JP2006224677A - Support medium for planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new support medium for a planographic printing plate replacing an aluminum grain support medium. <P>SOLUTION: The support medium for a planographic printing plate comprises a hydrophilic layer which contains a hydrophilic resin and a water dispersible filler in at least one surface of the substrate, wherein the water dispersible filler is particles of silica, the surface of the particles of the silica is provided with the treatment by a hydrophilic resin, an inorganic processing and/or an organic processing, the average particle diameter is in the range of 0.2-10 μm, the center line surface roughness Ra of the surface of the hydrophilic layer is in the range of 0.1≤Ra≤1.2 μm, and the dissolution loss in quantity of the hydrophilic layer is not more than 1% when being immersed in the water of 25°C for one hour. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a new lithographic printing plate support that replaces a grained support of an aluminum plate.

  The mainstream of printing at present is lithographic printing. In lithographic printing, the image area and the non-image area are basically in the same plane, the image area is ink-receptive, and the non-image area is ink repellent. As a property, it means a method in which ink is applied only to an image area using an ink adhesion difference, and then the ink is transferred to a printing medium such as paper and printed. A PS plate is used for such lithographic printing.

  Furthermore, in recent years, a method for producing a lithographic printing plate by developing after digital exposure with laser light based on image information has been widely used for the purpose of quickly obtaining a high-resolution lithographic printing plate and for the purpose of filmlessness. Yes. For example, a light source is modulated by an image signal transmitted through a communication line or an output signal from an electronic plate making system or an image processing system, and a printing plate is formed by directly scanning and exposing a photosensitive material. System.

  In such a system, a direct plate making material using a photopolymerization process is used. These plate-making materials have a structure in which a photopolymerizable layer is provided on a grained aluminum support, and an oxygen barrier layer is provided, as in the case of conventional PS plates. A typical photopolymerizable layer comprises an acrylic monomer, an alkali-soluble resin, a photopolymerizable initiator, and, if necessary, a sensitizing dye to adapt to the wavelength, especially when performing laser writing. Contains. This material is imagewise exposed and the unexposed portion is eluted and removed by alkaline aqueous development to form an image.

  Such a method has excellent printability and placement plate suitability similar to those of conventional PS plates, but requires liquid development treatment as in the case of conventional PS plates. In addition to the problem that maintenance and the like are necessary, the grained aluminum support has the problem that the manufacturing process is complicated.

  From this point, it can be said that a lithographic plate using a dry image forming method in which liquid development processing is not performed and not using a grained aluminum plate is a very simple and environmentally preferable method.

  As such a material, for example, an image receiving layer such as toner is formed on a support such as paper, and an image is formed using PPC, and the non-image portion is subjected to a desensitization treatment with an etchant or the like. Direct-drawing lithographic printing original plates that are used by converting a receiving layer into an ink repellent layer have been widely put into practical use. Specifically, what provided the image receiving layer which consists of a water-soluble binder polymer, an inorganic pigment (filler), a water-proofing agent etc. on a water-resistant support body is common, These are USP2,532,865 gazette, JP-B-40-23581, JP-A-48-9802, JP-A-57-205196, JP-A-60-2309, JP-A-57-1791, JP-A-57-15998 JP, 57-96900, 57-205196, 63-166590, 63-166591, 63-317388, JP 1-1114488, JP-A-4-367868, and the like.

  These direct-drawing lithographic printing original plates are simply PVA, starch, hydroxyethylcellulose, casein, gelatin, polyvinylpyrrolidone, vinyl acetate-crotonic acid copolymer, styrene-maleic acid copolymer as an image receiving layer to be converted into an ink repellent layer. Water-soluble binder polymers such as polymers and water-dispersible polymers such as acrylic resin emulsions, inorganic pigments such as silica and calcium carbonate, and water-proofing agents such as melamine / formaldehyde resin condensates What is composed is also proposed. Japanese Laid-Open Patent Publication No. 63-256493 proposes a direct-drawing lithographic printing original plate using as a main component a hydrophobic polymer that is hydrolyzed by a desensitizing treatment to generate a hydrophilic group.

  Such direct-drawing type lithographic printing original plates all have a desensitization treatment in order to convert the image-receiving layer into an ink repellent layer, and without such treatment, the ink repellent property is hardly exhibited. There was insufficient hydrophilicity.

  Further, when such an image forming method is used, it is required to receive and strongly hold an oleophilic image, and there is a situation in which the hydrophilicity of the image receiving portion cannot be increased.

  On the other hand, a lithographic printing plate comprising a hydrophilic resin, a lipophilic component-containing capsule and the like disclosed in JP-A-7-1849 is an oleophilic substance whose exposed portion is released from the capsule upon exposure. For this reason, it is possible to design the hydrophilicity of the non-image area to be high, which is a preferable method.

  However, these methods also require an etching treatment, and it cannot be said that sufficient hydrophilicity has been obtained.

  The present invention has been made in view of the above situation. That is, an object of the present invention is to provide a novel support that replaces the conventional grained support of an aluminum plate, and specifically, it is high without etching treatment like the PS plate. An object of the present invention is to provide a support for lithographic printing having hydrophilicity and printing durability.

The configuration of the present invention that achieves the object of the present invention is as follows.
1. A lithographic printing plate support having a hydrophilic layer containing a hydrophilic resin and a water-dispersible filler on at least one surface of a substrate, wherein the water-dispersible filler is silica fine particles, and the surface of the silica fine particles Is subjected to a treatment with a hydrophilic resin, an inorganic treatment and / or an organic treatment, the average particle diameter is in the range of 0.2 to 10 μm, and the centerline surface roughness Ra of the surface of the hydrophilic layer is 0.1. A support for a lithographic printing plate having a range of ≦ Ra ≦ 1.2 μm, wherein the hydrophilic layer has a dissolution loss of 1% or less when immersed in water at 25 ° C. for 1 hour.
2. 2. The lithographic printing plate support according to 1 above, wherein the content of the silica fine particles is in the range of 5 to 70% by mass.
3. The support for a lithographic printing plate as described in 1 or 2 above, wherein the relationship between the average particle diameter x (μm) of the silica fine particles and the content y (mass%) is in the range represented by the following formula 1. body.

Formula 1
(72.895-5.7895x) ≧ y ≧ (15.526-1.0526x)
4). 4. The lithographic printing plate support according to 1, 2 or 3, wherein the hydrophilic layer has a thickness of 1 to 50 μm.
5. 5. The lithographic printing plate support according to any one of 1 to 4 above, wherein γh on the surface of the hydrophilic layer is 20 or more.
6). The lithographic printing plate as described in any one of 1 to 5 above, wherein the hydrophilic resin is at least one selected from resins having a skeleton of polyacrylamide, gelatin, polyvinyl alcohol, polyester, or polyurethane. Support.
7). 7. The lithographic printing plate support according to any one of 1 to 6, wherein the hydrophilic resin is gelatin.
8). The support for a lithographic printing plate as described in any one of 1 to 7 above, wherein the silica fine particles have an average particle size of 0.6 to 7 µm.

  ADVANTAGE OF THE INVENTION According to this invention, the novel support body replaced with the grain-grained support body of the aluminum plate conventionally used is provided. Specifically, a lithographic printing plate support having high hydrophilicity and printing durability without etching is provided in the same manner as a grained aluminum plate used in conventional PS plates. This provides a heat-sensitive lithographic printing plate material that can produce an image without going through a complicated process such as development.

  The lithographic printing plate support of the present invention has a hydrophilic layer on a substrate. This type of hydrophilic layer is required to satisfy both high hydrophilicity and water resistance at the higher order. The present invention has been made in view of this requirement, and the invention according to claim 1 achieves the object of the present invention by physically improving the wettability of the surface of a lithographic printing plate. According to the inventions according to claims 2 to 8, the physical wettability is further enhanced, and the chemical wettability is also improved, whereby the printability is greatly improved as compared with the conventional lithographic printing plate support. is there.

  Hereinafter, the present invention will be described in detail.

  The lithographic printing plate support of the present invention will be described.

  As the substrate on which the hydrophilic layer of the lithographic printing plate support of the present invention is provided, conventionally known ones can be used without particular limitation as the support of the photosensitive lithographic printing plate, depending on the purpose of use, etc. The layer configuration and size can be selected and used as appropriate. Examples of the substrate include various papers such as paper, coated paper, and synthetic paper (polypropylene, polystyrene, or a composite material obtained by combining them with paper), vinyl chloride resin sheet, ABS resin sheet, polyethylene terephthalate film, poly Single layer of butylene terephthalate film, polyethylene naphthalate film, polyarylate film, polycarbonate film, polyether ketone film, polysulfone film, polyethersulfone film, polyetherimide film, polyimide film, polyethylene film, polypropylene film or the like Various plastic films or sheets laminated with two or more layers, films or sheets formed of various metals, films formed of various ceramics, Over DOO, further, it is possible to use aluminum, stainless steel, chromium, metal plate such as nickel, which a thin film of metal laminated or deposited paper with a resin coating.

  Conventionally known surface modification techniques can be suitably applied to the substrate. Examples of such surface modification techniques include sulfuric acid treatment, oxygen plasma etching treatment, corona discharge treatment, and application of water-soluble resin, all of which are preferably used. Further, an intermediate layer such as an adhesive layer can be provided between the substrate and the hydrophilic layer.

  The hydrophilic layer in the present invention contains at least a hydrophilic resin and a water-dispersible filler. In this specification, “resin” means a resinous substance, and “filler” means fine particles that can increase the surface roughness of the layer by being contained in the hydrophilic layer. In the present invention, fine particles of silica are used. .

  A conventionally well-known thing can be especially used as a hydrophilic resin without a restriction | limiting. For example, hydrophilic groups such as hydroxyl groups, carboxyl groups, (secondary or tertiary) amine-containing groups, amino groups, amide groups, carbamoyl groups, sulfonic acid groups, sulfonamide groups, phosphonic acid groups, mercapto groups, alkyl ether groups. Examples thereof include polymer compounds having a functional group, and examples thereof include polyvinyl alcohol, polysaccharides, polyvinyl pyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, and closed octaacetate. , Ammonium alginate, sodium alginate, polyvinylamine, polyallylamine, polystyrene sulfonic acid, polyacrylic acid, polyamide, polyacrylamide, maleic anhydride copolymer, polyureta , A polyester or the like. As the hydrophilic resin, a single resin or a mixture of two or more of these compounds can be used as a main component.

  In the present invention, the hydrophilic resin is preferably a resin having a skeleton of polyacrylamide, gelatin, polyvinyl alcohol, polyester, or polyurethane, and most preferably gelatin.

  A preferred embodiment of the present invention is an embodiment in which at least one selected from polyacrylamide, gelatin, polyvinyl alcohol, polyester and polyurethane is used as a main component as the hydrophilic resin. Here, a main component means containing 50% or more of the total mass of hydrophilic resin, and a more preferable aspect is containing 70% or more of the total mass of hydrophilic resin.

  Gelatin is alkali method gelatin, acid method gelatin, modified gelatin (for example, modified gelatin described in JP-B-38-4854, JP-A-40-12237, British Patent 2,525,753, etc.), etc. Can be used alone or in combination of two or more. For example, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate, Bull. Soc. Sci. Photo. Japan. No. 16. Enzyme-treated gelatin as described in P30 (1966) can also be used.

As a resin having a polyvinyl alcohol skeleton, an anion modification modified with an anion such as a carboxyl group or a sulfo group containing at least 50 mol% of a copolymerized polyvinyl alcohol or polyvinyl alcohol skeleton portion in addition to polyvinyl alcohol having various polymerization degrees. Random copolymers such as polyvinyl alcohol, cation-modified polyvinyl alcohol modified with cations such as amino group, ammonium group, silanol-modified polyvinyl alcohol, alkoxyl-modified polyvinyl alcohol, epoxy-modified polyvinyl alcohol, thiol-modified polyvinyl alcohol; anion-modified, cation Modifications such as modification, thiol modification, silanol modification, alkoxyl modification, and epoxy modification are performed only on the terminal group, such as polyvinyl alcohol, acrylamide, acrylic acid, etc. Block copolymer of polyvinyl alcohol obtained by introducing a water-soluble monomer, graft copolymerization of poly (vinyl alcohol) grafted silanol group, further, (- COCH ₂ COCH ₃₎ reactive groups that use the introduced copolymerized polyvinyl alcohol such as Can do.

  The polyvinyl alcohol preferably has a saponification degree of 70 mol% or more, more preferably 85 mol% or more, and particularly preferably 90% or more. Polyvinyl alcohol having a high saponification degree is preferable because the crystallinity is changed by heat treatment and water resistance can be imparted.

In the copolymerized polyvinyl alcohol, the following monomers can be used as the copolymerization monomer.
(1) Monomers having an aromatic hydroxyl group: for example, o-hydroxystyrene, p-hydroxystyrene, m-hydroxystyrene, o-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate and the like.
(2) Monomers having an aliphatic hydroxyl group: For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxy Pentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.
(3) Monomer having an aminosulfonyl group: for example, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl acrylate, p-aminophenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide N- (p-aminosulfonylphenyl) acrylamide and the like.
(4) Monomers having a sulfonamide group: for example, N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.
(5) α, β-unsaturated carboxylic acids: for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like.
(6) Substituted or unsubstituted alkyl acrylate: for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic Acid decyl, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate and the like.
(7) Substituted or unsubstituted alkyl methacrylate: for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, methacryl Acid decyl, undecyl methacrylate, undecyl methacrylate, dodecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like.
(8) Acrylamide or methacrylamide: For example, acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.
(9) Monomer containing a fluorinated alkyl group: for example, trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N-butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.
(10) Vinyl ethers: For example, ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ethers.
(11) Vinyl esters: For example, vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.
(12) Styrenes: For example, styrene, methyl styrene, chloromethyl styrene and the like.
(13) Vinyl ketones: For example, methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone and the like.
(14) Olefin: For example, ethylene, propylene, isobutylene, butadiene, isoprene and the like.
(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.
(16) Monomer having a cyano group: for example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o-cyanostyrene, m-cyanostyrene, p-cyanostyrene etc.
(17) Monomer having an amino group: for example, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-isopropylacrylamide, N, N-diethylacrylamide and the like.

  The polyvinyl alcohol used in the present invention is preferably a polyvinyl alcohol having a reactive group introduced therein or a polyvinyl alcohol having an anionic group introduced therein. Among them, polyvinyl alcohol having a reactive group introduced is preferred. Examples of the reactive group include a silanol group, an acetoacetyl group, a thiol group, and an epoxy group. Among these, particularly preferred reactive groups are a silanol group, an acetoacetyl group, and a thiol group.

  The above polyvinyl alcohols may be used alone or in combination of two or more.

  Next, a resin having a polyurethane or polyester skeleton will be described. In the present invention, a polyurethane resin having a hydrophilic group, a polyester resin having a hydrophilic group, and a polyamide resin having a hydrophilic group can be preferably used as the resin. In the practice of the present invention, those having a carboxyl group, a hydroxyl group, a sulfonic acid group, an amino group and a sulfonamide group in the side chain are preferred as the hydrophilic group.

  The preferred polyurethane resin having a hydrophilic group that can be used in the present invention has at least one kind of the above-mentioned hydrophilic group, and at least one kind selected from a urethane bond, a urea bond, a burette bond, and an allophanate bond in the main chain. It is a polymer containing the above repeating units, and such a bond is formed mainly by selecting a reactive group that undergoes an addition reaction with isocyanate.

  Examples of the diisocyanate compound suitably used in this reaction include conventionally known 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane. Aromatic diisocyanate compounds such as diisocyanate, 1,5-naphthalene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate; trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, Aliphatic diisocyanate compounds such as dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) And aliphatic diisocyanate compounds such as methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, and more than three molecules of these diisocyanate compounds. A trifunctional or higher functional isocyanate compound produced by a reaction product of these diisocyanate compounds and a trihydric or higher polyhydric alcohol can also be suitably used.

  Examples of the polyfunctional alcohol that forms a urethane bond by addition reaction with an isocyanate compound include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, octanediol, diethylene glycol, and triethylene glycol; glycerin and trimethylol Aliphatic polyfunctional alcohols such as ethane, trimethylolpropane, pentaerythritol, diglycerin, 1,2,6-hexanetriol, sorbitol, mannitol, and glucose; a hydroxyl group is formed at the terminal by condensation of dicarboxylic acid and polyhydric alcohol Polyester polyols prepared by ring-opening polymerization of alkylene oxide or polyether polyol added to alkylene oxide and polyhydric alcohol.

  Depending on the alcohol valence of these compounds, the desired reaction product can be obtained by adding and reacting at a ratio of 2 moles of isocyanate to 1 mole of hydroxyl groups.

  In order to impart a hydrophilic group to a polyurethane resin, a method of polymerizing a urethane prepolymer having an isocyanate group remaining at the terminal with a diol having a tertiary amino group and quaternizing the tertiary amino group; an isocyanate group at the terminal A method of polymerizing a urethane prepolymer having a residual amino group with a diol having a tertiary amino group, neutralizing the tertiary amino group with an acid and subjecting to an amine chloride; a urethane prepolymer having an isocyanate group remaining at the terminal has a quaternary salt Method of polymerizing with diols; Method of polymerizing a urethane prepolymer having an isocyanate group remaining at the terminal with a diaminophenylcarboxylate and removing the solvent; Termination of the urethane prepolymer having an isocyanate group remaining at the terminal with sodium bisulfite To block with a compound such as A method of polymerizing a urethane prepolymer that has left an isocyanate group with diaminoalkanesulfonate; A method of polymerizing a urethane prepolymer that has left an isocyanate group with bis (2-cyanoethylamino) ethane; Examples include a method of polymerizing a polymer with an alkylene oxide of a long chain alcohol, and other methods such as those described in Keiji Iwata “Polyurethane Resin Handbook”, Nikkan Kogyo Shimbun, pages 496 to 506 can be arbitrarily employed. .

  In addition, as commercially available polyurethane resins that can be employed in the present invention, Takeda Pharmaceutical Co., Ltd. Takerak W series (W-621, W-6015, W-7004, W-511, W-635, XW-76-P15, XW-74-P6012C, ACW-31H, ACW-54HD, XW-904-X05, XW-97-W4 to polyester urethane self-emulsifying type), the same (W-310, W-512 to polyester urethane forced emulsifying type), Series containing alkoxysilyl groups (XW-77-X25, XW-75-X09, XW-74-X13, XS-72-V01, XS-72-V02, XS-72-V03, XS, manufactured by Takeda Pharmaceutical Co., Ltd. -72-V04, XS-72-V05-polyester urethane self-emulsifying type), manufactured by Toho Chemical Industry Co., Ltd. (S-8531, S-8532, S-8533, S-8530, S-8529, S-8528, S-6254, S-6262, B-1306), NeoRez series (R-) manufactured by Enomoto Kasei Co., Ltd. 960, R-962, R-972, R-974, R-9314, R-9320, R-9617, XR-9621, XR-9624, R-9637, XR-9679, XR-9699, XR-9770 to Aliphatic polyester urethane), NeoRez series manufactured by Enomoto Kasei Co., Ltd. (R-966, R-967, XR-9000, AX-311, AX-7113 to aliphatic polyether urethane), NeoRez series manufactured by Enomoto Kasei Co., Ltd. (R-940, R-9030, XR-9409, R-9920, XR-7061-aromatic polyether urethane), cocoon NeoRez series made by Kasei Co., Ltd. (XU-7015, R-9603, special urethane, aliphatic polycarbonate urethane), Yodozol series made by Kaneboue NSC Co., Ltd. (9D102, 9D205Z, 9D232Z), Toa Gosei Chemical Co., Ltd. Neotan series made by UE1101, UE-1200, UE-1300, UE-1402, UE-2103, UE-2200, UE-2600, UE-2900-polyester urethane, Neotan series made by Toa Gosei Chemical Co., Ltd. (UE-5404, UE-5600 to polyether urethane), Nenrange series (R-1489, R-1780) manufactured by Takamatsu Yushi Co., Ltd., Crown bond series (UA-28, UA-41) manufactured by Takamatsu Yushi Co., Ltd. U-176R, RI-793, RI-623, U-113), Dispacol series (U-42, U-53, KA8481, KA8584) manufactured by Sumitomo Bayer Urethane Co., Ltd., and the like.

A polyester resin having a preferred hydrophilic group that can be used in the present invention is a polymer having at least one hydrophilic group described above and containing a repeating unit of an ester bond in the main chain. As a method for synthesizing a resin having a bond, for example, a hydrophilic group may be introduced into a prepolymer of a polyester resin formed by the method described in “Polyester Resin Handbook”, pages 21 to 28, and polymerized. Examples of commercially available polyester resins that can be used in the present invention include pesresin A series (110, 120, 121, 193, 510, 610, and 810--hydrophilic group is —SO ₃ R) manufactured by Takamatsu Yushi Co., Ltd. ) Pesresin A series (210, 620, 820-new aqueous group is -COOR), Takamatsu Oil Co., Ltd. Pesresin A series (115G, 124G, 124GH, 193G, 215G, 515G, 615G, 813GL to hydrophilic group -SO ₃ R and glycidyl), Pesresin A series (124S, 115S-hydrophilic groups are -SO ₃ R and Si (OR) ₃ ) manufactured by Takamatsu Yushi Co., Ltd., plus coat series (Z -3402, Z-4121, Z-446, Z-461, Z-448, Z-441, Z-450, Z-710, Z-711, Z 770, Z-766 to water-soluble), plus coat series (Z-820, Z-3109, Z-3308, Z-857, Z-850, Z-802, Z-856, Z) manufactured by Kyoyo Chemical Industry Co., Ltd. -4201, RZ-27, RZ-50, RZ-56, RZ-105), Toyobo Co., Ltd. Bironal series (MD-1200, MD-1200, MD-1250, MD-1100, MD-1330, MD-1930).

  In the present invention, the hydrophilic resin is preferably contained in the hydrophilic layer in the range of 10 to 98% by mass. When the hydrophilic resin is less than 10% by mass, the strength of the hydrophilic layer is insufficient, and when it is more than 98% by mass, the effect of containing the water-dispersible filler is small and the effect of the present invention cannot be exhibited. The content of the hydrophilic resin is more preferably 20 to 97% by mass, still more preferably 30 to 96% by mass.

  In the present invention, as the hydrophilic resin, one or more of the same kind of hydrophilic resins may be used, or two or more kinds of different kinds of hydrophilic resins may be used in combination.

  In the present invention, silica fine particles are used as the filler as described above. Further, other organic or inorganic fine particles may be used.

  Organic fine particles include fine particles of acrylic polymer such as polymethyl methacrylate (PMMA), fine particles of styrene polymer, fine particles of olefin polymer such as polyethylene and polypropylene, fine particles of fluorine polymer such as polytetrafluoroethylene, and others. And radical polymerization polymer fine particles, and condensation polymer fine particles such as polyester and polycarbonate.

  Any method can be adopted as a method for producing the organic fine particles as described above. For example, (A) a method of growing particles during polymerization, such as emulsion polymerization, soap-free polymerization, or dispersion polymerization (B ) It is possible to employ a method in which droplets are polymerized as they are, such as suspension polymerization, nozzle vibration method, swelling seed polymerization, and two-stage swelling polymerization.

  In addition to the method of obtaining fine particles by polymerizing in a dispersion medium such as (A) or (B) above, a poor solvent is added after dissolving the polymer in a rich solvent, if necessary, under heating. Or by cooling to deposit the polymer to obtain fine particles (a fine particle can be easily obtained by applying a shearing force during precipitation), and the polymer is pulverized and dispersed in a solvent by a dispersing means such as a sand mill or a ball mill. Can be obtained by a method of obtaining fine particles by pulverizing a polymer in a dry state and passing through a classification step.

  Examples of the inorganic fine particles include calcium alginate, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, barium sulfate, calcium carbonate, and zircon fine particles.

  Any method can be adopted as a method for producing silica fine particles and inorganic fine particles according to the present invention. For example, a bulk material is subdivided, a breakdown method, molecules or fine particles are assembled. There is a build-up method. As a breakdown method, a pulverization method using a jet mill, a stirring mill, a ball mill, a roller mill, a stamp mill, a high-speed rotary mill, etc., and further introducing the second component into the active part formed by pulverization by these methods A method of performing surface modification by doing so is also preferably used. Such a method is described in “Fine Particle Handbook” (Asakura Shoten) p234-235. Moreover, after dissolving / dispersing in various solvents to form fine particles, a method of evaporating / drying the solvent can be used. As build-up methods, gas evaporation methods, sputtering methods, arc plasma evaporation methods, laser vapor deposition methods, high frequency plasma vapor deposition methods, and other methods using evaporation aggregation, thermal CVD methods, plasma CVD methods, laser CVD methods, etc. It can be produced by various methods described in “Fine Particle Handbook” (Asakura Shoten) p226-320, such as a particle formation method utilizing the above.

  Among these, particularly preferred physically and / or chemically improved wettability is a fine particle substantially consisting of at least one selected from alumina, polytetrafluoroethylene, acrylic resin, magnesium oxide and calcium alginate. (Here, “substantially” means that other substances may be contained within a range that does not impair the effects of the present invention), and more preferably acrylic resin fine particles.

  The fine particles of silica according to the present invention mainly play a role of enhancing chemical wettability, and the particles produced by the above method can be suitably used. Among them, silica fine particles produced by a pulverization method are preferable in that they have high surface activity and high hydrophilicity. In addition, performing a treatment such as classification for the purpose of narrowing the particle size distribution of the particles is a preferable method from the viewpoint of further improving the physical wettability.

  As the shape of silica fine particles (hereinafter also referred to as silica particles), silica particles having a porous shape are preferable, and the pore volume of the silica particles is preferably 0.5 ml / g or more. Among these, 1.0 ml / g or more is more preferable, and 1.5 ml / g or more is particularly preferable.

  The hydrophilic layer of the present invention is a layer containing the silica particles dispersed as a filler in a continuous phase containing a hydrophilic resin. Since the hydrophilic layer is required to have high water resistance, it is preferable to contain a crosslinking agent. Although the crosslinking agent mainly reacts with the polar group of the hydrophilic resin, the silica particles having a high surface activity may impair the stability of the coating solution for coating the hydrophilic layer, and in the coating solution during the drying process. It is a preferable embodiment to modify the surface of the silica particles from the viewpoint of forming a preferable shape by preventing secondary aggregation.

  It is preferable that the surface of the silica particles is subjected to treatment with a hydrophilic resin, inorganic treatment, and / or organic treatment. Here, “treatment with hydrophilic resin, inorganic treatment and / or organic treatment” is known, and the following surface treatment is performed on the surface of the silica particles.

  For example, a method for impregnating the surface of particles with surfactants, polymers, waxes, inorganics, etc., and topochemical modification using radical reaction, chelation reaction, coupling reaction, sol adsorption, etc. with surface active groups. And a mechanochemical reforming method using an organic material graft reaction with the pulverized active surface, an inorganic adsorption reaction, and the like. For example, Leoroseal MT10, QS10, QS102, QS30 (above, manufactured by Tokuyama Soda Co., Ltd.), Cyloid 83, 378, 161, 162C, C907, ED41, ED20, ED30, ED40, ED44, ED50, ED52, ED56, ED80, 7000 (above, manufactured by Grace Japan Co., Ltd.), Silicia 256, 256N, 358, 435, 445, 436, 446, 456 (above, manufactured by Fuji Silysia Chemical Co., Ltd.) it can.

As the water-dispersible filler, the acrylic resin fine particles mainly play a role of enhancing the physical wettability of the surface of the hydrophilic layer, and may be used in the present invention. A conventionally well-known thing can be especially used as this acrylic resin without a restriction | limiting. The acrylic resin can be obtained by copolymerizing the monomers described below by the method described above.
(1) Monomers having an aromatic hydroxyl group, such as o-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate and the like.
(2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxy Pentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide and the like.
(3) Monomer having an aminosulfonyl group, such as m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl acrylate, p-aminophenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide N- (p-aaminosulfonylphenyl) acrylamide and the like.
(4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.
(5) α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid.
(6) Substituted or unsubstituted alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic Acid decyl, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate and the like.
(7) substituted or unsubstituted alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, methacryl Decyl, undecyl methacrylate, undecyl methacrylate, dodecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like.
(8) Acrylamide or methacrylamide, for example, acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.
(9) Monomers containing fluorinated alkyl groups, such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, etc. .
(10) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-cyanoethyl acrylate, etc. (11) Monomers having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylamino Ethyl acrylate, N, N-dimethylaminoethyl methacrylate and the like.

  The water-dispersible filler that can be preferably used in the present invention is preferably a substance that imparts dispersion stability and high hydrophilicity with a hydrophilic resin from the viewpoint of enhancing chemical wettability, specifically a monomer unit having a polar group. The thing which has is more preferable. Preferable polar groups include a hydroxyl group, a carboxyl group, an amino group, an amide group, a sulfonic acid group, a phosphoric acid group, and the like, and the introduction ratio thereof is preferably used in the range of 0 to 70%.

  The water-dispersible filler preferably has an average particle size in the range of 0.2 to 10 μm. Here, the average particle diameter is a value measured according to JIS K-1150. The average particle size of the water dispersible filler is more preferably 0.6 to 7 μm. By including the water-dispersible filler having such an average particle diameter in the hydrophilic layer, the strength as a support can be improved and high hydrophilicity can be obtained.

  As the water-dispersible filler, the same kind of water-dispersible filler may be used, or two or more kinds of different water-dispersible fillers may be mixed and used. From the viewpoint of surface shape control, use the same kind of water-dispersible fillers with different particle diameters in combination and silica and PMMA particles for the purpose of improving the balance between chemical wettability and physical wettability This is a preferred embodiment.

  Also, inorganic ultrafine particles (particles having a particle size of 100 nm or less) can be used as long as the conditions regarding the average particle size of the silica particles of the present invention are satisfied. Examples of such inorganic ultrafine particles include silica (colloidal silica), alumina, or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or hydrate, suspicious boehmite, etc.), surface-treated cationic colloidal. Silica, aluminum silicate, magnesium silicate, magnesium carbonate, titanium dioxide, zinc oxide, light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white , Aluminum silicate, diatomaceous earth, calcium silicate, synthetic amorphous silica, aluminum hydroxide, lithopone, zeolite, hydrous halloysite, magnesium hydroxide, synthetic mica and the like. Among the inorganic fine particles, porous inorganic fine particles are preferable, and examples of the porous inorganic fine particles include porous synthetic amorphous silica, porous calcium carbonate, porous alumina and the like. Amorphous silica is preferred.

  Similarly to the inorganic ultrafine particles, ultrafine particles such as styrene resin, acrylic resin, polyethylene, microcapsule, urea resin, urethane resin, polyester resin, melamine resin, and fluorine resin can be used.

  The primary particle diameter of the inorganic ultrafine particles is 100 nm or less, preferably 50 nm or less. The smaller the particle diameter, the more preferable the surface coating becomes. These inorganic ultrafine particles are usually used after being dispersed in a colloidal form while maintaining a primary particle size in a solvent.

In the present invention, the content of the silica particles contained in the hydrophilic layer is in the range of 5 to 70% by mass and / or the relationship between the average particle size x (μm) of the silica particles and the content y (% by mass). But,
Formula 1
(72.895-5.7895x) ≧ y ≧ (15.526-1.0526x)
It is preferable from the viewpoint of achieving the object of the present invention to a higher degree.

  In the present invention, the hydrophilic layer preferably contains a crosslinking agent in order to have high water resistance. As the crosslinking agent, conventionally known crosslinking agents can be widely used as long as the hydrophilic resin can be crosslinked. Examples of the cross-linking agent include amino resins, aziridine compounds, amine compounds, aldehydes, isocyanate compounds, carboxylic acids or acid anhydrides, halides, phenol-formaldehyde resins, and compounds having two or more epoxy groups. Can be mentioned. The crosslinking agent may be a low molecular weight compound, or an oligomer or polymer.

  Examples of amino resins include resins obtained by reacting melamine, benzoguanamine, urea and the like with aldehydes and ketones, and specific examples include melamine-formaldehyde resins, urea-formaldehyde resins, methylolated melamine, and the like. It is done. These amino resins are effective for hydrophilic resins having a hydroxyl group, a carboxyl group, a mercapto group, and the like.

  Examples of the halide include, for example, U.S. Pat. Nos. 3,325,287, 3,288,775, 3,549,377, and Belgian Patent 6,622,226. Examples include dichlorotriazine-based compounds described in the specification. These halides are effective for the hydrophilic resin of the present invention having a hydroxyl group, an amino group or the like.

  Examples of the amine compound and the aziridine compound include an aziridine compound described in US Pat. No. 3,392,024, an ethyleneimine compound described in US Pat. No. 3,549,378, and the like. The following compounds are mentioned.

  These amine compounds and aziridine compounds are effective for hydrophilic resins having a hydroxyl group, a carboxyl group or the like.

  The isocyanate compound also includes an isocyanate having a protecting group (blocked-isocyanate). Examples of these isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, Examples include isophorone diisocyanate, xylene diisocyanate, triphenylmethane diisocyanate, and bicycloheptane diisocyanate.

  These isocyanate compounds are effective for the hydrophilic resin of the present invention having a hydroxyl group, a carboxyl group, a mercapto group, an amino group and the like.

  Examples of the aldehydes include formaldehyde, glyoxal, US Pat. Nos. 3,291,624, 3,232,764, French Patent 1,543,694, British Patent 1 , 270, 578 specification. These aldehydes are effective for the hydrophilic resin of the present invention having a hydroxyl group.

  Among these, amino resins, aziridine compounds, aldehydes and isocyanates are preferable.

  As an example, when gelatin is used as the hydrophilic resin of the hydrophilic layer, examples of the crosslinking agent include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds. (Dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis- (vinylsulfonyl) methyl ether, N, N′-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, phenoxymucochlor) Acid etc.), isoxazole , Dialdehyde starch, 2-chloro-6-hydroxy-triazinyl gelatin, isocyanates, carboxyl groups activated crosslinking agent, can be preferably used singly or in combination.

  The crosslinking agent for crosslinking the hydrophilic resin is used in the hydrophilic layer in the range of 0 to 40% by mass. The use is preferably in the range of 1 to 30%, particularly preferably 2 to 20%.

  As the crosslinking agent, one kind or two or more kinds of the same kind of crosslinking agents may be used, or two or more kinds of different kinds of crosslinking agents may be used in combination.

  Furthermore, it is also preferable to add and use a reaction accelerator in order to react the cross-linking agent and the hydrophilic resin with high efficiency. The reaction accelerator promotes the cross-linking reaction and thus can reduce the overall plate production time while maintaining the high level of cross-linking required to obtain high printing resistance.

  As the reaction accelerator, known reaction accelerators can be used. For example, ammonium salt systems such as ammonium chloride, ammonium acetate, ammonium sulfate, ammonium nitrate, ammonium phosphate, dibasic ammonium phosphate, ammonium thiocyanate, ammonium sulfamate Organic amine salt systems such as compounds, dimethylaniline hydrochloride, pyridine hydrochloride, picoline monochloroacetic acid, catalyst AC (manufactured by Monsanto Co., Ltd.), cattanit A (manufactured by Nitto Chemical Co., Ltd.), and Sumilizer ACX-P (manufactured by Sumitomo Chemical) Examples thereof include inorganic salt compounds such as compounds, stannic chloride, ferric chloride, magnesium chloride, zinc chloride, and zinc sulfate.

Moreover, the precursor of a reaction accelerator can also be used. The precursor of the reaction accelerator is converted into a reaction accelerator upon heating, and the reaction accelerator is formed as shown in the image. Suitable precursors for reaction accelerators are, for example, precursors that release acid upon heating. Examples of these precursors include sulfonium compounds disclosed in British Patent No. 612,065, European Patent No. 615,233, and US Pat. No. 5,326,677, particularly benzyl. Sulfonium compounds, inorganic nitrates (for example, Mg (NO ₃ ) ₂ .6H ₂ O disclosed in European Patent No. 462,763, WO81 / 1755, US Pat. No. 4,370,401) , Ammonium nitrate), organic nitrates (eg, guanidinium nitrate, pyridinium nitrate) and the like, compounds that release sulfonic acids disclosed in US Pat. No. 5,312,721, such as 3-sulfolenes, such as 2 , 5-dihydrothio-thiophene-1,1-dioxides, disclosed in British Patent 1,204,495 Thermally decomposable compounds, disclosed in US Pat. No. 3,669,747 and co-crystallized adducts of amines and volatile organic acids, disclosed in US Pat. No. 3,166,583 Aralkyl cyanoforms, disclosed in European Patent No. 159,725 and West German Patent No. 351,576, Thermo Acid, US Pat. No. 5,278,031 Square Acid Generating Compound, US Pat. No. 5,225,314, US Pat. No. 5,227,277, and Research Disclosure No. 1993 November. 11511 is an acid generating compound disclosed in 11511.

  In addition to the above, the hydrophilic layer can contain various additives as long as the effects of the present invention are not impaired.

  In the present invention, the center line surface roughness Ra of the surface of the hydrophilic layer is in the range of 0.1 ≦ Ra ≦ 1.2 μm. The Ra value can be measured using an optical three-dimensional surface roughness meter “RST Plus” manufactured by WYKO. Measurement conditions are objective lens × 40 and intermediate lens × 1.0, and a field of view of 111 μm × 150 μm is measured at N = 5 to obtain an average value.

  In the present invention, the weight loss of the hydrophilic layer in water at 25 ° C. is 1% or less and / or the γh of the surface of the hydrophilic layer is 20 or more in order to achieve the object of the present invention to a higher degree. Is preferable. The dissolution weight loss and γh will be described later.

  In the lithographic printing plate support, a layer such as an adhesive layer can be provided between the substrate and the hydrophilic layer.

  The lithographic printing plate support of the present invention can be used as a heat-sensitive lithographic printing plate material by providing an image forming layer described later, and can be used for the following applications.

For example, preparation of a lithographic printing plate by a) a melt thermal transfer system, b) a sublimation thermal transfer system, c) an ablation transfer system, d) an ink jet system or the like can be mentioned.
a) As the melt thermal transfer method, for example, the lithographic printing plate support of the present invention is prepared by melting a lipophilic and heat-meltable transfer layer provided on the support by converting heat / light energy into heat. And a method of transferring onto the hydrophilic layer. Specifically, a transfer method in which the surface of the original plate and the surface of the thermal transfer sheet described in JP-A No. 56-13168 are adhered to each other and laser exposure is performed, and a hydrophilic plate material described in JP-A No. 62-280038 is coated with an ink sheet using a thermal head. A method of transferring the ink of the present invention, a method of containing a photocurable component in the thermal transfer layer described in JP-A-4-94937, and forming an image by post-heating, and a thermosetting component contained in the thermal transfer layer described in JP-A-4-94938 And a method of image formation by post-heating.
b) As the sublimation thermal transfer method, for example, the lithographic printing plate support of the present invention is obtained by sublimating a lipophilic and heat sublimable substance provided on the support by converting heat / light energy into heat. A method for transferring onto a hydrophilic layer, a hydrophilic and sublimable substance provided on a support, which is sublimated by converting heat / light energy into heat, and thereby supporting the lithographic printing plate support of the present invention. A method of transferring onto the hydrophilic layer is mentioned. Specific examples include a method of transferring a lipophilic image to a hydrophilic and porous support surface described in JP-A No. 54-53009 by sublimation.
c) As an ablation transfer method, for example, the hydrophilicity of the lithographic printing plate support of the present invention is obtained by converting a lipophilic substance provided on a hydrophilic support into high-intensity light energy and ablating. Examples thereof include a method of transferring onto a hydrophilic layer and a method of transferring a hydrophilic substance provided on an oleophilic support by converting high-intensity light energy into heat and ablating.
d) As an ink jet method, it is described in JP-A-7-70490, 8-165447, 9-3377, etc. on the hydrophilic layer of the lithographic printing plate support of the present invention. Examples thereof include a method of forming an image using hot melt ink.

  Next, a heat-sensitive lithographic printing plate to which the lithographic printing plate support of the present invention can be applied will be described.

  The heat-sensitive lithographic printing plate material includes a hydrophilic resin, a compound that generates hydrophobicity by heat, and a water-dispersible filler, and has an image forming layer on the support that has a hydrophilicity that decreases by heat. A plate material, wherein the average particle diameter of the water-dispersible filler is in the range of 0.2 to 10 μm, and the center line surface roughness Ra of the image forming layer is in the range of 0.1 ≦ Ra ≦ 1.2 μm. It is characterized by that.

  The substrate of the heat-sensitive lithographic printing plate material corresponds to the substrate of the support of the present invention. As this substrate, a conventionally known one can be used as the support of the photosensitive lithographic printing plate without any particular limitation, and the material, layer structure, size, etc. are appropriately selected and used according to the purpose of use. be able to. For example, various papers such as paper, coated paper, synthetic paper (polypropylene, polystyrene, or composite material obtained by bonding them with paper), vinyl chloride resin sheet, ABS resin sheet, polyethylene terephthalate film, polybutylene terephthalate film, Polyethylene naphthalate film, polyarylate film, polycarbonate film, polyether ketone film, polysulfone film, polyether sulfone film, polyetherimide film, polyimide film, polyethylene film, polypropylene film, etc., or two or more layers thereof Various plastic films or sheets laminated, films or sheets formed of various metals, films or sheets formed of various ceramics, and Aluminum, stainless steel, chromium, metal plate such as nickel, can be used as the metal thin film to the paper was resin coated and laminated or deposited.

  Conventionally known surface modification techniques can be suitably applied to the substrate. Examples of such surface modification techniques include sulfuric acid treatment, oxygen plasma etching treatment, corona discharge treatment, and application of water-soluble resin, all of which are preferably used.

  As the hydrophilic resin contained in the image forming layer of the heat-sensitive lithographic printing plate material, conventionally known resins can be used without particular limitation. For example, hydrophilic groups such as hydroxyl groups, carboxyl groups, (secondary or tertiary) amine-containing groups, amino groups, amide groups, carbamoyl groups, sulfonic acid groups, sulfonamide groups, phosphonic acid groups, mercapto groups, alkyl ether groups. Examples thereof include polymer compounds having a functional group, and examples thereof include polyvinyl alcohol, polysaccharides, polyvinyl pyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, and closed octaacetate. , Ammonium alginate, sodium alginate, polyvinylamine, polyallylamine, polystyrene sulfonic acid, polyacrylic acid, polyamide, polyacrylamide, maleic anhydride copolymer, polyureta , A polyester or the like. As the hydrophilic resin, a single resin or a mixture of two or more of these compounds can be used as a main component.

  As the hydrophilic resin, a resin having a polyacrylamide, gelatin, polyvinyl alcohol, polyester, or polyurethane skeleton is preferable, and gelatin is most preferable.

  Gelatin is alkali method gelatin, acid method gelatin, modified gelatin (for example, modified gelatin described in JP-B-38-4854, JP-A-40-12237, British Patent 2,525,753, etc.), etc. Can be used alone or in combination of two or more. For example, in addition to lime-processed gelatin, acid-processed gelatin may be used. Hydrolyzate of gelatin, Bull. Soc. Sci. Photo. Japan. No. 16. p. 30 (1966) can also be used.

As polyvinyl alcohol, in addition to polyvinyl alcohol having various polymerization degrees, copolymerized polyvinyl alcohol, an anion-modified polyvinyl alcohol modified with anions such as a carboxyl group and a sulfo group containing 50 mol% or more of a polyvinyl alcohol skeleton, an amino group , Random copolymers such as cation-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, alkoxyl-modified polyvinyl alcohol, epoxy-modified polyvinyl alcohol, and thiol-modified polyvinyl alcohol modified with cations such as ammonium groups; anion-modified, cation-modified, thiol-modified, Water-soluble monomers such as polyvinyl alcohol, acrylamide, and acrylic acid that are modified only on the terminal groups, such as silanol modification, alkoxyl modification, and epoxy modification Introduced a block copolymer of polyvinyl alcohol, graft copolymer of polyvinyl alcohol grafted silanol group or the like, - can be used (COCH ₂ COCH ₃₎ or the like copolymerized polyvinyl alcohol and the reactive group is introduced, such as.

  The polyvinyl alcohol preferably has a saponification degree of 70 mol% or more, more preferably 85 mol% or more, and particularly preferably 90% or more. Polyvinyl alcohol having a high saponification degree is preferable because the crystallinity is changed by heat treatment and water resistance can be imparted.

In the copolymerized polyvinyl alcohol, the following monomers can be used as the copolymerization monomer.
(1) Monomers having an aromatic hydroxyl group: for example, o-hydroxystyrene, p-hydroxystyrene, m-hydroxystyrene, o-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate and the like.
(2) Monomers having an aliphatic hydroxyl group: For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxy Pentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.
(3) Monomer having an aminosulfonyl group: for example, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl acrylate, p-aminophenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide N- (p-aminosulfonylphenyl) acrylamide and the like.
(4) Monomers having a sulfonamide group: for example, N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.
(5) α, β-unsaturated carboxylic acids: for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like.
(6) Substituted or unsubstituted alkyl acrylate: for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic Acid decyl, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate and the like.
(7) Substituted or unsubstituted alkyl methacrylate: for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, methacryl Acid decyl, undecyl methacrylate, undecyl methacrylate, dodecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like.
(8) Acrylamide or methacrylamide: For example, acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.
(9) Monomer containing a fluorinated alkyl group: for example, trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N-butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.
(10) Vinyl ethers: For example, ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ethers.
(11) Vinyl esters: For example, vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.
(12) Styrenes: For example, styrene, methyl styrene, chloromethyl styrene and the like.
(13) Vinyl ketones: For example, methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone and the like.
(14) Olefin: For example, ethylene, propylene, isobutylene, butadiene, isoprene and the like.
(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.
(16) Monomer having a cyano group: for example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o-cyanostyrene, m-cyanostyrene, p-cyanostyrene etc.
(17) Monomer having an amino group: for example, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-isopropylacrylamide, N, N-diethylacrylamide and the like.

  As polyvinyl alcohol to be used, polyvinyl alcohol introduced with a reactive group and polyvinyl alcohol introduced with an anionic group are preferable, and among them, polyvinyl alcohol introduced with a reactive group is preferable. Examples of the reactive group include a silanol group, an acetoacetyl group, a thiol group, and an epoxy group. Among these, particularly preferred reactive groups are a silanol group, an acetoacetyl group, and a thiol group.

  The above polyvinyl alcohols may be used alone or in combination of two or more.

  Next, a resin having a polyurethane or polyester skeleton will be described. In the present invention, a polyurethane resin having a hydrophilic group, a polyester resin having a hydrophilic group, and a polyamide resin having a hydrophilic group can be preferably used as the resin. In the practice of the present invention, those having a carboxyl group, a hydroxyl group, a sulfonic acid group, an amino group and a sulfonamide group in the side chain are preferred as the hydrophilic group.

  Further, the polyurethane resin having a hydrophilic group has at least one kind of the above-mentioned hydrophilic group and contains at least one repeating unit selected from a urethane bond, a urea bond, a burette bond, and an allophanate bond in the main chain. Such a bond is mainly formed by selecting a reactive group that undergoes an addition reaction with isocyanate.

  Examples of the diisocyanate compound suitably used in this reaction include conventionally known 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane. Aromatic diisocyanate compounds such as diisocyanate, 1,5-naphthalene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate; trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, Aliphatic diisocyanate compounds such as dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) And aliphatic diisocyanate compounds such as methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, and more than three molecules of these diisocyanate compounds. A trifunctional or higher functional isocyanate compound produced by a reaction product of these diisocyanate compounds and a trihydric or higher polyhydric alcohol can also be suitably used.

  Examples of the polyfunctional alcohol that forms a urethane bond by addition reaction with an isocyanate compound include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, octanediol, diethylene glycol, and triethylene glycol; glycerin and trimethylol Aliphatic polyfunctional alcohols such as ethane, trimethylolpropane, pentaerythritol, diglycerin, 1,2,6-hexanetriol, sorbitol, mannitol, and glucose; a hydroxyl group is formed at the terminal by condensation of dicarboxylic acid and polyhydric alcohol Polyester polyols prepared by ring-opening polymerization of alkylene oxide or polyether polyol added to alkylene oxide and polyhydric alcohol.

  Depending on the alcohol valence of these compounds, the desired reaction product can be obtained by adding and reacting at a ratio of 2 moles of isocyanate to 1 mole of hydroxyl groups.

  In order to impart a hydrophilic group to a polyurethane resin, a method of polymerizing a urethane prepolymer having an isocyanate group remaining at the terminal with a diol having a tertiary amino group and quaternizing the tertiary amino group; an isocyanate group at the terminal A method of polymerizing a urethane prepolymer having a residual amino group with a diol having a tertiary amino group, neutralizing the tertiary amino group with an acid and subjecting to an amine chloride; a urethane prepolymer having an isocyanate group remaining at the terminal has a quaternary salt Method of polymerizing with diols; Method of polymerizing a urethane prepolymer having an isocyanate group remaining at the terminal with a diaminophenylcarboxylate and removing the solvent; Termination of the urethane prepolymer having an isocyanate group remaining at the terminal with sodium bisulfite To block with a compound such as A method of polymerizing a urethane prepolymer that has left an isocyanate group with diaminoalkanesulfonate; A method of polymerizing a urethane prepolymer that has left an isocyanate group with bis (2-cyanoethylamino) ethane; Examples include a method of polymerizing a polymer with an alkylene oxide of a long chain alcohol, and other methods such as those described in Keiji Iwata “Polyurethane Resin Handbook”, Nikkan Kogyo Shimbun, pages 496 to 506 can be arbitrarily employed. .

  Moreover, Takeda Pharmaceutical Co., Ltd. Takerak W series (W-621, W-6015, W-7004, W-511, W-635, XW-76-P15, XW-74 can be used as commercially available polyurethane resins. -P6012C, ACW-31H, ACW-54HD, XW-904-X05, XW-97-W4 to polyester urethane self-emulsifying type), the same (W-310, W-512 to polyester urethane forced emulsifying type), Takeda Series containing alkoxysilyl groups (XW-77-X25, XW-75-X09, XW-74-X13, XS-72-V01, XS-72-V02, XS-72-V03, XS-72-) V04, XS-72-V05-polyester urethane self-emulsifying type), high tack series (S 8531, S-8532, S-8533, S-8530, S-8529, S-8528, S-6254, S-6262, B-1306), NeoRez series (R-960, R-) manufactured by Enomoto Kasei Co., Ltd. 962, R-972, R-974, R-9314, R-9320, R-9617, XR-9621, XR-9624, R-9637, XR-9679, XR-9699, XR-9770 to aliphatic polyester urethane ), NeoRez series (R-966, R-967, XR-9000, AX-311, AX-7113 to aliphatic polyether urethane) manufactured by Enomoto Kasei Co., Ltd. NeoRez series (R-940) manufactured by Enomoto Kasei Co., Ltd. R-9030, XR-9409, R-9920, XR-7061-aromatic polyether urethane), Enomoto Kasei ( ) NeoRez series (XU-7015, R-9603-Special urethane, aliphatic polycarbonate urethane), Kanebo UESC Yodosol series (9D102, 9D205Z, 9D232Z), Toa Gosei Chemical Co., Ltd. Neotan series (UE-111, UE-1200, UE-1300, UE-1402, UE-2103, UE-2200, UE-2600, UE-2900 to polyester urethane), Neotan series (UE- manufactured by Toa Synthetic Chemical Co., Ltd.) 5404, UE-5600 to polyether urethane), Nenrange Series (R-1489, R-1780) manufactured by Takamatsu Yushi Co., Ltd., Crown Bond Series (UA-28, UA-41, U-) manufactured by Takamatsu Yushi Co., Ltd. 176R, RI-793, RI-623, U-11 3), Dispacol series (U-42, U-53, KA8441, KA8584) manufactured by Sumitomo Bayer Urethane Co., Ltd., and the like.

The polyester resin having a hydrophilic group that can be used is a polymer having at least one of the above-mentioned hydrophilic groups and containing a repeating unit of an ester bond in the main chain, and a resin having such an ester bond. For example, a hydrophilic group may be introduced into a prepolymer of a polyester resin formed by the method described in “Polyester Resin Handbook”, pages 21 to 28, and polymerized by any method. Examples of commercially available polyester resins that can be used in the present invention include pesresin A series (110, 120, 121, 193, 510, 610, and 810--hydrophilic group is —SO ₃ R) manufactured by Takamatsu Yushi Co., Ltd. ) Pesresin A series (210, 620, 820-new aqueous group is -COOR), Takamatsu Oil Co., Ltd. Pesresin A series (115G, 124G, 124GH, 193G, 215G, 515G, 615G, 813GL to hydrophilic group -SO ₃ R and glycidyl), Pesresin A series (124S, 115S-hydrophilic groups are -SO ₃ R and Si (OR) ₃ ) manufactured by Takamatsu Yushi Co., Ltd., plus coat series (Z -3402, Z-4121, Z-446, Z-461, Z-448, Z-441, Z-450, Z-710, Z-711, Z 770, Z-766 to water-soluble), plus coat series (Z-820, Z-3109, Z-3308, Z-857, Z-850, Z-802, Z-856, Z) manufactured by Kyoyo Chemical Industry Co., Ltd. -4201, RZ-27, RZ-50, RZ-56, RZ-105), Toyobo Co., Ltd. Bironal series (MD-1200, MD-1200, MD-1250, MD-1100, MD-1330, MD-1930).

  In the heat-sensitive lithographic printing plate material, the hydrophilic resin is preferably contained in the image forming layer in the range of 10 to 98% by mass. When the hydrophilic resin is less than 10% by mass, the strength of the hydrophilic layer is insufficient, and when it is more than 98% by mass, the effect of containing the water-dispersible filler is small and the effect of the present invention cannot be exhibited. The content of the hydrophilic resin is more preferably 20 to 97% by mass, still more preferably 30 to 96% by mass.

  A preferred embodiment of the heat-sensitive lithographic printing plate material is an embodiment in which at least one selected from polyacrylamide, gelatin, polyvinyl alcohol, polyester and polyurethane is used as a main component as the hydrophilic resin. Here, a main component means containing 50% or more of the total mass of hydrophilic resin, and a more preferable aspect is containing 70% or more of the total mass of hydrophilic resin. In the above, as the hydrophilic resin, one type or two or more types of hydrophilic resins may be used, or two or more types of hydrophilic resins may be used in combination.

  In the heat-sensitive lithographic printing plate material, organic or inorganic fine particles can be used as the water-dispersible filler to be contained in the image forming layer.

  Organic fine particles include fine particles of acrylic polymer such as polymethyl methacrylate (PMMA), fine particles of styrene polymer, fine particles of olefin polymer such as polyethylene and polypropylene, fine particles of fluorine polymer such as polytetrafluoroethylene, and others. And radical polymerization polymer fine particles, and condensation polymer fine particles such as polyester and polycarbonate.

  As a method for producing the organic fine particles as described above, any method can be adopted. For example, (A) a method of growing particles during polymerization, such as emulsion polymerization, soap-free polymerization, and dispersion polymerization, (B) A method in which droplets are polymerized as they are, such as suspension polymerization, nozzle vibration method, swelling seed polymerization, and two-stage swelling polymerization, can be used. In addition to the method of obtaining fine particles by polymerizing in a dispersion medium such as (A) or (B) above, a poor solvent is added after dissolving the polymer in a rich solvent, if necessary, under heating. Or by cooling to deposit the polymer to obtain fine particles (a fine particle can be easily obtained by applying a shearing force during precipitation), and the polymer is pulverized and dispersed in a solvent by a dispersing means such as a sand mill or a ball mill. Can be obtained by a method of obtaining fine particles by pulverizing a polymer in a dry state and passing through a classification step.

  Examples of the inorganic fine particles include calcium alginate, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, barium sulfate, calcium carbonate, silica (silicon oxide), and zircon fine particles.

  As a method for producing the inorganic fine particles, any method can be adopted, and examples thereof include a breakdown method in which a bulk material is subdivided and a buildup method in which molecules or fine particles are aggregated.

  Breakdown methods include jet mills, stirring mills, ball mills, roller mills, stamp mills, high speed rotary mills, etc., and the introduction of the second component into the active part formed by grinding using these methods. A method of performing surface modification by doing so is also preferably used. Such a method is described in “Particle Handbook” (Asakura Shoten) p. 234-235. Moreover, after dissolving / dispersing in various solvents to form fine particles, a method of evaporating / drying the solvent can be used.

  As build-up methods, gas evaporation methods, sputtering methods, arc plasma evaporation methods, laser vapor deposition methods, high frequency plasma vapor deposition methods, and other methods using evaporation aggregation, thermal CVD methods, plasma CVD methods, laser CVD methods, etc. It can be prepared by various methods described in “Fine Particle Handbook” (Asakura Shoten), pp.

  Among these, a water-dispersible filler that improves physical and / or chemical wettability is a fine particle substantially composed of silica, alumina, polytetrafluoroethylene, acrylic resin, magnesium oxide, and calcium alginate. (Here, “substantially” means that other substances may be contained within a range that does not impair the effects of the present invention), and most preferably silica fine particles and acrylic resin fine particles. .

  The silica fine particles mainly play a role of enhancing the chemical wettability of the surface of the image forming layer, and the particles produced by the above method can be suitably used. Among these, silica produced by a pulverization method has high surface activity and is preferable in terms of expressing high hydrophilicity. In addition, performing a treatment such as classification for the purpose of narrowing the particle size distribution of the particles is a preferable method from the viewpoint of further improving the physical wettability.

  As the shape of the silica particles, silica particles having a porous shape are preferable, and the pore volume of the silica particles is preferably 0.5 ml / g or more. Among these, 1.0 ml / g or more is more preferable, and 1.5 ml / g or more is particularly preferable.

  Silica particles having a high surface activity may impair the stability of the coating solution for coating the hydrophilic layer, and also from the viewpoint of forming a preferable shape by preventing secondary aggregation during the drying process in the coating solution. It is a preferred embodiment to modify the surface of the particles. Specifically, it is preferable that the surface of the silica particles has been subjected to treatment with a hydrophilic resin, inorganic treatment and / or organic treatment. The above-mentioned “treatment with a hydrophilic resin, inorganic treatment and / or organic treatment” is known, and the following surface treatment is performed on the surface of the silica particles.

  For example, a method of impregnating the surface of particles with a surfactant, polymer, wax, inorganic substance, etc., radical reaction with surface active groups, chelate reaction, coupling reaction, topochemical modification using sol adsorption, etc. And a mechanochemical reforming method using an organic material graft reaction with the pulverized active surface, an inorganic adsorption reaction, and the like.

  Examples of such surface-treated silica particles include Leolosil MT10, QS10, QS102, QS30 (manufactured by Tokuyama Soda Co., Ltd.), Cyloid 83, 378, 161, 162C, ED41, ED20, ED30, ED40, ED44. , ED50, ED52, ED56, ED80, 7000 (above, manufactured by Grace Japan Co., Ltd.), Silicia 256, 256N, 358, 435, 445, 436, 446, 456 (above, manufactured by Fuji Silysia Chemical Co., Ltd.), etc. Can be mentioned.

The fine particles of the acrylic resin mainly play a role of enhancing the physical wettability of the surface of the image forming layer, and conventionally known materials can be used without any particular limitation. The acrylic resin can be obtained by copolymerizing the following monomers by the method as described above.
(1) Monomers having an aromatic hydroxyl group, such as o-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate and the like.
(2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxy Pentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide and the like.
(3) Monomer having an aminosulfonyl group, such as m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl acrylate, p-aminophenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide N- (p-aaminosulfonylphenyl) acrylamide and the like.
(4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.
(5) α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid.
(6) Substituted or unsubstituted alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic Acid decyl, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate and the like.
(7) substituted or unsubstituted alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, methacryl Decyl, undecyl methacrylate, undecyl methacrylate, dodecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like.
(8) Acrylamide or methacrylamide, for example, acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.
(9) Monomers containing fluorinated alkyl groups, such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, etc. .
(10) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-cyanoethyl acrylate and the like.
(11) Monomers having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate and the like.

  The water-dispersible filler that is preferably used for the heat-sensitive lithographic printing plate material is preferably a material that imparts dispersion stability and high hydrophilicity with a hydrophilic resin in terms of enhancing chemical wettability. The thing which has the monomer unit which has a polar group is more preferable. Preferred polar groups for the present invention include a hydroxyl group, a carboxyl group, an amino group, an amide group, a sulfonic acid group, a phosphoric acid group, and the like, and the introduction ratio thereof is in the range of 0 to 70%. Is preferred.

  In the heat-sensitive lithographic printing plate material, the filler contained in the image forming layer has an average particle size in the range of 0.2 to 10 μm. Here, the average particle diameter is a value measured according to JIS K-1150. When the average particle size of the filler contained in the hydrophilic layer is less than 0.2 μm, the hydrophilicity is not sufficient, and when it exceeds 10 μm, the printing durability is lowered. The average particle diameter of the water dispersible filler is preferably 0.6 to 7 μm. By including the water-dispersible filler having such an average particle diameter in the image forming layer, the strength as a support can be improved and high hydrophilicity can be obtained.

  As the water-dispersible filler, the same kind of water-dispersible filler may be used, or two or more kinds of different water-dispersible fillers may be mixed and used. From the viewpoint of surface shape control, the same type of water-dispersible fillers with different particle sizes are used in combination, and silica and PMMA particles are used together for the purpose of improving the balance between chemical wettability and physical wettability. This is a preferred embodiment.

  Inorganic ultrafine particles (particles having a particle size of 100 nm or less) can also be used as long as the conditions regarding the average particle size of the water-dispersible filler of the heat-sensitive lithographic printing plate material are satisfied. Examples of such inorganic ultrafine particles include silica (colloidal silica), alumina, or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or hydrate, suspicious boehmite, etc.), surface-treated cationic colloidal. Silica, aluminum silicate, magnesium silicate, magnesium carbonate, titanium dioxide, zinc oxide, light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white , Aluminum silicate, diatomaceous earth, calcium silicate, synthetic amorphous silica, aluminum hydroxide, lithopone, zeolite, hydrous halloysite, magnesium hydroxide, synthetic mica and the like. Among the inorganic fine particles, porous inorganic fine particles are preferable, and examples of the porous inorganic fine particles include porous synthetic amorphous silica, porous calcium carbonate, porous alumina and the like. Amorphous silica is preferred.

  Similarly to the inorganic ultrafine particles, ultrafine particles such as styrene resin, acrylic resin, polyethylene, microcapsule, urea resin, urethane resin, polyester resin, melamine resin, and fluorine resin can be used.

  The primary particle diameter of the inorganic ultrafine particles is 100 nm or less, preferably 50 nm or less. The smaller the particle diameter, the more preferable the surface coating becomes. These inorganic ultrafine particles are usually used after being dispersed in a colloidal form while maintaining a primary particle size in a solvent.

  Next, the compound that generates hydrophobicity by heat contained in the image forming layer of the heat-sensitive lithographic printing plate material will be described.

  In the heat-sensitive lithographic printing plate material, in order to obtain an image forming layer whose hydrophilicity is lowered by heat, in addition to at least the above-mentioned hydrophilic resin and water-dispersible filler, a compound that generates hydrophobicity by heat (hereinafter referred to as “ It is necessary to contain a "hydrophobic generating compound". As such a compound, conventionally known compounds can be used without particular limitation, and examples thereof include wax dispersions, thermoplastic resin particles, low-molecular hydrophobic substances, water repellents, and crosslinkable particles.

  Examples of wax dispersions include plant materials such as carnauba wax, wood wax, aucuric wax, and espal wax; animal materials such as beeswax, insect wax, shellac, and whale oil; paraffin wax, microcrystal wax, polyethylene wax, amide wax, Examples thereof include petroleum waxes such as ester waxes, and mineral substances such as montan wax, ozokerite, and ceresin. Also, waxes described in JP-A-59-174394 can be used.

  Thermoplastic resin particles include ethylene copolymers, styrene copolymers, polyamide resins, polyester resins, polyurethane resins, polyolefin resins, acrylic resins, vinyl chloride resins, polyvinylidene chloride resins, Polyvinylcarbazole resin, cellulose resin, rosin resin, polyvinyl alcohol resin, polyvinyl acetal resin, ionomer resin, petroleum resin, etc .; natural rubber, styrene butadiene rubber, isoprene rubber, chloroprene rubber, diene copolymer Elastomers such as ester gum, rosin maleic acid resin, rosin phenol resin, hydrogenated rosin and other rosin derivatives; and particles such as phenol resin, terpene resin, cyclopentadiene resin, and aromatic hydrocarbon resin. . Moreover, the self-water dispersible resin particles described in paragraph Nos. 0023 to 0025 of JP-A-9-127683 can be used. Further, ionomer resins described in JP-B 63-42593, page 2, column 4, line 10 to page 3, column 5, line 21 are also preferred.

  Low molecular weight hydrophobic substances include terpineol, menthol, 1,4-cyclohexanediol, phenol and other alcohols; acetamides, benzamides and other amides; coumarins, benzyl cinnamate and other esters; diphenyl ethers, crown ethers and other ethers Ketones such as camphor and p-methylacetophenone; aldehydes such as vanillin and dimethoxybenzaldehyde; hydrocarbons such as norbornene and stilbene; higher fatty acids such as palmitic acid, stearic acid, margaric acid and behenic acid; palmitic alcohol , Higher alcohols such as stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, eicosanol; cetyl palmitate, myricyl palmitate, cetyl stearate, stearyl Higher fatty acid esters such as myricyl acid; amides such as acetamide, propionic acid amide, palmitic acid amide, stearic acid amide, amide wax; and higher amines such as stearylamine, behenylamine, palmitylamine; phthalic acid esters, Trimellitic acid esters, adipic acid esters, other saturated or unsaturated carboxylic acid esters, oxalic acid esters, epoxidized soybean oil, epoxidized linseed oil, stearic acid epoxies, orthophosphoric acid esters, phosphorous acid ester And glycol esters.

  As the water repellent, conventionally known silicone compounds, fluorine compounds, and the like can be suitably used. As such materials, silicone surfactants such as Silwet L720, FZ2122, FZ2120, and FZ2166 can be used. FZ2171 (manufactured by Nippon Unicar Co., Ltd.) and the like, and further silane coupling agents such as coupling agents containing unsaturated groups such as carboxyl groups, mercapto groups, isocyanic groups and amino group-containing coupling agents. Examples of fluorine-based water repellents include fluorine-based surfactants (acrylates, methacrylates and copolymers of (polyoxyalkylene) acrylates or (polyoxyalkylene) methacrylates containing fluoroaliphatic groups), JP-A-62-170950. And those described in JP-A-62-226143 and US Pat. No. 3,787,351. For example, MegaFuck F-171, 173, 177, 179, 142D, Defenser MCF300, 312, 313 (Dainippon Ink Chemical Co., Ltd.), Modiper F-100, 102, 110 (Nippon Yushi Co., Ltd.), Fluorinated acrylic resins described in JP-A No. 64-18142, fluorine-containing surfactants described in JP-B-6-105351, JP-B-8-3630, JP-A-3-17249, and JP-A-1-260055. And compounds described in JP-A-1-271478 and JP-A-4-63802 can be preferably used.

  Further, among these materials, a particularly preferred product is a fluorine-containing oligomer having hydrophilicity capable of forming a dispersed state in a room temperature / aqueous liquid. As specific products, Asahi Guard AG422, 428, 490, 530, 550, 710, 780, 880, 970, LS317 (Asahi Glass Co., Ltd.), TK guard 505 (Takamatsu Yushi Co., Ltd.), Dick Guard F-52S, F-70, F18, F-90, F-90N, FS -90H (Dainippon Ink Co., Ltd.) etc. can be mentioned. Among these, those having a perfluoroalkyl group having a side chain of 5 to 15 carbon atoms are preferred, and those having 6 to 12 carbon atoms are particularly preferred.

  As the crosslinkable particles, conventionally known water-soluble and water-dispersible self-crosslinking agents can be preferably used. Examples of such compounds include a methylol group-containing compound, a melamine group-containing compound, an epoxy group-containing compound, an isocyanate group-containing compound, and a compound that releases the above-described group by removing a protecting group in the presence of heat or a catalyst. Etc. can be used suitably. Specifically, the compounds described in “Crosslinking Agent Handbook” Taiseisha (Shinzo Yamashita, Tosuke Kaneko) can be suitably used. As the catalyst, the above-mentioned reaction accelerator can be preferably used, and among these, a compound that exhibits a catalytic effect by exposure energy (heat or light) can be particularly preferably used.

  The hydrophobicity-generating compound can be used alone or in combination of two or more. Particularly preferred among the hydrophobic generating compounds are wax dispersions, thermoplastic resin particles and crosslinkable particles. The hydrophobicity-generating compound is preferably used in the image forming layer in the range of 0.5 to 90% by mass, and more preferably in the range of 1 to 70% by mass.

  In addition, a method of encapsulating a hydrophobicity-generating compound in microcapsules or the like and depositing it in an image-like manner, functionally separating the image-forming layer, a layer containing a hydrophobic substance in the lower layer, and a layer containing a hydrophilic resin as the main component in the upper layer It can also be designed and used.

  In the above microcapsules, the wall material, inclusions and production method thereof are described in JP-A 64-90788, page 2, lower right column, line 18 to page 5, lower right column, line 13; No. 169801, page 7, can be used.

  In the heat-sensitive lithographic printing plate material, a crosslinking agent capable of crosslinking a hydrophilic resin can be used as the hydrophobic generating compound. Conventionally known crosslinking agents can be widely used as crosslinking agents, such as amino resins, aziridine compounds, amine compounds, aldehydes, isocyanate compounds, carboxylic acids or acid anhydrides, halides, phenol-formaldehyde resins, two or The compound which has the epoxy group beyond it is mentioned. The crosslinking agent may be a low molecular weight compound, and may be an oligomer or a polymer.

  Examples of amino resins include resins obtained by reacting melamine, benzoguanamine, urea and the like with aldehydes and ketones, and specific examples include melamine-formaldehyde resins, urea-formaldehyde resins, methylolated melamine, and the like. It is done. These amino resins are effective for the hydrophilic resin of the present invention having a hydroxyl group, a carboxyl group, a mercapto group and the like.

  Examples of the halide include, for example, U.S. Pat. Nos. 3,325,287, 3,288,775, 3,549,377, and Belgian Patent 6,622,226. Examples include dichlorotriazine-based compounds described in the specification. These halides are effective for the hydrophilic resin of the present invention having a hydroxyl group, an amino group or the like.

  Examples of the amine compound and the aziridine compound include an aziridine compound described in US Pat. No. 3,392,024, an ethyleneimine compound described in US Pat. No. 3,549,378, and the like. The following compounds are mentioned.

  These amine compounds and aziridine compounds are effective for the hydrophilic resin of the present invention having a hydroxyl group, a carboxyl group or the like.

  The isocyanate compound also includes an isocyanate having a protecting group (blocked-isocyanate). Examples of these isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, Examples include isophorone diisocyanate, xylene diisocyanate, lysine diisocyanate, triphenylmethane diisocyanate, and bicycloheptane diisocyanate. These isocyanate compounds are effective for hydrophilic resins having a hydroxyl group, a carboxyl group, a mercapto group, an amino group, and the like.

  Examples of the aldehydes include formaldehyde, glyoxal, US Pat. Nos. 3,291,624, 3,232,764, French Patent 1,543,694, British Patent 1 , 270, 578 specification. These aldehydes are effective for hydrophilic resins having a hydroxyl group.

  Among these, amino resins, aziridine compounds, aldehydes and isocyanate compounds are preferable.

  As an example, when gelatin is used as the hydrophilic resin, examples of the crosslinking agent include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, Methyloldimethylhydantoin), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis- (vinylsulfonyl) methyl ether, N, N ' -Methylenebis- [β- (vinylsulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.), Isoxazoles, dials Hydrate starch, 2-chloro-6-hydroxy-triazinyl gelatin, isocyanates, carboxyl groups activated crosslinking agent may be used singly or in combination.

  The crosslinking agent for crosslinking the hydrophilic resin is used in the range of 0 to 40% by mass in the image forming layer. The use is preferably in the range of 1 to 30%, particularly preferably 2 to 20%. As the crosslinking agent, one kind or two or more kinds of the same kind of crosslinking agents may be used, or two or more kinds of different kinds of crosslinking agents may be used in combination.

  Furthermore, it is also preferable to add and use a reaction accelerator in order to react the cross-linking agent and the hydrophilic resin with high efficiency. The reaction accelerator promotes the cross-linking reaction and thus can reduce the overall plate production time while maintaining the high level of cross-linking required to obtain high printing resistance. As such a reaction accelerator, a known reaction accelerator can be used. For example, ammonium chloride, ammonium acetate, ammonium sulfate, ammonium nitrate, ammonium phosphate, dibasic ammonium phosphate, ammonium thiocyanate, ammonium sulfamate, etc. Organic compounds such as ammonium salt compounds, dimethylaniline hydrochloride, pyridine hydrochloride, picoline monochloroacetic acid, catalyst AC (manufactured by Monsanto Co., Ltd.), catanite A (manufactured by Nitto Chemical Co., Ltd.), and Sumilizer ACX-P (manufactured by Sumitomo Chemical Co., Ltd.) Examples thereof include inorganic salt compounds such as amine salt compounds, stannic chloride, ferric chloride, magnesium chloride, zinc chloride, and zinc sulfate.

It is also advantageous to use reaction accelerator precursors. The precursor of the reaction accelerator is converted into a reaction accelerator upon heating, and the reaction accelerator is formed as shown in the image. Suitable precursors for reaction accelerators are, for example, precursors that release acid upon heating. Examples of these precursors include sulfonium compounds disclosed in British Patent No. 612,065, European Patent No. 615233, and US Pat. No. 5,326,677, in particular, benzylsulfonium compounds. Inorganic nitrates (for example, Mg (NO ₃ ) ₂ .6H ₂ O, ammonium nitrate disclosed in European Patent No. 462,763, WO81 / 1755, US Pat. No. 4,370,401) ), Organic nitrates (eg, guanidinium nitrate, pyridinium nitrate) and the like, compounds that release sulfonic acids disclosed in US Pat. No. 5,312,721, such as 3-sulfolenes, such as 2,5 -Dihydrothio-thiophene-1,1-dioxides, disclosed in British Patent 1,204,495 Thermally decomposable compounds, disclosed in US Pat. No. 3,669,747 and co-crystallized adducts of amines and volatile organic acids, disclosed in US Pat. No. 3,166,583 Aralkylcyanoforms, Thermo Acid disclosed in European Patent No. 159,725 and West German Patent No. 351,576, Square disclosed in US Pat. No. 5,278,031 Acid generating compounds, U.S. Pat. No. 5,225,314, U.S. Pat. No. 5,227,277, and Research Disclosure No. 1993 November. And acid generating compounds disclosed in 11511.

  The heat-sensitive lithographic printing plate material forms an image by heating, whereby the heated portion changes from hydrophilic to hydrophobic. Therefore, a lithographic printing plate can be obtained by imagewise heating using a thermal head or the like. In addition, when a compound (light-heat conversion agent) that causes light-heat conversion is present in the heat-sensitive lithographic printing plate material, light-heat conversion occurs due to irradiation with light such as a laser, and is heated. A change in physical properties to hydrophobicity can be obtained. Such image formation using light such as a laser enables high-precision writing. In applications other than a system that performs simple printing, it is preferable to include a light-heat conversion agent in the heat-sensitive lithographic printing plate material. By allowing the light-to-heat conversion agent to be present in the heat-sensitive lithographic printing plate material, high-precision writing using light such as a high-power laser can be performed in addition to writing by a thermal head.

  The light-to-heat conversion agent may be present anywhere as long as it can transfer heat generated by light-to-heat conversion to the image forming layer, and even if it exists in the image forming layer, it exists in a layer different from the image forming layer. You may let them. Moreover, you may make it exist in a support body.

  The light-heat conversion agent is preferably a material that absorbs light and efficiently converts it into heat. Depending on the light source used, for example, when using a semiconductor laser that emits near infrared light as the light source, Near-infrared light absorbers having an absorption band are preferable, for example, organic compounds such as carbon black, cyanine dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyrylium dyes, naphthoquinone dyes, anthraquinone dyes, Phthalocyanine-based, azo-based, and thioamide-based organometallic complexes are preferably used. Specifically, JP-A-63-139191, 64-33547, JP-A-1-160683, 1-280750, 1-293342, 2-2074, 3-26593, 3-30991, 3-34891, 3-36093, 3-36094, 3-36095, 3-42281, Examples thereof include compounds described in JP-A-3-97589 and JP-A-3-103476. These can be used alone or in combination of two or more.

  In addition to the above, the image forming layer may contain various additives including known substances to be contained in this type of layer.

  The light-to-heat conversion agent can also be used as a vapor deposition film. Examples of the light-to-heat conversion agent vapor deposition film include a carbon black vapor deposition film and gold described in JP-A-52-20842. , Silver black, aluminum, chromium, nickel, antimony, tellurium, bismuth, selenium and other metal black vapor-deposited films, colloidal silver-containing vapor-deposited films, and the like.

  When the light-heat conversion agent is present in a layer different from the image forming layer, it is preferably present in a layer to which a binder is added. As the binder, it is preferable to use a resin having a high Tg and a high thermal conductivity. For example, polymethyl methacrylate, polycarbonate, polystyrene, ethyl cellulose, nitrocellulose, polyvinyl alcohol, polyvinyl chloride, polyamide, polyimide, polyetherimide Common heat-resistant resins such as polysulfone, polyethersulfone, and aramid can be used. Moreover, a water-soluble polymer can also be used as a binder. The water-soluble polymer has good heat resistance at the time of light irradiation, and is preferable from the viewpoint of so-called scattering even against excessive heating. In the case of using a water-soluble polymer, it is desirable to use the light-heat converting substance by modifying it to water-soluble by means such as introducing a sulfo group or by dispersing in water. Gelatin and polyvinyl alcohol have little aggregation of water-soluble infrared-absorbing dyes, can stably coat light-to-heat conversion layers, have excellent storage stability of recording media, and do not cause color turbidity or sensitivity reduction due to aggregation of infrared-absorbing dyes. preferable.

  The thickness of the light-heat conversion layer is preferably from 0.1 to 3 μm, more preferably from 0.2 to 1.0 μm. The content of the light-to-heat conversion agent in the light-to-heat conversion layer is usually such that the absorbance at the wavelength of the light source used for image recording is 0.3 to 3.0, more preferably 0.7 to 2.5. Can be decided.

  When the light-heat conversion layer is provided between the support and the transfer layer and the adhesiveness to the support becomes a problem, it is effective to provide the adhesive layer.

  In the heat-sensitive lithographic printing plate material, the dissolution loss of the image forming layer in water at 25 ° C. is preferably 10% or less. The dissolution loss is the dissolution loss (% by mass) of the image forming layer when the heat-sensitive lithographic printing plate material is immersed in water at 25 ° C. for 1 hour.

In the present invention and the heat-sensitive lithographic printing plate material, the weight loss of the hydrophilic layer and the image forming layer, respectively, in water at 25 ° C. is a value measured by the following method for measuring the amount of dissolution.
Method for measuring dissolved amount A lithographic printing plate support or a heat-sensitive lithographic printing plate material having a known amount of hydrophilic layer or image forming layer was cut into 10 cm × 10 cm squares, and a desiccant was added at room temperature. Leave in a desiccator for 3 hours. This is quickly taken out and measured for mass, then immersed in pure water at 25 ° C. and left for 1 hour.

  After taking out from water, a JK wiper is mounted on DX-700 (manufactured by Tokyo Laminex Co., Ltd.) and conveyed under the following conditions to give high pressure and shear during swelling.

Temperature: 25 ° C
Pressure: 2kg / cm
Speed: 30mm / sec
Thereafter, after drying at 60 ° C. for 1 hour, the mixture is further allowed to stand in a desiccator containing a desiccant at room temperature for 3 hours, and quickly taken out and the mass is measured.

  The dissolution loss is determined as the difference between the mass before treatment and the mass after treatment relative to the weight.

  By measuring the dissolution loss in this manner, the strength and water resistance of the non-image area can be confirmed in a situation close to the time of printing the planographic printing plate.

  The lithographic printing plate support of the present invention and the above heat-sensitive lithographic printing plate material have a dissolution loss of 1% or less and 10% respectively when the hydrophilic layer or the image forming layer is immersed in water at 25 ° C. for 1 hour in advance. % Water or less can increase the water resistance of the resulting lithographic printing plate.

  In order to obtain a hydrophilic layer having a dissolution loss of 1% or less when immersed in water at 25 ° C. for 1 hour or an image forming layer having a content of 10% or less, the hydrophilic resin contained in these layers has high crystallinity. It is preferable to use a raw material or to add the above-mentioned crosslinking agent to these layers, and the addition of the crosslinking agent is particularly effective from the viewpoint of strength.

  Thus, high water resistance is imparted by subjecting a lithographic printing plate support or a heat-sensitive lithographic printing plate material to which a cross-linking agent is added and then heat-treating the entire surface after drying the coating liquid for each layer. It becomes possible. The temperature of the whole surface heat treatment is preferably in the range of 30 to 80 ° C, more preferably in the range of 35 ° C to 70 ° C, and particularly preferably in the range of 40 ° C to 60 ° C. The heating time varies depending on the amount and type of the crosslinking agent, the presence or absence of a reaction accelerator, etc., and is not uniform, but the hydrophilic layer has a weight loss of 1% or less when immersed in water at 25 ° C. for 1 hour or 10% or less. What is necessary is just to set arbitrarily so that the image formation layer which is may be obtained.

  The entire surface heat treatment can be carried out following the drying of the coating step of the hydrophilic layer or the image forming layer in the production process, but also uses a lithographic printing plate support or a heat-sensitive lithographic printing plate material. Can also be done prior to.

  In the present invention, by setting the γh of the hydrophilic layer surface of the lithographic printing plate support to 20 or more, the initial dampening water can be diffused more quickly. Further, in the heat-sensitive lithographic printing plate material, the initial dampening water can be diffused more quickly by setting the γh of the image forming layer before image formation to 20 or more. Here, γh is the surface energy.

As a method of measuring γh, a static contact angle (θ) is measured using two kinds of solutions having known surface energies, and the dispersion force component (γd of the surface energy of the image portion / non-image portion is determined from the measured value. ) And a hydrogen bond component (γh). Specifically, water with known γd and γh (γd = 21.8, γh = 51.0 (20 ° C.)) and methylene iodide (γd = 49.5, γh = 1.3 (20 ° C.)) using two liquids), and 20μl dropped on a solid surface at 20 ° C. in the measurement environment, the contact angle was measured after a lapse of 30 seconds, obtaining the gamma] s ^d and gamma] s ^h on the solid surface by the following simultaneous equations. In the following formula 2, 1) is for water and 2) is for methylene iodide.

The γs ^h obtained in this way and γh.

  In the heat-sensitive lithographic printing plate material, the image forming layer is provided by coating on a support. Preferably used coating methods include dipping coating, air doctor coating, curtain coating, hopper coating, and the like, and these various coating methods can be used. Also, simultaneous coating of two or more layers by the method described in U.S. Pat. Nos. 2,781,791 and 2,941,898 can be used.

  In this way, the hydrophilic layer or the image forming layer is provided by coating on a support and drying. The thickness of the hydrophilic layer or the image forming layer at this time is not particularly limited, but is preferably 1 to 50 μm, and more preferably 1 to 25 μm.

  In the heat-sensitive lithographic printing plate material, various types of back layers can be provided on the side opposite to the image forming layer side in order to prevent curling and to prevent sticking when superimposed immediately after printing.

  As a method of forming an image on the above heat-sensitive lithographic printing plate material, a method of directly applying image-like thermal energy by a thermal head or the like, or irradiating high-power light energy image-wise, which is converted into heat energy. The method of converting and giving is mentioned. The method of directly applying image-like thermal energy by a thermal head or the like is preferable when using low-cost, low resolution or line drawing image output as the main purpose, and irradiating high-power light energy image-wise. The method of converting this to thermal energy and applying it is preferable when high-definition writing can be easily performed and high resolution or halftone image output is used as the main purpose as in commercial printing.

  Examples of the light source for image exposure include a laser, a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a high-pressure mercury lamp, and an electrodeless light source.

  In order to irradiate the energy of high output light like an image, a mask material in which a pattern of a desired exposure image is formed of a light shielding material is superimposed on a photosensitive material, and a xenon lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp. Then, it is only necessary to perform batch exposure using a high-pressure mercury lamp, an electrodeless light source or the like.

  When using an array-type light source such as a light-emitting diode array or controlling the light source such as a halogen lamp, metal halide lamp, or tungsten lamp with an optical shutter material such as liquid crystal or PLZT, exposure is performed on the image signal. It is possible and preferable to perform digital exposure according to the above. In this case, direct writing can be performed without using a mask material.

  When a laser is used for exposure, light can be narrowed down into a beam and scanning exposure can be performed according to image data. Therefore, direct writing can be performed without using a mask material. When a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible. As the laser light source, an argon laser, a He—Ne gas laser, a YAG laser, a semiconductor laser, or the like can be preferably used.

  Among these, the use of a semiconductor laser or a YAG laser is more preferable because a high output suitable for the heat-sensitive lithographic printing plate material of the present invention can be incorporated into a small apparatus at a relatively low cost. As the laser scanning exposure method, there are exposure methods such as cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser irradiation is performed while rotating a drum around which a recording material is wound. In this case, the rotation of the drum is the main scanning and the movement of the laser beam is the sub-scanning. In the cylindrical inner surface scanning, a recording material is fixed to the inner surface of the drum, and a laser beam is irradiated from the inner side. In this case, main scanning is performed in the circumferential direction by rotating part or all of the optical system, and sub scanning is performed in the axial direction by linearly moving part or all of the optical system parallel to the axis of the drum. . In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning easily improve the accuracy of the optical system and are suitable for high-density recording.

  The image formation on the heat-sensitive lithographic printing plate material is characterized by the above-described image exposure, and the development using a liquid as in the prior art is not performed and the non-image area removal process is not performed. For this reason, image formation on the heat-sensitive lithographic printing plate material of the present invention can be performed with a dedicated exposure apparatus, and the obtained lithographic printing plate can be used by being loaded into a printing press. Thus, the system can be used as a system for performing image formation and printing as it is.

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

The surface of the polyethylene terephthalate (PET) film on the image forming layer side was subjected to corona discharge treatment with an energy of 15 W / (m ² · min) to obtain a substrate.
Preparation of Lithographic Printing Plate Support 1 A hydrophilic layer coating solution 1 having the following composition was coated on the substrate so as to have a dry film thickness of 2.0 μm and dried at 50 ° C. for 5 minutes. Subsequently, the whole surface was heat-processed at 55 degreeC for 3 hours, and the support body 1 for lithographic printing plates was produced.
Coating liquid for hydrophilic layer 1
Gelatin binder 60.0 parts by mass Silica particles (inorganic processed product, pore volume 1.4 ml / g, silicia 435,
30.0 parts by mass Melamine cross-linking agent (Smiles Resin 613, manufactured by Sumitomo Chemical Co., Ltd.)
10.0 parts by mass Prepared with pure water to a solid content of 8%.
Preparation of lithographic printing plate support 2 A lithographic printing plate support 2 was prepared in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 2 having the following composition was used.
Coating liquid for hydrophilic layer 2
Gelatin 40.0 parts by mass Silica particles (inorganic processed product, pore volume 1.4 ml / g, silicia 435,
FUJI SILICIA CHEMICAL CO., LTD.) 50.0 parts by mass Melamine cross-linking agent (Sumirez resin 613: Sumitomo Chemical Co., Ltd.)
10.0 parts by mass Prepared with pure water to a solid content of 8%.
Preparation of lithographic printing plate support 3 A lithographic printing plate support 3 was prepared in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 3 having the following composition was used.
Coating liquid 3 for hydrophilic layer
Gelatin 60.0 parts by mass Silica particles (organic processed product, pore volume 2.0 ml / g, syloid C907,
Grace Japan Co., Ltd.) 30.0 parts by mass Melamine cross-linking agent (Smiles Resin 613, manufactured by Sumitomo Chemical Co., Ltd.)
10.0 parts by mass Prepared with pure water to a solid content of 8%.
Preparation of lithographic printing plate support 4 A lithographic printing plate support 4 was prepared in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 4 having the following composition was used.
Coating liquid for hydrophilic layer 4
Gelatin 60.0 parts by mass Silica particles (organic processed product, pore volume 2.0 ml / g, syloid 7000,
Grace Japan Co., Ltd.) 30.0 parts by mass Melamine cross-linking agent (Smiles Resin 613, manufactured by Sumitomo Chemical Co., Ltd.)
10.0 parts by mass Prepared with pure water to a solid content of 8%.
Preparation of lithographic printing plate support 5 A lithographic printing plate support 5 was prepared in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 5 having the following composition was used.
Coating liquid 5 for hydrophilic layer
Gelatin 60.0 parts by mass Acrylic resin particles (MX-150, manufactured by Soken Chemical Co., Ltd.) 30.0 parts by mass Melamine cross-linking agent (Smileze Resin 613, manufactured by Sumitomo Chemical Co., Ltd.)
10.0 parts by mass Prepared with pure water to a solid content of 8%.
Preparation of lithographic printing plate support 6 A lithographic printing plate support 6 was prepared in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 6 having the following composition was used.
Coating liquid for hydrophilic layer 6
Gelatin 60.0 parts by mass Acrylic resin particles (5% polar group unit introduced, MX-150A,
30.0 parts by mass Melamine crosslinker (Smiles Resin 613, manufactured by Sumitomo Chemical Co., Ltd.)
10.0 parts by mass Prepared with pure water to a solid content of 8%.
Preparation of lithographic printing plate support 7 A lithographic printing plate support 7 was prepared in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 7 having the following composition was used.
Hydrophilic layer coating solution 7
Gelatin 60.0 parts by mass Fluorine-based particles (AD-1, manufactured by Asahi Glass Co., Ltd.) 30.0 parts by mass Melamine crosslinking agent (Smiles Resin 613, manufactured by Sumitomo Chemical Co., Ltd.)
10.0 parts by mass Prepared with pure water to a solid content of 8%.
Preparation of lithographic printing plate support 8 A lithographic printing plate support 8 was prepared in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 8 having the following composition was used.
Coating liquid for hydrophilic layer 8
Gelatin 66.7 parts by mass Silica particles (no surface treatment, pore volume 2.05 ml / g,
Psyloid P403, manufactured by Grace Japan Co., Ltd.) 33.3 parts by mass Prepared with pure water so that the solid content is 7.2%.
Preparation of lithographic printing plate support 9 A melamine cross-linking agent solution adjusted to 0.4% is applied onto the hydrophilic layer of the lithographic printing plate support 8 so that the coating film thickness is the same as described above. And dried at 50 ° C. for 5 minutes. Subsequently, the whole surface was heat-treated at 55 ° C. for 3 hours to prepare a lithographic printing plate support 9.
Production of lithographic printing plate support 10 (comparative example)
A hydrophilic layer coating solution 10 having the following composition was coated on the substrate so as to have a dry film thickness of 3.0 μm, and dried at 50 ° C. for 5 minutes. Subsequently, the whole surface was heat-processed at 55 degreeC for 3 hours, and the support body 10 for lithographic printing plates was produced.
Coating liquid 10 for hydrophilic layer
Gelatin 90.0 parts by mass Formaldehyde 10.0 parts by mass Prepared with pure water to a solid content of 8%.
Preparation of lithographic printing plate support 11 (comparative example)
A hydrophilic layer coating solution 11 having the following composition was coated on the substrate so as to have a dry film thickness of 3.0 μm, and dried at 50 ° C. for 5 minutes. Subsequently, the whole surface was heat-treated at 55 ° C. for 3 hours to prepare a lithographic printing plate support 11.
Coating liquid 11 for hydrophilic layer
Gelatin 60.0 parts by mass Silica particles (no surface treatment) 30.0 parts by mass Formaldehyde 10.0 parts by mass Prepared with pure water so that the solid content is 8%.
Preparation of lithographic printing plate support 12 (comparative example)
A lithographic printing plate support 12 was prepared in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 12 having the following composition was used.
Coating liquid for hydrophilic layer 12
Gelatin 66.7 parts by mass Silica particles (no surface treatment, pore area 1.2 ml / g, syloid 622,
Grace Japan Co., Ltd.) 33.3 parts by mass Prepared with pure water to a solid content of 7.2%.
Production of lithographic printing plate support 13 (comparative example)
The liquid of the melamine crosslinking agent adjusted to 0.4% was applied on the hydrophilic layer of the lithographic printing plate support 12 so as to have the same coating liquid film thickness as described above, and dried at 50 ° C. for 5 minutes. Subsequently, the whole surface was heat-treated at 55 ° C. for 3 hours to produce a lithographic printing plate support 13.
Preparation of lithographic printing plate support 14 (comparative example)
A hydrophilic layer coating solution 14 having the following composition was coated on the substrate so as to have a dry film thickness of 7.0 μm, and dried at 50 ° C. for 5 minutes. Subsequently, the whole surface was heat-treated at 55 ° C. for 3 hours to prepare a lithographic printing plate support 14.
Hydrophilic layer coating solution 14
Gelatin 60.0 parts by mass Silica particles (inorganic processed product, pore volume 1.4 ml / g, silicia 435,
30.0 parts by mass Melamine cross-linking agent (Smiles Resin 613, manufactured by Sumitomo Chemical Co., Ltd.)
10.0 parts by mass Prepared with pure water to a solid content of 8%.

  The amount of water-dispersible filler added to the hydrophilic layer of each lithographic printing plate support, the average particle diameter, and the center line surface roughness Ra, film thickness, and water at 25 ° C. of the surface of the hydrophilic layer The loss on dissolution and the surface γh are shown in Table 1 below. In Table 1, wt% represents mass%.

Preparation of heat-sensitive lithographic printing plate material 1 A coating solution 1 for an image forming layer having the following composition is applied on the base so that the dry film thickness is 3.0 μm, and dried at 50 ° C. for 5 minutes to form a photo-modified image forming layer. Then, the whole surface was heat-treated at 55 ° C. for 3 hours to prepare a heat-sensitive lithographic printing plate material 1.
Image forming layer coating solution 1
Polyvinyl alcohol (Z-100, manufactured by Nippon Synthetic Chemical Co., Ltd.)
40.0 parts by mass Wax emulsion (A101, manufactured by Gifu Shellac Co., Ltd.)
14.0 parts by mass Silica particles (Inorganic treated product, Silicia 435, manufactured by Fuji Silysia Chemical Ltd.)
30.0 parts by mass Melamine resin (Sumirez Resin 613, manufactured by Sumitomo Chemical Co., Ltd.)
5.0 parts by weight of organic amine salt (Sumirez Accelerator ACX-P,
Sumitomo Chemical Co., Ltd.) 1.0 part by mass as a solid component Carbon Black (SD9020: Dainippon Ink Co., Ltd.)
The solid content is adjusted to 10.0 parts by mass with pure water so that the solid content is 8%.
Preparation of heat-sensitive lithographic printing plate materials 2 and 3 An image-forming layer coating solution 2 having the following composition was applied on the substrate so as to have a dry film thickness of 1.5 μm, and dried at 50 ° C. for 5 minutes to give a photo-modified image. A formation layer was provided, and then the whole surface was heat-treated at 55 ° C. for 3 hours.
Image forming layer coating solution 2
Polyvinyl alcohol (Z-100, manufactured by Nippon Synthetic Chemical Co., Ltd.)
20.0 parts by mass Wax emulsion (A101, manufactured by Gifu Shellac Co., Ltd.)
30.0 parts by mass Silica particles (Inorganic processed product, Silicia 435, manufactured by Fuji Silysia Chemical Ltd.)
30.0 parts by mass Melamine resin (Sumirez Resin 613, manufactured by Sumitomo Chemical Co., Ltd.)
5.0 parts by weight of organic amine salt (Sumirez Accelerator ACX-P,
Manufactured by Sumitomo Chemical Co., Ltd.) 1.0 part by mass as a solid component carbon black (SD9020, manufactured by Dainippon Ink, Inc.)
14.0 parts by mass as a solid component The hydrophilic layer coating solution 1 was applied onto the image forming layer so that the dry film thickness was 1.5 μm, dried at 50 ° C. for 5 minutes, and then at 55 ° C. The whole surface was heat-treated for 3 hours to prepare a heat-sensitive lithographic printing plate material 2 having a two-layer photo-modified image forming layer.

A heat-sensitive lithographic printing plate material 3 was prepared in the same manner as the heat-sensitive lithographic printing plate material 2 except that the hydrophilic layer coating solution 4 was used instead of the hydrophilic layer coating solution 1.
Preparation of heat-sensitive lithographic printing plate material 4 On the image-forming layer of the heat-sensitive lithographic printing plate material 2, an image-forming layer coating solution 3 (thermally crosslinkable compound-containing coating solution) having the following composition is dried to a film thickness of 1.0 μm. This was coated and dried at 40 ° C. for 10 minutes to provide a two-layer photo-modified image forming layer, thereby producing a heat-sensitive lithographic printing plate material 4.
Image forming layer coating solution 3
Block isocyanate (Elastolon BN69, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
100.0 parts by mass Prepared with pure water to a solid content of 8%.
Image formation The thus produced heat-sensitive lithographic printing plate material was subjected to image exposure with a semiconductor laser (wavelength 830 nm, output 500 mw). The laser beam diameter was 10 μm at 1 / e ² of the intensity at the peak. The resolution was 2400 dpi in both the scanning direction and the sub-scanning direction.

  Table 2 below shows the center line surface roughness Ra, film thickness, dissolution loss in water at 25 ° C., and γh before image formation of the image forming layer of the heat-sensitive lithographic printing plate materials 1 to 4.

Use of lithographic printing plate support synthesis of binder In a three-necked flask under a nitrogen stream, 35 parts 2-hydroxyethylmethacrylamide, 3 parts methacrylic acid, 30 parts methylmethacrylate, 25 parts acrylonitrile, 2 parts ethylmethacrylate Then, 500 parts of ethanol and 3 parts of α, α′-azobisisobutyronitrile were added to 5 parts of lauryl acrylate and reacted in an oil bath at 80 ° C. for 6 hours in a nitrogen stream. Thereafter, 10 parts of hydroquinone was added as a reaction terminator to terminate the reaction. After completion of the reaction, the reaction solution was cooled to room temperature, precipitated in water, filtered and dried to obtain the target compound. The weight average molecular weight of the obtained compound was 130,000 as measured by pullulan standard by GPC and N, N-dimethylformamide solvent.
Preparation of transfer mold sheet Using the binder prepared above, the following transfer mold composition 1 was applied on a polyethylene terephthalate film having a thickness of 100 μm so as to have a dry film thickness of 2.0 μm, and dried at 80 ° C. for 3 minutes. A transfer type sheet 1 was produced.
Transfer type composition 1
Acrylic copolymer (synthetic binder) molecular weight Mw = 50,000 35.0 parts by mass 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl)
Benzophenone 4.0 parts by mass EO-modified tris (acryloxyethyl) isocyanurate
35.0 parts by mass Polytetramethylene glycol diacrylate 10.0 parts by mass Polyfunctional urethane acrylate (15HA, manufactured by Shin-Nakamura Chemical Co., Ltd.)
5.0 parts by mass 2-ter-butyl-6- (3-tert-butyl-2-hydroxy-5
-Methylbenzyl) -4-methylphenyl acrylate 0.5 parts by mass Fluorosurfactant (FC-431, manufactured by Sumitomo 3M Limited)
0.5 parts by mass Infrared absorbing dye (CY-9, manufactured by Nippon Kayaku Co., Ltd.) 8.0 parts by mass Silane coupling agent (TSL8370, manufactured by Toshiba Silicone Co., Ltd.)
8.0 parts by mass The above composition was prepared so that the solid content was 8% at cyclohexanone / MEK = 1/1.

  The transfer mold sheet 1 thus produced was faced with the lithographic printing plate support 1 and subjected to laser exposure to form an image to produce a lithographic printing plate (Experiment 1). Further, the transfer type sheet was respectively faced with the lithographic printing plate support 4 and subjected to laser exposure to form an image to produce a lithographic printing plate (Experiment 2).

Further, after image formation, the lithographic printing plate produced in Experiment 1 was heat-treated at 150 ° C. for 1 minute to produce a lithographic printing plate (Experiment 3). Similarly, after image formation, the lithographic printing plate produced in Experiment 2 was heat-treated at 150 ° C. for 1 minute to produce a lithographic printing plate (Experiment 4).
Sensitivity Evaluation Under the above conditions, the evaluation was performed with the exposure energy (mj / cm ² ) necessary for uniformly receiving the ink without the solid portion of the exposed portion missing at the sub-scanning pitch.
Evaluation of printing quality A 175-line image is produced with the exposure energy required to transfer the above-mentioned solid part uniformly, and the coated paper, printing ink (Toyo Ink Manufacturing ( It was printed and evaluated using dampening water (manufactured by Konica Corporation: SEU-3 2.5% aqueous solution).

At the time of this printing, printing stain (at the time of printing and after printing 10,000 sheets), film strength after 10,000 sheets printing, printing reproducibility, fillability, water width and dot gain were evaluated by the following methods. The results are shown in Table 3.
Print stain evaluation: The difference between the non-image area of the printed matter and the Macbeth reflection densitometer on the printing paper when the density reached 95% or more in the above evaluation of the inking property was measured at N = 5 And it evaluated in five steps from the average value. The meanings of the symbols in Table 3 are as follows.

◎ ・ ・ ・ No difference ○ ・ ・ ・ Within 0.02 △ ... Within 0.05 △ × ・ ・ Within 0.1 ×× 10000th evaluation of printing stain larger than 0.1: Imprinting The same evaluation was performed on the 10,000th printed matter.
Film strength evaluation: The printing plate after printing 10,000 sheets was visually observed with a 100-fold magnifier, the surface of the printing plate was observed, and evaluated in five stages. The meanings of the symbols in Table 3 are as follows.

◎ ・ ・ ・ No difference ○ ・ ・ ・ Small scratches are observed, but there are no defects △ ・ ・ ・ Scratches are observed and defects are in the form of scratches △ × ・ ・ There are scratches on the front surface and the defect is large × ・.. Completely defective print reproducibility: 175 lines 0, 2, 4, 6, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 92, 94, at appropriate density and appropriate water conditions 96, 98, and 100% images were printed, and the reproduction area was examined using a 100 × magnifier.
Solidity: Necessary from the start of printing until the M density reaches 95% or more of the final image area measured by the Macbeth reflection densitometer (1.33 or more if the final density is 1.4). The number of splinter paper (waste paper) was evaluated in five levels. The meanings of the symbols in Table 3 are as follows.

◎ ・ ・ ・ 10 sheets or less ○ ・ ・ ・ 11-15 sheets △ ・ ・ ・ 16-20 sheets △ × ・ ・ 21-30 sheets × ・ ・ ・ 31 sheets or more Water width evaluation: Water from normal water-ink balance Was printed with the dial value reduced by 1 and 2, and after changing the setting, the suitability of the water width was confirmed based on the occurrence of dirt when printing 500 sheets.

  The meanings of the symbols in Table 3 are as follows.

○: Dirt is not obtained under the 2 diaphragm conditions.
Dot gain evaluation: 175 lines 0, 2, 4, 6, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 92, 94, 96, 98, 100 at appropriate concentration and appropriate water conditions % Image was printed, X-RITE was used, 0-100 correction was performed, the reproduction area ratio of the printed matter was measured, and the difference from the image data was defined as the dot gain amount.

(Note) In Table 3, “heat-sensitive material” is an abbreviation for “heat-sensitive lithographic printing plate material”.

Claims (8)

A lithographic printing plate support having a hydrophilic layer containing a hydrophilic resin and a water-dispersible filler on at least one surface of a substrate, wherein the water-dispersible filler is silica fine particles, and the surface of the silica fine particles Is subjected to a treatment with a hydrophilic resin, an inorganic treatment and / or an organic treatment, the average particle diameter is in the range of 0.2 to 10 μm, and the centerline surface roughness Ra of the surface of the hydrophilic layer is 0.1. A support for a lithographic printing plate having a range of ≦ Ra ≦ 1.2 μm, wherein the hydrophilic layer has a dissolution loss of 1% or less when immersed in water at 25 ° C. for 1 hour. 2. The lithographic printing plate support according to claim 1, wherein the content of the silica fine particles is in the range of 5 to 70% by mass. 3. The planographic printing plate according to claim 1, wherein the relationship between the average particle diameter x (μm) and the content y (mass%) of the silica fine particles is in a range represented by the following formula 1. Support.
Formula 1
(72.895-5.7895x) ≧ y ≧ (15.526-1.0526x) The lithographic printing plate support according to claim 1, 2 or 3, wherein the hydrophilic layer has a thickness of 1 to 50 µm. The lithographic printing plate support according to any one of claims 1 to 4, wherein γh of the surface of the hydrophilic layer is 20 or more. The lithographic printing plate according to any one of claims 1 to 5, wherein the hydrophilic resin is at least one selected from resins having a skeleton of polyacrylamide, gelatin, polyvinyl alcohol, polyester, or polyurethane. Support. The lithographic printing plate support according to any one of claims 1 to 6, wherein the hydrophilic resin is gelatin. The lithographic printing plate support according to any one of claims 1 to 7, wherein an average particle diameter of the silica fine particles is 0.6 to 7 µm.