichloroethylene, a surfactant, or the like is widely employed. For the purpose of cleaning the surface, a method using an alkaline etching agent such as sodium hydroxide, potassium hydroxide, or the like is widely employed. The graining (surface-roughening) of the aluminum plate may be performed by a method appropriately selected from a variety of methods. Examples of these methods include a method wherein the surface is mechanically roughened, a method wherein the surface is roughened by being electrochemically dissolved, and a method wherein the surface is selectively dissolved in a chemical way. Examples of the mechanical methods include ball abrasion, blasting abrasion, and brush abrasion wherein the surface is abraded with a nylon brush using a water- dispersed slurry of an abrasive such as pumice. A preferred example of the chemical method is immersion in a saturated aqueous solution of an aluminum salt of a mineral acid as described in JP-A No. 54-31,187. A preferred electrochemical method is electrolysis by an a. c. current in an acidic electrolyte solution of hydrochloric acid, nitric acid, or a combination thereof. Among these methods for roughening the surface of aluminum, a method comprising a combination of mechanical roughening and electrochemical roughening as described in JP-A No. 55-137,993 is preferable because this method increases the bonding strength of an image recording layer to the substrate. Desirably, the graining is performed in such a way that the average roughness (Ra) along the center line on the aluminum plate is 0.3 to 1.0 µm. After the graining, the aluminum plate is subjected to water-rinsing or chemical etching, if necessary. When a chemical etching treatment is employed, the treating solution for etching is usually selected from an aqueous solution of a base or and acid capable of dissolving aluminum. After the treatment, the etched surface must not have a coating film formed thereon which derives from the components of the etching solution and is different from aluminum. Examples of the etching agents as basic aqueous solutions include aqueous solutions of sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate. Examples of the etching agents as acidic aqueous solutions include aqueous solutions of sulfuric acid, persulfuric acid, phosphoric acid, hydrochloric acid, and salts thereof. However, salts of metals, such as zinc, chromium, cobalt, nickel, and copper, having an ionizing tendency lower than that of aluminum, are not desirable because these salts produce an unnecessary film on the etched surface. Desirably, the concentration and temperature of the etching solution employed in the treatment are set such that the dissolution rate of aluminum or an aluminum alloy is 0.3 to 40 g/m 2 for each minute of immersion. However, a higher or lower dissolution rate may be adopted. The etching can be performed either by immersing an aluminum plate in the etching solution or by coating the etching solution on the aluminum plate. The desirable etched amount by the etching treatment is 0.5 to 10 g/m 2 . Because of its higher etching speed, the use of an aqueous solution of a base as a etching solution is preferable. In this case, since smut is formed, a desmutting treatment is usually employed. Examples of the acid to be used for the desmutting treatment include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, and fluoroboric acid. After the etching, the aluminum plate is subjected to water-rinsing and anodizing, if necessary. The anodizing may be performed according to a method conventionally employed in this field. More specifically, the anodizing is performed by applying ad. c. or a. c. current to aluminum in an aqueous or nonaqueous solution of, for example, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, or a mixture of two or more of these acids so that an anodized film is formed on the surface of the aluminum plate. Conditions for the anodizing vary depending on the type of electrolyte solution employed and cannot be stipulated unqualifiedly. However, usually employed conditions are as follows: concentration of the electrolyte solution is 1 to 80% by weight; temperature of the solution is 5 to 70°C; current density is 0.5 to 60 A/dm 2 ; voltage is 1 to 100V; and duration of the electrolysis is 30 seconds to 50 minutes. The amount of the anodized layer is preferably 1.0 g/m 2 or more. If the amount of the anodized layer is less than 1.0 g/m 2 , sufficient hardness cannot be obtained, or the non-image areas become scratched easily. In particular, in the case of a planographic printing plate precursor, so-called "scratch toning", which is caused by the adhesion of printing ink to scratch marks in printing operation, may easily occur. Among these anodizing processes, a process, wherein an aluminum plate is anodized in sulfuric acid by a high current density as described in U. K. Patent No. 1,412,768, and a process, wherein an aluminum plate is anodized by using phosphoric acid as an electrolysis bath as described in U. S. Patent No. 3,511,661, are preferable. If necessary, the substrate whose surface is already anodized may be subjected to a hydrophilization treatment. Preferred examples of the hydrophilization treatment include treating the surface with an aqueous solution of an alkali metal silicate (e.g., an aqueous solution of sodium silicate) as described in U. S. Patent Nos. 2,714,066 and 3,181,461. According to this method, the aluminum plate is immersed or electrolytically treated in an aqueous solution of sodium silicate. Further examples are a treatment of the surface with an aqueous solution of potassium fluorozirconate as described in JP-B No. 36-22,063 and a treatment of the surface with an aqueous solution of polyvinylphosphonic acid as described in U. S. Patent No. 4,153,461. <Others> The planographic printing plate precursor of the present invention can be prepared by forming an image recording layer on a desired substrate. If necessary, an undercoat layer may be formed on the substrate before the formation of the image recording layer. various organic compounds may be used as components of the undercoat layer. Examples of the organic compounds include carboxymethyl cellulose; dextrin; gum arabic; phosphonic acids having an amino group such as 2-aminoethylphosphonic acid; organic phosphonic acids which may have a substituent such as phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid, and ethylenediphosphonic acid; organic phosphoric acids which may have a substituent such as phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid, glycerophosphoric acid, metylenediphosphoric acid and etylenediphosphoric acid; organic phosphinic acids which may have a substituent such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid, and glycerophosphinic acid; amino acids such as glycine and β -alanine; and hydrochloric acid salts of amines having a hydroxyl group such as hydrochloric acid salt of triethanolamine. These compounds may be used singly or may be used in a combination of two or more. In addition, the use of diazonium salts as undercoat layers is also preferable. A suitable coating amount of the undercoat layer after drying is preferably 2 to 200 g/m 2 and more preferably 5 to 100 g/m 2 . If the coating amount is less than 2 g/m 2 , satisfactory film properties may not be obtained, whereas, even if the coating amount exceeds 200 g/m 2 , any better effect cannot be obtained. The undercoat layer may be formed by any method described below. For example, the above-mentioned organic compound is dissolved in water, an organic solvent such as methanol, ethanol, or methyl ethyl ketone, or a mixture thereof to prepare a coating solution, and thereafter the coating solution for the undercoat is coated on a substrate such as an aluminum plate to provide a layer which is then dried. Alternatively, the above-mentioned organic compound is dissolved in water, an organic solvent such as methanol, ethanol, or methyl ethyl ketone, or a mixture thereof to prepare a coating solution for the undercoat, and thereafter a substrate such as an aluminum plate is immersed in the coating solution so that the organic compound is adsorbed on the surface of the substrate to form a layer which is then rinsed with water or the like and dried. When the former method is employed, a solution containing 0.005 to 10% by weight of the organic compound is preferably used as a solution for forming the undercoat layer. When the latter method is employed, the parameters of the conditions are as follows: concentration of the solution for the undercoat layer is 0.01 to 20% by weight and preferably 0.05 to 5% by weight; immersion temperature is 20 to 90°C and preferably 25 to 50°C; and immersion time is 0.1 second to 20 minutes and preferably 2 seconds to 1 minute. The pH of the coating solution for the undercoat may be adjusted to a value within a range of 1 to 12 by use of a base such as ammonia, triethylamine or potassium hydroxide, or an acid such as hydrochloric acid or phosphoric acid. Further, when a planographic printing plate precursor is manufactured using the image forming materials of the present invention, a yellow dye may be incorporated into the coating solution so as to improve the tone reproducibility of the planographic printing plate precursor. The planographic printing plate precursor of the present invention can be prepared by coating a coating solution for image recording layer by a desired coating method on a desired substrate or an undercoat layer provided on the substrate as described above. <Method for manufacturing a planographic printing plate > On the planographic printing plate precursor of the present invention, images can be recorded directly by a heating device such as a thermal head according to digital signals of a computer or the like. Further, if the image recording layer contains a substance capable of converting light to heat, images can be recorded directly by scanning with a laser such as a infrared laser according to digital signals. Furthermore, recording by an ultraviolet light lamp is also possible. Among these methods, image recording by use of an infrared laser is more preferable. The laser light source is preferably a laser emitting infrared rays in a wavelength range of 760 to 1200 nm. A solid-state laser or a semiconductor laser emitting infrared rays in the wavelength range is more preferable. When images are recorded by direct heating according to digital signals of a computer or the like, the heating device is, for example, a thermal head. (Process for manufacturing a planographic printing plate from planographic printing plate precursor) A specific example of the process for manufacturing a planographic printing plate from a planographic printing plate precursor a process comprising irradiating a planographic printing plate precursor, comprised of a substrate having thereon an image recording layer containing a metal compound (I-a) which causes a decarboxylation reaction by heat and releases a polyvalent cation, a hydrophilic polymer (I-b) which has two or more hydrophilic groups within the same molecule and can coordinate with the polyvalent metal cation and whose main chains are crosslinked, and a substance (c) capable of converting light to heat, with infrared rays image-wise so that hydrophobic regions are formed on the image recording layer. As a crosslinked hydrophilic polymer is used as a binder, development processing is not necessary. When the image recording layer is subjected to image recording by use of a heating device such as a thermal head or by use of laser light, a hydrophobic region having affinity for ink (image area) is formed in the image recording layer, while the region, which has not been subjected to image recording, remains as a hydrophilic region (non-image area) capable of retaining dampening water. Therefore, after laser irradiation, the manufactured planographic printing plate can be directly set to a printing machine so that printing can be carried out. The incorporation of (c) a substance capable of converting light to heat into the image recording layer makes the recording layer writable with light. Although the recording with light may be carried out by exposure of the entire surface through a filter provided with a suitable pattern, particularly preferable is the image recording by use of an infrared laser, e.g., a solid-state laser or semiconductor laser emitting infrared rays having wavelengths of 760 to 1200 nm. The laser exposure makes it possible to carry out desired image-wise recording directly from the digital information of a computer. As stated above, in the present invention, a hydrophobic region having affinity for ink (image area) and a hydrophilic region (non-image area) capable of retaining dampening water are formed in the image recording layer after recording. Therefore, after laser irradiation, the planographic printing plate can be immediately set at a printing machine so that printing is carried out without necessitating a treatment to dissolve and develop the recording layer. A representative process for manufacturing a planographic printing plate by using the planographic printing plate precursor of the present invention is the second aspect, wherein a heat-sensitive type planographic printing plate precursor comprised of a substrate having thereon a recording layer, containing the metal complex compound (II-a), the hydrophilic polymer (b) which can coordinate with the metal generated from the metal complex compound by the action of heat and has two or more hydrophilic groups within the molecule and whose main chains are crosslinked, and the substance (c) capable of converting light to heat, is exposed to infrared laser light image-wise so as to form a hydrophobic region. The planographic printing plate obtained in the above-mentioned process is set to, for example, an offset printing machine so as to produce a large number of prints. In the case, it is also very desirable that the metal complex compound (II-a) is the metal compound(I-a). This is because a planographic printing plate precursor, which does not require development processing and has very good sensitivity, can be obtained. EXAMPLES The present invention is further explained below by way of examples. However, it must be noted that the scope of the present invention is not limited to these examples given below. "%" in the examples always means "weight %". (Example 1) <Synthesis of thermal decarboxylation-type metal compound (1) "illustrative compound in Table 1" > 6.8 g of 4-(sulfonylphenyl)phenylsulfonylacetic acid was dissolved in a solvent mixture of 50 ml of water and 150 ml of methanol. While being stirred, the resulting solution was added with a solution prepared by dissolving 1.76 g of calcium acetate monohydrate in 5 ml of water. The precipitate that was formed was collected by filtration and dried. In this way, 6.73 g of a crystalline product of the thermal decarboxylation-type metal compound (1) was obtained. The melting point (decomposition) of the crystalline product was found to be 193°C. The result of infrared absorption (IR) spectrum measurement confirmed the presence of a strong absorption at 1605 cm -1 pertaining to carboxylate. <Synthesis of thermal decarboxylation-type metal compound (5) "illustrative compound in Table 1" > 7.08 g of 2-methyl-5-(sulfonylphenyl)phenylsulfonylacetic acid was dissolved in a solvent mixture of 50 ml of water and 150 ml of methanol. While being stirred, the resulting solution was added with a solution prepared by dissolving 1.76 g of calcium acetate monohydrate in 5 ml of water. The precipitate that was formed was collected by filtration and dried. In this way, 5.93 g of a crystalline product of the thermal decarboxylation-type metal compound (5) was obtained. The melting point (decomposition) of the crystalline product was found to be 185°C. The result of infrared absorption (IR) spectrum measurement confirmed the presence of a strong absorption at 1605 cm -1 pertaining to carboxylate. By carrying out procedures similar to the above-described synthesis procedures, crystalline products of the thermal decarboxylation-type metal compounds (2) to (4) were obtained. The results of infrared absorption (IR) spectrum measurement of each product confirmed the presence of a strong absorption at 1605 cm -1 pertaining to carboxylate. <Preparation of a hydrophilic polymer (P-1)> 5.5 g of 2-methacryloyloxyethyl isocyanate and 0.1 g of dibutyltin dilaurate were added to a solution prepared by dissolving 18.0 g of polyacrylic acid (having a molecular weight of 25,000 and manufactured by Wako Pure Chemicals Industries, Ltd.) and the resulting solution was caused to react for 3 hours. Next, 80 equivalent % of the carboxyl group was neutralized with sodium hydroxide and acetone was added in order to precipitate a polymer. The polymer was well washed and purified. In this way, a hydrophilic polymer (P-1) was obtained. <Preparation of a dispersion of the thermal decarboxylation-type metal compound> 4.0 g of the illustrative thermal decarboxylation-type metal compound (1) obtained above, 6.0 g of a 10% aqueous solution of polyvinyl alcohol (trade name: PVA-405® manufactured by Kuraray Co., Ltd.), 20 g of water, and 10 g of glass beads were mixed for 15 minutes using a paint shaker. In this way, a dispersion of the thermal decarboxylation-type metal compound (1) was prepared. <Manufacture of a planographic printing plate precursor> First, a coating liquid (1) for image recording layer was prepared according to the following formulation. 10% aqueous solution of the hydrophilic polymer (P-1) 20.0 g Initiator A based on a water-soluble triazine given below 0.1 g Polyethylene glycol diallylate (trade name: A600® manufactured by Toagosei Chemical Industry Co., Ltd.) 2.0 g Water-dispersible carbon black (manufactured by Mikuni Shikiso Co., Ltd.) 0.4 g Dispersion of the thermal decarboxylation-type metal compound (1) 10.0 g 20% polymethyl methacrylate dispersion (having a particle diameter of 90 nm and containing polyvinyl alcohol as a stabilizer in an amount of 1% based on the content of polymethyl methacrylate) 2.5 g Water-soluble triazine initiator A Next, the coating liquid (1) for image recording layer was coated on a 200 µm thick polyethylene terephthalate (PET) sheet by using a wired bar No. 14 and the coating layer was dried for 1 minute at 100°C to form an image recording layer. The entire surface was exposed to UV light for 1000 counts using Eye Rotary Printer® manufactured by Eye Graphic Corp.) to obtain a planographic printing plate precursor (1) of the present invention having an image recording layer containing the hydrophilic polymer (P-1) having a crosslinked structure. The thickness of the recording layer was 3.7µm. <Evaluation of sensitivity> The planographic printing plate precursor (1) thus obtained was irradiated with an LD laser (having a laser beam diameter of 28 µm) emitting an infrared ray having a wavelength of 830 nm according to digital signals of a computer or the like. In this way, exposure to a desired image was carried out and a planographic printing plate (1) was obtained without development processing. The laser-scanned area of the planographic printing plate (1) was observed under a microscope and the line width as an indicator of sensitivity was measured. A line width that is closer to 28 µm means higher sensitivity. The results of measurements are shown in Table 2. < Evaluation of printing performance> After the image-wise laser exposure, the planographic printing plate (1) was set directly to a Hidel SOR-M printer without development processing and 2,000 prints were obtained. The prints were visually evaluated. Clear images were obtained in all of the prints and no stain was found in non-image areas. (Examples 2~5) Planographic printing plate precursors (2) ~ (5) of the present invention were obtained by carrying out the same procedure as in Example 1, except that the illustrative thermal decarboxylation-type metal compounds (2) - (5) were used respectively in place of the thermal decarboxylation-type metal compound (1) used in the dispersion (1) of the thermal decarboxylation-type metal compound of Example 1. The thicknesses of the image recording layers formed in the above-described manner were each 3.7 µm. Planographic printing plate s (2) ~ (5) were manufactured using the planographic printing plate precursors (2) - (5) by the same procedure as in Example 1. Further, sensitivity measurements were conducted in the same way and 2,000 prints were produced for each plate. The results are shown in Table 2. The prints were visually evaluated. Clear images were obtained in all of the prints and no stain was found in non-image areas. (Comparative Examples 1) Planographic printing plate precursor (6) was obtained by carrying out the same procedure as in Example 1, except that iron acetylacetonate was used in place of the thermal decarboxylation-type metal compound (1) used in the dispersion (1) of the thermal decarboxylation-type metal compound of Example 1. The thickness of the image recording layer was 3.7 µm. Planographic printing plate (6) was manufactured using the planographic printing plate precursor (6) by the same procedure as in Example 1. Further, sensitivity measurements were conducted in the same way and 2,000 prints were produced. The results are shown in Table 2. Clear images were obtained in all of the prints and no stain was found in non-image areas. Compound Hydrophilic polymeric compound Sensitivity [µm] Example 1 Thermal decarboxylation-type metal compound (1) P-1 26 Example 2 Thermal decarboxylation-type metal compound (2) P-1 24 Example 3 Thermal decarboxylation-type metal compound (3) P-1 20 Example 4 Thermal decarboxylation-type metal compound (4) P-1 18 Example 5 Thermal decarboxylation-type metal compound (5) P-1 18 Comparative example 1 Fe acetylacetonate P-1 15 As can be seen from Table 2, the planographic printing plates (1)-(5) (Example 1-5) having a thermal decarboxylation-type metal compound in the image recording layers provide high sensitivity and clear prints free from smudgy non-image areas. On the other hand, the planographic printing plate (6) (Comparative Example 1)having no thermal decarboxylation-type metal compound in the image recording layer does not provide sufficient sensitivity. As described above, the present invention makes it possible to provide a planographic printing plate precursor which can be engraved with high sensitivity by heat generated either by a heating device such as a thermal head or by light-to-heat conversion of laser light. In addition, the present invention makes it possible to provide a planographic printing plate directly with particularly high sensitivity by heat generated either by a heating device such as a thermal head or by light-to-heat conversion of laser light according to digital signals of a computer or the like. (Example 7) <Preparation of a hydrophilic polymer (P-3)> 18.0 g of polyacrylic acid ((having a molecular weight of 25, 000 and manufactured by Wako Pure Chemicals Industries, Ltd.) was dissolved in dimethylacetamide. The solution was added with 5.5 g of 2-methacryloyloxyethyl isocyanate (hereinafter abbreviated as MOI) and 0.1 g of dibutyltin dilaurate and the resulting solution was caused to react for 3 hours. Next, 80 equivalent % of the carboxyl group was neutralized with sodium hydroxide and acetone was added in order to precipitate a polymer. The polymer was well washed and purified. In this way, a hydrophilic polymer (P-3) was obtained. <Preparation of a dispersion of a metal complex> 4.0 g of aluminum complex of acetylacetone as a metal complex (Aluminum Chelate A® manufactured by Kawaken Fine Chemicals Co., Ltd.), 6.0 g of a 10% aqueous solution of polyvinyl alcohol (trade name: PVA-405® manufactured by Kuraray Co., Ltd.), 20 g of water, and 10 g of glass beads were stirred for 15 minutes using a paint shaker. In this way, a dispersion of a metal complex was prepared. <Manufacture of a planographic printing plate precursor> Next, a coating liquid for image recording layer was prepared according to the following formulation. (Coating liquid for image recording layer) 10% aqueous solution of the hydrophilic polymer (P-3) 20.0 g Initiator A based on a water-soluble triazine 0.1 g Polyethylene glycol diallylate (trade name: A600® manufactured by Toagosei Chemical Industry Co., Ltd.) 2.0 g Water-dispersible carbon black (manufactured by Mikuni Shikiso Co., Ltd.) 0.4 g Dispersion of aluminum complex of acetylacetone 10.0 g 20% polymethyl methacrylate dispersion (having a particle diameter of 90 nm and containing polyvinyl alcohol as a stabilizer in an amount of 1% based on the content of polymethyl methacrylate) 2.5 g Next, the coating liquid for image recording layer was coated on a 200 µm thick polyethylene terephthalate substrate by using a wired bar No. 14 and the coating layer was dried for 1 minute at 100°C. The entire surface was exposed to UV light (for 1000 counts using Eye Rotary Printer® manufactured by Eye Graphic Corp.) to obtain a heat-sensitive recording type planographic printing plate precursor having an image recording layer composed of a crosslinked polymer. The thickness of the recording layer was 3.7 µm. (Examples 8-11) Heat-sensitive planographic printing plate precursors were manufactured according to the same procedure as in Example 7, except that the dispersion was prepared by using the following compounds, respectively, in place of the aluminum complex of acetylacetone. Example 8: aluminum tris(ethylacetoacetate) (trade name: ALCH-TR® manufactured by Kawaken Fine Chemicals Co., Ltd.) Example 9: aluminum mono (acetylacetonate) - bis (ethylacetate) (trade name: Aluminum Chelate D® manufactured by Kawaken Fine Chemicals Co., Ltd.) Example 10: tetra-n-butoxyzirconium (manufacture by Nippon Soda Co., Ltd.) Example 11: dipropoxy-bis(acetylacetonate)titanium (trade name: Titanboard 50® manufacture by Nippon Soda Co., Ltd.) Evaluation of printing performance The planographic printing plate precursors obtained in Examples 7-11 were image-wise exposed to an LD laser emitting an infrared ray having a wavelength of 830 nm. After the exposure, the plate obtained was set to a printing machine (Hidel SOR-M manufactured by Heiderberg Corp.) directly without development processing. In this way, 2,000 prints were produced. Clear images were obtained in all of the prints and no stain was found in non-image areas irrespective of the kinds of metal complexes incorporated. The excellent effects according to the planographic printing plate precursor of the present invention, are that images can be formed with high sensitivity by heat or by the heat generated by light-to-heat conversion and that the printing plate precursor can be used for manufacturing a planographic printing plate directly from digital data by using an infrared laser or a thermal head without necessitating a special treatment such as wet development or rubbing after image-wise exposure. In addition, according to the process for manufacturing a planographic printing plate , constituting the second aspect of the present invention, it is possible to manufacture a planographic printing plate having excellent properties directly from digital data without necessitating a special treatment such as wet development or as rubbing after image-wise exposure.

Claims: Planographic printing plate precursor comprising a substrate having thereon an image recording layer comprising (a) a metal compound which releases a polyvalent metal cation upon heating selected from (I-a) compounds releasing the polyvalent metal cation under decarboxylation selected from trichloroacetate of Al, Ca and Zn, phenylsulfonylacetate of Al, Ca, Zn and Fe, p-chlorophenylsulfonylacetate of Al and Ca, phenyl-propiolate of Al, Ca and Zn, 2,4-dichlorophenyl-propriolate of Al and Ca, and metal salts of sulfonylacetic acids of the formula (1) or (2): where M represents a metal from the second to the sixth periods of the Periodic Table and (II-a) a metal complex compound; and (b) and a hydrophilic polymer whose main chains are crosslinked and which has at least two hydrophilic groups within the molecule and can coordinate with the polyvalent metal cation. Planographic printing plate precursor according to claim 1, wherein the metal complex compound (II-a) is a compound releases a polyvalent metal cation under decarboxylation when heated. Printing plate precursor according to claim 1 or 2, wherein the image recording layer further comprises a substance (c) capable of converting light to heat. Printing plate precursor according to any of claims 1-3, wherein the image recording layer further comprises a thermoplastic polymer (d). Process for manufacturing a planographic printing plate comprising the step of exposing a planographic printing plate precursor as defined in claim 3 image-wise to infrared laser light so as to form a hydrophobic region on a surface of a planographic printing plate precursor.

Inventors: KAWAMURA KOICHI, KAWAMURA, KOICHI
Applicants: FUJI PHOTO FILM CO LTD, FUJI PHOTO FILM CO., LTD.
Application year: 2000
Main classification: B41C1
IPC codes: B41C1, B41M5