JP5781892B2 - Lithographic printing plate support and negative photosensitive lithographic printing plate - Google Patents

Description

  The present invention relates to a lithographic printing plate support having at least a hydrophilic layer on the support, and a negative photosensitive lithographic printing plate using the lithographic printing plate support. More specifically, the present invention relates to a support for a lithographic printing plate suitable for a lithographic printing plate developed by chemicalless development substantially containing no alkali agent, and a negative photosensitive lithographic printing plate.

  In recent years, CTP (abbreviation of Computer To Plate) has been fully digitized due to the expansion of JDF (abbreviation of Job Definition Format), and work efficiency has been greatly improved. In addition, in terms of hardware, such as output machines and printing plates, the creation of products that take into consideration human health and the environment as well as increasing efficiency through the development of process-less and chemical-less products has become widespread. However, in thermal type and photopoly type CTP printing plates which are currently mainstream, after the printing plate is laser-exposed, the non-image area is eluted and removed using a developer containing a strong alkaline agent, and then washed with water and gummed. Since it becomes what is used for printing through a process, it cannot be said that it is enough as a chemical-less.

  There has been proposed a negative photosensitive lithographic printing plate that avoids the use of a strong alkaline agent-containing developer as described above and can be developed with water or the like. For example, Japanese Patent Application Laid-Open No. 2003-215801 (Patent Document 1) discloses a cationic water solution having a hydrophilic layer on a plastic film support and a phenyl group having a vinyl group substituted on the side chain on the hydrophilic layer. A negative photosensitive lithographic printing plate having a photosensitive polymer or a water-soluble polymer having a phenyl group substituted with a vinyl group in the side chain and a sulfonate group, and a photosensitive layer containing a photopolymerization initiator or an acid generator It is disclosed.

  In this publication, as the hydrophilic layer, a hydrophilic resin layer made of a (meth) acrylate polymer having a hydroxyalkyl group described in JP-B-49-2286, and a urea resin described in JP-B-56-2938 are disclosed. And a hydrophilic layer formed by curing an acrylamide polymer described in JP-A-48-83902 with aldehydes, and a water-soluble layer described in JP-A-62-280766 A hydrophilic layer obtained by curing a composition containing a melamine resin, polyvinyl alcohol, and a water-insoluble inorganic powder, and a water-soluble polymer comprising a repeating unit having an amidino group in the side chain described in JP-A-8-184967 Hydrolyzed layer containing a hydrophilic layer (co) polymer described in JP-A-8-272087 and hydrolyzed A hydrophilic layer cured with an alkyl orthosilicate, a hydrophilic layer having an onium group described in JP-A-10-296895, and a crosslinked hydrophilic polymer having a Lewis base moiety described in JP-A-11-311861 Examples thereof include a hydrophilic layer obtained by three-dimensional crosslinking by interaction with a valent metal ion, a hydrophilic layer containing a hydrophilic resin and a water-dispersible filler described in JP-A No. 2000-122269. However, it is difficult to obtain sufficient printing durability and stain resistance even when these hydrophilic layers are combined with the photosensitive layer containing the cationic water-soluble polymer or the water-soluble polymer having a sulfonate group. there were.

  As a technique for solving such a problem, Japanese Patent Application Laid-Open No. 2008-265297 (Patent Document 2) contains a water-soluble polymer on a support, a crosslinking agent for crosslinking the water-soluble polymer, and colloidal silica, A negative photosensitive lithographic printing plate having a hydrophilic layer in which the ratio of the water-soluble polymer and colloidal silica is specified is disclosed. Further, in JP-A-2009-226596 (Patent Document 3), the hydrophilic layer is at least a water-soluble polymer. And a negative photosensitive lithographic printing plate containing inorganic fine particles and having a film surface pH value of the hydrophilic layer of 7.0 or more. Such a negative photosensitive lithographic printing plate enables development with water or the like, but depending on the printing conditions, a phenomenon called smearing in which the shadow portion is stained may occur, or the image portion may be partially There is a case where it is missing and sufficient printing durability cannot be obtained, and improvement has been demanded.

  As means for improving the stain resistance of a negative photosensitive lithographic printing plate capable of chemicalless development with water or the like, for example, JP 2010-237559 A (Patent Document 4), JP 2010-231133 A (Patent No. Document 5), Japanese Patent Application Laid-Open No. 2010-224188 (Patent Document 6) and the like disclose that an intermediate layer is provided between the support and the hydrophilic layer, but this is not satisfactory.

  On the other hand, JP 2000-199964 A (Patent Document 7) contains two or more kinds of porous inorganic particles and metal oxide fine particles having different average particle diameters as a lithographic printing plate support having excellent stain resistance. A support for a lithographic printing plate having a hydrophilic layer is disclosed. In JP-A-2000-229485 (Patent Document 8), as a support for a printing plate excellent in printing durability and stain resistance, porous inorganic particles or A printing plate support having a hydrophilic layer containing thin layered inorganic particles is disclosed. Japanese Patent Application Laid-Open No. 2002-19315 (Patent Document 9) discloses a support for a lithographic printing plate having a hydrophilic layer containing particles having the same skeleton with different average particle diameters, and having an average particle diameter of 1 to 10 nm. Specific examples in which colloidal silica and 0.2 to 10 μm fine pore silica are combined are described. Japanese Patent Application Laid-Open No. 2003-231374 (Patent Document 10) describes a printing plate material in which a hydrophilic layer having a specific surface shape is provided on a substrate, and metal oxide fine particles having an average particle diameter of 3 to 100 nm; Specific examples in which porous metal oxide particles having an average particle diameter of 1 μm or more are combined are described. However, a lithographic printing plate support and a negative photosensitive lithographic printing plate that satisfy all of printing durability, stain resistance, anti-netting properties, and ink detachability cannot be obtained, and improvements are required. It was done.

JP 2003-215801 A JP 2008-265297 A JP 2009-226596 A JP 2010-237559 A JP 2010-231133 A JP 2010-224188 A JP 2000-199964 A JP 2000-229485 A JP 2002-19315 A JP 2003-231374 A

  An object of the present invention is to provide a support for a lithographic printing plate from which a lithographic printing plate excellent in all of printing durability, scumming resistance, ink detachment property and anti-screening property can be obtained. Another object of the present invention is to provide a negative photosensitive lithographic printing plate excellent in all of printing durability, background stain resistance, ink detachment property, and netting resistance.

The present invention has been achieved by the following invention.
1) A support for a lithographic printing plate having a hydrophilic layer containing an inorganic filler and a hydrophilic binder on a substrate, and the particle size distribution peak of the inorganic filler contained in the hydrophilic layer is 0.2 μm or more and 0 The distribution frequency of the inorganic filler existing in the range of less than 6 μm and in the range of 0.6 μm or more and less than 1.5 μm and in the range of 0.2 μm or more and less than 0.6 μm is fx, 0.6 μm or more and less than 1.5 μm A support for a lithographic printing plate, wherein the fx / fy ratio is 1.5 or more and the distribution frequency fy is 25% or more, where fy is the distribution frequency of the inorganic filler existing in the range of.
2) A negative photosensitive lithographic printing plate having at least a photopolymerizable photosensitive layer on the hydrophilic layer of the lithographic printing plate support described in (1) above.

  According to the present invention, it is possible to provide a support for a lithographic printing plate from which a lithographic printing plate excellent in all of printing durability, ground stain resistance, ink detachment property and anti-screening property can be obtained. Further, it is possible to provide a negative photosensitive lithographic printing plate that is excellent in all of printing durability, stain resistance, ink detachment property, and anti-screening property.

  The present invention will be described in detail below.

<Base material>
Examples of the substrate that the lithographic printing plate support of the present invention has include an aluminum plate, various plastic films, and paper laminated with various plastics. Among them, various plastic films that are flexible and are less deformed by tension are preferably used. Preferred examples of the plastic film substrate include polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polystyrene, polyvinyl acetal, polycarbonate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, and cellulose nitrate. In particular, polyethylene terephthalate and polyethylene naphthalate are preferably used.

  The surface of these base materials may be surface-treated in order to improve adhesion with a hydrophilic layer or a backing layer provided as necessary. Examples of such surface treatment include corona discharge treatment, flame treatment, plasma treatment, and ultraviolet irradiation treatment. As a further surface treatment, an undercoat layer may be provided on the base material in order to enhance the adhesiveness with the hydrophilic layer provided on the base material.

<Hydrophilic layer>
The lithographic printing plate support of the present invention has a hydrophilic layer on a substrate, and the hydrophilic layer contains an inorganic filler. The particle size distribution of the inorganic filler contained in the hydrophilic layer has peaks in at least two places of a range of 0.2 μm or more and less than 0.6 μm and a range of 0.6 μm or more and less than 1.5 μm. When the distribution frequency of the inorganic filler existing in the range of less than 6 μm is fx and the distribution frequency of the inorganic filler existing in the range of 0.6 μm or more and less than 1.5 μm is fy, the fx / fy ratio is 1.5 or more. And the distribution frequency fy is 25% or more. The fx / fy ratio is preferably 2.0 or more. The upper limit is desirably less than 3.5. In the above-mentioned range, for example, when a plurality of peaks are present in the range of 0.2 μm or more and less than 0.6 μm, the distribution frequency fx may be obtained with the higher peak. In the case where the height of the recess between two peaks is 60% or more of the higher peak, it is regarded as one peak in the present invention. As a result, a lithographic printing plate support that is particularly excellent in printing durability and background stain resistance can be obtained.

  The particle size distribution in the present invention is a volume-based particle size distribution, which is an index indicating what kind of particle size the sample particle group to be measured is and what ratio is configured, and is generally known It can be measured by the method. For example, a sieving method, a Coulter method (Coulter principle), a dynamic light scattering method, an image analysis method, a laser diffraction scattering method, etc. are known as the measuring method. In the present invention, the particle size to be measured and reproducibility are known. From the viewpoint of operability and the like, a laser diffraction / scattering method is preferably used, and for example, it can be measured by LA-920 (laser diffraction / scattering type particle size distribution measuring device) manufactured by HORIBA. The distribution frequency can be obtained as a distribution of the existence ratio for each size (particle diameter) based on the measurement result.

  The particle size distribution and distribution frequency in the present invention are measured by measuring the inorganic filler dispersed in the coating solution, or by measuring the inorganic filler in a solution obtained by re-dissolving the dried coating film of the applied hydrophilic layer with an alkali. You can ask for it. As will be described later, in the present invention, two or more kinds of inorganic fillers can be used together. However, in the laser diffraction scattering method preferably used in the present invention, the light intensity distribution pattern is obtained from the Fraunhofer diffraction theory and the Mie scattering theory. Therefore, a refractive index specific to the object is required, and it is difficult to accurately measure the particle size distribution and distribution frequency of a coating liquid containing two or more inorganic fillers having different refractive indexes. However, in such a case, the particle size distribution and distribution frequency of each inorganic filler alone are measured in advance, and two or more kinds of inorganic fillers are added by multiplying the obtained measurement result by the addition ratio in the coating liquid as a coefficient. The particle size distribution and distribution frequency of the coating liquid used in combination can be determined.

<Inorganic filler>
The inorganic filler contained in the hydrophilic layer may be one type of filler as long as it is an inorganic filler having the above particle size distribution, but the above particle size distribution can be made relatively easy by using two or more types in combination. Since it is obtained, it is preferable. Among them, it is preferable to use a combination of an inorganic filler having an average primary particle size of 0.1 μm or more and less than 0.6 μm and an inorganic filler having an average primary particle size of 0.6 μm or more and less than 2.0 μm. You may use an inorganic filler in combination with 3 types and 4 types further. The addition amount of the inorganic filler is preferably 60% by mass or more, more preferably 70% by mass or more, based on the total solid content of the hydrophilic layer.

  Examples of the inorganic filler used in the hydrophilic layer include calcium carbonate, magnesium carbonate, zinc oxide, titanium dioxide, barium sulfate, aluminum hydroxide, zinc hydroxide, colloidal silica, pore silica, and kaolin. Titanium dioxide, barium sulfate, and aluminum hydroxide are preferred. Moreover, it is preferable not to use silicon-containing compounds such as colloidal silica, fine pore silica, and kaolin, and the content of these silicon-containing compounds should be 5% by mass or less based on the total inorganic filler in the hydrophilic layer. It is preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

  Titanium dioxide preferably used as the inorganic filler may be either a rutile type or an anatase type, and the production method is not limited to either the sulfuric acid method or the chlorine method. You may use them individually or in mixture. Furthermore, from the viewpoint of dispersion stability and other functionality, it is possible to selectively use those subjected to various surface treatments. Examples of commercially available titanium dioxide include SR-1, R-650, R-5N, R-7E, R-3L, A-110, and A-190 from Sakai Chemical Industry Co., Ltd. ) From Taipei R-580, R-930, A-100, A-220, CR-58, Titanium Industry Co., Ltd., Kronos KR-310, KR-380, KA-10, KA -20 etc., Teica Co., Ltd., Titanics JR-301, JR-600A, JR-800, JR-701 etc., DuPont Co., Ltd. Taipure R-900, R-931 etc. are mentioned.

  As barium sulfate, it is preferable to use precipitated barium sulfate produced by adding a sulfate aqueous solution to a barium chlorine solution and chemically precipitating. Precipitated barium sulfate is commercially available, for example, as “Variace” from Sakai Chemical Industry Co., Ltd., having various particle diameters or surface-treated ones, but any of them can be used in the present invention.

  Aluminum hydroxide mixes bauxite, which is an ore containing alumina, with caustic soda or sodium aluminate solution, extracts the alumina component under high temperature and high pressure conditions, separates and removes red mud as a dissolution residue from the extract, A clarified sodium aluminate solution is obtained. Thereafter, seeds can be added to the solution to crystallize aluminum hydroxide, and the obtained aluminum hydroxide can be pulverized. Various grades of aluminum hydroxide are commercially available from Showa Denko Co., Ltd. as “Hijilite”, and any grade can be used in the present invention.

<Hydrophilic binder>
The hydrophilic layer of the lithographic printing plate support of the present invention contains a hydrophilic binder. Examples of such hydrophilic binders include natural products such as starch, seaweed mannan, agar and algae such as sodium alginate, mannan, pectin, tragacanth gum, caraya gum, xanthine gum, guar bin gum, locust bin gum, gum arabic and the like. Viscous mucus, dextran, glucan, xanthan gum, homopolysaccharides such as levan, microbial mucilage such as heteropolysaccharides such as succinoglucan, pullulan, curdlan, and xanthan gum, proteins such as glue, gelatin, casein and collagen, Examples include chitin and derivatives thereof. Semi-natural products (semi-synthetic products) include cellulose derivatives, modified gums such as carboxymethyl guar gum, cultured starches such as dextrin, processed starches such as oxidized starches and esterified starches. . On the other hand, synthetic products include polyvinyl alcohol, partially acetalized polyvinyl alcohol, allyl-modified polyvinyl alcohol, modified polyvinyl alcohols such as polyvinyl methyl ether, polyvinyl ethyl ether, and polyvinyl isobutyl ether, polyacrylates, and polyacrylate ester partial saponified products. , Polymethacrylic acid derivatives and polymethacrylic acid derivatives such as polymethacrylic acid salts and polyacrylamides, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, carboxyvinyl polymer, styrene / maleic acid copolymer Examples thereof include a polymer and a styrene / crotonic acid copolymer. Among these, gelatin is preferably used.

  Moreover, content of the hydrophilic binder in a hydrophilic layer has a preferable content ratio between the said inorganic fillers, and it is preferable that it is 5-30 mass% with respect to 100 mass parts of all inorganic fillers, and 10-25 masses. % Is more preferable. If it exceeds 30% by mass, the filler filling density is lowered and sufficient hydrophilicity cannot be imparted, and the soil resistance and the net resistance may be lowered. On the other hand, if it is less than 5% by mass, the handling property of the coating liquid may be lowered, or cracks may occur after forming the hydrophilic layer.

<Crosslinking agent>
The hydrophilic layer of the present invention preferably contains a crosslinking agent. As the crosslinking agent to be used, for example, melamine resin, polyisocyanate compound, aldehyde compound, silane compound, chromium alum, divinyl sulfone and the like can be suitably used, but particularly preferred crosslinking agent is divinyl when the hydrophilic binder is gelatin. Sulfone. The blending amount of the crosslinking agent is preferably 5 to 35% by mass, more preferably 10 to 25% by mass, based on the solid content of the hydrophilic binder. As for the method of adding the crosslinking agent, there are a method of adding the hydrophilic layer coating liquid when it is manufactured, a method of adding it in-line immediately before coating, and any method may be used.

  In order to sufficiently crosslink the hydrophilic layer, for example, 0.5 to 0.5 at a temperature of 30 to 60 ° C., preferably 40 to 50 ° C., between the formation of the hydrophilic layer and the application of the photopolymerizable photosensitive layer. It is preferable to perform a heating treatment for 10 days, preferably 1 to 7 days. Even if the hydrophilic layer is exposed by the development process after the exposure by such a heating process and is subjected to printing as a non-image part at the time of printing, it is natural as printability, but it is sufficient in terms of scratch resistance. Performance can be expressed.

<Photopolymerizable photosensitive layer>
Next, the negative photosensitive lithographic printing plate of the present invention will be described. The negative photosensitive lithographic printing plate of the present invention has at least a photopolymerizable photosensitive layer on the hydrophilic layer of the lithographic printing plate support described above. Such a photosensitive layer preferably contains a photopolymerization initiator and a compound having a polymerizable double bond group.

<Photopolymerization initiator>
Conventionally known compounds can be used as the photopolymerization initiator. For example, trihaloalkyl-substituted compounds (for example, s-triazine compounds and oxadiazole derivatives as trihaloalkyl-substituted nitrogen-containing heterocyclic compounds, trihaloalkylsulfonyl compounds), organic boron salts, hexaarylimidazoles, titanocene compounds, thio compounds And organic peroxides. Among these photopolymerization initiators, trihaloalkyl-substituted compounds and organic boron salts are particularly preferably used. More preferably, a combination of a trihaloalkyl-substituted compound and an organic boron salt is used. High sensitivity can be achieved by combining trihaloalkyl-substituted compounds and organic boron salts, and since the radical species generated by using these in combination can be stabilized, sensitivity can be further improved. Is preferable.

  The trihaloalkyl-substituted compound that is a photopolymerization initiator is specifically a compound having at least one trihaloalkyl group such as a trichloromethyl group or a tribromomethyl group in the molecule. Preferred examples include the trihaloalkyl group. S-triazine derivatives and oxadiazole derivatives are exemplified as compounds in which is bonded to a nitrogen-containing heterocyclic group, or a trihaloalkylsulfonyl in which the trihaloalkyl group is bonded to an aromatic ring or a nitrogen-containing heterocyclic ring via a sulfonyl group Compounds.

  Particularly preferred examples of compounds in which a trihaloalkyl group is bonded to a nitrogen-containing heterocyclic group and trihaloalkylsulfonyl compounds are shown below.

  The organoboron anion constituting the organoboron salt is represented by the following general formula 1.

In the formula, each of R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, and represents an alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group or heterocyclic group. Represent. Of these, it is particularly preferred that one of R ₁ , R ₂ , R ₃ and R ₄ is an alkyl group and the other substituent is an aryl group.

  Examples of the cation constituting the organic boron salt include alkali metal ions and onium compounds, but onium salts are preferred, for example, ammonium salts such as tetraalkylammonium salts, sulfonium salts such as triarylsulfonium salts, and triarylalkyls. Examples thereof include phosphonium salts such as phosphonium salts. Examples of particularly preferred organic boron salts are shown below.

  The content of the photopolymerization initiator as described above is preferably in the range of 1 to 50% by mass and more preferably in the range of 5 to 30% by mass with respect to the compound having a polymerizable double bond group described later. It is preferable.

<Compound having a polymerizable double bond group>
The compound having a polymerizable double bond group is a polymer compound having a polymerizable double bond group or a low molecular compound having a polymerizable double bond group. From the viewpoint of photopolymerization efficiency, it is preferable to use a low molecular weight compound having a polymerizable double bond group in combination.

  The polymer compound having a polymerizable double bond group will be described. The polymer compound having a polymerizable double bond group is a polymer compound formed by an arbitrary repeating unit, and a polymer compound in which a polymerizable double bond group is bonded to a side chain through an arbitrary linking group. It is. Among them, a polymer compound having a vinyl group as a reactive double bond group is preferably used, and a polymer compound in which a phenyl group substituted with a vinyl group is bonded to the main chain directly or via an arbitrary linking group is particularly preferably used. It is done. In addition, in order to enable development with an alkaline developer or a neutral developer (chemicalless developer), a carboxyl group, a sulfonic acid group, a quaternary ammonium group, etc., which are connected to the main chain via an arbitrary connecting group However, among them, a polymer compound having a sulfonic acid group can be preferably used because of its high developability. The sulfonic acid group may form a salt (for example, sodium salt, potassium salt, lithium salt, amine salt, etc.). These linking groups are not particularly limited, and include any group, atom, or a combination thereof. The phenyl group and sulfonic acid group substituted with a vinyl group may be independently bonded to the main chain, or the phenyl group and sulfonic acid group substituted with a vinyl group share part or all of the linking group. You may combine in the form to do.

  In the phenyl group substituted by the vinyl group, the phenyl group may be substituted, and the vinyl group is a halogen atom, carboxyl group, sulfo group, nitro group, cyano group, amide group, amino group, alkyl group. , An aryl group, an alkoxy group, an aryloxy group and the like may be substituted.

  The polymer compound in which the phenyl group substituted with the vinyl group of the present invention is bonded to the main chain directly or through an arbitrary linking group has, in detail, one having a group represented by the following general formula 2 in the side chain. preferable.

In the formula, R ₅ , R ₆ and R ₇ may be the same or different and are each a hydrogen atom, halogen atom, carboxyl group, sulfo group, nitro group, cyano group, amide group, amino group, alkyl group. Group, aryl group, alkoxy group, aryloxy group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, arylamino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group An alkyl group and an aryl group constituting these groups are a halogen atom, a carboxyl group, a sulfo group, a nitro group, a cyano group, an amide group, an amino group, an alkyl group, an aryl group, an alkenyl group, a hydroxy group, Alkoxy group, aryloxy group, alkylsulfanyl group, It may be substituted with a reelsulfanyl group, an alkylamino group, an arylamino group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, or the like. Among these groups, those in which R ₅ and R ₆ are hydrogen atoms and R ₇ is a hydrogen atom or a lower alkyl group having 4 or less carbon atoms (for example, a methyl group, an ethyl group, etc.) are particularly preferable.

In the formula, R ₈ is hydrogen atom, halogen atom, carboxyl group, nitro group, cyano group, amide group, amino group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylsulfanyl group, arylsulfanyl group, alkylamino. And a group selected from a group, an arylamino group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group. The alkyl group and aryl group constituting these groups are halogen atom, carboxyl group, sulfo group, nitro group, cyano group, amide group, amino group, alkyl group, aryl group, alkenyl group, alkynyl group, hydroxy group. , Alkoxy groups, aryloxy groups, alkylsulfanyl groups, arylsulfanyl groups, alkylamino groups, arylamino groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, etc. good.

In the formula, L ₁ represents an atom selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, or a polyvalent linking group consisting of an atom group selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. Represent. Specific examples include groups composed of the structural units exemplified below and the heterocyclic groups shown below. These groups may be used alone or in any combination of two or more.

The linking group L ₁ preferably includes a heterocyclic ring. Examples of the heterocyclic ring constituting L ₁ include pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, isoxazole ring, oxazole ring, oxadiazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thiazole Triazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzthiazole ring, benzselenazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline And a nitrogen-containing heterocycle such as a ring and a quinoxaline ring, a furan ring, a thiophene ring, and the like. These heterocycles may have a substituent.

  When the polyvalent linking group described above has a substituent, examples of the substituent include a halogen atom, a carboxyl group, a sulfo group, a nitro group, a cyano group, an amide group, an amino group, an alkyl group, an aryl group, an alkenyl group, and an alkynyl group. Group, hydroxy group, alkoxy group, aryloxy group, alkylsulfanyl group, arylsulfanyl group, alkylamino group, arylamino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, etc. It is done.

In the formula, m ₁ represents an integer of 0 to 4, p ₁ represents an integer of 0 or 1, and q ₁ represents an integer of ₁ to 4.

  The polymer compound having a polymerizable double bond group of the present invention may be a polymer comprising only a repeating unit having a phenyl group in which a vinyl group is substituted on the side chain and a repeating unit having a sulfonic acid group. As long as it does not interfere with the effects of the present invention, it may be a polymer into which another repeating unit is further introduced. Further, it may be a copolymer with another monomer, and such a monomer may be used alone or two or more of them may be used.

  Moreover, the high molecular compound which has a polymerizable double bond group of this invention can introduce | transduce arbitrary substituents into the terminal of a polymer principal chain by using a chain transfer agent. Specifically, linear alkane thiols, particularly linear alkane thiols substituted with silicon atoms bonded to alkoxy groups or halogen atoms, are preferably used because they can be used at the time of polymerization as a chain transfer agent. Can do. Examples of such chain transfer agents include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyldichloromethylsilane, 4 -Mercaptobutyltrimethoxysilane, 4-mercaptobutyldimethoxymethylsilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltrichlorosilane, 4-mercaptobutyldichloromethylsilane, and the like. May be bonded via an oxygen atom by hydrolytic condensation to form a siloxane bond.

  Preferred examples of the polymer compound having a polymerizable double bond group of the present invention are shown below, but the present invention is not limited to these examples. The numbers in the exemplified structural formulas represent the mass% of each repeating unit in the copolymer total composition of 100 mass%.

  The weight average molecular weight of the polymer compound having a polymerizable double bond group of the present invention is preferably in the range of 1,000 to 1,000,000, and more preferably in the range of 50,000 to 600,000. In the present invention, the polymer compound having a polymerizable double bond group may be used alone or in combination of two or more.

  Next, the low molecular weight compound having a polymerizable double bond group used in the present invention will be described. The low molecular compound having a polymerizable double bond group in this case can be preferably used as long as it is a compound that undergoes polymerization by radicals generated by the photodecomposition of the photopolymerizable initiator. Furthermore, when a compound having two or more polymerizable double bond groups in the molecule is used, a crosslinked product is formed as a result of polymerization by radicals. Therefore, a negative photosensitive lithographic printing plate material is used. When constituted, it forms a cross-linked hard image part film, so that it can be used very preferably to give a printing plate excellent in printing durability and ink transferability. Examples of compounds having a polymerizable double bond group that can be used for such purposes include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tetraethylene glycol diacrylate. Polyfunctional acrylic monomers such as trisacryloyloxyethyl isocyanurate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, etc., or acryloyl group, methacryloyl group Polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, etc. are also used in the same way as various oligomers introduced with That.

  The photosensitive layer of the negative photosensitive lithographic printing plate of the present invention preferably contains a compound for sensitizing the above-mentioned photopolymerization initiator. As compounds that increase the sensitivity in the wavelength region of 400 to 430 nm, cyanine dyes, coumarin compounds described in JP-A-7-271284, JP-A-8-29973, etc., JP-A-9-230913, Carbazole compounds described in JP-A No. 2001-42524 and the like, carbomerocyanine dyes described in JP-A-8-262715, JP-A-8-272096, JP-A-9-328505, and the like, JP-A-4-194857, JP-A-6-295061, JP-A-7-84863, JP-A-8-220755, JP-A-9-80750, JP-A-9-236913, etc. Aminobenzylidene ketone dyes, JP-A-4-184344, JP-A-6-301208, The pyromethine dyes described in Kaihei 7-225474, JP-A-7-5585, JP-A-7-281434, JP-A-8-6245, etc., and JP-A-9-80751 Styryl dyes or (thio) pyrylium compounds. Of these, cyanine dyes, coumarin compounds or (thio) pyrylium compounds are preferred.

  As other elements constituting the photosensitive layer of the negative photosensitive lithographic printing plate of the present invention, various colorants are preferably added for the purpose of improving visibility. As a colorant added for such purposes, an aqueous dispersion of a color pigment can be most preferably used. As an example of an aqueous dispersion of such a pigment, any material in which various colored pigments such as black, blue, red, green and yellow are dispersed in water in the presence of various water-soluble dispersants can be used. . In particular, carbon black, phthalocyanine blue, phthalocyanine green, and the like as pigments are particularly preferred because they are readily available and relatively easy to disperse in water. Examples of dispersants that can be used to disperse these pigments in water include water-soluble nonionic surfactants having an oxyethylene group such as polyethylene glycol and polypropylene glycol, polyacrylic acid, and polyvinylpyrrolidone. , Polystyrene-maleic acid half ester copolymer, polystyrene-maleic acid copolymer, and other various water-soluble polymers. Such a dispersant is preferably contained in a range of 5 to 50 parts by mass with respect to 100 parts by mass of the color pigment. Furthermore, when using a color pigment, it is preferable that it is contained in 1-30 mass parts with respect to 100 mass parts of compounds which have a polymerizable double bond.

  The photosensitive layer of the negative photosensitive lithographic printing plate of the present invention preferably contains a silane coupling agent. An excellent printing durability can be obtained when the photosensitive layer contains a silane coupling agent, but in the negative photosensitive lithographic printing plate having the hydrophilic layer of the present invention, stain resistance, anti-glare property, In addition, the printing durability is improved without deteriorating the ink detachability and the like, and therefore, it is particularly preferable.

  The silane coupling agent is not particularly limited as long as the purpose is achieved, and any silane coupling agent can be used. For example, epoxycyclohexylethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxy Silane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane , Vinyltris (3-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimeth Sisilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -amino Propylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane 3-isocyanatopropyltriethoxysilane and the like. Among them, epoxycyclohexylethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltri Particularly preferred are trialkoxysilanes such as ethoxysilane. In addition, a silane coupling agent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the silane coupling agent contained in the photosensitive layer is preferably in the range of 0.2 to 20% by mass, more preferably 0.5%, based on the compound having a polymerizable double bond group contained in the photosensitive layer. It is the range of -10 mass%.

  As another element constituting the photosensitive layer, a polymerization inhibitor is preferably added in order to prevent a curing reaction in a dark place due to thermal polymerization, for long-term storage. Polymerization inhibitors preferably used for such purposes include hydroquinones, catechols, naphthols, cresols and other compounds having various phenolic hydroxyl groups, quinone compounds, 2,2,6,6-tetramethylpiperidine- N-oxyls, N-nitrosophenylhydroxylamine salts and the like are preferably used. In this case, the polymerization inhibitor is preferably added in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition of the present invention.

  Regarding the dry solid content coating amount of the photosensitive layer itself, it is preferably formed with a dry solid content coating amount in the range of 0.3 to 10 g per square meter in dry mass, and more preferably in the range of 0.5 to 3 g. It is extremely preferable for exhibiting good resolution and ensuring printing durability of fine line images and fine dot images, and at the same time, greatly improving ink transportability.

<Protective layer>
In the negative photosensitive lithographic printing plate material of the present invention, a protective layer is preferably further provided on the photosensitive layer. The protective layer prevents exposure of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer to further improve exposure sensitivity in the atmosphere. It has a favorable effect of improving. Furthermore, an effect of preventing the photosensitive layer surface from scratches is also expected. Therefore, the properties desired for such a protective layer are low permeability of low molecular weight compounds such as oxygen and excellent mechanical strength, and further, transmission of light used for exposure is not substantially inhibited. It is desirable that it has excellent adhesiveness and can be easily removed in the development step after exposure.

  Such a device relating to the protective layer has been conventionally devised, and is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729. As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, and polyacrylic are used. Water-soluble polymers such as acids are known, and among these, using polyvinyl alcohol as a main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. There is a preferred range for the coating amount of dry solids when applying such a protective layer, and it is preferable to form a dry solids coating amount in the range of 0.1 to 10 g per square meter on the photosensitive layer. Furthermore, the range of 0.2-2g is preferable. The protective layer is coated and dried on the photosensitive layer using various known coating methods.

  When applying the hydrophilic layer of the lithographic printing plate support of the present invention, the photopolymerizable photosensitive layer provided thereon, the protective layer, or the like, the support is composed of the above-described elements. It is produced by applying and drying a coating liquid of the composition. As the coating method, various known methods can be used, and examples thereof include bar coater coating, slide hopper coating coating, curtain coating, blade coating, air knife coating, roll coating, spin coating, and dip coating. it can.

<Development processing>
The developer used in the development processing may contain a surfactant or an alkali agent as necessary for the purpose of improving the image quality and shortening the development time. When the compound having a polymerizable double bond has an acidic group such as a carboxyl group or a sulfo group, and the acidic group is in the form of a metal salt or an amine salt in the photosensitive layer, it will be described later. It is possible to develop with a developer substantially not containing an alkali agent, that is, a neutral developer having a pH of less than 9. In particular, when the compound having a polymerizable double bond has a neutralized salt of a sulfo group, good developability can be obtained and elution with pure water is possible. In the case where sufficient solubility cannot be obtained even with the sulfo group neutralized salt, an activator can be added to the neutral developer for the purpose of improving developability.

  Nonionic properties such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters as surfactants, alkylbenzene sulfonates, alkylnaphthalene sulfonic acids Anionic surfactants such as salts, alkyl sulfates, alkyl sulfonates, sulfosuccinate esters, amphoteric surfactants such as alkyl betaines, amino acids, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol And water-soluble organic solvents such as diacetone alcohol.

  On the other hand, when the compound having a polymerizable double bond has an acid group that is not neutralized such as a carboxyl group or a sulfo group, the developer preferably contains an alkali agent. Alkaline agents include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, diphosphoric acid Inorganic alkali salts such as sodium, sodium triphosphate, dibasic ammonium phosphate, tribasic ammonium phosphate, sodium borate, potassium borate, ammonium borate, or monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine , Diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, etc. Is, they were added, can be used as an alkaline developing solution by adjusting to pH9 above. In addition, it is preferable to add the activator or the like used as the neutral developer to the alkali developer to improve the developability.

  The development is usually carried out by a known development method such as immersion development, spray development, brush development, ultrasonic development, etc., preferably at a temperature of about 10 to 60 ° C., more preferably about 15 to 45 ° C. for 5 seconds to It takes about 10 minutes. At that time, the protective layer provided as necessary on the photosensitive layer may be removed in advance with water or the like, or may be removed during development.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited by this description. In the following description, “%” and “part” are based on mass unless otherwise specified.

Example 1
<Hydrophilic layer or lithographic printing plate support>
A hydrophilic layer coating solution 1 having the following composition was applied on a polyethylene terephthalate film having a thickness of about 200 μm by a slide hopper coating method. At that time, the moisture application amount was set in advance to be 35 g / m ² . Immediately after coating, the coating film was gelled with cold air of 1 to 5 ° C., and then dried using a dry air set at 50 ° C. After drying, the support for lithographic printing plate was completed by putting it in a thermo-hygrostat adjusted to 40 ° C. and 40% RH and heating for 7 days.

<Hydrophilic layer coating solution 1>
Alkali-treated gelatin 1.2 parts Inorganic filler 1: Titanium dioxide 4.0 parts (TISR1, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size≈0.3 μm, relative refractive index≈2.04)
Inorganic filler 2: 1.6 parts of barium sulfate (B35, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size≈0.3 μm, relative refractive index≈1.23)
Inorganic filler 3: 0.4 parts of aluminum hydroxide (H42, manufactured by Showa Denko KK, average primary particle size ≈ 1.0 μm, relative refractive index ≈ 1.24)
Dispersant (acrylic acid copolymerized metal salt, 10% solution) 1.0 part Surfactant (POE nonylphenyl ether sulfate, 10% solution) 0.4 part Hardener (divinylsulfone, 5% solution) The total amount was 35 parts with 0 parts water.

  Regarding the particle size distribution and distribution frequency of the inorganic filler contained in the hydrophilic layer coating liquid 1, the inorganic fillers 2 and 3 contained in the hydrophilic layer coating liquid 1 are not added, but in the hydrophilic layer coating liquid. In addition, an inorganic filler 1 alone is prepared, and a coating liquid in which the inorganic fillers 2 and 3 are present alone in the hydrophilic layer coating liquid is prepared in the same manner. The particle size distribution and distribution frequency of the filler were measured using a laser diffraction / scattering type particle size distribution measuring device (LA920 manufactured by HORIBA Co., Ltd.), and the particle size distribution of each obtained single dispersion was multiplied by the addition ratio as a coefficient. The particle size distribution and distribution frequency of the hydrophilic layer coating solution 1 were calculated. The results are shown in Table 1.

<Photopolymerizable photosensitive layer>
On the hydrophilic layer obtained above, the following photopolymerizable photosensitive layer coating solution was applied so that the solid content was 1.5 g / m ^2, and dried for 10 minutes in a 75 ° C. drier after coating. did.

<Photopolymerizable photosensitive layer coating solution>
Sulfonic acid type polymer SP-2 (weight average molecular weight 400,000) 1 part Pentaerythritol tetraacrylate 0.5 part 3-acryloxypropyltrimethoxysilane 0.08 part Photopolymerization initiator BC-6 0.1 part Photopolymerization Initiator T-8 0.1 part Sensitizer Following structure 0.05 part Colorant Pigment Blue 15 0.2 part Acetone 5 parts Ethanol 5 parts Tetrahydrofuran 10 parts

<Protective layer>
A coating solution is prepared according to the following protective layer formulation, coated on the photopolymerizable photosensitive layer so that the solid content is 1.5 g / m ^2, and dried for 10 minutes in a 75 ° C. drier after coating. A negative photosensitive lithographic printing plate was obtained.

<Protective layer prescription>
Polyvinyl alcohol PVA-102 (manufactured by Kuraray Co., Ltd.) 1 part Ion-exchanged water 9 parts

<Exposure / Development>
About the negative photosensitive lithographic printing plate obtained above, a test chart image was exposed using a blue-violet semiconductor laser (output 50 mW) emitting at 405 nm as an exposure light source and setting the plate surface exposure energy to 200 μJ / cm ² . Thereafter, the plate was immersed in ion exchange water at 25 ° C. for 15 seconds, and the surface having the photopolymerizable photosensitive layer / protective layer was rubbed and developed with cellulose sponge, and then dried to prepare a printing plate. Using this printing press plate, printing durability, background stain resistance, ink detachment property, and netting resistance were evaluated by the following methods.

<Print durability>
The printing machine uses an offset sheet-fed press Heidelberg QM46, the printing ink is New Champion F gloss ink H manufactured by DIC Corporation, and the dampening liquid is 1% of Astro Mark III manufactured by Nikken Chemical Laboratory. Printing was performed using the diluent. In the plate finishing, a gauge film was used, and the standard 200 μm was set to 300 μm (+100 μm). As an evaluation, the printing paper surface at the start and the printing paper surface at the time of printing 10,000 sheets are compared, and the attenuation factor of the highlight halftone dot portion and the fine defect in the solid portion are 25 times magnifier. Careful observation and judgment were made using the following evaluation criteria. The results are shown in Table 1.
A: Almost no change is observed in the highlight part and the solid part.
○: Slight attenuation (within an attenuation rate of 10% or less) is observed in the highlight portion.
However, no defects are observed in the solid part.
Δ: A clear attenuation (attenuation rate of 10% or more) is observed in the highlight portion.
However, no defects are observed in the solid part.
X: The highlight part is attenuated by 50% or more.
Or abnormalities such as defects are observed in the solid portion.

<Soil resistance>
The printing press uses the Heidelberg QM46 offset sheet-fed press as well as the printing durability. The printing ink uses New Champion F gloss purple S, and the dampening solution uses 1% diluted solution of CombiFIX-XL manufactured by Huber Group. Printing was done. Note that the standard plate finishing was 200 μm. For evaluation of soil resistance, the printing paper surface at the start and the printing paper surface at the time of printing 3,000 sheets were compared and judged using the following evaluation criteria. The results are shown in Table 1.
A: No soiling is observed up to the 3,000th sheet.
A: Soil is recognized between 2,000 and less than 3,000 sheets.
(Triangle | delta): Ground dirt is recognized between 1,000-less than 2,000 sheets.
X: Soil is recognized between 1 and less than 1,000 sheets.

<Ink detachability>
The printing press uses the Heidelberg QM46 offset sheet-fed press as well as the printing durability. The printing ink is Toyo Ink Co., Ltd.'s High Unity Neo-Soy Red LZ, and the dampening solution is made by Nikken Chemical Co., Ltd. Printing was performed using a 1% dilution of Astro Mark III. Note that the standard plate finishing was 200 μm. As for the printing method, printing was performed by first touching the ink foam roller twice on the plate surface before touching the water foam roller on the dry printing plate, and then touching the water foam roller simultaneously with paper feeding. The following criteria were used to evaluate ink detachment from the number of printed sheets required to completely eliminate stains on the printed paper surface. The results are shown in Table 1.
A: Less than 1 to 20 sheets completely eliminates stains on non-image areas.
A: Less than 20 to 50 sheets completely eliminates stains on the non-image area.
(Triangle | delta): The stain | pollution | contamination of a non-image part is eliminated completely by less than 50-100 sheets.
X: 100 or more sheets are required to completely remove non-image area contamination.

<Reticulation resistance>
In order to evaluate the ink detachability, after printing 500 sheets or more, the printer was temporarily stopped and only the blanket was washed. Thereafter, printing was carried out by a method of starting paper feeding after the water foam roller was again touched on the plate surface for 5 or more rotations as usual. The evaluation of the resistance to netting was determined using the following evaluation criteria by observing the 5,000th printed paper surface. The results are shown in Table 1.
A: No entanglement is observed even in shadow portions of 90% or more.
And there is no problem in reproducibility.
○: Slight entanglement is observed at halftone dots of 85% or more and less than 90%,
There is no problem in practical use.
(Triangle | delta): A tangle is recognized by the halftone dot part of 70% or more and less than 85%.
X: Tangle is observed at a halftone dot portion of less than 70%, and a problem is observed in reproducibility.

(Example 2)
A negative photosensitive lithographic printing plate of Example 2 was obtained in the same manner as in Example 1 except that the hydrophilic layer coating liquid 1 used in Example 1 was changed to the following hydrophilic coating liquid 2. The particle size distribution and distribution frequency of the inorganic filler in the hydrophilic layer coating liquid 2 were determined by the same method as in Example 1. Further, the printability of the obtained negative photosensitive lithographic printing plate was also evaluated in the same manner as in Example 1. These results are shown in Table 1.
<Hydrophilic layer coating solution 2>
Alkali-treated gelatin 1.2 parts Inorganic filler 1: Titanium dioxide 4.0 parts (TISR1, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size≈0.3 μm, relative refractive index≈2.04)
Inorganic filler 2: Barium sulfate 1.0 part (B35, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size ≈ 0.3 μm, relative refractive index ≈ 1.23)
Inorganic filler 3: Aluminum hydroxide 1.0 part (H42, Showa Denko K.K., average primary particle size≈1.0 μm, relative refractive index≈1.24)
Dispersant (acrylic acid copolymerized metal salt, 10% solution) 1.0 part Surfactant (POE nonylphenyl ether sulfate, 10% solution) 0.4 part Hardener (divinylsulfone, 5% solution) The total amount was 35 parts with 0 parts water.

(Comparative Example 1)
A negative photosensitive lithographic printing plate of Comparative Example 1 was obtained in the same manner as in Example 1 except that the hydrophilic layer coating solution 1 used in Example 1 was changed to the following hydrophilic coating solution 3. The particle size distribution and distribution frequency of the inorganic filler in the hydrophilic layer coating liquid 3 were determined in the same manner as in Example 1. Further, the printability of the obtained negative photosensitive lithographic printing plate was also evaluated in the same manner as in Example 1. These results are shown in Table 1.
<Hydrophilic layer coating solution 3>
Alkali-treated gelatin 1.2 parts Inorganic filler 1: Titanium dioxide 4.0 parts (TISR1, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size≈0.3 μm, relative refractive index≈2.04)
Inorganic filler 2: 0.4 parts of barium sulfate (B35, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size ≈ 0.3 μm, relative refractive index ≈ 1.23)
Inorganic filler 3: Aluminum hydroxide 1.6 parts (H42, manufactured by Showa Denko KK, average primary particle size ≈ 1.0 μm, relative refractive index ≈ 1.24)
Dispersant (acrylic acid copolymerized metal salt, 10% solution) 1.0 part Surfactant (POE nonylphenyl ether sulfate, 10% solution) 0.4 part Hardener (divinylsulfone, 5% solution) The total amount was 35 parts with 0 parts water.

(Example 3)
A negative photosensitive lithographic printing plate of Example 3 was obtained in the same manner as in Example 1 except that the hydrophilic layer coating liquid 1 used in Example 1 was changed to the following hydrophilic coating liquid 4. Since the composition of the inorganic filler is a single composition, the particle size distribution and distribution frequency of the inorganic filler were obtained directly from the hydrophilic layer coating solution 4. Further, the printability of the obtained negative photosensitive lithographic printing plate was evaluated in the same manner as in Example 1. These results are shown in Table 1.
<Hydrophilic layer coating solution 4>
Alkali-treated gelatin 1.2 parts Inorganic filler 1: Titanium dioxide 6.0 parts (TISR1, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle diameter≈0.3 μm, relative refractive index≈2.04)
Dispersant (acrylic acid copolymerized metal salt, 10% solution) 1.0 part Surfactant (POE nonylphenyl ether sulfate, 10% solution) 0.4 part Hardener (divinylsulfone, 5% solution) The total amount was 35 parts with 0 parts water.

(Comparative Example 2)
A negative photosensitive lithographic printing plate of Comparative Example 2 was obtained in the same manner as in Example 1 except that the hydrophilic layer coating solution 1 used in Example 1 was changed to the following hydrophilic coating solution 5. Since the inorganic filler has a single composition, the particle size distribution and distribution frequency of the inorganic filler were directly determined from the hydrophilic layer coating solution 5. Further, the printability of the obtained negative photosensitive lithographic printing plate was evaluated in the same manner as in Example 1. These results are shown in Table 1.
<Hydrophilic layer coating solution 5>
Alkali-treated gelatin 1.2 parts Inorganic filler 1: Barium sulfate 6.0 parts (B35, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle diameter≈0.3 μm, relative refractive index≈1.23)
Dispersant (acrylic acid copolymerized metal salt, 10% solution) 1.0 part Surfactant (POE nonylphenyl ether sulfate, 10% solution) 0.4 part Hardener (divinylsulfone, 5% solution) The total amount was 35 parts with 0 parts water.

Example 4
A negative photosensitive lithographic printing plate of Example 4 was obtained in the same manner as in Example 1 except that the hydrophilic layer coating liquid 1 used in Example 1 was changed to the following hydrophilic coating liquid 6. The particle size distribution and distribution frequency of the inorganic filler in the hydrophilic layer coating liquid 6 were determined by the same method as in Example 1. Further, the printability of the obtained negative photosensitive lithographic printing plate was also evaluated in the same manner as in Example 1. These results are shown in Table 1.
<Hydrophilic layer coating solution 6>
Alkali-treated gelatin 1.2 parts Inorganic filler 1: Titanium dioxide 4.0 parts (TISR1, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size≈0.3 μm, relative refractive index≈2.04)
Inorganic filler 2: 2.0 parts of barium sulfate (B35, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size≈0.3 μm, relative refractive index≈1.23)
Dispersant (acrylic acid copolymerized metal salt, 10% solution) 1.0 part Surfactant (POE nonylphenyl ether sulfate, 10% solution) 0.4 part Hardener (divinylsulfone, 5% solution) The total amount was 35 parts with 0 parts water.

(Comparative Example 3)
A negative photosensitive lithographic printing plate of Comparative Example 3 was obtained in the same manner as in Example 1 except that the hydrophilic layer coating solution 1 used in Example 1 was changed to the following hydrophilic coating solution 7. The particle size distribution and distribution frequency of the inorganic filler in the hydrophilic layer coating liquid 7 were determined by the same method as in Example 1. Further, the printability of the obtained negative photosensitive lithographic printing plate was also evaluated in the same manner as in Example 1. These results are shown in Table 1.
<Hydrophilic layer coating solution 7>
Alkali-treated gelatin 1.2 parts Inorganic filler 1: Titanium dioxide 2.0 parts (TISR1, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size ≈ 0.3 μm, relative refractive index ≈ 2.04)
Inorganic filler 2: 4.0 parts of barium sulfate (B35, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size≈0.3 μm, relative refractive index≈1.23)
Dispersant (acrylic acid copolymerized metal salt, 10% solution) 1.0 part Surfactant (POE nonylphenyl ether sulfate, 10% solution) 0.4 part Hardener (divinylsulfone, 5% solution) The total amount was 35 parts with 0 parts water.

(Comparative Example 4)
A negative photosensitive lithographic printing plate of Comparative Example 4 was obtained in the same manner as in Example 1 except that the hydrophilic layer coating solution 1 used in Example 1 was changed to the following hydrophilic coating solution 8. The particle size distribution and distribution frequency of the inorganic filler in the hydrophilic layer coating liquid 8 were determined by the same method as in Example 1. Further, the printability of the obtained negative photosensitive lithographic printing plate was also evaluated in the same manner as in Example 1. These results are shown in Table 1.
<Hydrophilic layer coating solution 8>
Alkali-treated gelatin 1.2 parts Inorganic filler 1: Porous silica 2.0 parts (SYLOJET P403, manufactured by GRACE Davison Co., Ltd., average primary particle size≈3 μm, relative refractive index≈1.09)
Inorganic filler 2: 0.2 parts of colloidal silica (Snowtex OXS, manufactured by Nissan Chemical Industries, Ltd., average particle diameter ≈5 nm, relative refractive index ≈1.85)
Inorganic filler 3: Colloidal silica 4.0 parts (Snowtex OL, manufactured by Nissan Chemical Industries, average particle size ≈ 45 nm, relative refractive index ≈ 1.85)
Dispersant (acrylic acid copolymerized metal salt, 10% solution) 1.0 part Surfactant (POE nonylphenyl ether sulfate, 10% solution) 0.4 part Hardener (divinylsulfone, 5% solution) The total amount was 35 parts with 0 parts water.

(Comparative Example 5)
A negative photosensitive lithographic printing plate of Comparative Example 5 was obtained in the same manner as in Example 1 except that the hydrophilic layer coating solution 1 used in Example 1 was changed to the following hydrophilic coating solution 9. The particle size distribution and distribution frequency of the inorganic filler in the hydrophilic layer coating liquid 9 were determined by the same method as in Example 1. Further, the printability of the obtained negative photosensitive lithographic printing plate was also evaluated in the same manner as in Example 1. These results are shown in Table 1.
<Hydrophilic layer coating solution 9>
Alkali-treated gelatin 1.2 parts Inorganic filler 1: Porous silica 4.2 parts (Silicia 435, manufactured by Fuji Silysia Co., Ltd., average primary particle size ≈ 4.1 μm, relative refractive index ≈ 1.09)
Inorganic filler 2: 1.8 parts of colloidal silica (Snowtex S, manufactured by Nissan Chemical Industries, Ltd., average particle size ≈9.5 nm, relative refractive index ≈1.85)
Dispersant (acrylic acid copolymerized metal salt, 10% solution) 1.0 part Surfactant (POE nonylphenyl ether sulfate, 10% solution) 0.4 part Hardener (divinylsulfone, 5% solution) The total amount was 35 parts with 0 parts water.

  As can be seen from Table 1, the present invention provides a lithographic printing plate support and a negative photosensitive lithographic printing plate that are excellent in printing durability and water retention, ink detachment properties, and netting resistance. I understand.

Claims (2)

  A support for a lithographic printing plate having a hydrophilic layer containing an inorganic filler and a hydrophilic binder on a substrate, wherein the particle size distribution peak of the inorganic filler contained in the hydrophilic layer is 0.2 μm or more and 0.6 μm The distribution frequency of the inorganic filler existing in the range of less than 0.6 μm and less than 1.5 μm and in the range of 0.2 μm and less than 0.6 μm is fx, and the range of 0.6 μm to less than 1.5 μm A support for a lithographic printing plate, wherein an fx / fy ratio is 1.5 or more and a distribution frequency fy is 25% or more when the distribution frequency of the inorganic filler present in the substrate is fy.   A negative photosensitive lithographic printing plate having at least a photopolymerizable photosensitive layer on the hydrophilic layer of the lithographic printing plate support according to claim 1.