WO1996025295A1 - Lithographic form plate - Google Patents

Abstract

An original form plate for a novel photosensitive lithographic form plate, in which development processing is simple, and which possesses a high ink repellent property without undergoing a desensitization and can use pure water as a dampening water, can be produced by using a lithographic form plate, in which (1) a non-printing area portion made of a hydrophilic swelling layer has an amount of water absorption of 1 to 50 g/m2 and a printing area portion has a less amount of water absorption than that of the non-printing area portion; (2) the non-printing area portion made of a hydrophilic swelling layer has an initial elastic modulus of 0.01 to 10 kg/mm2 and the printing area portion has a larger initial elastic modulus than that of the non-printing area portion; (3) the non-printing area portion made of a hydrophilic swelling layer has a water swelling rate of 10 to 2000 % and the printing area portion has a less water swelling rate than that of the non-printing area portion; or (4) the non-printing area portion made of a hydrophilic swelling layer has a phase separation structure composed of at least two phases, that is, a phase, of which a main component comprises at least a hydrophilic polymer, and a phase, of which a main component comprises a hydrophobic polymer.

Description

 Specification

Lithographic printing plate technical field

 The present invention relates to a lithographic printing plate, in particular, a novel photosensitive lithographic plate which is simple in development processing, has high ink repellency without performing desensitization treatment, and can use pure water as a fountain solution. It relates to a lithographic printing plate that can be produced from a printing plate precursor. Background art

 Lithographic printing means that the image area and the non-image area are basically present on almost the same plane, the image area is ink-receptive, and the non-image area is ink repellency. Utilizing this method means that ink is applied only to the image area, and then the ink is transferred to a printing medium such as paper and printed. A PS plate is usually used for such lithographic printing.

 The PS version mentioned here means the following.

 In other words, as described in Teruhiko Yonezawa, “PS Version Overview”, Printing Society Press, Ltd. (1993) p18-p81, lipophilicity is applied on a hydrophilicized aluminum substrate. The photosensitive resin layer is applied, and the photosensitive layer remains in the image area by photolithography technology, while the non-image area exposes the surface of the aluminum substrate, and a dampening water layer is formed on the surface. A PS plate with water that repels ink and forms a rooster image, and a PS plate without water, which uses a silicone rubber layer as an ink repellent layer instead of a dampening solution layer, a so-called waterless lithographic plate.

 The lithographic plate without water used here means that the non-surface area is made of a substance such as silicone rubber or fluorine-containing compound that has a repelling property against oily ink used in normal lithographic printing, and does not use fountain solution. It means a printing plate on which an image can be formed between the image area and the printable plate.

The former with water PS plate is a printing plate excellent in practical use, usually aluminum is used for the support. The aluminum surface has water retention and is lipophilic photosensitive during printing. It was necessary to have excellent adhesion to the photosensitive layer so that the resin layer did not peel off from the surface. Therefore, the aluminum surface is usually grained, and if necessary, a treatment such as anodizing is performed on the grained surface to improve water retention and enhance adhesion to the photosensitive resin layer. I have been. Further, in order to obtain the storage stability of the photosensitive resin layer, the aluminum surface is generally subjected to a chemical treatment such as zirconium fluoride or sodium gayate.

 As described above, the production process of the Ps plate with water is complicated and its simplification has been desired. However, it is widely used due to the excellent printing characteristics (printing durability, image reproducibility, etc.) of the plate. In order to solve the problem, there is a proposal of a new lithographic material having printing characteristics equal to or better than that of an aluminum substrate, which is inexpensive in material cost and different from an aluminum substrate by a simple manufacturing process. For example, in Japanese Patent Publication No. 56-29338, a support coated with an ink repellent layer made of a hydrophilic polymer material is used in place of the aluminum substrate, and a photosensitive layer is formed on the support. Have been proposed. However, in this method, since a urea resin is simply applied as a hydrophilic layer on a water-resistant layer of an aldehyde condensate of polyvinyl chloride, polyurethane, or polyvinyl alcohol, the layer is made of a. The ink repellency was insufficient, the adhesion to the photosensitive resin layer was poor, and the printing durability was insufficient. Also, in Japanese Patent Application Laid-Open No. 57-179852, a hydrophilic radical polymerizable compound is coated on a support, and the surface of the support is hydrophilized by irradiation with actinic light to obtain a photosensitive polymer. A method of applying a resin layer has been proposed. However, the hydrophilic surface layer formed by this method was also rigid, had insufficient ink repellency, and had poor press life. When developing PS plates with water, the photosensitive layer is dissolved to expose the surface of the aluminum substrate. Therefore, it is essential that the components of the photosensitive layer be dissolved in the developing solution. During this time, the composition fluctuates greatly, resulting in fatigue, resulting in the generation of a large amount of waste image liquid.

 Therefore, the developer had to be frequently maintained and replaced. In addition, the processing of the generated developing waste liquid required a great deal of labor and cost.

Also, as a simple form of the PS version with water, a toner or other material is placed on a support such as paper. A direct-drawing lithographic printing plate precursor, which has an image receiving layer, forms an image using a PPC, desensitizes non-image areas with an etchant or the like, converts the image receiving layer into an ink repellent layer, and uses it. Widely used for practical use. Specifically, generally, an image-receiving layer composed of a water-soluble binder polymer, an inorganic pigment, a water-proofing agent, etc. is provided on a water-resistant support.

P2 5 3 2 8 6 5 JP, JP-B-40-23581, JP-A-48-9802, JP-A 57-205 5196 Gazette, Japanese Patent Application Laid-Open No. 60-23909, Japanese Patent Application No. 57-1791, Japanese Patent Application Laid-Open No. 57-15998, Japanese Patent Application Laid-Open No. 57-969 No. 00, Japanese Unexamined Patent Publication No. 57-205 196, Japanese Unexamined Patent Publication No. 63-166 590, Japanese Unexamined Patent Publication No. 63-166591, Japanese Patent Application Laid-Open Nos. 63-317,888, JP-A-11-44888, and JP-A-4-366786 are examples. These direct-drawing lithographic printing plate precursors are used as an image-receiving layer to be converted to an ink repellent layer, using PVA, starch, hydroxyshethyl cellulose, casein, gelatin, polyvinylpyrrolidone, and vinyl acetate-crotonic acid copolymer. Water-soluble binder polymers such as styrene-maleic acid copolymer, etc., which have been hydrophilic before desensitization treatment, water-dispersible polymers such as acryl-based resin emulsions, silica, calcium carbonate, etc. A composition comprising a water-resistant agent such as an inorganic pigment and a melamine-formaldehyde resin condensate has been proposed. Also, Japanese Patent Application Laid-Open No. 63-2566493 proposes a direct-drawing lithographic printing plate precursor using as a main component a hydrophobic polymer which is hydrolyzed by a desensitizing treatment to generate a hydrophilic group. Have been.

 Such a direct-drawing lithographic printing plate precursor must have a desensitizing treatment in order to convert the image receiving layer into an ink repellent layer, and has a property of exhibiting almost no ink repellency without the treatment. Met.

In other words, in order to obtain a practical level of ink repellency, it is necessary to desensitize and use a large amount of a hydrophilic binder polymer, but the water resistance tends to be poor, and the printing durability is reduced. Further, when the hydrophilicity is increased, there is a problem that the adhesiveness to an image such as a toner tends to decrease. On the other hand, if the water resistance is increased by increasing the amount of a water-proofing agent or by adding a hydrophobic polymer to improve printing durability, the hydrophilicity is reduced, and the ink repellency is significantly reduced. There was a problem. In addition, the current technology utilizing the hydrophilic / hydrophobic conversion reaction developed by Union Carbide The technology of the so-called one-step version of only exposure, which does not require any image, lacquer embossing and desensitizing treatment, is disclosed in Japanese Patent Publication No. Sho 42-131, Japanese Patent Publication No. Sho 42-5365, Japanese Patent Publication No. 42-1404328, Japanese Patent Publication No. 42-20127, USP3 2 3 1 377, USP3 2 31 381, USP32 It is disclosed in, for example, Japanese Patent Publication No. 31382. The plate is coated with an association of polyethylene oxide and phenolic resin together with a photosensitizer, or the non-image area is rigid and inferior in flexibility, and the ink repellency is insufficient. The difference in the ink repulsion / ink between the section and the image area was small, and the practicality was poor.

 In addition, PS plates with water require constant control of the dampening solution volume during printing, and considerable skill and experience has been required to control the appropriate dampening solution volume. In addition, the use of 1PA (isopropanol), which is added as an essential component to dampening water, has recently been strictly regulated from the standpoints of occupational health and wastewater treatment, and measures have become urgently needed. ing.

On the other hand, in the case of the PS plate without water in which a silicone rubber layer is used as an ink repellent layer instead of the dampening solution, Japanese Patent Publication No. 54-26923 and Japanese Patent Publication No. 57-300600 Gazette, Japanese Patent Publication No. 56-128628, Japanese Patent Publication No. 56-231150, Japanese Patent Publication No. 56-38056, Japanese Patent Publication No. 60-600 No. 1, Japanese Patent Publication No. 6 1-5 4 220, Japanese Patent Publication No. 61-154, 222, Japanese Patent Publication No. 61-54, 223, Japanese Patent Publication No. 61-61 Japanese Patent Publication No. 6, Japanese Patent Publication No. Sho 63-3-23544, Japanese Patent Publication No. Hei 2-252 498, Japanese Patent Publication No. 3-6566 No. 2 Publication, Japanese Patent Publication No. Hei 4 4-28098 Japanese Patent Application Laid-Open No. Hei 5-9-1934, Japanese Unexamined Patent Application Publication No. 2-63050, Japanese Unexamined Patent Application Publication No. 2-63051, etc. Since printing can be performed without using the former, there is no need to control the dampening solution required for the ps version with water at all times, making printing extremely easy. Therefore, although it is a highly practical plate material that has been rapidly spreading in recent years, lack of durability was pointed out because the silicone rubber layer with low mechanical strength was used as the ink repellent layer. There is a strong need for good ink repellent materials. Further, at the time of development, since the silicone rubber layer must be mechanically peeled and removed by brush rubbing, a large amount of developing waste liquid containing the silicone rubber residue that has been peeled and removed is generated. For this reason, the service life of the brush is short and it is necessary to replace the brush frequently. In addition, maintenance measures such as collecting and discarding the silicone rubber debris were required. Disclosure of the invention

 The present inventors have made it possible to increase the control width of the dampening solution for lithographic printing of the conventional PS plate with water and to eliminate the IPA from the dampening solution which has been considered impossible. Unlike the lithographic printing plate precursor, it does not have a complicated plate making process such as forming an image by the PPC method and desensitizing it. A phase-separated structure consisting of a specific material group as a result of intensive studies on the development of an ideal lithographic material that does not require the development maintenance required for conventional PS plates and has a simple manufacturing process. It has been found that this can be realized by using a lithographic printing plate having a hydrophilic swelling layer having an ink repellent layer as a swelling layer. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a schematic diagram illustrating an example of a phase separation structure of a hydrophilic swelling layer of a lithographic printing plate according to the present invention.

 FIG. 2 is a schematic view illustrating an example of a phase separation structure of a hydrophilic swelling layer of a lithographic printing plate according to the present invention.

 FIG. 3 is a schematic view illustrating an example of a phase separation structure of a hydrophilic swelling layer of a lithographic printing plate according to the present invention.

 FIG. 4 is a schematic view of a TEM (transmission electron microscope) image of the lithographic printing plate of Example 59 obtained by the measurement method (B) at the time of swelling of an image portion and a non-image portion. FIG. 5 is a SEN1 (scanning electron microscope) photograph showing an example of the appearance of the image portion and the non-image portion of the lithographic printing plate according to the present invention during water swelling. BEST MODE FOR CARRYING OUT THE INVENTION

The non-image area of the lithographic printing plate according to the invention is characterized in that it comprises a hydrophilic swelling layer. The hydrophilicity referred to in the present invention is a property that is substantially insoluble in water and exhibits water swellability. A known hydrophilic polymer is applied on a substrate or laminated by transfer or the like, and is cross-linked or pseudo-cross-linked using a known method, and a water-swellable water-swellable layer made insoluble in water and made water-swellable is used. be able to. Such a hydrophilic swelling layer preferably has a phase-separated structure composed of at least two phases of a phase mainly composed of a hydrophilic polymer and a phase mainly composed of a hydrophobic polymer.

 The hydrophilic polymer used in the hydrophilic swelling layer of the present invention will be described.

 The hydrophilic polymer is a known water-soluble polymer (which means completely soluble in water), a pseudo-water-soluble polymer (which means amphipathic), which is substantially insoluble in water and shows water swellability. In addition, the term “mac mouth” means a substance which dissolves in water but the mouth includes a non-dissolved portion), and a water-swellable polymer (meaning a substance which swells in water but does not dissolve). That is, a polymer that adsorbs or absorbs water under normal use conditions, and a polymer that dissolves in water or swells in water.

 In the present invention, known polymers can be used as the hydrophilic polymer, and examples thereof include animal polymers, plant polymers, and synthetic polymers. For example, “Functiona 1 Monomers” (by Y. Nyquist, Dekker), “Water-soluble high-molecules” (by Nakamura, Chemical Industry Co., Ltd.), “Water-soluble high-molecular-weight resins And application development Comprehensive Technical Data Book ”(Management Development Center Publishing Division),“ New, Water-soluble Polymer Applications and Markets ”(CMC) and other hydrophilic polymers. Specific examples are described below.

 (A) Natural polymers

Starch-acrylonitrile-based graft polymer hydrolysate, starch-acrylic acid-based graft polymer, starch-styrene sulfonate-based graft polymer, starch-vinylsulfonate-based graft polymer, starch — Acrylamide-based graft polymer, carboxylated methylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxyshethylcellulose, xanthylcellulose, cellulose-acrylonitrile-based graft polymer, cell Loose styrene sulfonate-based graft polymer, carboxymethylcellulose-based crosslinked product, hyaluronic acid, agarose, collagen, milk casein, acid casein, rennet casein, ammonia casein, calinized casein, borane Casein, glue, Gelatin, gluten, soy protein, alginate, ammonium alginate, potassium alginate, sodium alginate gum arabic, tragacanth gum, karaya gum, guar gum, locust bean gum, Irish moss, soy lecithin, pectic acid, starch , Carboxylated starch, agar, dextrin, mannan, etc.

(B) Synthetic polymers

 Polyvinyl alcohol, polyethylene oxide, poly (ethylene oxide-co-propylene oxide), aqueous urethane resin, water-soluble polyester, ammonium polyacrylate, sodium polyacrylate, N-vinyl carboxylate Acid amide-based polymer, polyammonium acrylate, acrylic copolymer, acrylic emulsion copolymer, polyvinyl alcohol-based crosslinked polymer, polyacrylic acid sodium-based crosslinked polymer, polyacrylonitrile Ryl polymer saponified product, hydroxy (meth) acrylate polymer (In the following description, (meta) □□□□ stands for □□□□ or meta □□□□ ), Poly (vinyl methyl ether-CO-maleic anhydride), maleic anhydride copolymer, Nirupirori Don based copolymer polymers, polyethylene glycidyl Koruji (meth) § click Li rate based crosslinked polymer, polyps Ropirenguri Koruji (meth) § click Li rate based crosslinked polymer such.

 The hydrophilic compound may contain monomers or copolymer components having different substituents for the purpose of imparting flexibility or controlling hydrophilicity, as long as the effects of the present invention are not changed.

 Each hydrophilic polymer will be described in detail.

 (1) Natural protein system

Examples of the protein used in the hydrophilic swelling layer of the present invention include at least one kind of protein selected from casein, gelatin, soy protein, albumin, and the like. Casein is the main component of milk protein and is not a single protein but a mixture of at least three similar proteins. Commercially available caseins include lactate casein, sulfate casein, casein hydrochloride, rennet casein, etc., depending on the industrial production method, and the quality and composition differ depending on the production method. The casein used in the present invention may be any casein which is a natural polymer in which various amino acids are condensed. it can.

 As the gelatin, there can be used known so-called photographic gelatin, which is mainly obtained by subjecting cattle bone or skin to acid treatment or lime treatment. The types of amino acids that make up gelatin are extremely large, and various types of amino acids can be obtained depending on the purification conditions.The quality and composition differ depending on the raw material, but the gelatin used in the present invention condenses many types of amino acids. Any gelatin that is a natural polymer can be used. In addition, natural proteins such as soy protein (soy casein) and albumin having chemical properties similar to casein can be used in the present invention.

 Specific examples include milk casein, acid casein, rennet casein, ammonium casein, calicacasein, borax casein, glue, gelatin, gluten, soy lecithin, soy protein, collagen and the like.

 (2) Alginate

 Examples include ammonium alginate, potassium alginate, and sodium alginate.

 (3) Starch type

 A polymer obtained by graft polymerization of a synthetic monomer such as acrylic acid on water-soluble starch to produce a polymer having a higher molecular weight and then subjected to three-dimensional cross-linking is preferably used. For example, in the case of a starch-acrylonitrile-based graft polymer hydrolyzate, the obtained polymer has a structure having a branch of an acrylic acid derivative chain having an ionic group with a starch as a base, and thus has a strong hydrophilic property. Has the property. In addition, the radical polymerization end of the acrylonitrile undergoes a force-punching reaction during the graph polymerization, forming a cross-linked structure between the polymer chains to form a three-dimensional cross-link. Further, the gel is mixed with a polymer of an ionic group having a sign opposite to that of the grafted ionic group (cationic group if the graft chain is anionic) to form a polyion complex, thereby increasing gel strength. Are also preferably used.

 () Cellulose

As in the case of starch, three-dimensional cross-linking by graft polymerization is preferably used. Further, as disclosed in Japanese Patent Application Laid-Open No. 61-89364, cellulose obtained by subjecting cellulose to sodium propyloxycellulose and further crosslinking is preferably used. Can be

 Specific examples include carboxylated methylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxyshethylcellulose, and xanthate cellulose.

 (5) Hyaluronic acid

 Natural polysaccharides as disclosed in Japanese Patent Publication No. Sho 61-8083, Japanese Patent Laid-Open No. 58-56692, Japanese Patent Laid-Open No. 60-49797, etc. The polymer is preferably used.

 (6) Polyvinyl alcohol-based

 Polyvinyl alcohol alone has slightly weak water absorption, so it usually has a three-dimensional crosslinked structure after introducing an ionic hydrophilic group, usually in the form of saponified methyl acrylate-vinyl acetate copolymer. Is preferably used. Further, a hydrophilic elastomer obtained by repeating a freeze-thaw operation of polyvinyl alcohol as disclosed in Japanese Patent Application Laid-Open No. 58-61744 is also used. Blending with other polymers is also possible.

 (7) Acrylate type

 From the viewpoint of water absorption and durability, one group in the molecule that can be derived to a carboxyl group or a carboxyl group such as a carboxyl group, a carboxylate, a carboxylic acid amide, a carboxylic acid imide, or a carboxylic anhydride is used. Alternatively, a crosslinked polymer containing two α, β monounsaturated compounds as monomer components is preferably used.

Specific examples of the α, S-unsaturated compound include acrylic acid, methacrylic acid, acrylamide, methacrylamide, maleic anhydride, maleic acid, and maleic acid. Acid amide, maleic acid imide, itaconic acid, crotonic acid, fumaric acid, mesaconic acid, etc., and other monomer components that can be copolymerized as long as they exhibit the hydrophilicity required for the present invention. It is possible to combine with Examples of other copolymerizable monomer components are: ethylene, propylene, isobutylene, 1-butylene, diisobutylene, methyl vinyl ether, styrene, vinyl acetate, acrylates, methacrylates, Α-olefins such as acrylonitrile, vinyl compounds, and vinylidene compounds. When combined with other monomers, the carboxyl group or The α, / 3-unsaturated compound containing a group which can be converted into the compound is usually at least 10 mol% and preferably at least 40 mol% in all monomer components.

 The polymer containing, as a monomer, an α, β monounsaturated compound containing a carboxyl group or a group that can be converted to the carboxyl group is usually prepared by radical polymerization. The degree of polymerization is not particularly limited.

 Among the polymers prepared in this manner, particularly preferred are polymers or copolymers of acrylic acid, methacrylic acid, α-olefins, and copolymers of vinyl compounds and maleic anhydride. New

 These polymers or copolymers include hydroxides, oxides or carbonates of alkali metals or alkaline earth metals such as sodium, potassium, magnesium, and barium. It is preferable to further increase the hydrophilicity by reacting the compound with ammonia, ammonia, or the like. In these reactions, the polymer or the copolymer is dissolved or dispersed in various organic solvents or water, and an alkali metal compound, an alkaline earth metal compound, ammonia, amine, or the like is added thereto. It is carried out by adding under stirring.

 (8) Other

 Poly (vinyl methyl ether-CO-maleic anhydride), vinylpyrrolidone-based copolymer, polyacrylamide, acrylamide-based copolymer, N-vinylcarboxylic acid-based polymer, polyethylene oxide, poly (ethylene Oxide-co-propylene oxide), arabia gum, tragacanth gum, karaya gum, guar gum, locust bean gum, Irish moss, pectic acid, agar, dextrin, mannan, and the like.

 Specific examples of the hydrophilic polymer preferably used in the present invention are shown below, but the present invention is not limited to these examples.

(1) Maleic acid or maleic anhydride, maleic acid amide or maleic acid derivative such as maleic acid imide and carbon number of ethylene, propylene, butylene, isobutylene or disobutylene etc. Reaction of a copolymer of a linear or branched α-olefin with 2 to 12 carbon atoms, preferably 2 to 8, with an alkali metal compound, an alkaline earth metal compound, ammonia, or amine Crosslinked product. (2) Copolymerization of maleic acid or its derivatives with vinyl or vinylidene compounds such as styrene, vinyl acetate, methyl vinyl ether, acrylate, methacrylate or acrylonitrile A crosslinked product of the product of the coalescence and an alkali metal compound, alkaline earth metal compound, ammonia, or amine.

 (3) A reaction product of a copolymer of acrylic acid or methacrylic acid with the vinyl or vinylidene compound of the above (2), and an alkali metal compound, an alkaline earth metal compound, ammonia, or an amine Crosslinked product.

 Polyoxyalkylene-based hydrophilic polymers disclosed in Japanese Patent Application Laid-Open Nos. 58-37027, and Polyvinyl Alkylene Polymers disclosed in Japanese Patent Application Laid-Open No. Crosslinked products such as nilpyrrolidone, polystyrenesulfonate having a sulfonate group as a hydrophilic group, and acrylamide methylpropanesulfonate copolymer, JP-A-60-42416 Examples thereof include polyurethane resins obtained by crosslinking a polyisocyanate with a hydrophilic polymer having a hydroxyl group or an amino group disclosed in a gazette or the like.

 Further, the hydrophilic polymers used in the present invention can be used alone or in an appropriate mixture of two or more kinds.

 Next, the hydrophobic polymer used in the hydrophilic swelling layer of the present invention will be described. As the hydrophobic polymer used in the present invention, a polymer mainly composed of an aqueous emulsion is preferably used.

 The aqueous emulsion referred to in the present invention means a hydrophobic aqueous polymer dispersion in which particles comprising fine polymer particles and, if necessary, a protective layer surrounding the particles are dispersed in water.

That is, it means a self-emulsifying or forced emulsified aqueous solution basically composed of emulsion particles composed of polymer particles as a dispersoid, a protective layer formed as required, and a dilute aqueous solution as a dispersion medium. As completely as examples of aqueous Emaruji ₃ emissions used in the present invention, vinyl polymers latexes, such as conjugated diene polymer based latexes and aqueous or water-dispersible poly urethane resin.

Examples of the vinyl polymer latex include an acrylic type, a vinyl chloride type, a vinylidene chloride type, and a styrene type. As a conjugated diene polymer latex , Styrene / butadiene type (hereinafter abbreviated as SB type), acrylonitrile / butadiene type (hereinafter abbreviated as NB type), methyl methacrylate / butadiene type (hereinafter abbreviated as MB type) Abbreviated), black-mouthed plene system, etc.

 Examples of the acrylate latex include copolymers containing acrylate and methacrylate as essential components. Specifically, at least one or more of methyl methacrylate, ethyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, and styrene are copolymerized. Things.

 Examples of the vinyl acetate latex include vinyl acetate alone or a copolymer with acrylate, higher vinyl acetate, ethylene, or the like.

 Examples of the vinylidene chloride-based latex include copolymers of vinylidene chloride with methyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, vinyl chloride, and the like. Can be

 The SB latex contains styrene and butadiene as essential components, methyl methacrylate, higher acrylates, acrylonitrile, acrylamide, and hydroxyl acrylate. And copolymers with unsaturated carboxylic acids (such as itaconic acid, maleic acid, acrylic acid, and methacrylic acid).

 As the aqueous or water-dispersed polyurethane resin, a hydrophobic polyurethane resin composed of a polyester polyol, a polyether polyol, a poly (ester / ether) polyol and a polyisocyanate is forcibly applied using a surfactant. A forced emulsification type in which the resin itself is emulsified and a self-emulsification type in which a hydrophilic group or a hydrophilic segment is added to the resin itself to make it self-dispersible and emulsified, and a non-reactive type in both. And a blocking agent having a reactive group such as an isocyanate group blocked.

 Among these aqueous emulsions, the hydrophobic polymer particularly preferably used in the present invention includes a latex containing a conjugated compound such as SB, NB, MB, and chloroprene.

The conjugated rubbers mentioned here are 1.3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3, butadiene, 2 1,1-butadiene (chloroprene) and other unsubstituted or substituted 1,3-substituted compounds having a carbon-carbon double bond at the 1,3-position, etc. Homogeneous or block copolymer rubber (polymer) as a component is exemplified.

 Block copolymer rubbers include 1,3-butadiene, 1,3-methyl-1,3-butadiene (isoprene), and other styrene, and styrene and α-methyl, which give a glassy polymer at room temperature. A block copolymer with a monovinyl-substituted aromatic compound such as styrene and vinyltoluene is exemplified.

 As such a copolymer rubber, various known types can be exemplified, and a Α—Β—A type block copolymer rubber (where A is a monovinyl-substituted aromatic compound, and is preferably Represents a polymer segment having a glass transition point of 70 ° C. or more and a degree of polymerization of 10 to 250, and B represents 1,3-gen, preferably a number average (Which means an amorphous polymer segment having a molecular weight of 50,000 to 2,500). The same applies to the hydrogenated product of the block copolymer rubber.

 Specific examples of the homo- and copolymer rubbers used in the present invention include polybutadiene, polyisoprene (including natural rubber), polychloroprene, styrene-butadiene copolymer, and carboxy-modified styrene-butadiene copolymer. Polymer, acrylate / butadiene copolymer (for example, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-butadidecyl acrylate copolymer), methacrylate / butadiene copolymer Copolymer, isobutylene-isoprene copolymer, acrylonitrile-lilubutadiene copolymer, carboxy-modified acrylonitrile-reloopagen copolymer, acrylonitrile-isoprene copolymer, vinylpyridine Even copolymers, vinyl pyridine-styrene-butadiene copolymers And styrene-chloroprene copolymer and styrene-soprene copolymer.

Conjugated Jenporima based latex used properly preferred in the present invention is manufactured by a known method, for example, as an essential component 0 for vinyl monomer compositions comprising a conjugated diene compound. Emulsion polymerization of 1-2 0 weight ° ₀ In an aqueous medium containing a dispersant (such as a surfactant) and 2 to 50% by weight of water, the mixture is degassed with nitrogen, emulsified, and emulsified as necessary. After adding the additives used for the emulsion polymerization (molecular weight modifier, antioxidant, etc.), add the initiator for the emulsion polymerization (for example, hydrogen peroxide, potassium persulfate, etc.) and follow the usual methods. It can be obtained by emulsion polymerization.

 In the raw vinyl monomer composition, the vinyl monomer used other than the conjugated diene compound is not particularly limited, but mainly includes the following group I: hydrophobic monomer, group π: hydrophilic monomer, group m: cross-linkable monomer. Can be classified into two groups.

 Group I: The hydrophobic monomer is a hydrophobic vinyl monomer having one vinyl group (the hydrophobicity means a solubility in water of 20 weight% or less at 20). Examples include acrylates, methacrylates, vinyl esters, styrenes, and olefins.

 Specific examples of acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and isobutyl acrylate. , Sec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethyl hexyl acrylate, octyl acrylate, 2-hexyl acrylate, 2-black ethyl acrylate Relates, benzyl acrylates, cyclohexyl acrylates, tetrahydrofurfuryl acrylates, phenyl acrylates, 2-methoxyl acrylates, 2-methoxy acrylates and the like.

 Specific examples of methacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate. , Sec-butyl methacrylate, amino remeth acrylate, hexyl meth acrylate, cyclohexyl meth acrylate, benzyl meth acrylate, acetate acetate Evening rate, octylmethacylate, furfurylmethacylate, tetrahydrofurylmethacrylate, phenylmethacrylate, trimethylolpromonomonomethacrylate, 2-methoxylmethacrylate RELAY, 2—Etoxyshirume Such as click relay Bok, and the like.

Specific examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloroacetate, vinyl dichloroacetate, Examples include vinyl methoxy acetate, vinyl acetate acetate, vinyl benzoate, vinyl salicylate, and vinyl chlorobenzoate.

 Specific examples of styrenes include styrene, α-methyl styrene, chloromethyl styrene, trifluoromethyl styrene, acetomethyl methyl styrene, methoxy styrene, chloronostyrene, dichlorostyrene, trichlorostyrene, bromostyrene and the like. Is mentioned.

 Specific examples of the olefins include propylene, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide, and vinylidene fluoride. Other examples include acrylonitrile and maleic anhydride.

 Group ：: The hydrophilic monomer is a hydrophilic vinyl monomer having one vinyl group. (Hydrophilic herein means a monomer that has a high solubility in water and cannot be used alone in aqueous emulsion polymerization.) Monomers having a functional group such as a mino group, a carboxyl group, a sulfonate group, an amide group, and a hydroxyl group are exemplified.

 Specific examples of the monomer having an amino group include dimethylaminomethyl acrylate, dimethylaminomethyl methacrylate, getylaminomethyl methacrylate, getylaminomethyl methacrylate, and tert-butylaminomethylethyl acrylate. And tert-butylaminoethyl methacrylate.

 Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, fumaric acid, methylenemalonic acid, and monoalkyl itaconate (for example, itaconic acid). Monomethyl, monoethyl itaconate, monobutyl itaconate, etc., monoalkyl maleate (eg, monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.), citraconic acid, sodium acrylate, Examples include ammonium acrylate and ammonium methacrylate.

Specific examples of the monomer having a sulfonate group include styrenesulfonate, vinylbenzylsulfonate, vinylsulfonate, vinylsulfonate, and acryloyloxyalkylsulfonate (for example, Acryloyloxymethylsulphonic acid, acryloyloxypropylsulphonic acid, acryloyloxybutylsulphonic acid, etc.) Re Oral oxymethylsulfonate, methacryloyloxymethylsulfonate, methacryloyloxypropylsulfonate, methacryloyloxybutylsulfonate, etc.), acrylic acid Dialkylsulfonates (eg, 2—acrylamide 2—methylethanesulfonate, 2-acrylylamide 2—methylpyrusulfonate, 2—acrylylamide 1—methylbutanesulfonate) Acid), methacrylamide alkylsulfonate (eg, 2—methacrylamide 2—methylphenylsulfonate, 2—methacrylamide 2—methylpyrusulfonate, 2— Methacrylamide 2-methylbutanesulfonate).

 Specific examples of the monomer having an amide group include acrylamide, methylacrylamide, and propylacrylamide.

 Specific examples of the monomer having a hydroxyl group include aryl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypyrucyl acrylate, and 2-hydroxypropyl. Examples include metal acrylate and aryl ether of polyhydric alcohol.

 Other examples include N-acryloyl biperidine, vinyl viridin, and vinyl alcohol.

 ffl group: Monomers having a reactive cross-linking group (glycidyl group, hydroxymethyl amide group, alkoxymethyl amide group, acyloxymethyl amide group, isocyanate group, etc.) as cross-linkable monomers. And polyfunctional monomers having two or more vinyl groups.

 Specific examples of monomers having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, glycidyl p-vinyl benzoate, glycidyl crotonate, diglycidyl itaconate, diglycidyl maleate, Examples include diglycidylmethylene diluent, glycidyl vinyl ether, arylglycidyl ether, and glycidyl-α-chloroacrylate.

Specific examples of the monomer having a hydroxymethylamide group include hydroxymethylacrylamide, hydroxymethylmethacrylamide, and the like. Specific examples of monomers having an alkoxymethylamide group include methoxymethyl Acrylamide, Methoxymethylmethacrylamide, Ethoxymethylacrylamide, Ethoxymethylmethacrylamide, Butoxymethylacrylylamide, Butoxymethylmethacrylamide, Hexyloxymethylmethacrylate Lilamide and others.

 Specific examples of monomers having an acyloxymethylamide group include acetomethylmethylacrylamide, acetooxymethylmethacrylamide, propionyloxymethylacrylamide, and the like.

 Specific examples of monomers having an isocyanate group include vinyl isocyanate and aryl isocyanate.

Specific examples of polyfunctional monomers include divinylbenzene, polyethylene glycol diacrylate (ethylene number n = l to 23), polyethylene glycol dimethacrylate (ethylene number n = l to 23), and the like. Application Benefits trimethylol pro-Roh, ⁰ down Bok reactance Li rate, capital re-trimethylol pro-Ha ⁰ down door Increment Taku relay Bok, and the like Pentaerisuri Tonore door Ria-click re-rate.

 In preparing the conjugated diene polymer latex preferably used in the present invention, a suitable combination of monomers includes, in addition to the conjugated diene compound which is an essential component,

(1) Copolymer of at least one group I monomer

 (2) Copolymers with at least one or more Group I monomers and at least one or more Group I monomers

 (3) Copolymers with at least one or more Group I monomers and at least one or more Group I monomers and at least one or more Group I monomers

 (4) Copolymers of at least one or more] group monomers and group II monomers

And the like, but the present invention is not limited to these combinations. Specific examples of the conjugated diene polymer latex preferably used in the present invention include:

, JSR 0561 (SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR 0589 (SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR 0602 (, SB Copolymer latex: Nippon Synthetic Rubber Co., Ltd.), JSR 070 (butadiene polymer latex: Nippon Synthetic Rubber Co., Ltd.), JSR 210 (SB copolymer latex: Nippon Synthetic Rubber Co., Ltd.) ), JSR 0650 (vinylpyridine-SB copolymer Tex: Nippon Synthetic Rubber Co., Ltd.), JSR 0652 (Vinylpyridine-SB Copolymer Latex: Nippon Synthetic Rubber Co., Ltd.), JSR 0545 (Carboxy Modified SB Copolymer Latex): Nippon Synthetic Rubber Co., Ltd.), JSR 0548 (carboxy-modified SB copolymer latex: Nippon Synthetic Rubber Co., Ltd.), JSR 0596 (Carboxy-modified SB copolymer latex: Nippon Synthetic Rubber) JSR 0597 (Carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR 0598 (Carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.) JSR 0619 (carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR 0624 (carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR 0640 (Carboxy-modified SB copolymer latex: NIPPON GOHSEI JSR 0693 (carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR 0966 (carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.) ), JSR0854 (carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR0863 (carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR08 984 (carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), Rackstar 4940B (carboxy-modified NB copolymerized latex: manufactured by Dainippon Ink & Chemicals, Inc.), rackstar 6 8-0 7 3 S (Carboxy-modified NB copolymer latex: manufactured by Dainippon Ink & Chemicals, Inc.), Lux Star DN-704 (carboxy-modified NB copolymer latex: Dainippon Ink & Chemicals, Inc.) Lux Yuichi DN 702 (Carboxy-modified NB copolymer latex: manufactured by Dainippon Ink and Chemicals, Inc.), Luxstar 68-8-074 (Carboxy-modified NB copolymer latex: manufactured by Dainippon-Ink and Chemicals, Inc.) ), Luckstar DN-703 (carboxy-modified NB copolymer latex: manufactured by Dainippon Ink & Chemicals, Inc.), Luckster DM-801 (carboxy-modified MB copolymer latex: Dainippon Ink & Chemicals, Inc.) Industrial Co., Ltd.), Lux Yuichi DM-401 (carboxy-modified MB copolymer latex: manufactured by Dainippon Ink and Chemicals, Inc.), Luckstar 495 C (carboxy-modified MB copolymer) Latex: manufactured by Dainippon Ink and Chemicals, Inc.), Luckstar DM-806 (carboxy-modified MB copolymer latex: manufactured by Dainippon Ink and Chemicals, Inc.) and the like. These conjugated genpolymer-based latexes can be used alone or in an appropriate mixture of two or more.

 The hydrophilic swelling layer of the present invention is formed on a substrate by mixing the above-mentioned hydrophilic polymer and hydrophobic polymer, cross-linking or pseudo-cross-linking as necessary, and insolubilizing in water.

 For the crosslinking, it is preferable to carry out a crosslinking reaction using a reactive functional group of the hydrophilic polymer and the hydrophobic polymer.

 The cross-linking reaction may be covalent cross-linking or ionic cross-linking.

 Examples of the compound used for the cross-linking reaction include known polyfunctional compounds having cross-linking properties, such as polyepoxy compounds, polyisocyanate compounds, poly (meth) acryl compounds, polymercap compounds, and polyalkoxysilyl compounds. Examples include a compound, a polyvalent metal salt compound, a polyamine compound, an aldehyde compound, a polyvinyl compound, and hydrazine. The crosslinking reaction is carried out by adding a known catalyst to accelerate the reaction.

 In preparing an aqueous emulsion that is preferably used as the hydrophobic polymer of the present invention, a carboxyl group, a hydroxyl group, a methylolamide group, an epoxy group, an arbonyl group, an amino group, or the like may be used as a copolymer component. And a method of forming a crosslinked structure using the above-mentioned polyfunctional compound as a crosslinking agent.

 Specific examples of known polyfunctional compounds having crosslinkability include the following compounds.

(1) Sublimated sulfur, by-product sulfur generated by oxidizing hydrogen sulfide, and colloidal sulfur generated by oxidizing hydrogen sulfide by wet methods. In addition, thiuram-based compounds such as dithiomorpholine, thioplastotetramethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuramtetrasulfide which decompose when heated to generate sulfur, Ginpentamethylenethiocarbamate, pipecoline pipecolyldithylrubite, dimethyldithiocarbamate sodium and other dithiocaproluvate compounds, sodium isopropylxanthate, butyl Xanthate compounds such as zinc xanthate, thiourea compounds such as thioperia, thiocarbanilide, zinc salts of thiazoles such as diphenylguanidine, sodium salts of mercaptobenzothiazole, dibenzothiazyl disulfide, Thiazolyl compounds such as mercaptobenzothiazole hexylamine salt.

 (2) Aldehydoamine compounds such as butylaldehyde monobutylamine condensate, butylaldehyde doaniline condensate, heptane aldehyde doaniline reactant, chloride ethylformaldehyde ammonia reactant, zinc oxide, tellurium, Rhenium, ammonium zirconium carbonate, and organic peroxides such as benzoyl peroxide and dicumyl peroxide.

 Further, as a crosslinking accelerator, zinc carbonate, stearic acid, oleic acid, lauric acid, zinc stearate, dibutylammonium methanol, diethanolamine, triethanolamine, diethylene Glycol and the like.

 (3) Polyepoxy compounds, urea resins, polyamines, melamine resins, benzoguanamine resins, acid anhydrides and the like.

 Specific examples of the polyepoxy compound include glycerin dipolyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyglycidyl ether, and sorbitol. Monopoly polyglycidyl ether and the like.

 Specific examples of the polyamine include ethylenediamine, diethylenetriamine, triethylenetetrathamine, tetraethylenepentamine, polyethyleneimine, and polyamide.

 (4) Polyisocyanate compounds.

Examples of polyisocyanate compounds include tri-diisocyanate, hexamethylene diisocyanate, diphenyl methane diisocyanate, liquid diphenyl methane diisocyanate, and polymethylene polyphenyl isocyanate. , Xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropyl Benzene 1,2,4-diisocyanate, polypropylene glycol tri-diisocyanate addition products.

 These crosslinking agents can be used alone or in combination of two or more. Water is mainly used as the dispersion medium, but a known organic solvent can be added as necessary. As a method of adding the organic solvent, a method of adding as a polymerization solvent and a method of adding as a mixed solvent to the emulsion solution after emulsion polymerization are possible.

 Examples of the method for mixing the hydrophilic polymer and the hydrophobic polymer of the hydrophilic swelling layer of the present invention include a roll mixer such as a three-roll mill, a method of kneading using a mixer such as a kneader, a homogenizer, and a disperser such as a ball mill. It is preferably mixed by a known method used when producing a paint or putty, such as a method of wet mixing and dispersing using a varnish.

 As a method for forming the hydrophilic swelling layer of the present invention, since an aqueous emulsion is preferably used as the hydrophobic polymer, each component (hydrophilic polymer, hydrophobic polymer, etc.) is mixed in an aqueous solution, and if necessary, The method in which a crosslinking agent is added is preferred from the viewpoint of realizing a homogeneous phase-separated structure and improving the ink repulsion.

 Therefore, it is particularly preferable to use a water-soluble polyfunctional compound as the crosslinking agent. That is, it is preferable to use a water-soluble polyepoxy compound, polyamine compound, melamine compound, or the like.

 Next, the phase separation structure of the hydrophilic swelling layer according to the present invention will be described.

 The hydrophilic swelling layer used in the present invention is characterized in that it has a phase-separated structure composed of at least two phases of the above-mentioned phase mainly composed of the hydrophilic polymer and the phase mainly composed of the hydrophobic polymer. I have.

 By using a phase-separated structure composed of a phase mainly composed of a hydrophilic polymer and a phase mainly composed of a hydrophobic polymer, it is possible to achieve both ink repulsion and printing durability in a wide composition range. It becomes possible.

 The composition ratio of the hydrophilic polymer phase and the aqueous polymer phase constituting the phase separation structure is free,

(1) one of which is a continuous phase and the other is a dispersed phase, (2) A form in which the hydrophilic and hydrophobic polymer phases have a continuous phase and a dispersed phase, respectively.

(3) Form in which both hydrophilic and hydrophobic polymer phases are continuous phases

Can be freely selected from

 Examples of the above phase separation structures (1) to (3) are shown in FIGS. 1 to 3, respectively.

 That is, when a material whose hydrophilic polymer exhibits relatively strong hydrophilicity (such as a water-soluble polymer and a pseudo-water-soluble polymer) is selected, the proportion of the hydrophilic polymer contained in the hydrophilic swelling layer is determined by the ink repellency and printing. From the viewpoint of durability, a relatively small amount is sufficient, and the ratio of the water-repellent polymer is relatively large.

It is preferable to adopt the form of (1) or (2). On the other hand, when a material whose hydrophilic polymer exhibits relatively weak hydrophilicity (such as a water-swellable polymer) is selected, the ratio of the hydrophilic polymer contained in the hydrophilic swelling layer is determined by the ink repellency and printing durability. From the above, a relatively large amount is required, and the proportion of the hydrophobic polymer is relatively small.

It is preferable to adopt the form of 1), (2) or (3).

 That is, the preferred phase separation structure of the hydrophilic swelling layer used in the present invention differs depending on the rubber elasticity and water swelling property of the layer, but differs depending on the degree of hydrophilicity of the hydrophilic polymer.

 In the case of the form (1), in order that the hydrophobic polymer phase is mainly a continuous phase, the composition of the hydrophobic polymer is preferably 50% by weight or more and preferably 60 to 95% by weight. More preferably, it is 70 to 90% by weight. When the composition ratio of the hydrophobic polymer is 50% by weight or less, the performance of the hydrophilic swelling layer as an ink repellent layer is improved in the initial stage of printing, but the printing durability tends to sharply decrease. . On the other hand, if the composition ratio of the hydrophobic polymer exceeds 95% by weight, the hydrophilic polymer in the hydrophilic swelling layer cannot absorb water sufficiently, and the hydrophilicity is insufficient, and the ink repellency is extremely reduced. There is a tendency.

 In the case of the forms (2) and (3), both the hydrophilic polymer and the hydrophobic polymer are at least 20% by weight, and preferably at least 40% by weight.

 The hydrophilic swelling layer preferably has rubber elasticity.

 The rubber elasticity of the hydrophilic swelling layer is characterized by the value of the initial elastic modulus measured by the method described below.

[Method of measuring initial elastic modulus of hydrophilic swelling layer] A solution having the same composition as each of the non-image area and the area corresponding to the image area of the lithographic printing plate to be measured is spread on a Tef jar and dried and cured for 60 to 24 hours. The obtained dried and cured film is cut into a strip-shaped test piece with a length of 4 O mm, a width of 1.95 mm and a thickness of about 0.2 mm using a razor blade or the like. If processing is performed after the solution is applied and before the printing plate is formed, the same processing is performed on the test piece.

 The test piece obtained was left for 24 hours or more in an environment of 25 ° C 509 ° R 測定 before measurement, and after adjusting the humidity, the thickness was measured with a micro gauge, and the initial elasticity was measured under the following tensile conditions. Measure the rate. Data processing was performed in accordance with JIS K6301.

 Pulling speed 200 mmZ min

 Distance between chucks 20 mm

 4 repetitions

Measuring machine “RTM-100” manufactured by Orientec Co., Ltd. The initial elastic modulus of the hydrophilic swelling layer used in the present invention may be in the range of 0.01 to 10 kgf / mm ² . It is preferable from the viewpoint of shape retention. Preferably, it is in the range of 0.01 to 5 kgf / mm ² , more preferably in the range of 0.01 to 2 kgf / mm ² .

That is, when the initial elastic modulus is less than 0.01 kgf / 'mm ² , the shape retention of the hydrophilic swelling layer is extremely reduced, and the durability during printing tends to be extremely reduced. On the other hand, if the initial elastic modulus is larger than 10 kgf / mm ² , the rubber elasticity becomes insufficient, and the repulsion of the ink tends to be extremely reduced.

 On the other hand, the initial elastic modulus of the image area (ink-filled area) needs to be larger than the initial elastic modulus of the hydrophilic swelling layer of the non-image area, and it is more than 2 times to perform image formation advantageously. Preferably, it is three times or more.

 In addition, the hydrophilic swelling layer used in the present invention preferably has a water absorption value measured according to the following definition within a specific range.

Water absorption (g κ m ² )

 Water absorption (%) => 1 0 0

The hydrophilic swellable layer thickness (g / m ²⁾

 However, the water absorption means a value measured according to the following definition.

Water absorption (g κ m ² ) = WWET— WDRY WDRV: Weight in dry state (g Roh m ²⁾

WWET: weight after immersion 2 5 Te> for 10 minutes in water (g / m ²⁾

 [Method of measuring water absorption]

The lithographic printing plate to be measured is cut into predetermined areas, each having only a non-image area and an image area, and immersed in 25 purified water. After immersion for 10 minutes, excess water adhering to the front and back surfaces of the hydrophilic swelling layer of the lithographic printing plate was quickly wiped off with “Heise gauze” (cotton cloth: manufactured by Asahi Kasei Kogyo Co., Ltd.). The swelling weight WWET of the lithographic printing plate is weighed. Thereafter, the lithographic printing plate is dried in an oven at 60 ° C. for about 30 minutes, and the dry weight W _DRY is weighed.

 The hydrophilic swelling layer used in the present invention can have a water absorption of 100 to 200 ° C., but preferably has a water absorption of 50 to 1 from the viewpoints of ink repellency and shape retention. 700%, more preferably 50-700%. When the water absorption is less than 10%, the ink repellency tends to be extremely low, and defects such as pinholes are likely to occur during coating. On the other hand, when it exceeds 200 °, the shape retention tends to be extremely lowered.

It is important that the water absorption of the non-image area (ink-repellent portion) composed of the hydrophilic swelling layer is 1 to 50 g / m ² from the viewpoints of ink-repellency and shape retention. 0 g / 'm and more preferably 2 to 7 g / m ² . The water absorption of the non-image portion comprising a hydrophilic swellable layer is liable scumming occurs during printing becomes insufficient Lee Nki resilience is less than 1 g / m ^2, whereas water absorption of 5 0 g / m ² If it exceeds, the shape retention is remarkably reduced, and the durability of the printing plate is insufficient.

 On the other hand, the water absorption of the image area must be less than the water absorption of the non-image area for image formation. It is preferably below 0% U and more preferably below 30%.

 When compared with a hydrophilic swelling layer having the same composition, the water absorption increases as the thickness of the layer increases, and the ink rebound tends to improve.

If the water absorption to form a hydrophilic swellable layer with a relatively low material, in order to achieve a particular amount of water absorption is 1 ~ 5 0 g / m ² exhibit the effect of the present invention is thicker the layer thickness When the layer is formed using a material having a relatively high water absorption, By forming the layer to be thinner than the above, it is possible to obtain the same ink repellency. Therefore, if a hydrophilic swelling layer is formed using a material having an excessively high water absorption, a water absorption of 1 to 50 g / m ² can be realized, but this is disadvantageous in terms of shape retention during swelling.

For example, when the water absorption is about to form a hydrophilic swellable layer with 1 0 ¾ material, water absorption 1 g, m ² is achieved by setting the hydrophilic swelling layer thickness 1 0 g / m ² However, when a material having a water absorption of less than 10% is used, it is necessary to set the thickness of the hydrophilic swelling layer further thicker. The lithographic printing plate of the present invention is preferably characterized in that the difference in water absorption between the image area and the non-image area of the hydrophilic swelling layer is realized by a photosensitive compound described below. If the thickness of the hydrophilic swelling layer is excessively large, it is necessary to use a large amount of a photosensitive compound in order to realize the difference in water absorption, which is economically disadvantageous.

 The hydrophilic swelling layer thickness referred to in the present invention is measured by a gravimetric method by peeling off the coating layer of the hydrophilic swelling layer corresponding to the non-image area of a dried lithographic printing plate applied on a substrate and measuring the weight by a gravimetric method. Means the value of The thickness of the hydrophilic swelling layer was measured according to the following equation.

The hydrophilic swellable layer thickness ^{(g / m 2) = (} W - W o) / a

 W: Dry weight (g) of the lithographic printing plate obtained by cutting the portion formed only from the non-image area

 W o: Dry weight (g) after the hydrophilic swelling layer was dropped off from above W

a: Measurement area of lithographic printing plate (m ² )

 [Method of measuring hydrophilic swelling layer thickness]

A portion formed only of the non-image area of the lithographic printing plate to be measured is cut into a predetermined area α, dried in a 60 oven for about 30 minutes, and the dry weight W is weighed. After that, the lithographic printing plate is immersed in purified water to swell the hydrophilic swelling layer, and the swelling layer is peeled off using a scrubber or the like. The lithographic printing plate from which the hydrophilic swelling layer has been peeled off is again dried in an oven at 60 ° C for about 30 minutes, and the dry weight Wo is weighed. The hydrophilic swelling layer used in the present invention can have a thickness of 0.1 to 100 g / m ² , but preferably has a thickness of 0.2 from the viewpoint of ink repellency and form retention. 110 gzm ² . When the thickness is less than 0.2 g / m ² , the repulsion of the ink tends to extremely decrease, and defects such as pinholes are likely to occur during coating. If it is 10 g / m ² or more, the shape retention during water swelling tends to deteriorate, which is economically disadvantageous.

 Next, the water swelling ratio of the image portion / non-image portion of the planographic printing plate of the invention will be described. The feature of the lithographic printing plate of the present invention is that the non-image portion composed of the hydrophilic swelling layer is substantially swollen by water absorption. The thickness of the hydrophilic swelling layer corresponding to the non-image area increases due to swelling due to water absorption, while the swelling due to water absorption in the image area is smaller or almost non-existent than in the non-image area. An image can be formed by a difference in water absorption, that is, a difference in degree of swelling.

 The water swelling ratio in the present invention means a value measured according to the following definition.

Water swelling ratio (%) = (9 WET-Θ ΡΚΥ) / θ ϋΚν Χ 1 0 0

 © DRV: Thickness of non-image area or hydrophilic swelling layer consisting of image area in dry state (βm)

e wET: Thickness (μm) of hydrophilic swelling layer consisting of non-image area or image area in swollen state

 [Method of measuring water swelling ratio (A)]

Cut the section of the lithographic printing plate to be measured so that the part including the non-image part or the image part has a cross section. After vacuum-drying this section at room temperature for one day and night, the thickness of the hydrophilic swelling layer at the site is observed with an optical microscope, and this is set to 6 _DRY (m). Observation with an optical microscope was 23 and 2009. We went quickly under RH environment. Further, an excess water droplet was placed on the lithographic printing plate section, the cross section was observed with an optical microscope in a state where the hydrophilic swelling layer was sufficiently swollen with water, and the thickness of the hydrophilic swelling layer at the site was read. μm).

 [Method of measuring water swelling ratio (B)]

The lithographic printing plate to be cane measurement after fixing the hydrophilic swellable layer by ◦ s 0 ₄ exposed overnight (including the non-image portion or image portion) in an atmosphere of O s 0 ₄ aqueous solution, predetermined parts Ultra-thin sections are prepared by cutting with a microtome so that the position becomes a cross section. The section was subjected to hydrophilic swelling at a magnification of about 10,000 to 50,000 times using a transmission electron microscope (TEM). Observe the layer thickness and call it e _DRY (zm).

On the other hand, the immersed hydrophilic Rise Junso solidifies Z fixed with water-swollen state 2-3 days a lithographic printing plate to be cane measured 0 s 0 ₄ aq. Ultra-thin sections are prepared by micro-toming to cut a specified part into a cross section, and the section is subjected to transmission electron microscopy (TEM) at a magnification of about 10,000 to 50,000 times to obtain the hydrophilicity of the part. Read the swelling layer thickness and use it as e _{WE T} (μm).

 The water swelling ratio of the non-image area (ink repellent portion) composed of the hydrophilic swelling layer of the present invention is preferably from 10 to 200 o / o from the viewpoints of ink repulsion and shape retention. , 50 to 170%, more preferably 50 to 700%. When the water swelling ratio is too small, the ink repellency of the non-image portion is low. On the other hand, when the water swelling ratio of the non-image portion is too high, the shape retention of the non-image portion is low. The wire part is easily damaged.

 On the other hand, the water swelling rate of the image area needs to be lower than the water swelling rate of the non-image area for image formation, but the water swelling rate of the non-image area is advantageous for image formation. The ratio is preferably 50% or less, more preferably 30% or less.

 Fig. 5 shows an SEM (scanning electron microscope) photograph showing an example of the image area and the non-image area on the plate surface during water swelling. It can be seen that shadow dots are formed due to the difference in the water swelling ratio.

 In the hydrophilic swelling layer used in the present invention, in addition to the above-mentioned hydrophilic polymer, hydrophobic polymer and optionally a crosslinking agent, a known antioxidant usually added in a rubber composition, It is possible to add an inhibitor, an ozone deterioration inhibitor, an ultraviolet absorber, a dye, a pigment, a plasticizer, and the like as long as the effects of the present invention are not impaired. The hydrophilic swelling layer may be subjected to a heat treatment at the time of coating or after the coating to give various heat histories. In this case, even if the constituent components of the hydrophilic swelling layer are the same, the water swelling property such as the water absorption and the water absorption may change depending on the heat history.

 For the purpose of improving the adhesion to the lower layer, a known silane coupling agent, a diisocyanate compound, a catalyst, or the like may be added, or an intermediate layer may be provided between the substrate and the substrate.

Next, an example of a method for producing a lithographic printing plate according to the present invention will be described. Is not limited to this.

 The image of the lithographic printing plate of the present invention can be formed, for example, by irradiating the plate surface of a photosensitive lithographic printing plate precursor having a hydrophilic swelling layer on a substrate with actinic rays. That is, the difference between the image portion and the non-image portion is caused by irradiation with actinic rays. The hydrophilic swelling layer of such a photosensitive lithographic printing plate precursor has the same water absorption, initial elastic modulus, water swelling ratio, phase separation structure, thickness, water absorption and the like as the non-image area in the lithographic printing plate. It is preferable.

 The lithographic printing plate of the present invention is produced by negative-passing image formation. That is, the initial elastic modulus of the portion of the hydrophilic swelling layer irradiated with actinic light (hereinafter referred to as an exposed portion) is increased as compared with the portion not irradiated with actinic light (hereinafter referred to as an unexposed portion). As a result, the image area of the ink-inking is formed, and the unexposed area becomes the non-image area of the ink repellency.

 A known photosensitive compound is used for such image formation.

 In other words, the known swelling layer of the original plate contains a known photocrosslinking or photocurable photosensitive compound, selectively crosslinks and / or cures the exposed area, and raises the initial elastic modulus, thereby forming an image. Achieved.

 Examples of the known photocrosslinkable or photocurable photosensitive compound include the following specific examples (1) to (5).

 (1) Photopolymerizable monomer or sesame

Alcohols (ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpump, pentaerythritol, isoamyl alcohol, lauryl alcohol, stearyl alcohol, butoxyethyl alcohol, ethoxyethylene glycol, methanol (Meth) acrylic acid esters and carboxylic acids (toxic acid, propionic acid, benzoic acid, etc.) of toxic ethylene glycol, methicane propylene glycol, phenoxyethanol, phenoxyethylene glycol, and tetrahydrofurfuryl alcohol. Acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) and (meth) glycidyl acrylate or tetraglycidyl m Xylylenediamine or tetraglycidyl-m-addition reaction with m-tetrahydroxylylenediamine, Examples include amide derivatives (acrylamide, methacrylamide, n-methylolacrylamide, methylenebisacrylamide, etc.), and addition products of epoxy compounds with (meth) acrylic acid.

 More specifically, the resin described in JP-B-48-41708, JP-B-50-634, and JP-A-51-71393 is disclosed. RELAT, polyesters described in JP-A-48-183, JP-B-49-431, JP-B-52-34090 Polyfunctional epoxy (meth) acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, and N-methylolacrylamide derivatives described in US Pat. No. 4,540,649. Can be mentioned. Furthermore, photocurable monomers and oligomers introduced in the Japan Adhesion Society, VOL. 20, No. 7, p. 300-308 can be used.

 (2) Photodimerizable photosensitive resin composition

 For example, a photosensitive layer containing polyvinyl cinnamate and the like, for example, a 1: 1 polycondensation unsaturated polyester or cinnamilidedenmalonic acid of P-phenylenediacrylic acid and 1,4-dihydroxyshetyloxycyclohexane Photosensitive polyesters derived from glycerol and difunctional glycols, and carboxylic acid esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, and cellulose.

 (3) A composition comprising a combination of a monomer, an oligomer or a polymer having an epoxy group and a known photoacid generator.

 When exposed to light, the photoacid generator generates Lewis acid / Brensted acid, and the epoxy group is cationically polymerized and crosslinked. Examples of photoacid generators include aryldiazonium salt compounds, diaryldonium salt compounds, triarylsulfonium salt compounds, triarylselenonium salt compounds, dialkylphenol-nacilsulfonium chloride compounds, 4-phenacylsulfonium salt compound, α-hydroxymethylbenzenezoin sulfonate, Ν-hydroxyiminosulfonate, a-sulfonioxyxetone, sulfonyloxiketone, iron Arene complex compounds (such as benzene-cyclopentageneru iron (II) hexafluorophosphorate) and o-nitrobenzylsilyl ether compounds.

The following are preferred as monomers, oligomers or polymers having an epoxy group. It is used well.

 Methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether, pentyl glycidyl ether, cyclohexyl glycidyl ether, 2-ethyl hexyl glycidyl ether, etc. .

 (4) Composition of monomer, oligomer or polymer having an aryl group and / or vinyl group and monomer, oligomer or polymer having a mercapto group

When exposed to light, a mercapto group is added to an aryl group and / or a vinyl group to crosslink.

 (5) Composition of diazonium salt compound and hydroxyl-containing compound

Examples of the diazo compound used in the present invention include a water-insoluble organic solvent-soluble diazo resin represented by a condensate of p-diazodiphenylamine and formaldehyde.

 Specific examples include those described in JP-B-47-11667 and JP-B-57-43990.

Examples of the diazo monomer in the diazo resin preferably used in the present invention include, for example, 4 diazo diphenylamine, 1 diazo 141 N.N-dimethylamino benzene, 1 diazo 141 N, N-Jethylaminobenzene, 1-Diazo-1-4—N-Ethyl-N-Hydroxyshetylaminobenzene, 1-Diazo-14-N-Metyl-N-Hydroxyshetylamino-benzene, 1-Diazo1-2,5—Diethoxy-14 Benzoylaminobenzene, 1—Diazo4—N—Benzylaminobenzene, 1Diazo4-1N, N—Dimethylaminobenzene, 1Diazo4-1Moleforminobenzene, 1Diazo1-2,5 —Dimethoxy 41-p-tolylmethylcaptobenzene, 1-diazo 1 2—ethoxin 4-N, N-dimethylaminobenzene, p-diazo— Methylaniline, 1-diazo-2,5—dibutoxy—41 morpholinobenzene, 1-diazo-2,5—diethoxy-4 morpholinobenzene, 1-diazo1-2,5—dime Toxic 4 1 morpholinobenzene, 1 — diazo 1 2, 5 — diethoxy 4 1 p — trimercaptobenzene, 1 _ diazo 1 4 1 N-ethyl-N-hydroxyschilaminobenzene, 1 1 diazo 1 3 —Ethoxy 1 4 1 N-Methyl-I \ '-Benzylaminobenzene, 1-Diazo-3-chloro-4-dethylaminobenzene, 1-Diazo-3-methyl-1-pyrrolidinobenzene, 1-Diazo1-2-Chloro4-1N , N-Dimethylamino-1-5-methoxybenzene, 1-Diazo-3-Methoxy4-1pyrrolidinobenzene, 3-Methoxy-4-1Diazodiphenylamine, 3-Ethoxy-4-1 Diazodiphenylamine, 3 — (n-propoxy) — 4-diazodiphenylamine, 3 — (isopropoxy) 14-diazodiphenylamine, etc. .

 Examples of the aldehyde used as a condensing agent with these diazomonomers include formaldehyde, acetate aldehyde, propionaldehyde, butyl aldehyde, isobutyl aldehyde, and benzaldehyde. Furthermore, water-soluble diazo resins can be obtained by using chloride ions or trichloroporous zincic acid as anions, and boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalene sulfonate can be obtained. Acid, 4.4'-biphenylsulphonic acid, 2,5-dimethylbenzenesulphonic acid, 2-nitrobenzenesulphonic acid, 2-methoxy-4-hydroxyl-5-benzo An organic solvent-soluble diazo resin can be obtained by using benzene sulfonic acid or the like.

 In addition, these diazo resins are generally used by mixing a high molecular compound having a hydroxyl group as described below.

That is, examples of the polymer having a hydroxyl group include monomers having an alcoholic hydroxyl group, such as 2-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyhydroxymethyl (meth) acrylate. , 3-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylamide, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) ) Accredit, 1, 3-Prono. At least one monomer selected from the group consisting of diol mono (meth) acrylate, 1,4-butanediol mono (meta) acrylate, and di (2-hydroxyhexyl) maleate Or a monomer having a phenolic hydroxyl group, such as N- (4-hydroxyphenyl) (meth) acrylamide, N— (4-hydroxy) (Doxyphenyl) maleid, o—, m—, p—hydroxystyrene, o—, m—, p Copolymers with hydroxy- (meth) acrylate, etc., and ring-opening reaction products of P-hydroxybenzoic acid with glycidyl (meth) acrylate, and salicylic acid. Copolymers of hydroxy acid-containing monomers, such as reaction products of phosphoric acid and 2-hydroxyhydryl (meth) acrylate, may be mentioned. Further, polyvinyl alcohol, cellulose, polyethylene glycol, polypropylene glycol, glycerin, pentaerythritol and the like, an epoxy addition reaction product thereof, and other natural polymer compounds containing a hydroxyl group can also be used.

 (5) A photosensitive composition mainly composed of polyisoprene rubber or polybutadiene rubber cyclized with a bisazide compound, or cresol novolac resin.

 These photosensitive compounds are added to the composition when forming the hydrophilic swelling layer on the substrate, and are allowed to exist in the layer. Alternatively, after forming the hydrophilic swelling layer, the photosensitive composition is coated on the layer. It is added using a method of coating and impregnating the layer.

 In the case of a photosensitive composition using a polymer or an oligomer having a relatively high molecular weight, the former method of simultaneous addition during the formation of the hydrophilic swelling layer is advantageously performed, and a monomer or an oligomer having a relatively low molecular weight is used. In the case of a photosensitive composition using the latter, the latter impregnation method is advantageous.

A known photosensitizer can be added to the hydrophilic swelling layer of the master plate for the purpose of sensitizing these photosensitive compounds. As the known photosensitizer, a known photosensitizer can be freely selected, and various substituted benzophenone-based compounds, substituted thioxanthonone-based compounds, and substituted acridone-based compounds are preferable. Used. Also, a vicinal polyketaldonyl compound described in US Pat. No. 236766, an α-carbonyl compound disclosed in US Pat. No. 23 67661, US Pat. No. 2367670, and an α-carbon compound disclosed in US Pat. Aromatic acylone compounds substituted with hydrogen, polynuclear quinone compounds disclosed in U.S. Pat. No. 3,046,127 and U.S. Pat. No. 2,951,758, and triarylimidazolguma / ρ-amino disclosed in U.S. Pat. Combinations of phenyl ketones, benzothiazole compounds disclosed in U.S. Pat. No. 3,870,524, benzothiazole compounds / trihalomethyl-s-triazine compounds disclosed in U.S. Pat. Acryzine and phenazine compounds disclosed in U.S. Pat. No. 4,212,970. Zole compounds, trihalomethyl-s-triazine compounds having a chromophore group disclosed in U.S. Pat. No. 3,954,475, U.S. Pat. No. 4,189,323, and the like. Specific examples include a benzophenone group-containing peroxyester compound disclosed in Japanese Patent Application Laid-Open No. 60-7653.

 The substrate of the lithographic printing plate used in the present invention is not limited at all, except that it is required to have flexibility that can be attached to a normal lithographic printing press and to withstand a load applied during printing.

 Typical examples include a metal plate of aluminum, copper, iron, or the like, a plastic film such as polyester film / polypropylene film, a coated paper, a rubber sheet, and the like. Further, the substrate may be a composite of the above materials.

 In addition, the surface of the substrate can be subjected to various surface treatments such as electrochemical treatment, acid-base treatment, corona discharge treatment and the like for the purpose of improving plate inspection and adhesion.

 In addition, a primer layer can be formed on these substrates by applying a coating or the like for the purpose of improving adhesiveness and preventing halation, and can be used as substrates.

 Next, a plate making method using the photosensitive lithographic printing plate precursor will be described.

 The photosensitive lithographic printing plate precursor can be made into a printing plate through a negative working plate making process. That is, the image is exposed through a negative original film by a normal exposure light source.

 Examples of the light source used in this exposure step include a high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, and a fluorescent lamp. After such normal exposure, rinsing with water or a developing solution dissolves and removes or desensitizes the photosensitive compound present in the hydrophilic swelling layer in the unexposed area, and is suitable for repelling the ink. The exposed part has a higher initial elastic modulus and a lower water swelling property than the unexposed part due to photocrosslinking and curing of the photosensitive compound due to photo-crosslinking and curing of the photosensitive compound. It becomes an image part.

As described above, the photosensitive lithographic printing plate precursor forms an image by changing the rubber elasticity and water swelling property of the phase separation structure of the hydrophilic swelling layer with the help of the photochemical reaction of the photosensitive compound. is there. Next, a printing method using the planographic printing plate of the invention will be described.

 For the lithographic printing of the present invention, a known lithographic printing machine is used. That is, sheet-fed and rotary printing presses of the offset and direct printing systems are used.

 After an image is formed on the lithographic printing plate of the present invention, the lithographic printing plate is mounted on a plate cylinder of these lithographic printing presses, and the plate surface is supplied with ink from an inking roller which comes into contact with the plate.

 The non-image area having the hydrophilic swelling layer on the plate swells with the dampening solution supplied from the dampening solution supply device and repels the ink. On the other hand, the image portion receives the ink, and supplies the ink to the surface of the offset blanket cylinder or the surface of the printing medium to form a printed image.

 The fountain solution used when printing the lithographic printing plate of the present invention has water.It is possible to use the etchant used for the Ps plate, but it is possible to use pure water containing no additives. can do.

When printing using the photosensitive lithographic printing plate of the present invention, it is preferable to use pure water having no additive.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Examples 1 to 7, Comparative Examples 1 to 5

The following composition using the hydrophilic polymer shown in Table 1 was applied to a 0.2-band aluminum plate (manufactured by Sumitomo Light Metal Co., Ltd.) and heat-treated at 150 ° C for 60 minutes. A hydrophilic swelling layer having a thickness of 2 g Zm ² was applied.

Hydrophilic swelling layer composition>

 (1) 100 parts by weight of the hydrophilic polymer shown in Table 1

(2) Ethylene glycol diglycidyl ether 20 parts by weight

(3) 2-aminopropyltrimethoxysilane 2 parts by weight

(4) 900 parts by weight of purified water Table 1

On the hydrophilic swelling layer coated as described above, apply the photosensitive composition having the following composition.

Heat treatment was performed at 100 × X for 3 minutes to impregnate 0.5 g / m ² of the photosensitive composition into the hydrophilic swelling layer.

However, in Example 7, 1 5 0 ° was coated with a parent aqueous swelling layer of C x 1 2 0 minute heat treatment to ² gZm 2 thickness, and heat-treated 1 0 0 ° C x 3 min 0.7 g / 'm ² of the photosensitive group The product was impregnated into the hydrophilic swelling layer.

 Thereafter, a single-sided matted biaxially stretched polypropylene film having a thickness of 12 micron was laminated using a calender roller so that the non-matted surface was in contact with the hydrophilic swelling layer, and a negative mold was prepared. A lithographic printing plate precursor was obtained.

The obtained lithographic printing plate was contact exposed for 90 seconds through a negative film with PCW (PLATE C0NT0R0L WEDGE: manufactured by KALLE) using a high-pressure mercury lamp “Jet Light 3303 kW; manufactured by Oak Manufacturing Co., Ltd.” (3.6 mW / cm ² ). Next, the entire surface of the plate was rinsed with running water, and the unexposed portions of the photosensitive composition were washed to form a printing plate.

 (1) Xylylenediamine / glycidylmethacrylate

 10 parts by weight

_{(2) CH 2 = CHC00- (} C 2 H 4 0) M- C0CH: CH 2 1 0 part by weight

(3) 2 parts by weight of Michler's ketone

(4) 2, 4-diethylthioxanthone 2 parts by weight

(5) Ethyl alcohol 76 parts by weight The obtained printing plate was mounted on a sheet-fed offset printing machine “Sprint 25: manufactured by Komori Corporation” and then purified commercially as a dampening solution. Printing was performed using high-quality paper (62,5 kg chrysanthemum) while supplying water. The ink repellency and the ink inking property were evaluated by visually observing the printed matter. The water absorption and the water absorption of the image area and the non-image area were measured according to the definitions. Table 2 shows the evaluation results.

Table 2 夹! ¾ 奋 レ

 Ink inking property / water absorption Ink repulsion no water absorption Water absorption 军 * Ϊ

 ttt * ヽ,

(g / m (non-image area) (gZm ² )

 Example 丄 5 2. 0 1 U U 关 Cursed example C 〇 2. U 〇 7.0 o 5 U

 她 6 〇 2.5 O o, υ 4 U U ¾ 2 ¾ 4 n u. 〇 1. 0 5 0

 5 〇 1.0 〇 5.0 o ς 0

 Example 6 〇 2.0 〇 1 0. 0 5 0 0

 Example 7 〇 3.5 〇 3 3. 0 1 6 5 0

 Comparative Example 1 〇 <0. X 0.5 2 5

 Comparative Example 2 〇 <0. X 0.84 0

 Comparative Example 3 〇 <0. X 0.525

 Comparative Example 4 〇 <0. X 0.84 0

 Comparative Example 5 〇 <0. X 0.84 0

Examples 8 to 14, Comparative Examples 6 to 9

 A lithographic printing plate was prepared in the same manner as in Example 1 except that the hydrophilic swelling eyebrow thickness was changed using the hydrophilic polymer of Example 1. However, in Examples 12 to 14, when the heat treatment time of the hydrophilic swelling layer was set to 150 ° C. × 60 minutes, the ink inking property at the time of printing was poor. By setting it at 120 ° C. for 120 minutes, a printing plate giving good inking property was obtained.

 Further, the appearance of the obtained lithographic printing plate was visually inspected, and the presence or absence of a pinhole as a defect during coating was examined. The shape retention was judged from the degree of damage to the printing plate by rubbing the non-image area consisting of the hydrophilic swelling layer 20 times with pure water in “Hize gauze”.

Table 3 shows the evaluation results. Table 3 Experiment No.Hydrophilic swelling layer Ink adhesion Z water absorption Ink repulsion Z water absorption Defects during coating Morphology

(Image area) (g / m ² ) (non-image area) (g / m ² ) Pinhole retention Comparative Example 6 0.1 〇 <0.1 X 0. 1 Yes 比較 Comparative Example 7 0.2 〇 <0.1 Δ 0.3 0.3 None 無 Comparative Example 8 0.5 〇 0.1 Δ 0.5 0.5 None 比較 Comparative Example 9 0.8 〇 0.2 Δ 0.8 0.8 None 〇 Example 8 1.0 〇 0.3 〇 1.0 0 No 〇 Example 9 5.0 〇 0.5 〇 5.0 No 〇 Example 1 0 8. 0 〇 0.8 〇 8.0 No 〇 Example 1 1 1 0. 0 〇 1.0 〇 1 0. 0 No 〇 Example 1 2 1 2. 0 χ → 〇 1-2 〇 1 2. 0 No Example 1 3 1 5. 0 1.5 〇 15.0 No Δ Example 1 4 20.0 χ → 〇 2.0 〇 20.0 None △

Examples 15 to 17 and Comparative Examples 10 to 11

 A lithographic printing plate was prepared in the same manner as in Example 1 except that the hydrophilic polymer of Example 6 was used and the thickness of the hydrophilic swelling layer was changed. Table 4 shows the evaluation results. Table 4 Experiment No.Hydrophilic swelling layer Ink adhesion / water absorption Ink repulsion Z water absorption Defects during coating Morphology

(g / m ² ) (image area) (gZm ² ) (non-image area) (g / m ^z ) Pinhole retention Comparative Example 1 0 0.1. <0.1 1 0.1 Yes 〇 Perform Example 1 5 0.2 〇 <0.1 〇 1.0 0 No 〇 Example 16 5 0 1.5 〇 25.0 No 〇 Example 1 7 1 0. 0 〇 3.0 〇 50. 0 None 比較 Comparative Example 1 1 1 2.0 X 3.6 〇 60.0 None X

Example 18 to 22

The same lithographic printing plate was prepared using the hydrophilic polymers of Comparative Examples 1 to 5, except that the thickness of the hydrophilic swelling layer was changed. Table 5 shows the thickness of the hydrophilic swelling layer and the evaluation results. Table 5 Experiment No.Hydrophilic swelling layer

(/ m ^J ) (image area) (gZm ² ) (non-image area) (g no m ² ) Example 1 84.0 〇 <0.1 〇 1.0

 Same as Comparative Example 1

 Example 1 9 3.0 〇 <0.1 〇 1.2

 Same as Comparative Example 2

 Example 20 2.0 〇 <0.1 〇 1.0

 Same as Comparative Example 3

 Example 2 1 3.0 〇 <0.1 〇 1.2

 Same as Comparative Example 4

 Example 22 3.0 〇 <0.1 〇 1.2

 Same as Comparative Example 5

From the above examples, a lithographic printing plate having a hydrophilic swellable layer of the present invention, within the scope water absorption of the non-image area is l~ 5 0 gZm ^2, inking property, Inki resilience good It can be seen that there was no defect at the time of coating, and that it had sufficient shape retention.

Further, in Table 3 and Table 4, in a range water absorption of a given, especially when the hydrophilic swellable layer thickness of 0. 2~ 1 O gZm ^2, inking property, Inki resilience It can be seen that the appearance during coating and the shape retention were good.

 Further, in Table 5, the hydrophilic swelling eyebrows having a water absorption of 100 to 200% have a predetermined water absorption by appropriately setting the layer thickness within a predetermined range. It can be seen that a swelling layer can be produced, and thus can be used as a lithographic printing plate having good ink adhesion and ink repellency.

Example 23

 The lithographic printing plate used in Example 1 and a normal PS plate (FNS; manufactured by Fuji Photo Film Co., Ltd.) were exposed and developed to form a printing plate, which was mounted on the same plate cylinder and used as a dampening solution. Printing was performed in the same manner as in Example 1 while supplying commercially available purified water.

When the supply amount of dampening water was increased from the standard condition, the ink density of the image area was extremely reduced in the area where the PS plate was used, and poor ink deposition due to so-called “water loss” occurred. On the other hand, in the portion where the lithographic printing plate used in Example 1 was used, the degree of incomplete deposition was slight. In addition, when the dampening water supply was reduced from the standard condition, ink contamination occurred on the entire surface using the PS plate. On the other hand, in the part using the lithographic printing plate used in Example 1, good printed matter was obtained. The amount of dampening water supplied was compared relatively using the dial scale of the printing press. Table 6 shows the evaluation results. Table 6

As described above, the lithographic printing plate of the present invention has a wide supply range of dampening water, and can obtain a good printing surface image by using pure water as dampening water.

Examples 24 to 30, Comparative Examples 12 to 16

 The following composition using the hydrophilic polymer shown in Table 7 was applied to a 0.2-thick aluminum plate (manufactured by Sumitomo Light Metal Co., Ltd.), and heat-treated at 150 ° C for 60 minutes. A hydrophilic swelling layer having a thickness of g / m 2 was applied.

 <Hydrophilic swelling layer composition (parts by weight)>

 (1) 100 parts by weight of hydrophilic polymer shown in Table 7

(2) Tetraethylene glycol diglycidyl ether 20 parts by weight

(3) 2-Aminoprovir trimethoxysilane 2 parts by weight (4) Purified water 900 parts by weight O 96/25295

 Table 7

On the hydrophilic swelling layer coated as described above, apply a photosensitive composition having the following composition, heat it for 100 minutes and then heat it for 3 minutes to obtain 0.5 g Zm ² of the photosensitive composition in the hydrophilic swelling layer. Was impregnated.

However, embodiments in Example 3 0, 1 50 ° CX 1 after heat treatment for 20 minutes by coating a hydrophilic swelling layer of 2 g of Roh m ² thickness, 1 00 ° CX 3 minutes heat treatment to 0. 7 gZm ² Photosensitivity The composition was impregnated into the hydrophilic swelling layer.

 Thereafter, a single-side matted biaxially stretched polypropylene film having a thickness of 12 micron was laminated using a calender roller 1 such that the non-matted surface was in contact with the hydrophilic swelling layer. A negative type lithographic printing original plate was obtained.

The obtained lithographic printing plate was contact-exposed for 90 seconds through a negative film on which PCW (PLATE C0NT0R0 and WEDGE: manufactured by KALLE) was affixed using a high-pressure mercury lamp "Jetlight 330 kW; manufactured by Oak Manufacturing Co., Ltd." (3.6 mW / cm ² ). Next, the entire surface of the plate was rinsed with tap water, and the unexposed portion of the photosensitive composition was washed to obtain a printing plate.

 (1) Xylylene diamine Z glycidyl methacrylate z 1 2 2 mol of methyl glycidyl ether

(2) CH2 = CHCOO- (C2H40) 14-COCH = CH2 10 parts by weight (3) Michler's ketone 2 parts by weight

(4) 2,4-diethylthioxanthone 2 parts by weight

(5) 76 parts by weight of ethyl alcohol The obtained printing plate was mounted on a sheet-fed offset printing press “Sprint 25: manufactured by Komori Corporation” and marketed as fountain solution. The paper was printed using high quality paper (62.5 kg Z chrysanthemum) while supplying purified water. The ink repellency and the ink inking property were evaluated by visually observing the printed matter. The initial elastic modulus and water absorption of the image area and the non-image area were measured according to the definitions. Table 8 shows the evaluation results.

Table 8 Experiment No. Ink inking property ΖInitial elastic modulus Inky repulsion / initial elastic modulus ΠΤΙ | c J¾

 ヽ

 (¾ line part) (kgf / mm2) (Non-surface line tit * part Alt) (kgf / 麵 2)

 r> Λ C.

 Example 2 4 〇 0.35 〇 U U 1 Ό 0 yj Example 2 5 〇 0.6 .6 〇 u L n U Q Π u Π u

 Example 2 6 〇 U. C Π U 〇 υ o o c D n U

 Example 2 1 U 1.2 0 4 0 Q Π

 2 8 〇 0. 45 〇 0 1 0 ^ c u: Π

 Example 2 9 〇 0.30 〇 0 0 5 4 5 0

 Example 30 mm 0.22 〇 0 0 3 1 6 5 0

 Comparative Example 1 2 〇 25 .1 X 1 2 .5 2 5

 Comparative Example 13 例 26 .5 X 1 3.8 .40

 Comparative Example 14 〇 20.2 X 1 2 .5 2 5

 Comparative Example 15 〇 30.1 X 13.0.40

 Comparative Example 16 〇 35.0 X 15 .8 4 0

Example 3 1 to 3 4

 A lithographic printing plate was prepared in the same manner as in Example 24 except that the hydrophilic swelling layer thickness was different using the hydrophilic polymer. Table 9 shows the hydrophilic swelling layer thickness and the evaluation results.

Table 9

Example 3 5

 The lithographic printing plate used in Example 24 and the normal PS plate (FNS; manufactured by Fuji Photo Film Co., Ltd.) were exposed and developed to form a printing plate. Printing was performed in the same manner as in Example 24, while supplying commercially available purified water.

When the dampening water supply is increased from the standard condition, The ink concentration in the part decreased extremely, resulting in poor inking of the ink due to so-called “water loss”. On the other hand, in the part using the lithographic printing plate used in Example 24, the degree of incomplete deposition was slight.

 In addition, when the dampening water supply was reduced from the standard condition, ink stain occurred on the entire surface using the PS plate. On the other hand, in the part using the lithographic printing plate used in Example 24, good printed matter was obtained. The amount of dampening water supplied was compared relatively using the dial scale of the printing press. Table 10 shows the evaluation results. Table 10

Example 3 6 to 4 2

A 0.2-thick aluminum plate (manufactured by Sumitomo Light Metal Co., Ltd.) is coated with the following composition using the hydrophilic polymer shown in Table 11, and then heat-treated at 150 ° C for 60 minutes. Thus, a hydrophilic swelling layer having a thickness of 2 g Z m ² was provided.

 Hydrophilic swelling layer composition (parts by weight)>

 (1) 28 parts by weight of hydrophilic polymer shown in Table 11

(2) 5 parts by weight of tetraethylene glycol diglycidyl ether

(3) Aqueous latex `` JSR 0 5 9 6 '' 65 parts by weight

[Carboxy-modified styrene-butadiene copolymer latex: Dainippon Ink Chemical Industry Co., Ltd.]

(4) 2-aminoprovirt methoxysilane 2 parts by weight (5) Purified water 900 parts by weight Table 11

On the hydrophilic swelling layer applied as described above, a photosensitive composition having the following composition was applied and heat-treated at 100 ° C. for 3 minutes so that 0.5 g / m ² of the photosensitive composition was subjected to aqueous swelling. The layers were impregnated.

 Thereafter, a single-sided matted biaxially stretched polypropylene film having a thickness of 12 μm was laminated using a calendar roller so that the non-matted surface was in contact with the hydrophilic swelling layer. A lithographic printing original plate was obtained.

The obtained lithographic printing plate was passed through a negative film on which PCW (PLATE C0NT0L WEDGE: KALLE) was affixed using a high-pressure mercury lamp “Jet Light 330kW: manufactured by Oak Manufacturing Co., Ltd.”. Contact exposure (3.6 mW / cm ² ) was performed for ² seconds. Next, the entire surface of the plate was rinsed with tap water, and the unexposed portions of the photosensitive composition were washed and removed to obtain a printing plate.

The hydrophilic swellable layer corresponding to Inki rebound portion of the resulting printing plate in Example 3 6 4 2 while being water-swellable, 0 s 0 ₄ stained, and observed TEM (transmission electron microscope). As a result of the observation, it was found that the hydrophilic polymer-based phase and hydrophobic phase as shown in Fig. 2 Has a phase-separated structure composed of a phase mainly composed of conductive polymer

(1) Xylylenediamine glycidyl methacrylate z / Methyl glycidyl ether l / 2/2 mol ratio reaction product 10 parts by weight

(2) CH ₂ = CHC00- (C ₂ H ₄ 0) ₁₄ -C0CH = CH ₂ 10 parts by weight

(3) 2 parts by weight of Michler's ketone

(4) 2,4—2 parts by weight of getylthioxanthone

(5) 76 parts by weight of ethyl alcohol The obtained printing plate was mounted on a sheet-fed offset printing press “Sprint 25: manufactured by Komori Corporation” and marketed as fountain solution. The paper was printed using high-quality paper (62.5kgZ chrysanthemum) while supplying purified water. The ink repellency and the ink inking property were evaluated by visually observing the printed matter. The initial elastic modulus and water absorption of the image area and the non-image area were measured according to the definitions. Table 12 shows the evaluation results. Table 1 2 Experiment number Ink inking property Initial elastic modulus Ink repulsion Initial elastic modulus Water absorption

(Image area) (kgf / mm ² ) (non-surface area) (kgf / inm ² ) (%) Example 36 〇 0.34 〇 0.008 340

 Example 37 〇 0.65 〇 0.18 1 90

 Example 38 〇 0.83 〇 0.2 1 260

 Example 3 Θ 〇 1.22 〇 0.40 70

 Example 4 0 〇 0.47 〇 0.10 1 60

 Example 4 1 〇 0.33 〇 0.009 370

 Example 42 △ 0.22 〇 0.05 05 390

At the time when about 1000 sheets were printed, no ink stain was generated on each printing plate, and a clear print having sufficient contrast was obtained.

 Comparative Example 1 7

The following composition was applied to a 0.2 mm thick aluminum plate (manufactured by Sumitomo Light Metal Co., Ltd.), and then heat-treated at 150 ° C. for 120 minutes to give a hydrophilic swelling having a thickness of 2 g / m ^2. Layers were applied.

Hydrophilic swelling layer composition (parts by weight)> (1) 93 parts by weight of the hydrophilic polymer used in Example 38

(2) tetraethylene glycol diglycidyl ether 5 parts by weight

(3) 2-Aminoprovir trimethoxysilane 2 parts by weight

(4) 900 parts by weight of purified water After the photosensitive composition was applied on the obtained hydrophilic swelling layer in the same manner as in Example 36, a light-sensitive lithographic printing plate was obtained, and the same as in Example 36. After the plate making process described above, a printing plate was obtained. The water absorption of the hydrophilic swelling layer was 2500%. The hydrophilic swelling layer corresponding to the ink repellent portion of the obtained printing plate was swollen with water and stained with O s C, and observed under a transmission electron microscope (TEM).

 As a result of the observation, it was confirmed that the hydrophilic swelling layer had a uniform phase structure composed of a phase containing a hydrophilic polymer as a main component.

 As a result of printing evaluation, when about 50 sheets were printed, the hydrophilic swelling layer dropped off from the substrate, and ink stains occurred.

Example 4 3 to 4 6

Example 38 A photosensitive lithographic printing plate was produced in the same manner as in Example 8, except that the aqueous latex was changed to a polymer shown in Table 13 below. Parent aqueous swelling layer to ink repellent portion of the resulting printing plate corresponding to a state of being water-swellable, 〇 5 0 ₄ stained, and observed TEM (transmission electron microscope).

 As a result of the observation, each hydrophilic swelling layer has a phase-separated structure in which a phase mainly composed of a hydrophobic polymer is a continuous phase and a phase mainly composed of a hydrophilic polymer is a dispersed phase as shown in FIG. It was confirmed that.

Table 14 shows the evaluation results.

Table 13

Table 1 4 Experiment No.Ink inking property / initial elasticity Ink repulsion / initial elasticity Water absorption

(Image area) (kgf / mmz) (non-image area) (kgf / oiDi ² ) ()

 Example 4 3 〇 0.40 〇 0.20 1 4 0 Example 4 4 〇 0.56 〇 0.30 1 9 0 Example 4 5 〇 0.70 〇 0.25 1 5 0 Example 4 6 〇 0.80 〇 0.35 1 0 0

At the time of printing about 500 sheets, no ink stain was generated on each printing plate, and a clear printed matter having a sufficient contrast was obtained.

Example 4 7 to 5 3

The following composition using the hydrophilic polymer shown in Table 11 was applied to a 0.2 mm thick aluminum plate (manufactured by Sumitomo Light Metal Co., Ltd.), and then heat treated at 150 ° C for 60 minutes. Then, a hydrophilic swelling layer having a thickness of 2 g / m ² was applied.

Hydrophilic swelling layer composition (parts by weight)〉

 (1) 28 parts by weight of hydrophilic polymer shown in Table 11

(2) 5 parts by weight of tetraethylene glycol diglycidyl ether

(3) Aqueous polymer emulsion 7 Β — 7 3 5 ”65 parts by weight

[Acryl-based emulsion: manufactured by Dainippon Inki Chemical Industry Co., Ltd.] (4) 2-Aminoprovir trimethoxysilane 2 parts by weight

(5) 900 parts by weight of purified water The same photosensitive composition as in Example 36 was applied on the hydrophilic swollen eyebrows applied as described above, and heat-treated at 100 ° C for 3 minutes. The photosensitive composition 0.5 gZm ² was impregnated in the hydrophilic swelling layer. Thereafter, a single-sided matted biaxially stretched polypropylene film having a thickness of 12 μm was laminated using a force length roller so that the non-matted surface was in contact with the hydrophilic swelling layer, and a negative type After obtaining a lithographic printing plate precursor, a plate was made through the same plate making process as in Example 36. The resulting printing plate hydrophilic swellable layer corresponding to Inki repulsive portion in a state of being water-swellable, O s 0 ₄ stained, and observed TEM (transmission electron microscope).

 As a result of the observation, it was confirmed that the polymer had a phase-separated structure composed of a phase mainly composed of a hydrophilic polymer and a phase mainly composed of a hydrophobic polymer as shown in FIG. Table 15 shows the evaluation results. Table 15 5 Experiment No.Ink inking property / initial elasticity Ink repulsion / initial elasticity Water absorption

(Image area) (kgf / min ² ) (non-image area) (kgf / mrn ² ) (%) Example 47 〇 0.34 〇 0.08 440 Example 48 〇 0.69 〇 0.21 290 Example 49 〇 0.83 〇 0.27 360 Example 50 〇 1.22 〇 0.43 1 00 Example 5 1 〇 0.47 〇 0.12 260 Example 52 〇 0.33 〇 0. 07 470 Example 53 Δ 0.22 〇 0.03 490

At the time of printing about 5,000 sheets, no ink stain was generated on each printing plate, and a clear printed matter having a sufficient contrast was obtained.

Example 5 4 to 5 7

A photosensitive lithographic printing plate was prepared in the same manner as in Example 38 except that the latex in Example 16 was changed to the polymer shown in Table 16 below. The resulting printing plate was subjected to O s O staining while the hydrophilic swelling layer corresponding to the ink repellent portion was swollen with water, and observed by TEM (transmission electron microscope). As a result of the observation, each hydrophilic swelling layer as shown in FIG. 2 has a phase hybrid structure in which a phase mainly composed of a hydrophobic polymer is a continuous phase and a phase mainly composed of a hydrophilic polymer is a dispersed phase. It was confirmed to have.

 Table 17 shows the evaluation results. Table 16

 Experiment number Ink inking property Z initial elastic modulus Inky repulsion Z initial elastic modulus Water absorption

(Image area) (kgf / nim ² ) (non-image area) (kgf / image ² ) (%) Example 54 〇 0.35 〇 0.30 150

 Example 55 〇 0.66 〇 0.28 200

 Example 56 〇 0.80 〇 0.27 1 1 0

 Example 57 〇 0.90 〇 0.35 90

At the time when about 500 sheets were printed, no ink stain was generated on each printing plate, and a clear printed matter having a sufficient contrast was obtained.

Example 5 8

Example 36 A lithographic printing plate used in Example 6 and a normal PS plate (FNS; manufactured by Fuji Photo Film Co., Ltd.) were exposed and developed to form a printing plate, which was mounted on the same plate cylinder and dampened. Printing was performed in the same manner as in Example 36, while supplying commercially available purified water. When the dampening water supply was increased from the standard conditions, the ink density of the image area was extremely reduced in the area where the PS plate was used, causing poor ink deposition due to so-called “water loss”. On the other hand, in the part using the lithographic printing plate used in Example 36, the degree of poor inking was slight.

 In addition, when the dampening water supply was reduced from the standard condition, ink stains occurred on the entire surface using the PS plate. On the other hand, in the part using the lithographic printing plate used in Example 36, good printed matter was obtained. The amount of dampening water supplied was compared relatively using the dial scale of the printing press. Table 18 shows the evaluation results. Table 18

Example 5 9 to 6 5

The following composition using the hydrophilic polymer shown in Table 19 was applied to a 0.2 mm thick aluminum plate (manufactured by Sumitomo Light Metal Co., Ltd.), and then heat-treated at 150 ° for X 60 minutes. To give a hydrophilic swelling layer having a thickness of 2 gm ² .

Hydrophilic swelling layer composition>

 (1) 100 parts by weight of hydrophilic polymer shown in Table 19

(2) Ethylene glycol diglycidyl ether 20 parts by weight

(3) 2-aminopropyl trimethoxysilane 2 parts by weight

(4) 900 parts by weight of purified water Table 19

On the hydrophilic swelling layer coated as described above, apply the photosensitive composition having the following composition.

Then, heat treatment was performed at 100 ° C. for 3 minutes to impregnate the hydrophilic swelling layer with 0.5 g / m ² of the photosensitive composition.

However, in Example 65, after heat-treating at 150 ° C. for 120 minutes to apply a hydrophilic swelling layer having a thickness of 2 g Zm ² , heat-treating at 100 ° C. for 3 minutes was performed at 0.7 ° C. for 0.7 minute. g / m ² of the photosensitive composition was impregnated in the hydrophilic wetting layer.

 Thereafter, a one-sided, biaxially oriented, biaxially oriented polypropylene film having a thickness of 12 micron was laminated using a calender roller so that the non-matted surface was in contact with the hydrophilic swelling layer, and negative type lithographic printing was performed. A master version was obtained.

The obtained lithographic printing plate was contact-exposed for 90 seconds using a high-pressure mercury lamp “Jetlight 330 kW; manufactured by Oak Manufacturing Co., Ltd.” through a negative film on which PCW (PLATE C0NT0R0L WEDGE: manufactured by KALLE) was attached (3.6 seconds). mW / cm ² ). Next, the entire surface of the plate was rinsed with tap water, and the unexposed portions of the photosensitive composition were washed to form a printing plate.

 (1) Xylylene diamine Z glycidyl methacrylate l / 4mol ratio reactant

 10 parts by weight

_{(2) CH 2 = CHC00- (} C 2 H40) -C0CH = CH2 1 0 parts by weight (3) Michler's barge ton 2 parts by weight (4) 2,4—2 parts by weight of getylthioxanthone

(5) Ethyl alcohol 76 parts by weight The obtained printing plate was mounted on a sheet-fed offset printing machine “Sprint 25: made by Komori Corporation”, and then commercially available purified water was used as dampening water. The paper was printed using high-quality paper (62.5 kg chrysanthemum) while supplying paper. The ink repellency and ink adhesion were evaluated by visually observing the printed matter. The water swelling ratio and water absorption of the image area and the non-image area were measured according to the definitions. Table 20 shows the evaluation results. Table 20

FIG. 4 is a schematic diagram of a TEM (transmission electron microscope) image of the lithographic printing plate of Example 9 obtained by the method (B) for measuring the water swelling ratio at the time of swelling of the image portion and the non-image portion. Show. The non-image areas that have swelled and have a large layer thickness and the surface line areas where the layer thickness is thinner than the non-image areas can be observed in contrast because the water swelling ratio is small.

 Further, the water swelling ratio of the image area of the planographic printing plate of Example 59 and the water absorption rate of the non-image area were measured, and were 15% and 144%, respectively.

Comparative Example 1 8

 A lithographic printing plate was produced in the same manner as in Example 59, except that chloroprene latex was used instead of the hydrophilic polymer of Example 59. The evaluation results are shown in Table 20.

Example 6 6

Example 59 The lithographic printing plate used in Example 9 and a normal PS plate (FNS; Fuji Photo Film ( Was exposed and developed to form a printing plate. The plate was mounted on the same plate cylinder, and printing was performed in the same manner as in Example 59 while supplying commercially available purified water as dampening water. Was.

 When the dampening water supply was increased from the standard condition, the ink density of the image area was extremely reduced in the area where the PS plate was used, and poor ink deposition due to so-called “water loss” occurred. On the other hand, in the part using the lithographic printing plate used in Example 59, the degree of poor inking was slight.

 In addition, when the dampening water supply was reduced from the standard condition, ink stains occurred on the entire surface using the PS plate. On the other hand, in the part using the lithographic printing plate used in Example 59, good printed matter was obtained. The amount of dampening water supplied was compared relatively using the dial scale of the printing press. Table 21 shows the evaluation results. Table 2 1

Above-moss ij ffl let

 The lithographic printing plate of the present invention has a specific amount of water absorption, an initial elastic modulus, a water swelling ratio, and uses a hydrophilic swelling layer having a phase-separated structure as a non-image portion. Ink can be repelled efficiently with the supplied water amount, and the control range of dampening water is expanded. In addition, printing can be performed without using a solvent such as isopropanol which is usually added to the dampening solution.

 When an image is formed from the photosensitive lithographic printing plate precursor according to the present invention with the aid of a photosensitive compound, physical development required for a conventional PS plate is not required at all, and the plate making process is extremely simple. In addition, since a special surface treatment for the substrate required for exhibiting the repellency of the ink is not required, an inexpensive photosensitive lithographic printing plate precursor can be manufactured.

Claims

The scope of the claims

1. A lithographic plate characterized in that the non-image area composed of the hydrophilic swelling layer has a water absorption of 1 to 50 gz m ² , and the water absorption of the image area is less than the water absorption of the non-image area. Print version.

2. a hydrophilic swellable layer initial elastic modulus 0. 0 1~ 1 0 kgfzmm ² of plane-line portion consisting of, and that the initial elastic modulus of the image area is larger than the initial elastic modulus of the non-imaging portion A lithographic printing plate characterized by the following.

3. The non-image area composed of the hydrophilic swelling layer has a water absorption of 1 to 50 g / m ² , and the water absorption of the image area is less than the water absorption of the non-image area. A lithographic printing plate as set forth in claim 2.

 4. The water swelling rate of the non-image area composed of the hydrophilic swelling layer is 10 to 200 °, and the water swelling rate of the image area is less than the water swelling rate of the non-image area. A lithographic printing plate characterized by the following.

5. The non-image area comprising the hydrophilic swelling layer has a water absorption of 1 to 50 g / m ² , and the water absorption of the image area is less than the water absorption of the non-image area. A lithographic printing plate as defined in claim 4.

6. an initial modulus of 0. 0 1 ~ 1 0 kgf Zm m 2 of non-image areas consisting of a hydrophilic swellable layer, and initial modulus of the image area than the initial elastic modulus of the non-imaging portion The lithographic printing plate according to claim 4, wherein the lithographic printing plate is large.

 7. A non-image area composed of a hydrophilic swelling layer must have a phase separation structure composed of at least two phases consisting of at least a phase composed mainly of a hydrophilic polymer and a phase composed mainly of a hydrophobic polymer. Lithographic printing plate featuring.

 8. The lithographic printing plate according to claim 7, wherein the hydrophobic polymer is mainly composed of an aqueous emulsion.

 9. The lithographic printing plate according to claim 7, wherein the hydrophobic polymer is mainly composed of a latex containing a conjugated diene compound.

10. The lithographic printing plate according to claim 7, wherein the hydrophobic polymer has a weight of 90 to 95 in the hydrophilic swelling layer.

1 1. The water absorption of the non-image areas consisting of a hydrophilic swellable layer is 1~ 5 0 g / m ^2, and 8. The lithographic printing plate according to claim 7, wherein the water absorption of the image area is less than the water absorption of the non-image area.

1 2. the initial elastic modulus of the non-image areas consisting of a hydrophilic swellable layer is 0. 0 1~ 1 0 kgf / mm 2, and the initial modulus of the image area is from the initial elastic modulus of the non-imaging portion The lithographic printing plate according to claim 7, wherein the lithographic printing plate is also large.

 1 3. The water swelling rate of the non-image area composed of the hydrophilic swelling layer is 1 mm to 2000 mm, and the water swelling rate of the image area is less than the water swelling rate of the non-image area. The lithographic printing plate according to claim 7, characterized in that:

1 4. range billed first to Toku徵to that the thickness of 0. 2~ 1 0 g / m ² of hydrophilic swelling layer, 2, 4 or 7 a lithographic printing plate as claimed.

 1 5. The lithographic printing plate according to claim 1, 2, 4 or 7, wherein the hydrophilic swelling layer has a water absorption of 10 to 2000.

 1 6. Irradiating the plate surface of a photosensitive lithographic printing plate precursor with a hydrophilic swelling layer on the substrate with actinic light to produce a difference in water absorption between the image area and the non-image area. The method for producing a lithographic printing plate according to claim 1.

 1 7. Irradiation of actinic rays on the surface of a photosensitive lithographic printing plate precursor with a hydrophilic swelling layer on the substrate to create a difference in the initial elastic modulus between the image area and the non-image area 3. The method for producing a lithographic printing plate according to claim 2, which is characterized in that:

 1 8. Irradiation of actinic rays on the surface of a photosensitive lithographic printing plate precursor with a hydrophilic swelling layer on the substrate to cause a difference in the water swelling ratio between the image area and the non-image area 5. The method for producing a lithographic printing plate according to claim 4, wherein:

 1 9. A photosensitive lithographic plate provided with a hydrophilic swelling layer having a phase-separated structure composed of at least two phases composed of at least two phases composed mainly of a hydrophilic polymer and a phase composed mainly of a hydrophobic polymer. 8. The method for producing a lithographic printing plate according to claim 7, wherein the plate surface of the printing plate precursor is irradiated with actinic rays.

20. A lithographic printing plate precursor comprising a substrate having a hydrophilic swelling layer, wherein the hydrophilic swelling layer has a water absorption of l to 50 g / m ² .

2.1. A lithographic printing plate precursor having a hydrophilic swellable layer on a substrate, the lithographic printing, characterized in that the initial modulus of the hydrophilic swellable layer is 0. 0 1~ 1 0 kgf / mm 2 Original version.

22. The lithographic printing plate precursor according to claim 21, wherein the hydrophilic swelling layer has a water absorption of 1 to 50 g / m ² .

 2 3. A lithographic printing plate precursor comprising a substrate and a hydrophilic swelling layer, wherein the hydrophilic swelling layer has a water swelling ratio of 10 to 2000 mm. .

24. The lithographic printing plate precursor as claimed in claim 23, wherein the hydrophilic swelling layer has a water absorption of 1 to 50 g / m ² .

25. The lithographic printing plate precursor as claimed in claim 23, wherein the hydrophilic swelling layer has an initial elastic modulus of 0.01 to 10 kgf / mm ² .

 2 6. A lithographic printing plate precursor having a hydrophilic swelling layer on a substrate, wherein the hydrophilic swelling layer has at least a phase mainly composed of a hydrophilic polymer and a phase mainly composed of a hydrophobic polymer. A lithographic printing plate precursor characterized by having a phase-separated structure composed of at least two phases.

 27. The lithographic printing plate precursor as claimed in claim 26, wherein the hydrophobic polymer is mainly composed of an aqueous emulsion.

 28. The lithographic printing plate precursor as claimed in claim 26, wherein the hydrophobic polymer is mainly composed of a latex containing a conjugated diene compound.

 27. The lithographic printing plate precursor as claimed in claim 26, wherein the water-soluble polymer is 60 to 95% by weight in the hydrophilic swelling layer.

30. The lithographic printing plate precursor according to claim 26, wherein the hydrophilic swelling layer has a water absorption of l to 50 g / m ² .

31. The lithographic printing plate precursor as claimed in claim 26, wherein the hydrophilic swelling layer has an initial elastic modulus of 0.01 to 10 kgf / mm ² .

3 2. The lithographic printing plate precursor according to claim ²⁶ , wherein the water swelling ratio of the hydrophilic swelling layer is 10 to ^{200 000} .

3 3. Hydrophilic thickness swelling layer is 0. 2~ 1 0 g / m ² billed ranging second 0, characterized in that it is,

A lithographic printing plate precursor as described in 21, 23 or 26.

3 4. The lithographic printing plate precursor according to claim 20, wherein the hydrophilic swelling layer has a water absorption of 10 to 200 °.