JP2013130697A - Support for planographic printing plate and photosensitive planographic printing plate of negative type - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a support for planographic printing plate excellent in all of the following features: coating stability, resistance to soil on a base, tangle resistance, and ink separability, and to provide a photosensitive planographic printing plate of a negative type.SOLUTION: The support for the planographic printing plate has on a plastic film substrate a hydrophilic layer containing a hydrophilic binder, inorganic filler, and polyoxyethylene alkyl ether acetate. The photosensitive planographic printing plate of the negative type uses the support.

Description

  The present invention relates to a lithographic printing plate support having a hydrophilic layer on a plastic film substrate. The present invention also relates to a lithographic printing plate material using such a lithographic printing plate support.

  As a lithographic printing plate support, an aluminum plate having a roughened surface such as a PS plate and having an anodized film is widely used. On the other hand, a lithographic printing plate material using a paper or film as a support. Is widely used. A lithographic printing plate material using a flexible substrate such as a plastic film is cheaper and easier to handle than an aluminum support, and in particular uses a CTP (Computer To Plate) method. In the plate making system, it is preferably used because it can be accommodated in an exposure apparatus in a compact manner as a rolled lithographic printing plate material.

  In recent years, CTP has been fully digitized by 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 developer containing a strong alkali agent 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.

  Further, as a hydrophilic layer of a negative photosensitive lithographic printing plate that can be developed with water or the like and can be developed chemically, for example, Japanese Patent Application Laid-Open No. 2008-265297 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2000-2000. No. 158839 (Patent Document 3), JP 2008-233820 A (Patent Document 4), JP 2010-234723 A (Patent Document 5) and the like contain a hydrophilic polymer and an inorganic filler on a support. A hydrophilic layer is disclosed. Japanese Patent Application Laid-Open No. 09-99662 (Patent Document 6) discloses an image acceptance having a three-dimensional network structure formed of inorganic fine particles having an average primary particle diameter of 100 nm or less and a water-soluble resin and having a porosity of 30 to 80%. An offset printing plate substrate provided with a layer is disclosed.

  However, when a hydrophilic layer containing a hydrophilic polymer and an inorganic filler is coated on a plastic film substrate, the coating becomes unstable at the edge of the substrate, and it is difficult to apply uniformly, which is a major problem in the manufacturing process. It was. Further, depending on the printing conditions, a lithographic printing plate satisfying all of the background stain resistance, reticulation resistance, and ink detachability cannot be obtained, and further improvement has been demanded.

JP 2003-215801 A JP 2008-265297 A JP 2000-158839 A JP 2008-233820 A JP 2010-234723 A JP 09-99662 A

  An object of the present invention is to provide a lithographic printing plate support suitable for the production of a lithographic printing plate which is excellent in coating stability, excellent in soil resistance, netting resistance, and ink detachment properties. It is in. In addition, to provide a negative photosensitive lithographic printing plate that is suitable for laser drawing, capable of chemical-free development, and excellent in all of soil resistance, anti-netting property, and ink detachment property. is there.

The present invention has been achieved by the following invention.
1) A lithographic printing plate support having a hydrophilic layer containing at least a hydrophilic binder, an inorganic filler, and a polyoxyethylene alkyl ether acetate on a plastic film substrate.
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, there is provided a lithographic printing plate support suitable for producing a lithographic printing plate having excellent coating stability, excellent ground stain resistance, reticulation resistance, and ink detachment properties. Can do. In addition, it is possible to provide a negative photosensitive lithographic printing plate that is suitable for laser drawing, capable of chemical-free development, and excellent in all of soil resistance, anti-netting property, and ink detachment property. it can.

  The present invention will be described in detail below.

<Hydrophilic layer>
The lithographic printing plate support of the present invention has a hydrophilic layer on a plastic film substrate, and the hydrophilic layer contains at least a hydrophilic binder, an inorganic filler, and polyoxyethylene alkyl ether acetate.

<Polyoxyethylene alkyl ether acetate>
The hydrophilic layer of the lithographic printing plate support of the present invention contains polyoxyethylene alkyl ether acetate as a surfactant in order to improve the coating property and increase the hydrophilicity of the non-image area.

  The alkyl ether of the polyoxyethylene alkyl ether acetate is preferably an alkyl ether having 8 or more carbon atoms, particularly a linear alkyl ether having 8 to 20 carbon atoms. Examples of the salt include sodium salt and potassium salt. Examples of such compounds include Nikko Chemicals Co., Ltd. NIKKOL ECT-3NEX, ECTD-3NEX, ECTD-6NEX, AKYPO-RLM45NV, etc., Daiichi Kogyo Seiyaku Co., Ltd. Neo Haitenol ECL-45, Kao Akipo RLM-45W, Kao Akipo RLM-100W, etc. are commercially available from Kao Corporation, and NJ Corp 2P45-S etc. are available from Shin Nippon Rika Co., Ltd., and these can be obtained and used.

  The amount of polyoxyethylene alkyl ether acetate added is preferably 0.5 to 20% by mass, more preferably 2 to 10% by mass, based on the hydrophilic polymer in the hydrophilic layer.

<Inorganic filler>
Examples of the inorganic filler used in the hydrophilic layer of the lithographic printing plate support of the present invention include calcium carbonate, magnesium carbonate, zinc oxide, titanium dioxide, barium sulfate, aluminum hydroxide, zinc hydroxide, colloidal silica, and pore silica. , Kaolin and the like. Of these, titanium dioxide, barium sulfate, aluminum hydroxide, and colloidal silica are preferable.

  Titanium dioxide 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.

  The colloidal silica used in the present invention may have a spherical shape, and a chain or pearl necklace colloidal silica is also preferably used.

The colloidal silica may be composed of a simple substance of SiO ₂ , but it is also possible to use a silica whose surface is slightly modified with Al ₂ O ₃ or the like in order to change the pH dependence of the dispersibility of silica. Further, an alkali dispersion or an acidic dispersion of colloidal silica can be selected and used depending on the pH of the coating liquid for the hydrophilic layer.

  Examples of the spherical silica include “Snowtex XS”, “Snowtex S”, “Snowtex 20”, “MP-2040”, “MP-1040”, and “Snowtex ZL” manufactured by Nissan Chemical Industries, Ltd. Etc. These colloidal silicas have a pH of 9 or more, but when preparing an acidic coating solution, it is possible to use “Snowtex O”, “Snowtex OL”, etc., which are made by demineralizing Na ions to make them acidic. it can. Examples of the chain silica include “Snowtex UP” manufactured by Nissan Chemical Industries, Ltd., and examples of the necklace-like silica include “Snowtex PS-S” and “Snowtex PS-M”.

  Further, the inorganic filler contained in the hydrophilic layer is present in the range of the particle size distribution of the inorganic filler in the range of 0.2 μm or more and less than 0.6 μm and the 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. More preferably, the distribution frequency fy is 25% or more. The fx / fy ratio is preferably 2.0 or more, and the upper limit of the fx / fy ratio is preferably 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 which is particularly excellent in soil stain resistance and netting 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.

  In order to obtain the particle size distribution of the inorganic filler described above, 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 are combined. It is preferable to use it, and if it is such a combination, the inorganic filler may be further used in combination with three or four kinds. 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.

  Further, in the hydrophilic layer having the above particle size distribution, it is preferable not to use silicon-containing compounds such as colloidal silica, pore silica, and kaolin, and the content of these silicon-containing compounds is reduced to the total inorganic filler in the hydrophilic layer. Is preferably 5% by mass or less, more preferably 3% by mass or less, particularly preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

<Hydrophilic binder>
As the hydrophilic binder used in the hydrophilic layer of the lithographic printing plate support of the present invention, natural products such as starch, seaweed mannan, agar, and algae such as sodium alginate, mannan, pectin, tragacanth gum, Plant mucilage such as karaya gum, xanthine gum, guar bin gum, locust bin gum, gum arabic gum, homopolysaccharides such as dextran, glucan, xanthan gum and levan, heteropolysaccharides such as succinoglucan, pullulan, curdlan and xanthan gum, etc. Examples include microorganism mucilage, glue, protein such as gelatin, casein and collagen, 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, a styrene / crotonic acid copolymer, and a water-soluble polymer described in JP-A No. 2008-265297. 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. When it exceeds 30% by mass, the filler filling density is lowered and sufficient hydrophilicity cannot be imparted, and the soil resistance and the entanglement 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.

<Substrate>
As the plastic film substrate that the lithographic printing plate support of the present invention has, polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polystyrene, polyvinyl acetal, polycarbonate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, A typical example is cellulose nitrate, and examples thereof include paper laminated with various plastics. Among them, various plastic films that are flexible and are less deformed by tension are preferably used. As a preferable plastic film substrate, polyethylene terephthalate, polyethylene naphthalate, paper laminated with plastic is particularly preferably used.

  The surface of these plastic film substrates may be subjected to a surface treatment in order to improve adhesion to a backing layer or the like provided as necessary in addition to the hydrophilic layer. 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 substrate in order to enhance the adhesion to the hydrophilic layer provided on the substrate.

<Crosslinking agent>
The hydrophilic layer of the lithographic printing plate support 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, epoxy compound, divinyl sulfone and the like can be suitably used, but particularly preferred crosslinking when the hydrophilic binder is gelatin. The agent is divinyl sulfone, and a particularly preferable crosslinking agent is an epoxy compound when polyacrylic acid and a copolymer thereof, polymethacrylic acid and a copolymer thereof, polyvinyl alcohol, and the like. The epoxy compound is sold, for example, under the trade name “Denacol” from Nagase ChemteX Corporation and can be easily obtained. 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 a method for 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, hexaarylbiimidazoles, titanocene compounds, thios Examples thereof include 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, ammonium 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, thia 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 the pigment, carbon black, phthalocyanine blue, phthalocyanine green and the like are easily available and can be used.

  The photosensitive layer of the negative photosensitive lithographic printing plate of the present invention preferably contains a silane coupling agent. Although excellent printing durability can be obtained by the photosensitive layer containing a silane coupling agent, in the negative photosensitive lithographic printing plate having the hydrophilic layer of the present invention, anti-staining, reticulation resistance, 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 0.3-3g 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 planographic printing plate of the present invention, the photopolymerizable photosensitive layer provided thereon, the protective layer, etc., the composition comprising the above-described elements on the support It is produced by applying and drying a coating liquid. 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 or ion-exchanged water is possible. When sufficient solubility cannot be obtained even in the case of a salt or a 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
<Support for lithographic printing plate 1>
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 1 for a 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: 0.4 parts of sodium polyoxyethylene tridecyl ether acetate (Nikko Chemicals Co., Ltd. NIKKOL ECTD-3NEX, 10% solution)
Hardener (divinyl sulfone, 5% solution) 4.0 parts The total amount was 35 parts with 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. As a result, the distribution frequency fx of the inorganic filler existing in the range of 0.2 μm or more and less than 0.6 μm is 64.8%, and the distribution frequency fy of the inorganic filler existing in the range of 0.6 μm or more and less than 1.5 μm is It was 30.1% and fx / fy was 2.15.

<Support 2 for planographic printing plate>
Similar to the hydrophilic layer coating solution 1 except that the surfactant in the hydrophilic layer coating solution 1 is changed to a 10% solution of NIKKOL AKYPO-RLM45NV (polyoxyethylene lauryl ether sodium acetate) manufactured by Nikko Chemicals Co., Ltd. Thus, a hydrophilic layer coating solution 2 was produced. Thereafter, a lithographic printing plate support 2 was completed in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 2 was used in place of the hydrophilic layer coating solution 1.

<Support for Lithographic Printing Plate 3>
In the same manner as in the hydrophilic layer coating solution 1, except that the surfactant of the hydrophilic layer coating solution 1 is changed to a 10% solution of AKYPO-OP-80 (octylphenoxy-sodium polyethoxy acetate) manufactured by CHEMY. Layer coating solution 3 was prepared. Thereafter, a lithographic printing plate support 3 was completed in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 3 was used in place of the hydrophilic layer coating solution 1.

<Support for lithographic printing plate 4>
The hydrophilic layer coating solution 1 except that the surfactant in the hydrophilic layer coating solution 1 was changed to a 10% solution of PRISURF A212C (polyoxyethylene tridecyl ether phosphate) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. In the same manner as described above, a hydrophilic layer coating solution 4 was prepared. Thereafter, a lithographic printing plate support 4 was completed in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 4 was used in place of the hydrophilic layer coating solution 1.

<Support for Lithographic Printing Plate 5>
The hydrophilic layer coating solution except that the surfactant in the hydrophilic layer coating solution 1 was changed to a 10% solution of Neo Haitenol S-70 (disodium polyoxyethylene alkylsulfosuccinate) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. In the same manner as Liquid 1, a hydrophilic layer coating liquid 5 was produced. Thereafter, a lithographic printing plate support 5 was completed in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 5 was used in place of the hydrophilic layer coating solution 1.

<Support for Lithographic Printing Plate 6>
The same as the hydrophilic layer coating solution 1 except that the surfactant of the hydrophilic layer coating solution 1 is changed to a 10% solution of NIKKOL TLP-4 (sodium polyoxyethylene lauryl ether phosphate) manufactured by Nikko Chemicals Co., Ltd. Thus, a hydrophilic layer coating solution 6 was produced. Thereafter, a lithographic printing plate support 6 was completed in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 6 was used in place of the hydrophilic layer coating solution 1.

<Lithographic printing plate support 7>
Similar to the hydrophilic layer coating solution 1 except that the surfactant of the hydrophilic layer coating solution 1 is changed to a 10% solution of NIKKOL TDP-8 (tripolyoxyethylene alkyl ether phosphate) manufactured by Nikko Chemicals Co., Ltd. Thus, a hydrophilic layer coating solution 7 was produced. Thereafter, a lithographic printing plate support 7 was completed in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 7 was used in place of the hydrophilic layer coating solution 1.

<Support for Lithographic Printing Plate 8>
The hydrophilic layer coating solution except that the surfactant of the hydrophilic layer coating solution 1 was changed to a 10% solution of Taipol NPS-436 (sodium polyoxyethylene nonylphenyl ether sulfate) manufactured by Taiko Oil Chemical Co., Ltd. In the same manner as in Example 1, a hydrophilic layer coating solution 8 was prepared. Thereafter, a lithographic printing plate support 8 was completed in the same manner as the lithographic printing plate support 1 except that the hydrophilic layer coating solution 8 was used in place of the hydrophilic layer coating solution 1.

<Coating stability>
The coated surface of the hydrophilic layer of the lithographic printing plate support obtained above was visually observed and judged using the following evaluation criteria. The results are shown in Table 1.
◎: There is no non-uniform application part at both ends of application ○: There is a non-uniform application part with a width of 5 mm or more and less than 15 mm at both ends △: There is a non-uniform application part with a width of 15 mm or more and less than 30 mm at both ends With uniform application part

<Photopolymerizable photosensitive layer>
On the hydrophilic layers of the lithographic printing plate supports 1 to 8 obtained above, the following photopolymerizable photosensitive layer coating solution was applied so that the solid content was 1.5 g / m ^2. Dried for 10 minutes in a dryer at 0 ° C.

<Photopolymerizable photosensitive layer coating solution>
Sulfonic acid type polymer SP-2 (weight average molecular weight 400,000) 1.0 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 5.0 part Ethanol 5.0 part Tetrahydrofuran 10.0 part

<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. Negative photosensitive lithographic printing plates 1 to 8 were obtained.

<Protective layer prescription>
Polyvinyl alcohol PVA-102 (manufactured by Kuraray Co., Ltd.) 1.0 part Ion exchange water 9.0 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.

<Soil resistance>
The printing machine was an offset sheet-fed press Heidelberg QM46, and printing was performed using New Champion F Gloss Purple S as the printing ink and 1% diluted solution of CombiFIX-XL manufactured by Huber Group as the dampening liquid. . Note that the standard plate finishing was 200 μm. As the background stain resistance evaluation, the printing paper surface from the start to the 3,000th printing was determined 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 machine uses an offset sheet-fed press Heidelberg QM46, the printing ink is Toyo Ink Co., Ltd.'s High Unity Neo Soy Red LZ, and the dampening liquid is Nitro Chemical Laboratory Co., Ltd. Astro Mark III. Printing was performed using a 1% diluted solution. Note that the standard plate finishing was 200 μm. Regarding 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. For evaluation of the resistance to netting, the respective printing paper surfaces of the 2,000th sheet and the 5,000th sheet were observed and judged using the following evaluation criteria. 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.

  As can be seen from Table 1, according to the present invention, the lithographic printing plate support and the negative photosensitive lithographic plate, which are excellent in coating stability and excellent in all of soil resistance, reticulation resistance and ink detachment properties. It can be seen that a printing plate can be obtained.

(Example 2)
<Lithographic printing plate support 9>
On a polyethylene terephthalate film having a thickness of about 200 μm, a hydrophilic layer coating solution 9 having the following composition was applied 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 application, the coating film was thickened with cold air of 1 to 5 ° C., and thereafter dried using a dry air set at 50 ° C. After drying, the support 9 for a 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 9>
Water-soluble polymer (polyacrylamide / polyacrylic acid copolymer) 1.0 part Cross-linking agent (Nagase Chemtex Co., Ltd. Denacol EX-810) 0.2 part Colloidal silica 10.0 parts (Nissan Chemical Co., Ltd.) ) Snowtex PS-M, 20% solution)
Titanium oxide (SR-1 manufactured by Sakai Chemical Industry Co., Ltd.) 3.0 parts Surfactant: 0.4 parts of sodium polyoxyethylene tridecyl ether acetate (Nikko Chemicals Corporation NIKKOL ECTD-3NEX, 10% solution)
Ethanol 5.0 parts The pH was adjusted to 7.0 with 1N sodium hydroxide and adjusted to 48 parts by mass with water.

<Support for Lithographic Printing Plate 10>
Similar to the hydrophilic layer coating solution 9 except that the surfactant of the hydrophilic layer coating solution 9 is changed to a 10% solution of NIKKOL AKYPO-RLM45NV (sodium polyoxyethylene lauryl ether acetate) manufactured by Nikko Chemicals Co., Ltd. Thus, a hydrophilic layer coating solution 10 was produced. Thereafter, a lithographic printing plate support 10 was completed in the same manner as the lithographic printing plate support 9 except that the hydrophilic layer coating solution 10 was used in place of the hydrophilic layer coating solution 9.

<Support 11 for lithographic printing plate>
In the same manner as the hydrophilic layer coating solution 9, except that the surfactant of the hydrophilic layer coating solution 9 is changed to a 10% solution of AKYPO-OP-80 (octylphenoxy-sodium polyethoxy acetate) manufactured by CHEMY. A layer coating solution 11 was prepared. Thereafter, a lithographic printing plate support 11 was completed in the same manner as the lithographic printing plate support 9 except that the hydrophilic layer coating solution 11 was used in place of the hydrophilic layer coating solution 9.

<Support for lithographic printing plate 12>
The hydrophilic layer coating solution 9 except that the surfactant in the hydrophilic layer coating solution 9 was changed to a 10% solution of SURFsurf A212C (polyoxyethylene tridecyl ether phosphate) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. In the same manner as described above, a hydrophilic layer coating solution 12 was prepared. Thereafter, a lithographic printing plate support 12 was completed in the same manner as the lithographic printing plate support 9 except that the hydrophilic layer coating solution 12 was used in place of the hydrophilic layer coating solution 9.

<Support for lithographic printing plate 13>
The hydrophilic layer coating solution except that the surfactant of the hydrophilic layer coating solution 9 was changed to a 10% solution of Neo Haitenol S-70 (disodium polyoxyethylene alkylsulfosuccinate) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. In the same manner as Liquid 9, a hydrophilic layer coating liquid 13 was produced. Thereafter, the lithographic printing plate support 13 was completed in the same manner as the lithographic printing plate support 9 except that the hydrophilic layer coating solution 13 was used in place of the hydrophilic layer coating solution 9.

<Support for Lithographic Printing Plate 14>
Similar to the hydrophilic layer coating solution 9 except that the surfactant of the hydrophilic layer coating solution 9 is changed to a 10% solution of NIKKOL TLP-4 (sodium polyoxyethylene lauryl ether phosphate) manufactured by Nikko Chemicals Co., Ltd. Thus, a hydrophilic layer coating solution 14 was produced. Thereafter, a lithographic printing plate support 14 was completed in the same manner as the lithographic printing plate support 9 except that the hydrophilic layer coating solution 14 was used in place of the hydrophilic layer coating solution 9.

<Support for lithographic printing plate 15>
Similar to the hydrophilic layer coating solution 9 except that the surfactant of the hydrophilic layer coating solution 9 is changed to a 10% solution of NIKKOL TDP-8 (tripolyoxyethylene alkyl ether phosphate) manufactured by Nikko Chemicals Co., Ltd. Thus, a hydrophilic layer coating solution 15 was produced. Thereafter, a lithographic printing plate support 15 was completed in the same manner as the lithographic printing plate support 9 except that the hydrophilic layer coating solution 15 was used in place of the hydrophilic layer coating solution 9.

<Support for lithographic printing plate 16>
The hydrophilic layer coating solution 9 except that the surfactant of the hydrophilic layer coating solution 9 was changed to a 10% solution of Taipol NPS-436 (sodium polyoxyethylene nonylphenyl ether sulfate) manufactured by Taiko Oil Chemical Co., Ltd. In the same manner as in No. 9, a hydrophilic layer coating solution 16 was produced. Thereafter, a lithographic printing plate support 16 was completed in the same manner as the lithographic printing plate support 9 except that the hydrophilic layer coating solution 16 was used in place of the hydrophilic layer coating solution 9.

<Coating stability>
The coated surfaces of the hydrophilic layers of the lithographic printing plate supports 9 to 16 obtained above were observed visually, and the coating stability was determined in the same manner as the lithographic printing plate supports 1 to 8. The results are shown in Table 2.

On the hydrophilic layers of the lithographic printing plate supports 9 to 16 obtained above, the above-mentioned photopolymerizable photosensitive layer coating solution is applied so that the solid content is 1.5 g / m ^2. It dried for 10 minutes in a 75 degreeC dryer. Thereafter, a coating solution is prepared according to the above-mentioned protective layer formulation, and coated on the photopolymerizable photosensitive layer so that the solid content is 1.5 g / m ^2. Drying was performed for a minute to obtain negative photosensitive lithographic printing plates 9-16.

  With respect to the negative photosensitive lithographic printing plates 9 to 16 thus obtained, in the same manner as the above-described negative photosensitive lithographic printing plates 1 to 8, the stain resistance, the netting resistance, and the ink detachment. Sex was judged. The results are shown in Table 2.

  As can be seen from Table 2, according to the present invention, the lithographic printing plate support and the negative photosensitive lithographic plate, which are excellent in coating stability, excellent in soil resistance, tie-off resistance, and ink detachment properties. It can be seen that a printing plate can be obtained.

Claims (2)

  A support for a lithographic printing plate comprising a hydrophilic layer containing at least a hydrophilic binder, an inorganic filler, and a polyoxyethylene alkyl ether acetate on a plastic film substrate.   A negative photosensitive lithographic printing plate comprising at least a photopolymerizable photosensitive layer on the hydrophilic layer of the lithographic printing plate support according to claim 1.