WO2019151447A1 - On-press development type lithographic printing plate precursor, method for fabricating lithographic printing plate, on-press development type lithographic printing plate dummy plate, and printing method - Google Patents

On-press development type lithographic printing plate precursor, method for fabricating lithographic printing plate, on-press development type lithographic printing plate dummy plate, and printing method Download PDF

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Publication number
WO2019151447A1
WO2019151447A1 PCT/JP2019/003499 JP2019003499W WO2019151447A1 WO 2019151447 A1 WO2019151447 A1 WO 2019151447A1 JP 2019003499 W JP2019003499 W JP 2019003499W WO 2019151447 A1 WO2019151447 A1 WO 2019151447A1
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Prior art keywords
printing plate
lithographic printing
compound
plate precursor
development type
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PCT/JP2019/003499
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French (fr)
Japanese (ja)
Inventor
優介 難波
彬 阪口
修知 嶋中
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to CN201980010097.5A priority Critical patent/CN111655504B/en
Priority to JP2019569586A priority patent/JP7055821B2/en
Publication of WO2019151447A1 publication Critical patent/WO2019151447A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • B41N1/14—Lithographic printing foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/03—Chemical or electrical pretreatment
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

Definitions

  • the present invention relates to an on-press development type lithographic printing plate precursor, a lithographic printing plate preparation method, an on-press development type lithographic printing plate dummy plate, and a printing method.
  • a lithographic printing plate is composed of an oleophilic image portion that receives ink during the printing process and a hydrophilic non-image portion that receives dampening water.
  • Lithographic printing utilizes the property that water and oil-based ink repel each other, so that the oleophilic image area of the lithographic printing plate is dampened with the ink receiving area and the hydrophilic non-image area is dampened with the water receiving area (ink non-receiving area). ), A difference in ink adhesion is caused on the surface of the lithographic printing plate, the ink is applied only to the image area, and then the ink is transferred to a printing medium such as paper for printing.
  • image exposure is carried out by CTP (computer to plate) technology. That is, image exposure is performed by scanning exposure or the like directly on a lithographic printing plate precursor using a laser or a laser diode without using a lith film.
  • CTP computer to plate
  • On-press development is a method in which the lithographic printing plate precursor is subjected to image exposure and then subjected to the conventional wet development treatment, and is directly attached to the printing press, and the non-image portion of the image recording layer is removed at the initial stage of the normal printing process. is there.
  • Patent Document 1 discloses that hydrophilicity is provided on the image recording layer side plate surface at the ends of two opposing side surfaces of a lithographic printing plate precursor having a support and an image recording layer.
  • hydrophilic component contained in the region A of the image recording layer side plate surface up to 3 mm from the end of the two side surfaces facing each other of the lithographic printing plate precursor.
  • a laminate of a lithographic printing plate precursor in which the content per unit area is 10 mg / m 2 or more higher than the content per unit area of the hydrophilizing component in the region other than the region A has been proposed.
  • the water-soluble compound in the end region A is applied by means such as applying a coating solution containing the hydrophilic component. It is characterized in that the content is increased by 10 mg / m 2 or more compared to the content of the hydrophilic component in the region other than the end region A.
  • a hydrophilic treatment such as applying a coating liquid containing a hydrophilic component is applied to the edge region of the lithographic printing plate precursor, the image forming property is lowered in the edge region subjected to the hydrophilic treatment. Was found to occur.
  • the problem to be solved by the present invention is an on-press development type lithographic printing plate that exhibits good edge stain resistance even after long-term storage without deteriorating the properties such as image forming properties and on-press developability at the edges. It is to provide a method for preparing a lithographic printing plate using an original plate and an on-press development type lithographic printing plate precursor. Further, the problem to be solved by the present invention is an on-press development type lithographic printing plate precursor dummy plate that exhibits good edge stain resistance even after long-term storage without degrading on-press developability and other properties, and It is to provide a printing method.
  • An on-press development type lithographic plate having a layer containing a compound having support adsorptivity on the surface, and the content of the compound being substantially the same in the plane of the layer containing the compound having support adsorbing property A printing plate master.
  • n represents an integer of 2 to 10
  • R1, R2, and R3 each independently represent a hydrogen atom, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an alkyl group, or an alkylene oxide group.
  • n represents an integer of 2 to 10
  • R1, R2, and R3 each independently represent a hydrogen atom, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an alkyl group, or an alkylene oxide group.
  • (7) The on-press development type lithographic printing plate precursor as described in any one of (1) to (6), wherein the compound is phosphoric acid, polyphosphoric acid, phosphonic acid, phosphinic acid or a salt thereof.
  • the on-press development type lithographic printing plate precursor as described in any one of (1) to (7), wherein the content of the compound is 20 to 150 mg / m 2 .
  • the polymer particle is a polymer particle including a monomer unit derived from a styrene compound and / or a monomer unit derived from a (meth) acrylonitrile compound. Original edition.
  • the image recording layer contains a polymerization initiator, an infrared absorber and a polymerizable compound.
  • the on-press development type lithographic printing plate precursor according to any one of (1) to (14) is selected from a step of image exposure with an infrared laser, and a printing ink and a fountain solution on the printing press. And a step of removing an unexposed portion of the image recording layer by at least one.
  • a printing method comprising the on-press development of the on-press development type lithographic printing plate dummy plate according to (16) and the on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support.
  • an on-press development type lithographic printing plate precursor exhibiting good edge stain resistance even after long-term storage without deteriorating properties such as image forming property and on-press developability at the end, and machine A method for preparing a lithographic printing plate using the upper development type lithographic printing plate precursor can be provided.
  • an on-press development type lithographic printing plate precursor dummy plate and a printing method exhibiting good edge stain resistance even after long-term storage without deteriorating on-press developability and other characteristics are provided. can do.
  • R represents an alkyl group, an aryl group or a heterocyclic group
  • R is an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted group” Represents a heterocyclic group or a substituted heterocyclic group.
  • (meth) acrylate means “at least one of acrylate and methacrylate”. The same applies to “(meth) acryloyl group”, “(meth) acrylic acid”, “(meth) acrylic resin” and the like.
  • the on-press development type lithographic printing plate precursor according to the present invention has at least an aluminum support having an anodized film and an image recording layer, has a sagging shape at the end of the lithographic printing plate precursor,
  • the aluminum plate used for the aluminum support is made of a dimensionally stable aluminum-based metal, that is, aluminum or an aluminum alloy. It is preferably selected from a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements.
  • Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. Content of the different element in an alloy is 10 mass% or less.
  • a pure aluminum plate is suitable, but since completely pure aluminum is difficult to manufacture in terms of smelting technology, an alloy plate containing a slightly different element may be used.
  • the composition of the aluminum plate used for the aluminum support is not specified, and conventionally known aluminum plates such as JIS A 1050, JIS A 1100, JIS A 3103, and JIS A 3005 can be used as appropriate. I can do it.
  • the thickness of the aluminum plate is preferably about 0.1 to 0.6 mm.
  • An anodized film means an anodized aluminum film that is formed on the surface of an aluminum plate by an anodizing treatment and that is substantially perpendicular to the surface of the film and has extremely fine pores (also referred to as micropores) that are uniformly distributed. .
  • the micropores extend in the thickness direction from the surface of the anodized film.
  • the method for producing the aluminum support is not particularly limited.
  • a step of roughening the aluminum plate (roughening step), a step of anodizing the roughened aluminum plate (anodizing step), Examples include a method including a step (pore wide treatment step) in which an aluminum plate having an anodized film obtained in the anodizing treatment step is brought into contact with an acid aqueous solution or an alkaline aqueous solution to increase the diameter of micropores in the anodized film. .
  • the roughening treatment step is a step of performing a roughening treatment including an electrochemical roughening treatment on the surface of the aluminum plate.
  • the roughening treatment step is preferably performed before the anodizing step described later, but may not be performed if the surface of the aluminum plate already has a preferable surface shape.
  • the surface roughening treatment may be performed only by electrochemical surface roughening treatment, but may be performed by combining electrochemical surface roughening treatment with mechanical surface roughening treatment and / or chemical surface roughening treatment. Also good. When the mechanical surface roughening treatment and the electrochemical surface roughening treatment are combined, it is preferable to perform the electrochemical surface roughening treatment after the mechanical surface roughening treatment.
  • the electrochemical surface roughening treatment is preferably performed in an aqueous solution of nitric acid or hydrochloric acid.
  • the mechanical surface roughening treatment is generally performed for the purpose of setting the surface of the aluminum plate to a surface roughness Ra: 0.35 to 1.0 ⁇ m.
  • Various conditions for the mechanical surface-roughening treatment are not particularly limited, and for example, they can be applied according to the method described in JP-B-50-40047.
  • the mechanical surface roughening treatment can be performed by brush grain processing using a pumiston suspension or can be performed by a transfer method.
  • the chemical surface roughening treatment is not particularly limited, and can be performed according to a known method.
  • the following chemical etching treatment is preferably performed.
  • the chemical etching process performed after the mechanical roughening process smoothes the uneven edges of the surface of the aluminum plate, prevents ink from being caught during printing, and improves the stain resistance of the lithographic printing plate At the same time, it is performed to remove unnecessary materials such as abrasive particles remaining on the surface.
  • acid etching or alkali etching is known, but as a method that is particularly excellent in terms of etching efficiency, chemical etching treatment using an alkaline solution (hereinafter also referred to as “alkali etching treatment”). ).
  • the alkaline agent used in the alkaline solution is not particularly limited, and preferred examples include caustic soda, caustic potash, sodium metasilicate, sodium carbonate, sodium aluminate, and sodium gluconate. Further, the alkaline agent may contain aluminum ions.
  • the concentration of the alkaline solution is preferably 0.01% by mass or more, more preferably 3% by mass or more, more preferably 30% by mass or less, and more preferably 25% by mass or less. preferable.
  • the temperature of the alkaline solution is preferably room temperature or higher, more preferably 30 ° C. or higher, preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
  • the etching amount is preferably 0.1 g / m 2 or more, more preferably 1 g / m 2 or more, more preferably 20 g / m 2 or less, and 10 g / m 2 or less. Is more preferable.
  • the treatment time is preferably 2 seconds to 5 minutes corresponding to the etching amount, and more preferably 2 to 10 seconds from the viewpoint of improving productivity.
  • a chemical etching process (hereinafter also referred to as “desmut process”) is performed using a low-temperature acidic solution in order to remove products generated by the alkali etching process. It is preferable to apply.
  • the acid used for an acidic solution is not specifically limited, For example, a sulfuric acid, nitric acid, and hydrochloric acid are mentioned.
  • the concentration of the acidic solution is preferably 1 to 50% by mass.
  • the temperature of the acidic solution is preferably 20 to 80 ° C. When the concentration and temperature of the acidic solution are within this range, the spot-like stain resistance of the lithographic printing plate using the aluminum support is further improved.
  • the above roughening treatment is a treatment in which an electrochemical roughening treatment is performed after a mechanical roughening treatment and a chemical etching treatment if desired, but the electrochemical roughening treatment is performed without performing the mechanical roughening treatment.
  • the chemical etching treatment can be performed using an alkaline aqueous solution such as caustic soda before the electrochemical roughening treatment. Thereby, impurities existing in the vicinity of the surface of the aluminum plate can be removed.
  • the electrochemical roughening treatment is suitable for making a lithographic printing plate having excellent printability because it is easy to impart fine irregularities (pits) to the surface of the aluminum plate.
  • the electrochemical surface roughening treatment is performed using direct current or alternating current in an aqueous solution mainly composed of nitric acid or hydrochloric acid.
  • the following chemical etching treatment after the electrochemical surface roughening treatment.
  • Smut and intermetallic compounds exist on the surface of the aluminum plate after the electrochemical roughening treatment.
  • the chemical etching process performed after the electrochemical surface roughening process it is preferable to first perform a chemical etching process (alkali etching process) using an alkaline solution in order to efficiently remove smut.
  • the treatment temperature is preferably 20 to 80 ° C.
  • the treatment time is preferably 1 to 60 seconds.
  • a chemical etching treatment using an alkaline solution is performed, and then a chemical etching treatment (desmut treatment) is performed using a low-temperature acidic solution in order to remove the resulting products. Is preferred. Even when the alkali etching treatment is not performed after the electrochemical surface roughening treatment, it is preferable to perform a desmut treatment in order to efficiently remove the smut.
  • Any of the above chemical etching processes can be performed by a dipping method, a shower method, a coating method, or the like, and is not particularly limited.
  • an aluminum oxide film having micropores extending in the depth direction (thickness direction) is formed on the surface of the aluminum plate by anodizing the aluminum plate that has been subjected to the roughening treatment. It is a process.
  • an aluminum anodic oxide film having micropores is formed on the surface of the aluminum plate.
  • the anodizing treatment can be performed by a method conventionally used in this field, but manufacturing conditions are appropriately set so that the micropores can be finally formed.
  • the average diameter (average opening diameter) of the micropores formed in the anodizing treatment step is usually about 4 to 14 nm, preferably 5 to 10 nm. Within the above range, micropores having a predetermined shape can be easily formed, and the performance of the obtained lithographic printing plate precursor and lithographic printing plate is further improved.
  • the depth of the micropore is usually about 10 nm or more and less than 100 nm, preferably 20 to 60 nm. Within the above range, micropores having a predetermined shape can be easily formed, and the performance of the obtained lithographic printing plate precursor and lithographic printing plate is further improved.
  • the pore density of the micropores is not particularly limited, but the pore density is preferably 50 to 4000 / ⁇ m 2 , more preferably 100 to 3000 / ⁇ m 2 . Within the above range, the resulting lithographic printing plate is excellent in printing durability and neglectability and on-press developability of the lithographic printing plate precursor.
  • an aqueous solution of sulfuric acid, phosphoric acid, oxalic acid or the like can be mainly used as an electrolytic bath.
  • chromic acid, sulfamic acid, benzenesulfonic acid, etc., or an aqueous solution or a non-aqueous solution combining two or more of these may be used.
  • direct current or alternating current is passed through the aluminum plate in the electrolytic bath, an anodized film can be formed on the surface of the aluminum plate.
  • the electrolytic bath may contain aluminum ions.
  • the content of aluminum ions is not particularly limited, but is preferably 1 to 10 g / L.
  • the conditions of the anodizing treatment are appropriately set depending on the electrolytic solution used.
  • the concentration of the electrolytic solution is 1 to 80% by mass (preferably 5 to 20% by mass)
  • the liquid temperature is 5 to 70 ° C. ( Preferably 10 to 60 ° C.)
  • current density 0.5 to 60 A / dm 2 (preferably 5 to 50 A / dm 2 )
  • voltage 1 to 100 V preferably 5 to 50 V
  • electrolysis time 1 to 100 seconds preferably The range of 5 to 60 seconds is appropriate.
  • the pore wide treatment step is a treatment (pore diameter enlargement treatment) for enlarging the diameter (pore diameter) of the micropores present in the anodized film formed by the anodization treatment step.
  • pore wide treatment a treatment for enlarging the diameter (pore diameter) of the micropores present in the anodized film formed by the anodization treatment step.
  • the average diameter of the micropores after the pore wide treatment is suitably more than 10 nm and not more than 100 nm.
  • the average diameter of the micropores after pore-wide processing is preferably 15 to 60 nm, more preferably 20 to 50 nm, and still more preferably 24 to 40 nm.
  • the pore-wide treatment is performed by bringing the aluminum plate obtained by the anodizing treatment step into contact with an acid aqueous solution or an alkali aqueous solution.
  • the method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred.
  • an alkaline aqueous solution When an alkaline aqueous solution is used in the pore-wide treatment step, it is preferable to use at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide, and lithium hydroxide.
  • the concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass.
  • the aluminum plate After adjusting the pH of the alkaline aqueous solution to 11 to 13, the aluminum plate is placed in the alkaline aqueous solution for 1 to 300 seconds (preferably 1 to 50 seconds) under the condition of 10 to 70 ° C. (preferably 20 to 50 ° C.). It is appropriate to make it contact.
  • the alkali treatment liquid may contain a metal salt of a polyvalent weak acid such as carbonate, borate or phosphate.
  • an aqueous acid solution When an aqueous acid solution is used in the pore-wide treatment step, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or a mixture thereof.
  • the concentration of the acid aqueous solution is preferably 1 to 80% by mass, more preferably 5 to 50% by mass. It is appropriate that the aluminum plate is brought into contact with the acid aqueous solution for 1 to 300 seconds (preferably 1 to 150 seconds) under the condition that the aqueous solution of the acid aqueous solution is 5 to 70 ° C. (preferably 10 to 60 ° C.).
  • the alkaline aqueous solution or the acidic aqueous solution may contain aluminum ions.
  • the content of aluminum ions is not particularly limited, but is preferably 1 to 10 g / L.
  • the pore-wide treatment step is performed only in a partial region (end portion) on the support. As described above, the pore-wide treatment is performed not on the entire surface of the support but on a part of the support, thereby preventing the scratch resistance from being lowered.
  • Pore wide treatment can be performed only in certain areas as die coating method, dip coating method, air knife coating method, curtain coating method, roller coating method, wire barcode method, gravure coating method, slide coating method, inkjet coating method.
  • known methods such as a method, a dispenser coating method, and a spray method can be used, an inkjet coating method or a dispenser coating is necessary because an acid aqueous solution or an alkaline aqueous solution needs to be applied to a part of the support.
  • the method is preferred.
  • coat corresponds to 2 sides which the lithographic printing original plate after a cutting
  • the acid aqueous solution or the alkaline aqueous solution may be applied from the end of the support, may be applied to a position other than the end of the support, or a combination of these application positions.
  • coat to the band shape with a fixed width
  • a preferable coating width is 1 to 50 mm. It is preferable that the coating region having a coating width is cut and the coating region is present within 1 cm from the end after cutting. The cutting may be performed at one place on the application area or at two places on the same application area.
  • the manufacturing method of an aluminum support body may have the hydrophilic treatment process which performs a hydrophilic treatment after the said pore wide process process.
  • the hydrophilization treatment a known method disclosed in paragraphs 0109 to 0114 of JP-A-2005-254638 can be used.
  • Hydrophilic treatment is performed by a method of immersing in an aqueous solution of an alkali metal silicate such as sodium silicate or potassium silicate, or a method of forming a hydrophilic undercoat layer by applying a hydrophilic vinyl polymer or a hydrophilic compound. It is preferred to do so.
  • an alkali metal silicate such as sodium silicate or potassium silicate
  • Hydrophilization treatment with an aqueous solution of an alkali metal silicate such as sodium silicate and potassium silicate is described in US Pat. No. 2,714,066 and US Pat. No. 3,181,461. It can be performed according to methods and procedures.
  • the aluminum support may be formed on the surface opposite to the image recording layer by an organic polymer compound described in JP-A-5-45885 or an alkoxy compound of silicon described in JP-A-6-35174. You may have the backcoat layer containing these.
  • the image recording layer constituting the on-press development type lithographic printing plate precursor will be described.
  • the image recording layer is a layer having a property that the non-image portion is removed on the printing machine by at least one selected from printing ink and fountain solution.
  • As the image recording layer a known image recording layer constituting the on-press development type lithographic printing plate precursor can be used.
  • the image recording layer preferably contains polymer particles.
  • the polymer particles contribute to improvement of on-press developability.
  • the polymer particles are preferably polymer particles that can convert the image recording layer to hydrophobic when heat is applied.
  • the polymer particles are at least one selected from hydrophobic thermoplastic polymer particles, heat-reactive polymer particles, polymer particles having a polymerizable group, microcapsules containing a hydrophobic compound, and microgel (crosslinked polymer particles). It is preferable that
  • Hydrophobic thermoplastic polymer particles include Research Disclosure No. 1 of January 1992. 33303, hydrophobic thermoplastic polymer particles described in JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250 and European Patent No. 931647 are suitable. It is mentioned in.
  • polymer constituting the hydrophobic thermoplastic polymer particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, polyalkylene structure And homopolymers or copolymers of monomers such as acrylates or methacrylates, or mixtures thereof.
  • polystyrene, a copolymer containing styrene and acrylonitrile, and polymethyl methacrylate are used.
  • the average particle size of the hydrophobic thermoplastic polymer particles is preferably 0.01 to 2.0 ⁇ m.
  • thermally reactive polymer particles examples include polymer particles having a thermally reactive group.
  • the polymer particles having a thermoreactive group form a hydrophobized region by crosslinking by a thermal reaction and a functional group change at that time.
  • thermoreactive group in the polymer particles having a thermoreactive group may be any functional group that performs any reaction as long as a chemical bond is formed, and is preferably a polymerizable group.
  • examples include ethylenically unsaturated groups that undergo radical polymerization reactions (eg, acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, etc.), cationic polymerizable groups (eg, vinyl groups, vinyloxy groups, epoxy groups, oxetanyl groups).
  • Etc. isocyanato group that performs an addition reaction or a block thereof, an epoxy group, a vinyloxy group, and a functional group having an active hydrogen atom that is a reaction partner thereof (for example, an amino group, a hydroxy group, a carboxy group, etc.), a condensation reaction Preferred examples include a carboxyl group to be performed and a hydroxy group or amino group which is a reaction partner, an acid anhydride which performs a ring-opening addition reaction, and an amino group or hydroxy group which is a reaction partner.
  • microcapsule examples include those in which all or part of the constituent components of the image recording layer are encapsulated in the microcapsule as described in JP-A Nos. 2001-277740 and 2001-277742.
  • the constituent components of the image recording layer can also be contained outside the microcapsules.
  • the image recording layer containing microcapsules is preferably a mode in which hydrophobic constituent components are encapsulated in microcapsules and hydrophilic constituent components are contained outside the microcapsules.
  • the microgel can contain a part of the constituent components of the image recording layer in at least one of the inside and the surface thereof.
  • a reactive microgel is formed by having a radical polymerizable group on the surface thereof is preferable from the viewpoint of image forming sensitivity and printing durability.
  • the average particle size of the microcapsules or microgel is preferably 0.01 to 3.0 ⁇ m, more preferably 0.05 to 2.0 ⁇ m, and particularly preferably 0.10 to 1.0 ⁇ m. Within this range, good resolution and stability over time can be obtained.
  • the polymer particles are preferably polymer particles containing a monomer unit derived from a styrene compound and / or a monomer unit derived from a (meth) acrylonitrile compound from the viewpoint of contribution to on-press developability. Also preferred are polymer particles further comprising monomer units derived from poly (ethylene glycol) alkyl ether methacrylate compounds.
  • the polymer particles may be used alone or in combination of two or more.
  • the content of polymer particles is preferably 5 to 90% by mass, more preferably 5 to 80% by mass, and still more preferably 10 to 75% by mass in the total solid content of the image recording layer.
  • the image recording layer preferably contains a polymerization initiator, an infrared absorber, and a polymerizable compound.
  • the polymerization initiator is a compound that generates polymerization initiation species such as radicals and cations by energy of light, heat, or both, and is a known thermal polymerization initiator, a compound having a bond with a small bond dissociation energy, a photopolymerization initiator. It can select suitably from etc. and can be used.
  • a polymerization initiator an infrared photosensitive polymerization initiator is preferable.
  • a radical polymerization initiator is preferable.
  • radical polymerization initiator examples include organic halides, carbonyl compounds, azo compounds, organic peroxides, metallocene compounds, azide compounds, hexaarylbiimidazole compounds, disulfone compounds, oxime ester compounds, and onium salt compounds. It is done.
  • organic halide for example, compounds described in paragraphs 0022 to 0023 of JP-A-2008-195018 are preferable.
  • carbonyl compound for example, compounds described in paragraph 0024 of JP-A-2008-195018 are preferable.
  • azo compound include azo compounds described in JP-A-8-108621.
  • organic peroxide for example, compounds described in paragraph 0025 of JP-A-2008-195018 are preferable.
  • metallocene compound for example, a compound described in paragraph 0026 of JP-A-2008-195018 is preferable.
  • the azide compound include compounds such as 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
  • hexaarylbiimidazole compound for example, a compound described in paragraph 0027 of JP-A-2008-195018 is preferable.
  • the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2002-328465.
  • oxime ester compound for example, compounds described in paragraphs 0028 to 0030 of JP-A-2008-195018 are preferable.
  • onium salts such as iodonium salts, sulfonium salts, and azinium salts.
  • Iodonium salts and sulfonium salts are particularly preferred. Specific examples of iodonium salts and sulfonium salts are shown below, but the present invention is not limited thereto.
  • a diphenyl iodonium salt is preferable, and a diphenyl iodonium salt having an electron donating group as a substituent, for example, substituted with an alkyl group or an alkoxyl group is preferable, and an asymmetric diphenyl iodonium salt is also preferable. preferable.
  • diphenyliodonium hexafluorophosphate
  • 4-methoxyphenyl-4- (2-methylpropyl) phenyliodonium hexafluorophosphate
  • 4- (2-methylpropyl) phenyl-p-tolyliodonium hexa Fluorophosphate
  • 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium hexafluorophosphate
  • 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium tetrafluoroborate
  • 4-octyloxy Phenyl-2,4,6-trimethoxyphenyliodonium 1-perfluorobutanesulfonate
  • 4-octyloxyphenyl-2,4,6-trimethoxyphenyliodonium hexafluorophosphate, bis ( -t- butylphenyl) iodonium
  • a triarylsulfonium salt is preferable, and in particular, a triarylsulfonium salt having an electron withdrawing group as a substituent, for example, at least a part of the group on the aromatic ring is substituted with a halogen atom is preferable. Further, a triarylsulfonium salt in which the total number of halogen atoms on the aromatic ring is 4 or more is more preferable.
  • triphenylsulfonium hexafluorophosphate
  • triphenylsulfonium benzoylformate
  • bis (4-chlorophenyl) phenylsulfonium benzoylformate
  • bis (4-chlorophenyl) -4-methylphenylsulfonium tetrafluoro.
  • polymerization initiator the following five kinds of polymerization initiators can also be used.
  • Alkyl or aryl art complex It is considered that a carbon-hetero bond is oxidatively cleaved to generate an active radical. Specific examples include borate compounds.
  • Aminoacetic acid compound It is considered that the C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical.
  • X is preferably a hydrogen atom, a carboxy group, a trimethylsilyl group or a benzyl group.
  • N-phenylglycines which may have a substituent on the phenyl group
  • N-phenyliminodiacetic acid which may have a substituent on the phenyl group
  • Sulfur-containing compound A compound obtained by replacing the nitrogen atom of the above-mentioned aminoacetic acid compound with a sulfur atom can generate an active radical by the same action.
  • Specific examples include phenylthioacetic acid (which may have a substituent on the phenyl group).
  • Tin-containing compound A compound in which the nitrogen atom of the above-mentioned aminoacetic acid compound is replaced with a tin atom can generate an active radical by the same action.
  • Sulfinic acid salts An active radical can be generated by oxidation. Specific examples include arylsulfin sodium.
  • borate compounds are preferred.
  • a tetraaryl borate compound or a monoalkyltriaryl borate compound is preferable, and from the viewpoint of compound stability, a tetraaryl borate compound is more preferable.
  • the counter cation possessed by the borate compound is preferably an alkali metal ion or a tetraalkylammonium ion, more preferably a sodium ion, a potassium ion or a tetrabutylammonium ion.
  • X c + represents a monovalent cation, preferably an alkali metal ion or a tetraalkylammonium ion, and more preferably an alkali metal ion or a tetrabutylammonium ion.
  • Bu represents an n-butyl group.
  • a polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
  • the content of the polymerization initiator is preferably 0.01 to 50% by mass, more preferably 0.05 to 30% by mass, and still more preferably 0.1 to 20% by mass in the total solid content of the image recording layer.
  • the infrared absorber has a function of being excited by infrared rays and transferring electrons and / or energy to a polymerization initiator or the like. Moreover, it has the function to convert the absorbed infrared rays into heat.
  • the infrared absorber preferably has a maximum absorption in a wavelength region of 750 to 1,400 nm. Examples of the infrared absorber include dyes and pigments, and dyes are preferably used.
  • dyes commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes Is mentioned. Of the dyes, cyanine dyes, squarylium dyes, and pyrylium salts are preferred, cyanine dyes are more preferred, and indolenine cyanine dyes are particularly preferred.
  • cyanine dyes represented by the following formula (a).
  • X 1 represents a hydrogen atom, a halogen atom, —N (R 9 ) (R 10 ), —X 2 —L 1 or a group shown below.
  • R 9 and R 10 may be the same or different and each independently represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a hydrogen atom, 9 and R 10 may be bonded to each other to form a ring.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms or the alkyl group having 1 to 8 carbon atoms may have a substituent.
  • Both R 9 and R 10 are preferably phenyl groups.
  • X 2 represents an oxygen atom or a sulfur atom
  • L 1 represents a hydrocarbon group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom.
  • the hetero atom represents N, S, O, a halogen atom, or Se.
  • Ra represents a hydrogen atom, or an alkyl group, an aryl group, a substituted or unsubstituted amino group and a substituent selected from halogen atoms.
  • R 1 and R 2 each independently represents a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the image recording layer coating solution, R 1 and R 2 are preferably hydrocarbon groups having 2 or more carbon atoms, and R 1 and R 2 are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.
  • Ar 1 and Ar 2 may be the same or different and each represents an aromatic hydrocarbon group.
  • the aromatic hydrocarbon group may have a substituent.
  • Preferable aromatic hydrocarbon groups include a benzene ring group and a naphthalene ring group.
  • a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned.
  • Y 1 and Y 2 may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms.
  • R 3 and R 4 may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms.
  • the hydrocarbon group having 20 or less carbon atoms may have a substituent.
  • Preferable substituents include an alkoxy group having 12 or less carbon atoms, a carboxy group, and a sulfo group.
  • R 5 , R 6 , R 7 and R 8 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. In view of easy availability of the raw material, a hydrogen atom is preferred.
  • Za ⁇ represents a counter anion. However, Za ⁇ is not necessary when the cyanine dye represented by the formula (a) has an anionic substituent in its structure and neutralization of charge is not necessary.
  • Za ⁇ is preferably a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, or a sulfonate ion in view of storage stability of the image recording layer coating solution, and is a perchlorate ion or a hexafluorophosphate ion. Or an aryl sulfonate ion is more preferable.
  • X 1 is more preferably a diphenylamino group. More preferably, X 1 is a diphenylamino group, and Y 1 and Y 2 are both dimethylmethylene groups.
  • cyanine dyes include compounds described in paragraphs 0017 to 0019 of JP-A-2001-133969, paragraphs 0016 to 0021 of JP-A-2002-023360, paragraphs 0012 to 0037 of JP-A-2002-040638.
  • compounds described in paragraphs 0008 to 0009 of JP-A-5-5005 and paragraphs 0022 to 0025 of JP-A-2001-222101 can also be preferably used.
  • As the pigment compounds described in paragraphs 0072 to 0076 of JP-A-2008-195018 are preferable.
  • An infrared absorber may be used individually by 1 type, and may use 2 or more types together.
  • the content of the infrared absorber is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.2 to 10% by mass in the total solid content of the image recording layer.
  • the polymerizable compound may be, for example, a radical polymerizable compound or a cationic polymerizable compound, but is an addition polymerizable compound having at least one ethylenically unsaturated bond (ethylenically unsaturated compound). Preferably there is.
  • ethylenically unsaturated compound a compound having at least one terminal ethylenically unsaturated bond is preferable, and a compound having two or more terminal ethylenically unsaturated bonds is more preferable.
  • the polymerizable compound can have a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer or an oligomer, or a mixture thereof.
  • Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), esters thereof, and amides.
  • esters of unsaturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyvalent amine compound are used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used.
  • an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and an addition reaction product of a monofunctional or polyfunctional alcohol, amine or thiol, further a halogen atom A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • a compound group in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene, vinyl ether, or the like can be used.
  • JP-T-2006-508380 JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, JP-A-9-179297. JP, 9-179298, JP 2004-294935, JP 2006-243493, JP 2002-275129, JP 2003-64130, JP 2003-280187, It is described in JP-A-10-333321.
  • monomers of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) -modified triacrylate, and polyester acrylate oligomer.
  • acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate
  • Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaery
  • Methacrylic acid esters include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] Examples thereof include dimethylmethane and bis [p- (methacryloxyethoxy) phenyl] dimethylmethane.
  • amide monomers of polyamine compounds and unsaturated carboxylic acids include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1,6-hexamethylene bismethacrylamide, Examples include diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
  • urethane-based addition-polymerizable compounds produced by the addition reaction of isocyanate and hydroxy groups.
  • Specific examples thereof include, for example, one molecule described in JP-B-48-41708.
  • a urethane compound etc. are mentioned.
  • R M4 and R M5 each independently represent a hydrogen atom or a methyl group.
  • Urethane compounds having an oxide skeleton, urethane compounds having a hydrophilic group described in US Pat. No. 7,153,632, JP-A-8-505958, JP-A-2007-293221, and JP-A-2007-293223 Are also suitable.
  • the content of the polymerizable compound is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, and still more preferably 5 to 20% by mass in the total solid content of the image recording layer.
  • the image recording layer can contain a binder polymer, a chain transfer agent, a low molecular weight hydrophilic compound, a sensitizer, and other components.
  • Binder polymer a polymer having a film property is preferable, and (meth) acrylic resin, polyvinyl acetal resin, polyurethane resin, and the like are preferable.
  • the binder polymer used for the image recording layer of the on-press development type lithographic printing plate precursor (hereinafter also referred to as on-press development binder polymer) will be described in detail.
  • the binder polymer for on-press development is preferably a binder polymer having an alkylene oxide chain.
  • the binder polymer having an alkylene oxide chain may have a poly (alkylene oxide) moiety in the main chain or a side chain. Further, it may be a graft polymer having poly (alkylene oxide) in the side chain, or a block copolymer of a block composed of poly (alkylene oxide) -containing repeating units and a block composed of (alkylene oxide) -free repeating units.
  • a polyurethane resin is preferred when it has a poly (alkylene oxide) moiety in the main chain.
  • the main chain polymer in the case of having a poly (alkylene oxide) moiety in the side chain, (meth) acrylic resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, polystyrene resin, novolak type Examples thereof include phenol resin, polyester resin, synthetic rubber, and natural rubber, and (meth) acrylic resin is particularly preferable.
  • the alkylene oxide is preferably an alkylene oxide having 2 to 6 carbon atoms, particularly preferably ethylene oxide or propylene oxide.
  • the repeating number of alkylene oxide at the poly (alkylene oxide) site is preferably 2 to 120, more preferably 2 to 70, and still more preferably 2 to 50. If the number of alkylene oxide repeats is 120 or less, both the printing durability due to wear and the printing durability due to ink acceptance are not deteriorated.
  • the poly (alkylene oxide) moiety is preferably contained as a side chain of the binder polymer in a structure represented by the following formula (AO), and represented by the following formula (AO) as a side chain of the (meth) acrylic resin. More preferably, it is contained in the structure.
  • y represents 2 to 120
  • R 1 represents a hydrogen atom or an alkyl group
  • R 2 represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group an alkyl group having 1 to 6 carbon atoms is preferable.
  • methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n- Examples include a hexyl group, an isohexyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a cyclopentyl group, and a cyclohexyl group.
  • y is preferably 2 to 70, more preferably 2 to 50.
  • R 1 is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
  • R 2 is particularly preferably a hydrogen atom or a methyl group.
  • the binder polymer may have crosslinkability in order to improve the film strength of the image area.
  • a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or side chain of the polymer.
  • the crosslinkable functional group may be introduced by copolymerization or may be introduced by a polymer reaction.
  • Examples of the polymer having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene and poly-1,4-isoprene.
  • polymers having ethylenically unsaturated bonds in the side chain of the molecule are polymers of esters or amides of acrylic acid or methacrylic acid, where the ester or amide residue (R of —COOR or —CONHR) is Mention may be made of polymers having an ethylenically unsaturated bond.
  • ester residue examples include —CH 2 CH ⁇ CH 2 , —CH 2 CH 2 O—CH 2 CH ⁇ CH 2 , —CH 2 C (CH 3 ) ⁇ CH 2 , —CH 2 CH ⁇ CH— C 6 H 5 , —CH 2 CH 2 OCOCH ⁇ CH—C 6 H 5 , —CH 2 CH 2 —NHCOO—CH 2 CH ⁇ CH 2 and —CH 2 CH 2 O—X wherein X is dicyclo Represents a pentadienyl residue.).
  • amide residue examples include —CH 2 CH ⁇ CH 2 , —CH 2 CH 2 —Y (wherein Y represents a cyclohexene residue) and —CH 2 CH 2 —OCO—CH ⁇ CH 2. Is mentioned.
  • the binder polymer having crosslinkability for example, has a free radical (polymerization initiation radical or a growth radical in the polymerization process of the polymerizable compound) added to the crosslinkable functional group, and the polymerization chain of the polymerizable compound is formed directly between the polymers. Through addition polymerization, a cross-link is formed between the polymer molecules and cured.
  • atoms in the polymer eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group
  • free radicals in the polymer are abstracted by free radicals to form polymer radicals that are bonded to each other so that crosslinking between the polymer molecules occurs. Forms and cures.
  • the content of the crosslinkable group in the binder polymer is 0.1 per 1 g of the binder polymer from the viewpoint of good sensitivity and good storage stability. ⁇ 10.0 mmol is preferable, 1.0 to 7.0 mmol is more preferable, and 2.0 to 5.5 mmol is more preferable.
  • a numerical value written together with each repeating unit represents a mole percentage of the repeating unit.
  • the numerical value written together with the repeating unit of the side chain indicates the number of repeating sites. Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.
  • the weight average molecular weight (Mw) is 2,000 or more, preferably 5,000 or more, more preferably 10,000 to 300,000 as a polystyrene conversion value by GPC method.
  • hydrophilic polymers such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination. Further, a lipophilic polymer and a hydrophilic polymer can be used in combination.
  • a binder polymer may be used individually by 1 type and may use 2 or more types together.
  • the content of the binder polymer is preferably 1 to 90% by mass and more preferably 5 to 80% by mass in the total solid content of the image recording layer.
  • the chain transfer agent contributes to improvement in printing durability in a lithographic printing plate produced from a lithographic printing plate precursor.
  • the chain transfer agent is preferably a thiol compound, more preferably a thiol having 7 or more carbon atoms from the viewpoint of boiling point (difficult to volatilize), and still more preferably a compound having a mercapto group on the aromatic ring (aromatic thiol compound).
  • the thiol compound is preferably a monofunctional thiol compound.
  • chain transfer agent examples include the following compounds.
  • a chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
  • the content of the chain transfer agent is preferably from 0.01 to 50 mass%, more preferably from 0.05 to 40 mass%, still more preferably from 0.1 to 30 mass%, based on the total solid content of the image recording layer.
  • the low molecular weight hydrophilic compound contributes to the improvement of the on-press developability of the lithographic printing plate precursor without reducing the printing durability of the lithographic printing plate prepared from the lithographic printing plate precursor.
  • the low molecular weight hydrophilic compound is preferably a compound having a molecular weight of less than 1,000, more preferably a compound having a molecular weight of less than 800, and still more preferably a compound having a molecular weight of less than 500.
  • the low molecular weight hydrophilic compound for example, as the water-soluble organic compound, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like glycols and ether or ester derivatives thereof, glycerin, Polyols such as pentaerythritol and tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkylsulfonic acid, toluenesulfonic acid and benzenesulfonic acid Acids and salts thereof, organic sulfamic acids such as alkylsulfamic acid and salts thereof, organic sulfuric acids such as alkylsulfuric acid and alkylethersulfuric acid and salts thereof, phenylphosphonic acid Organic phosphonic acids and salts thereof, tartaric acid, o
  • the low molecular weight hydrophilic compound is preferably at least one selected from polyols, organic sulfates, organic sulfonates, and betaines.
  • organic sulfonates include alkyl sulfonates such as sodium n-butyl sulfonate, sodium n-hexyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium cyclohexyl sulfonate, sodium n-octyl sulfonate; 5 , 8,11-Trioxapentadecane-1-sulfonic acid sodium salt, 5,8,11-trioxaheptadecane-1-sulfonic acid sodium salt, 13-ethyl-5,8,11-trioxaheptadecane-1-sulfone Alkyl sulfonates containing ethylene oxide chains such as sodium acid, sodium 5,8,11,14-tetraoxatetracosane-1-sulfonate; sodium benzenesulfonate, sodium p-toluenesulfonate, p-hydroxybenzen
  • organic sulfates examples include polyethylene oxide alkyl, alkenyl, alkynyl, aryl, or heterocyclic monoether sulfates.
  • the number of ethylene oxide units is preferably 1 to 4, and the salt is preferably a sodium salt, potassium salt or lithium salt. Specific examples include the compounds described in paragraphs 0034 to 0038 of JP-A-2007-276454.
  • the betaines are preferably compounds in which the hydrocarbon substituent on the nitrogen atom has 1 to 5 carbon atoms. Specific examples include trimethylammonium acetate, dimethylpropylammonium acetate, 3-hydroxy-4-trimethylammonium. Obtylate, 4- (1-pyridinio) butyrate, 1-hydroxyethyl-1-imidazolioacetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonio-1-propanesulfonate, 3 -(1-pyridinio) -1-propanesulfonate and the like.
  • the dampening solution penetrates into the exposed part of the image recording layer (image part) and reduces the hydrophobicity and film strength of the image part.
  • the ink receptivity and printing durability of the image recording layer can be maintained satisfactorily.
  • a low molecular weight hydrophilic compound may be used individually by 1 type, and may use 2 or more types together.
  • the content of the low molecular weight hydrophilic compound is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 2 to 10% by mass in the total solid content of the image recording layer.
  • the oil-sensitizing agent contributes to the improvement of ink inking property (hereinafter also simply referred to as “inking property”) in a lithographic printing plate produced from a lithographic printing plate precursor.
  • the sensitizer include phosphonium compounds, nitrogen-containing low molecular weight compounds, and ammonium group-containing polymers.
  • these compounds function as a surface coating agent for the inorganic layered compound and have a function of suppressing deterioration of the inking during printing by the inorganic layered compound. Have.
  • the sensitizer it is preferable to use a phosphonium compound, a nitrogen-containing low molecular weight compound, and an ammonium group-containing polymer in combination, and use a phosphonium compound, a quaternary ammonium salt, and an ammonium group-containing polymer in combination. Is more preferable.
  • nitrogen-containing low molecular weight compounds examples include amine salts and quaternary ammonium salts. Also included are imidazolinium salts, benzimidazolinium salts, pyridinium salts, and quinolinium salts. Of these, quaternary ammonium salts and pyridinium salts are preferred.
  • the ammonium group-containing polymer may have an ammonium group in its structure, and a polymer containing 5 to 80 mol% of (meth) acrylate having an ammonium group in the side chain as a copolymerization component is preferable.
  • Specific examples include the polymers described in paragraphs 0089 to 0105 of JP2009-208458A.
  • the ammonium group-containing polymer preferably has a reduced specific viscosity (unit: ml / g) determined in accordance with the measurement method described in JP-A-2009-208458, in the range of 5 to 120, and in the range of 10 to 110. Are more preferable, and those in the range of 15 to 100 are particularly preferable.
  • Mw weight average molecular weight
  • the content of the sensitizing agent is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, and still more preferably 1 to 10% by mass in the total solid content of the image recording layer.
  • the image recording layer can contain a surfactant, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, inorganic particles, an inorganic layered compound, and the like as other components. Specifically, each component described in paragraphs 0114 to 0159 of JP-A-2008-284817 can be used.
  • the image recording layer contains an infrared absorber, a polymerizable compound, a polymerization initiator, and at least one of a binder polymer and polymer particles.
  • the image recording layer preferably further contains a chain transfer agent.
  • the image recording layer contains an infrared absorber, heat-fusible particles, and a binder polymer.
  • the image recording layer is prepared by appropriately dispersing or dissolving each of the above-described components in a known solvent to prepare a coating solution. It can be formed by coating and drying on a support by a known method such as bar coater coating.
  • the coating amount (solid content) of the image recording layer after coating and drying varies depending on the application, but from the viewpoint of obtaining good sensitivity and good film properties of the image recording layer, it is about 0.3 to 3.0 g / m 2. Is preferred.
  • Layer containing a compound having support adsorptivity It describes about the layer containing the compound which has a support body adsorptivity which comprises an on-press development type lithographic printing plate precursor.
  • the layer (hereinafter also referred to as a specific compound-containing layer) containing a compound having support adsorptivity (hereinafter also referred to as a specific compound) contains a compound having support adsorbability.
  • the specific compound-containing layer is selected from printing ink and fountain solution on the printing press from the viewpoint of effectively exhibiting edge stain resistance without deteriorating the properties such as image forming property and on-press developability at the edge.
  • a layer having the property of being removed by at least one is preferable.
  • the specific compound-containing layer is more preferably water-soluble in order to easily elute the specific compound.
  • the specific compound-containing layer includes not only a continuous layer containing the specific compound but also a form in which the specific compound is scattered discontinuously in an island shape.
  • the specific compound-containing layer may be present on the image recording layer. In other words, it suffices to be located farther from the support than the image recording layer. For example, it is preferably in contact with the image recording layer.
  • support adsorptive means the adsorptivity to the anodized film of the aluminum support.
  • the presence or absence of adsorptivity to the anodized film can be easily determined by the following method. That is, a solution in which a test compound is dissolved in a readily soluble solvent (for example, water) is prepared. This solution is applied on an aluminum support having an anodized film and dried so that the coating amount after drying is 30 mg / m 2 .
  • the aluminum support on which the test compound is applied is washed and dried five times using the above-mentioned easily soluble solvent, and then the residual amount of the test compound that has not been removed by washing is measured.
  • the amount of the remaining test compound may be directly quantified, or the amount of the test compound dissolved in the cleaning solution may be quantified, and the amount of the remaining test compound may be calculated using this value.
  • the quantification of the test compound can be performed, for example, by fluorescent X-ray measurement, reflection spectral absorbance measurement, or the like. If the residual amount is 1 mg / m 2 or more, the test compound is determined to have support adsorbability.
  • the specific compound preferably has a group exhibiting adsorptivity to the anodized film of the aluminum support in order to have support adsorbability.
  • the group exhibiting adsorptivity to the anodized film of the aluminum support include a substance (for example, metal, metal oxide) or a functional group (for example, hydroxyl group) present on the surface of the anodized film, and a chemical bond ( For example, the functional group which can form an ionic bond, a hydrogen bond, and a coordination bond is mentioned.
  • Such functional groups are well known in the art. Of these functional groups, acid groups are preferred.
  • the acid group preferably has an acid dissociation constant (pKa) of 7 or less.
  • Examples of acid groups include phenolic hydroxyl groups, carboxyl groups, —SO 3 H, —OSO 3 H, —PO 3 H 2 , —OPO 3 H 2 , —CONHSO 2 —, —SO 2 NHSO 2 —, —COCH 2 COCH 3 and the like. In particular, —OPO 3 H 2 and —PO 3 H 2 are preferable.
  • the acid group may form a salt. Examples of the salt formed by the acid group include alkali metal salts, alkaline earth metal salts, and ammonium salts.
  • the molecular weight of the specific compound is preferably 1,000 or less. When the molecular weight is 1,000 or less, the specific compound easily moves from the specific compound-containing layer to the surface of the anodized film at the edge of the lithographic printing plate precursor during on-press development, and an excellent edge stain prevention effect is obtained. it is conceivable that.
  • the molecular weight is preferably 50 to 1,000, more preferably 50 to 800, and still more preferably 50 to 600.
  • Oxo acid can be used as the specific compound.
  • Oxo acid refers to a compound in which a hydroxyl group (—OH) and an oxo group ( ⁇ O) are bonded to the same atom, and the hydroxyl group gives an acidic proton.
  • Oxo acids may be used in the form of salts. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts and the like.
  • n represents an integer of 2 to 10
  • R1, R2, and R3 each independently represent a hydrogen atom, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an alkyl group, or an alkylene oxide group.
  • the alkyl group in Formula 1 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms.
  • the alkylene oxide group in Formula 1 is preferably an alkylene oxide group having 1 to 10 alkylene oxide units having 2 or 3 carbon atoms, more preferably an alkylene oxide group having 1 to 5 alkylene oxide units having 2 or 3 carbon atoms.
  • An alkylene oxide group having 1 to 3 alkylene oxide units having 2 or 3 carbon atoms is more preferable.
  • specific compounds include phosphoric acid, polyphosphoric acid, metaphosphoric acid, primary ammonium phosphate, secondary ammonium phosphate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, primary potassium phosphate, secondary phosphorus Potassium acid, sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, phosphinic acid, ethylphosphonic acid, propylphosphonic acid, i-propylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, dodecylphosphonic acid, octadecylphosphonic acid Acids, 2-hydroxyethylphosphonic acids and sodium or potassium salts thereof, alkylphosphonic acid monoalkyl esters such as methylphosphonic acid methyl, ethylphosphonic acid methyl, methyl 2-hydroxyethylphosphonic acid and their sodium Or potassium salts, alkylene diphosphonic acids such as m
  • phosphoric acid As the specific compound, phosphoric acid, polyphosphoric acid, phosphonic acid, phosphinic acid and salts thereof are particularly preferable from the viewpoint of adsorptivity to the anodized film.
  • a specific compound may be used individually by 1 type, and may use 2 or more types together.
  • the content of the specific compound in a specific compound-containing layer is preferably 20 ⁇ 150mg / m 2, more preferably 30 ⁇ 100mg / m 2, more preferably 50 ⁇ 100mg / m 2.
  • One feature of the lithographic printing plate precursor according to the invention is that the content of the specific compound is substantially the same in the plane of the specific compound-containing layer.
  • “the content of the specific compound is substantially the same in the plane of the specific compound-containing layer” means that the specific compound exists almost uniformly in the plane of the specific compound-containing layer, and the lithographic printing plate precursor It means that there is no substantial difference in the content of the specific compound between the central part and the end part.
  • the present invention is a state in which the specific compound is intentionally applied only to the edge of the lithographic printing plate precursor so that the content of the specific compound in the edge is greater than the content of the specific compound in the region other than the edge. Is different from forming
  • the specific compound-containing layer preferably contains a surfactant.
  • the surfactant has the effect of adjusting the surface tension of the specific compound-containing layer coating solution to give a uniform coated surface.
  • the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
  • Anionic surfactants and nonionic surfactants are preferred.
  • the anionic surfactant include compounds described as paragraphs [0022] in JP-A-2014-104631 as an anionic surfactant.
  • Examples of the nonionic surfactant include compounds described as a nonionic surfactant in paragraph [0031] of JP-A-2014-104631.
  • the content of the surfactant in the particular compounds containing layer is preferably 5 ⁇ 50mg / m 2, more preferably 5 ⁇ 20mg / m 2, more preferably 8 ⁇ 15mg / m 2.
  • the specific compound-containing layer preferably contains a water-soluble polymer.
  • the water-soluble polymer functions as a binder for the specific compound-containing layer. Further, the water-soluble polymer is dissolved by the action of dampening water during on-press development and has an effect of eluting the specific compound.
  • a water-soluble polymer used for a protective layer (sometimes referred to as an overcoat layer) of a lithographic printing plate precursor can be suitably used.
  • Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like. Two or more types of water-soluble polymers can be used as needed.
  • the content of the water-soluble polymer in the particular compounds containing layer is preferably 30 ⁇ 300mg / m 2, more preferably 30 ⁇ 150mg / m 2, more preferably 50 ⁇ 120mg / m 2.
  • the specific compound-containing layer can be formed, for example, by dissolving each necessary component in a solvent such as water as appropriate to prepare a coating solution, and coating and drying the coating solution on the image recording layer by a known method. it can.
  • the specific compound-containing layer can be integrated with the protective layer and formed on the image recording layer as one layer. Such a form is demonstrated in the protective layer mentioned later.
  • the on-press development type lithographic printing plate precursor according to the present invention may have an undercoat layer (sometimes referred to as an intermediate layer) between the image recording layer and the support.
  • the undercoat layer enhances the adhesion between the support and the image recording layer in the exposed area, and easily peels off the image recording layer from the support in the unexposed area. It contributes to improving.
  • the undercoat layer functions as a heat insulating layer, and thus has an effect of preventing the heat generated by the exposure from diffusing to the support and lowering the sensitivity.
  • Examples of the compound used for the undercoat layer include polymers having an adsorptive group and a hydrophilic group that can be adsorbed on the surface of the support. In order to improve the adhesion to the image recording layer, a polymer having an adsorptive group and a hydrophilic group and further having a crosslinkable group is preferable.
  • the compound used for the undercoat layer may be a low molecular compound or a polymer. The compounds used for the undercoat layer may be used as a mixture of two or more if necessary.
  • the compound used for the undercoat layer is a polymer
  • a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group is preferable.
  • the adsorptive group that can be adsorbed on the support surface include a phenolic hydroxy group, a carboxy group, —PO 3 H 2 , —OPO 3 H 2 , —CONHSO 2 —, —SO 2 NHSO 2 —, —COCH 2 COCH 3 Is preferred.
  • a hydrophilic group a sulfo group or a salt thereof, or a salt of a carboxy group is preferable.
  • the polymer may have a crosslinkable group introduced by salt formation between a polar substituent of the polymer, a substituent having a counter charge with the polar substituent, and a compound having an ethylenically unsaturated bond, Other monomers, preferably hydrophilic monomers, may be further copolymerized.
  • the phosphorus compound which has a heavy bond reactive group is mentioned suitably.
  • Crosslinkable groups (preferably ethylenically unsaturated bond groups) described in JP-A-2005-238816, JP-A-2005-12549, JP-A-2006-239867, and JP-A-2006-215263, a support
  • a low molecular or high molecular compound having a functional group interacting with the surface and a hydrophilic group is also preferably used.
  • More preferable are polymer polymers having an adsorbable group, a hydrophilic group and a crosslinkable group which can be adsorbed on the surface of the support described in JP-A Nos. 2005-125749 and 2006-188038.
  • the content of the ethylenically unsaturated bond group in the polymer used for the undercoat layer is preferably 0.1 to 10.0 mmol, more preferably 0.2 to 5.5 mmol per 1 g of the polymer.
  • the polymer used for the undercoat layer preferably has a mass average molecular weight (Mw) of 5,000 or more, more preferably 10,000 to 300,000.
  • the undercoat layer is a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group, or a functional group having a polymerization inhibitory ability and a support surface in order to prevent contamination with time.
  • a group that interacts with eg, 1,4-diazabicyclo [2.2.2] octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil, sulfophthalic acid, hydroxy Ethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, and the like).
  • the undercoat layer can be formed, for example, by dissolving or dispersing necessary components in a solvent as appropriate to prepare a coating solution, and coating and drying the coating solution on a support by a known method.
  • the coating amount (solid content) of the undercoat layer is preferably 0.1 ⁇ 100mg / m 2, and more preferably 1 ⁇ 30mg / m 2.
  • the on-press development type lithographic printing plate precursor according to the invention may have a protective layer (sometimes referred to as an overcoat layer) on the specific compound-containing layer.
  • a protective layer sometimes referred to as an overcoat layer
  • the specific compound-containing layer and the protective layer may be integrated and formed on the image recording layer as one layer.
  • the protective layer In addition to the function of suppressing the image formation inhibition reaction by blocking oxygen, the protective layer has a function of preventing scratches in the image recording layer and preventing ablation during high-illuminance laser exposure.
  • the protective layer having such characteristics is described in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729.
  • the polymer having low oxygen permeability used for the protective layer either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and if necessary, two or more types may be mixed and used. You can also.
  • Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like.
  • As the modified polyvinyl alcohol acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used.
  • Specific examples include modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137.
  • the protective layer preferably contains an inorganic layered compound in order to enhance oxygen barrier properties.
  • the inorganic layered compound is a particle having a thin flat plate shape, for example, mica group such as natural mica and synthetic mica, talc, teniolite, montmorillonite, saponite, hector represented by the formula: 3MgO ⁇ 4SiO ⁇ H 2 O Light, zirconium phosphate, etc. are mentioned.
  • the inorganic layered compound preferably used is a mica compound.
  • mica compound for example, the formula: A (B, C) 2-5 D 4 O 10 (OH, F, O) 2 [where A is any of K, Na, Ca, and B and C are One of Fe (II), Fe (III), Mn, Al, Mg, and V, and D is Si or Al. ]
  • Mica groups such as natural mica and synthetic mica represented by
  • natural mica includes muscovite, soda mica, phlogopite, biotite, and sericite.
  • synthetic mica non-swelling mica such as fluor-phlogopite mica KMg 3 (AlSi 3 O 10 ) F 2 , potassium tetrasilicon mica KMg 2.5 Si 4 O 10 ) F 2 , and Na tetrasilicic mica NaMg2 .
  • the swellable synthetic mica has a laminated structure composed of unit crystal lattice layers with a thickness of about 10 to 15 mm, and the substitution of metal atoms in the lattice is significantly larger than other clay minerals.
  • the lattice layer is deficient in positive charge, and in order to compensate for this, cations such as Li + , Na + , Ca 2+ , and Mg 2+ are adsorbed between the layers.
  • the cations present between these layers are called exchangeable cations and can be exchanged with various cations.
  • the bond between the layered crystal lattices is weak because the ionic radius is small, and the layer swells greatly with water. If shear is applied in this state, it will easily cleave and form a stable sol in water.
  • Swelling synthetic mica has a strong tendency and is particularly preferably used.
  • the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more.
  • the aspect ratio is the ratio of the major axis to the thickness of the particle, and can be measured, for example, from a projection drawing of a particle by a micrograph. The larger the aspect ratio, the greater the effect that can be obtained.
  • the average major axis of the mica compound is preferably 0.3 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m, and particularly preferably 1 to 5 ⁇ m.
  • the average thickness of the particles is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and particularly preferably 0.01 ⁇ m or less.
  • preferred embodiments have a thickness of about 1 to 50 nm and a surface size (major axis) of about 1 to 20 ⁇ m.
  • the content of the inorganic stratiform compound is preferably 0 to 60% by mass and more preferably 3 to 50% by mass with respect to the total solid content of the protective layer. Even when a plurality of types of inorganic layered compounds are used in combination, the total amount of the inorganic layered compounds is preferably the above content. Within the above range, the oxygen barrier property is improved and good sensitivity is obtained. Further, it is possible to prevent a decrease in inking property.
  • the protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coating properties, and inorganic fine particles for controlling the slipperiness of the surface. Further, the protective layer may contain the sensitizer described in the image recording layer.
  • the protective layer can be formed, for example, by dissolving or dispersing necessary components in a solvent as appropriate to prepare a coating solution, and coating and drying the coating solution on the image recording layer by a known method.
  • the coating amount of the protective layer (solid content) is preferably 0.01 ⁇ 10g / m 2, more preferably 0.02 ⁇ 3g / m 2, particularly preferably 0.02 ⁇ 1g / m 2.
  • the specific compound-containing layer and the protective layer may be integrated and formed on the image recording layer as one layer.
  • the specific compound-containing layer is prepared, for example, by appropriately dissolving or dispersing each component necessary for the specific compound-containing layer and the protective layer in a solvent to prepare a coating solution, and then applying the coating solution on the image recording layer by a known method. It can be formed by coating and drying.
  • the on-press development type lithographic printing plate precursor according to the invention has a sagging shape at the end.
  • the sagging shape preferably has a sagging amount X of 25 to 150 ⁇ m and a sagging width Y of 70 to 300 ⁇ m.
  • FIG. 1 is a diagram schematically showing a cross-sectional shape of an end portion of a lithographic printing plate precursor.
  • a planographic printing plate precursor 1 has a sag 2 at its end.
  • the distance X between the upper end of the end face 1c of the lithographic printing plate precursor 1 (boundary point between the sag 2 and the end face 1c) and the extended line of the specific compound-containing layer face (protective layer face if a protective layer is further formed) 1a Is referred to as “sag amount”, and the distance Y between the point at which the specific compound-containing layer surface 1a of the planographic printing plate precursor 1 begins to sag and the extension line of the end surface 1c is referred to as “sag width”.
  • the sagging amount at the end is more preferably 35 ⁇ m or more, and further preferably 40 ⁇ m or more.
  • the upper limit of the sagging amount is preferably 150 ⁇ m from the viewpoint of preventing deterioration of on-press developability due to deterioration of the end surface condition.
  • on-machine developability deteriorates, ink adheres to the remaining image recording layer and causes edge smearing. If the amount of sag is too small, the ink adhering to the end portion is easily transferred to the blanket, which may cause edge smearing.
  • the sagging width is preferably in the range of 70 to 300 ⁇ m, and more preferably in the range of 80 to 250 ⁇ m.
  • the range of the sag amount and the sag width is not related to the edge shape of the support surface 1b of the planographic printing plate precursor 1.
  • the boundary B between the image recording layer and the support and the support surface 1b are also sagging as in the case of the specific compound-containing layer surface 1a.
  • the end portion having the sagging shape can be formed, for example, by adjusting the cutting conditions of the planographic printing plate precursor. Specifically, it can be performed by adjusting the gap between the upper cutting blade and the lower cutting blade, the biting amount, the blade edge angle, etc. in the slitter apparatus used when cutting the lithographic printing plate precursor.
  • FIG. 2 is a conceptual diagram showing a cutting unit of a slitter device. In the slitter device, a pair of upper and lower cutting blades 10 and 20 are arranged on the left and right.
  • the cutting blades 10 and 20 are round blades on a circular plate, and the upper cutting blades 10a and 10b are supported on the rotating shaft 11 and the lower cutting blades 20a and 20b are supported on the rotating shaft 21 on the same axis.
  • the upper cutting blades 10a and 10b and the lower cutting blades 20a and 20b are rotated in opposite directions.
  • the planographic printing plate precursor 30 is cut into a predetermined width by passing between the upper cutting blades 10a and 10b and the lower cutting blades 20a and 20b.
  • an end portion having a sagging shape can be formed. .
  • the area ratio of cracks existing on the surface of the anodized film in the region corresponding to the sagging width Y is 20% or less.
  • the region corresponding to the sagging width Y is from the intersection of the extension line of the specific compound-containing layer surface in FIG. 1 (the protective layer surface when a protective layer is further formed) 1a and the extended line of the end surface 1c.
  • the extension line of 1a means the region until the specific compound-containing layer surface (or the protective layer surface when a protective layer is formed) is in contact.
  • the area ratio of cracks existing on the surface of the anodized film is calculated by the following method.
  • the constituent layers (undercoat layer, image recording layer, specific compound-containing layer, protective layer) of the lithographic printing plate precursor are removed using PlasmaReactor PR300 manufactured by Yamato Scientific Co., Ltd.
  • a sample is prepared by conducting a conductive treatment on the exposed surface of the anodized film of the aluminum support by depositing a Pt—Pd film by 3 nm. This sample was observed with an S-4800 field emission scanning electron microscope (FE-SEM) manufactured by Hitachi High-Technologies Corporation at an accelerating voltage of 30 kV. A continuous photograph is acquired toward the part, and an image of 150 ⁇ 50 ⁇ m is obtained.
  • FE-SEM field emission scanning electron microscope
  • the image processing software extracts the crack shape using the luminance difference between the crack portion and the surface of the anodized film layer, performs binarization processing, calculates the ratio of cracks in the 150 ⁇ 50 ⁇ m range, The area ratio of cracks.
  • the area ratio of cracks is particularly preferably 10% or less from the viewpoint of preventing the occurrence of edge contamination.
  • the amount of the anodized film of the anodized film is set to 0.5 to 5.0 g / it is preferably controlled in the range of m 2.
  • the amount of the anodized film is more preferably controlled in the range of 0.8 to 1.2 g / m 2 from the viewpoint of further suppressing edge contamination.
  • the amount of the anodized film of the anodized film is calculated by the following method.
  • the constituent layers (undercoat layer, image recording layer, specific compound-containing layer, protective layer) of the lithographic printing plate precursor are removed using PlasmaReactor PR300 manufactured by Yamato Scientific Co., Ltd.
  • the surface of the anodized film of the exposed aluminum support was measured with a fluorescent X-ray analyzer (ZSX Primus II, manufactured by Rigaku Corporation), and an anodized film amount (g / g) of the anodized film was prepared using a separately prepared calibration curve. m 2 ) is calculated.
  • the calibration curve was created from the relationship between the Compton scattered radiation intensity obtained from the fluorescent X-ray analyzer and the amount of the anodized film calculated by the Mason method. In order to improve the measurement accuracy of the Mason method, all new Mason solutions were used.
  • the conditions for the fluorescent X-ray analysis are as follows. X-ray tube: Rh, measurement spectrum: RhL ⁇ , tube voltage: 50 kV, tube current: 60 mA, slit: S2, spectral crystal: Ge, detector: PC, analysis area: 30 mm ⁇ , peak position (2 ⁇ ): 89.510 deg . , Background (2 ⁇ ): 87.000 deg. And 92.000 deg. , Integration time: 60 seconds / sample
  • the average diameter of the micropores existing on the surface of the anodized film is 5 to 35 nm. It is preferable to control within the range.
  • the average pore diameter of the anodized film is calculated by the following method.
  • the constituent layers (undercoat layer, image recording layer, specific compound-containing layer, protective layer) of the lithographic printing plate precursor are removed using PlasmaReactor PR300 manufactured by Yamato Scientific Co., Ltd.
  • a carbon or Pt—Pd film is vapor-deposited by 3 nm on the exposed surface of the anodized film of the aluminum support, and a sample is prepared. Using this sample, S-4800 field emission scanning electron microscope (FE-SEM) manufactured by Hitachi High-Technologies Corporation, continuous photographs were taken from the end to the center at an observation magnification of 150,000 times. 4 images of 400 ⁇ 600 nm are obtained.
  • FE-SEM field emission scanning electron microscope
  • the diameters of 90 micropores present in the four images are measured and averaged to obtain the average diameter of the micropores. If the shape of the micropore is not circular, a circle having the same projected area as the projected area of the micropore is assumed, and the diameter of the circle is the diameter of the micropore.
  • the on-press development type lithographic printing plate precursor according to the present invention has a sag shape at the end portion and a specific compound-containing layer on the image recording layer, so that the image forming property at the end portion and the on-press developability are obtained. It has a feature that it can exhibit good edge stain resistance even after long-term storage without deteriorating the characteristics such as. Furthermore, in the on-press development type lithographic printing plate precursor according to the present invention, a good edge can be obtained even after long-term storage without applying a hydrophilic treatment such as applying a coating solution containing a water-soluble compound to the edges. It has a feature that it can exhibit antifouling properties. The reason is not clear, but is presumed as follows.
  • the on-press development type lithographic printing plate precursor according to the invention has a specific compound-containing layer on the image recording layer. Even if the polymerizable compound in the image forming layer undergoes dark polymerization with active species under long-term storage, the specific compound contained in the specific compound-containing layer is present in a layer different from the image recording layer. It is less affected by the recording layer. Therefore, the specific compound is eluted with at least one selected from printing ink and fountain solution, and can be made hydrophilic by moving to the end of the on-press development type lithographic printing plate precursor, It is presumed that the edge dirt prevention property is further improved. In addition, the on-press development type lithographic printing plate dummy plate described later usually has no image recording layer, and thus is presumed to exhibit good edge stain resistance even under long-term storage.
  • the method for producing a lithographic printing plate according to the present invention comprises a step of exposing an image of the lithographic printing plate precursor according to the present invention (exposure step), and printing ink and dampening of the lithographic printing plate precursor after image exposure on a printing machine.
  • Image exposure is preferably performed by a method of scanning exposure of digital data with an infrared laser or the like.
  • the wavelength of the exposure light source is preferably 750 to 1,400 nm.
  • a solid laser or semiconductor laser that emits infrared light is suitable.
  • the exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
  • the exposure step can be performed by a known method using a plate setter or the like.
  • the exposure may be performed on the printing machine after the planographic printing plate precursor is mounted on the printing machine using a printing machine equipped with an exposure device.
  • On-press development process In the on-press development process, when printing is started by supplying printing ink and fountain solution on the printing press without performing any development processing on the lithographic printing plate precursor after image exposure, an initial stage of printing Thus, the unexposed portion of the lithographic printing plate precursor is removed, and accordingly, the hydrophilic support surface is exposed to form a non-image portion.
  • the printing ink and fountain solution known lithographic printing ink and fountain solution are used.
  • the lithographic printing plate precursor may be initially supplied with the printing ink or fountain solution, but the printing ink is first used in order to prevent the fountain solution from being contaminated by the removed image recording layer components. Is preferably supplied. In this way, the lithographic printing plate precursor is subjected to on-press development on an offset printing machine and used as it is for printing a large number of sheets.
  • the method for producing a lithographic printing plate according to the present invention may include other known steps in addition to the above steps.
  • Examples of other processes include a plate inspection process for confirming the position and orientation of the lithographic printing plate precursor before each process, a confirmation process for confirming a printed image after the on-machine development process, and the like.
  • On-press development type lithographic printing plate dummy In the field of multi-color printing such as color newspaper printing, when it is necessary to print a part of the paper surface with two colors or one color, etc. In some cases, a dummy plate is attached instead of the printing plate for printing. Such a dummy version is sometimes called a discarded version, a water version, or a blank version.
  • the present invention also relates to a dummy plate, specifically an on-press development type lithographic printing plate dummy plate.
  • An on-press development type lithographic printing plate dummy plate according to the present invention is an on-press development type lithographic printing plate dummy plate having a polymer layer on an aluminum support having an anodized film, and the lithographic printing plate dummy plate has an end face.
  • the content of the compound having a compound having the support adsorbing property Is an on-press development type lithographic printing plate dummy plate which is substantially the same as in FIG.
  • the aluminum support having an anodic oxide film constituting the on-press development type lithographic printing plate precursor dummy is not particularly limited, but is the same as the aluminum support having the anodic oxide film constituting the on-press development type lithographic printing plate precursor. Can be mentioned.
  • the polymer layer constituting the on-press development type lithographic printing plate dummy is present on an aluminum support having an anodized film.
  • the polymer layer preferably contains a binder polymer.
  • a binder polymer of the polymer layer a polymer having a film-forming property is suitable.
  • the binder polymer contained in the polymer layer include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile and the like.
  • the modified polyvinyl alcohol acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used. Specific examples include modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137.
  • a water-soluble polymer compound containing a repeating unit having a support-adsorbing group and a repeating unit having a hydrophilic group is particularly preferable.
  • Edge smear refers to the edge of a lithographic printing plate dummy when it is printed continuously on a roll-like printing paper using a rotary press, such as newspaper printing, so it adheres to the edge. This is a phenomenon in which the used ink is transferred to the printing paper and causes linear stains.
  • water-soluble polymer compound containing a repeating unit having a support adsorptive group and a repeating unit having a hydrophilic group will be described in detail.
  • Support adsorptive group examples include ionic bond formation, hydrogen bond formation, and polar interaction with metals, metal oxides, hydroxy groups, etc. present on the support subjected to anodization treatment or hydrophilization treatment. Examples include groups capable of acting. Specific examples of the support-adsorptive group are listed below.
  • M 1 and M 2 each independently represent a hydrogen atom, a metal atom contained in an alkali metal or alkaline earth metal, or an ammonium group.
  • the support adsorptive group is preferably at least one group selected from a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, and salts thereof.
  • the support-adsorbing group is more preferably a phosphonic acid group or a salt thereof (structure 1), a phosphate ester group or a salt thereof (structure 2), a carboxylic acid group or a salt thereof, and a phosphate ester group or a salt thereof. Or it is still more preferable that it is a phosphonic acid group or its salt.
  • the repeating unit having a support-adsorptive group is preferably represented by the following general formula (B1).
  • R a to R c each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom.
  • Q represents a support-adsorptive group, and a preferred embodiment is the same as described above.
  • L represents a single bond or a divalent linking group.
  • a divalent linking group can be from 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to It consists of up to 20 sulfur atoms, and more specifically, the following structural units or those constituted by a combination thereof can be mentioned.
  • R d and R e each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom.
  • n represents an integer of 1 to 4.
  • repeating unit having a support adsorptive group Specific examples of the repeating unit having a support adsorptive group are shown below, but the present invention is not limited thereto.
  • the polymer compound may have only one type of support adsorptive group or two or more types.
  • the content of the repeating unit having a support-adsorbing group is preferably 2 to 80 mol%, more preferably 2 to 70 mol%, still more preferably 5 to 50 mol%, based on all repeating units of the polymer compound. 10 to 40 mol% is particularly preferred.
  • the polymer compound has a repeating unit having a hydrophilic group in order to increase the hydrophilicity of the surface of the aluminum support and to suppress etch stains. Specific examples of the hydrophilic group are given below.
  • M 1 represents a hydrogen atom, a metal atom contained in an alkali metal or alkaline earth metal, or an ammonium group.
  • X + represents a group represented by -N + R 1 R 2- , -S + R 1- , -I + -, -P + R 1 R 2- .
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or an alkynyl group
  • R 3 represents an alkylene group
  • R 4 represents an alkyl group, an aryl group, an alkenyl group or an alkynyl group.
  • n represents an integer of 1 to 100.
  • L has the same meaning as L described above.
  • hydrophilic group any functional group having high affinity with water can be suitably used.
  • a sulfonic acid (salt) group an amide group, a polyalkylene oxide group, a hydroxyl group, and a monosulfuric acid group can be used.
  • Ester (salt) group, sulfonamide group, amino group, sulfuric monoamide (salt) group, betaine structure is preferable, sulfonic acid (salt) group, amide group, polyalkylene oxide group, hydroxyl group, sulfuric monoester (salt) group , Sulfonamido group, amino group, sulfuric monoamide (salt) group and betaine structure are more preferred, and sulfonic acid (salt) group, amide group, polyalkylene oxide group, hydroxyl group and betaine structure are particularly preferred.
  • the hydrophilic group is particularly preferably at least one group or structure selected from a sulfonic acid group and a salt thereof, an amide group, and a betaine structure.
  • the repeating unit having a hydrophilic group is preferably represented by the following general formula (B2).
  • R a to R c each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom.
  • L has the same meaning as L described above.
  • W represents a hydrophilic group, and a preferred embodiment is the same as described above.
  • repeating unit having a hydrophilic group examples include but not limited thereto.
  • the polymer compound may have only one kind of hydrophilic group or two or more kinds.
  • the content of the repeating unit having a hydrophilic group is preferably from 30 to 98 mol%, more preferably from 40 to 90 mol%, still more preferably from 50 to 90 mol%, based on all repeating units of the polymer compound.
  • the polymer compound has another repeating unit (hereinafter sometimes simply referred to as “other repeating unit”).
  • a copolymer may also be used. Examples of other repeating units include repeating units derived from various known monomers.
  • the polymer compound includes, for example, a repeating unit having a support-adsorbing group, a repeating unit having a hydrophilic group, a repeating unit corresponding to an alkyl (meth) acrylate or an aralkyl ester, (meth) acrylamide or the like. It may have a repeating unit corresponding to the derivative, a repeating unit corresponding to ⁇ -hydroxymethyl acrylate, and a repeating unit corresponding to the styrene derivative.
  • the alkyl group of the (meth) acrylic acid alkyl ester is preferably an alkyl group having 1 to 5 carbon atoms and an alkyl group having the aforementioned substituent having 2 to 8 carbon atoms, and a methyl group is more preferable.
  • Examples of the (meth) acrylic acid aralkyl ester include benzyl (meth) acrylate.
  • (meth) acrylamide derivatives include N-isopropylacrylamide, N-phenylmethacrylamide, N- (4-methoxycarbonylphenyl) methacrylamide, N, N-dimethylacrylamide, morpholinoacrylamide and the like.
  • Examples of ⁇ -hydroxymethyl acrylate include ethyl ⁇ -hydroxymethyl acrylate and cyclohexyl ⁇ -hydroxymethyl acrylate.
  • Examples of the styrene derivative include styrene and 4-tertbutylstyrene.
  • the content of other repeating units is preferably 40 mol% or less, more preferably 30 mol%, still more preferably 20 mol% or less, based on all repeating units of the polymer compound.
  • the polymer compound includes a repeating unit having at least one group selected from a phosphonic acid group, a phosphoric acid group, a carboxylic acid group and a salt thereof as the support adsorptive group, a sulfonic acid group as the hydrophilic group, and Particularly preferred is a copolymer comprising a salt, an amide group and a repeating unit having at least one group or structure selected from betaine structures.
  • the binder polymer contained in the polymer layer may be used alone or in combination of two or more.
  • the polymer layer may be a single layer or two or more layers.
  • the content of the binder polymer in the polymer layer is preferably 10 to 100% by mass, more preferably 30 to 95% by mass, and still more preferably 40 to 90% by mass with respect to the total solid content of the polymer layer.
  • the on-press development type lithographic printing plate dummy according to the present invention may have an undercoat layer (sometimes referred to as an intermediate layer) between the polymer layer and the support.
  • the undercoat layer is not particularly limited, but the above-described undercoat layer (sometimes referred to as an intermediate layer) that the on-press development type lithographic printing plate precursor may have between the image recording layer and the support. Can be mentioned.
  • the undercoat layer contains a polymer, the undercoat layer corresponds to the polymer layer.
  • the on-press development type lithographic printing plate dummy according to the present invention has a layer containing a compound having support adsorptivity on the polymer layer.
  • the layer containing the compound having support adsorptivity constituting the on-press development type lithographic printing plate dummy plate is the same as the layer containing the compound having support adsorbing property constituting the on-press development type lithographic printing plate precursor. It is.
  • the on-press development type lithographic printing plate dummy has a protective layer (sometimes referred to as an overcoat layer) on a layer containing a compound having a support adsorptivity (a specific compound-containing layer). be able to.
  • a layer containing a compound having support adsorptivity and a protective layer may be integrated and formed as a single layer on a layer containing a compound having support adsorbability.
  • the protective layer that the on-press development type lithographic printing plate dummy plate may have is the same as the protective layer that the on-press development type lithographic printing plate precursor may have.
  • the layer containing the compound having support adsorptivity and the protective layer may be integrated and formed on the polymer layer as one layer.
  • the layer containing the compound having support adsorptivity is prepared by, for example, appropriately dissolving or dispersing each component necessary for the layer containing the compound having support adsorptivity and the protective layer in a solvent.
  • the coating liquid can be formed on the image recording layer by coating and drying by a known method.
  • the on-press development type lithographic printing plate dummy has a sagging shape at the end.
  • the sag shape is the same as the sag shape described as the sag shape of the on-press development type lithographic printing plate precursor at the end.
  • the printing method according to the present invention includes a step of on-machine development of the on-press development type lithographic printing plate dummy plate and the on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support. More specifically, the printing method according to the present invention includes the on-press development type lithographic printing plate dummy plate mounted on the same plate cylinder of a printing press, and an image recording layer on the aluminum support. A step of on-press development of the on-press development type lithographic printing plate precursor;
  • the on-press development type lithographic printing plate dummy plate and the on-press development type lithographic printing plate precursor are mounted on the same plate cylinder of a printing press.
  • a printing machine for example, a newspaper offset rotary printing machine (manufactured by Tokyo Machine Works, Ltd. or Mitsubishi Heavy Industries, Ltd.) is used. Thereafter, printing is performed by a normal method. That is, when dampening water and printing ink are supplied, the constituent layers of the on-press development type lithographic printing plate dummy plate and on-press development type lithographic printing plate precursor are dissolved or dissolved by the supplied dampening water and / or printing ink.
  • the surface of the hydrophilic aluminum support or the aluminum support with the hydrophilic undercoat layer component adsorbed on the surface is exposed at the portion.
  • the fountain solution adheres to the exposed hydrophilic surface and the printing ink is prevented from adhering.
  • the surface of the on-press development type lithographic printing plate dummy plate and on-press development type lithographic printing plate precursor may be supplied with dampening water or printing ink. In order to promote the on-press developability of the layer, it is preferable to supply fountain solution first.
  • the on-press development type lithographic printing plate precursor is subjected to image exposure according to a conventional method before being mounted on a plate cylinder of a printing press.
  • Image exposure is preferably performed by a method of scanning exposure of digital data with an infrared laser or the like.
  • the wavelength of the exposure light source is preferably 750 to 1,400 nm.
  • As the light source of 750 to 1,400 nm a solid laser or semiconductor laser that emits infrared light is suitable.
  • the exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
  • Image exposure can be performed by a known method using a plate setter or the like.
  • exposure may be performed on the printing machine.
  • the on-press development type lithographic printing plate precursor used in the printing method has an image recording layer on an aluminum support.
  • the aluminum support known aluminum supports (including aluminum alloy supports) used for lithographic printing plate precursors are used. Among these, an aluminum plate that has been roughened and anodized by a known method is preferably used.
  • the aluminum support is not particularly limited, but the above-mentioned “on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, and the lithographic printing plate precursor has a sag shape at the end.
  • a layer containing a compound having support adsorptivity on the image recording layer, and the content of the compound is substantially the same in the plane of the layer containing the compound having support adsorptivity.
  • aluminum support having an anodized film in “on-press development type lithographic printing plate precursor” can be mentioned.
  • the image recording layer in the on-press development type lithographic printing plate precursor used in the above printing method is not particularly limited, but the above-mentioned on-press development type lithographic printing plate having an image recording layer on an aluminum support having an anodized film.
  • the image recording layer in the on-press development type lithographic printing plate precursor used in the printing method preferably contains a polymerization initiator.
  • the polymerization initiator is not particularly limited, but the above-mentioned “on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, and the lithographic printing plate precursor has a sag shape at the end.
  • a layer containing a compound having support adsorptivity on the image recording layer, and the content of the compound is substantially the same in the plane of the layer containing the compound having pre-support adsorptivity.
  • Examples of the polymerization initiator that may be contained in the image recording layer in the “on-press development type lithographic printing plate precursor” are the same as those described above.
  • the image recording layer in the on-press development type lithographic printing plate precursor used in the above printing method contains a polymerization initiator containing an organic boron-containing anion.
  • the organic boron-containing anion is preferably a tetraarylborate anion.
  • the tetraarylborate anion is represented by the following general formula (I).
  • R 1 , R 2 , R 3 and R 4 each independently represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms.
  • the aryl group and heteroaryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an aryl group.
  • aryl group examples include phenyl group, tolyl group, xylyl group, mesityl group, duryl group, methoxyphenyl group, dimethoxyphenyl group, chlorophenyl group, fluorophenyl group, trifluoromethylphenyl group, pentafluorophenyl group, naphthyl group.
  • Specific examples of the heteroaryl group include pyridyl group, pyrimidyl group, furanyl group, pyrrolyl group, imidazolyl group, triazolyl group, tetrazolyl group, indolyl group, quinolinyl group, oxadiazolyl group, and benzoxazolyl group.
  • R 1 , R 2 , R 3 and R 4 are preferably a substituted or unsubstituted phenyl group. More preferably, at least three of R 1 , R 2 , R 3 and R 4 are the same substituted or unsubstituted phenyl group.
  • the cation forming the counter ion of the organic boron-containing anion is preferably an iodonium cation, and more preferably a diaryl iodonium cation.
  • a diaryl iodonium cation a compound represented by the structure (I) of US Pat. No. 7,524,614 is preferable.
  • an iodonium compound containing an organic boron-containing anion and a diaryl iodonium cation is preferable.
  • Specific examples of iodonium compounds containing an organic boron-containing anion and a diaryliodonium cation include 4-octyloxyphenylphenyliodonium tetraphenylborate, [4-[(2-hydroxytetradecyl) oxy] phenyl] phenyliodonium tetraphenylborate, Bis (4-tert-butylphenyl) iodonium tetraphenylborate, 4-methylphenyl-4′-hexylphenyliodonium tetraphenylborate, 4-methylphenyl-4′-cyclohexylphenyliodonium tetraphenylborate, bis (tert-butylphenyl)
  • One kind of polymerization initiator containing an organic boron-containing anion may be used alone, or two or more kinds may be mixed and used.
  • the content of the polymerization initiator containing an organic boron-containing anion is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and more preferably 0.8 to 20% with respect to the total solid content of the image recording layer. Mass% is particularly preferred.
  • the image recording layer in the on-press development type lithographic printing plate precursor used in the above printing method preferably contains polymer particles.
  • the polymer particles are not particularly limited, but the above-mentioned “on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, and the lithographic printing plate precursor has a sag shape at the end. And having a layer containing a compound having support adsorptivity on the image recording layer, and the content of the compound is substantially the same in the plane of the layer containing the compound having support adsorptivity Examples of the polymer particles that may be contained in the image recording layer in the “on-press development type lithographic printing plate precursor” are the same.
  • the polymer particles are preferably copolymer particles containing styrene and acrylonitrile.
  • the polymer particles are preferably a microgel.
  • the on-press development type lithographic printing plate precursor used in the printing method of the present invention can have an undercoat layer (sometimes referred to as an intermediate layer) between the image recording layer and the support.
  • the undercoat layer is an “on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, wherein the lithographic printing plate precursor has a sag shape at the end, and the image recording layer
  • An on-press development type lithographic printing having a layer containing a compound having a support adsorptivity on the surface and the content of the compound being substantially the same in the plane of the layer containing the compound having a support adsorptivity It is the same as that described in the undercoat layer that the “plate original plate” may have.
  • the on-press development type lithographic printing plate precursor used in the printing method of the present invention can have a protective layer (sometimes referred to as an overcoat layer) on the image recording layer.
  • the protective layer is the above-mentioned on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, and the lithographic printing plate precursor has a sagging shape at the end, and the image recording layer
  • An on-press development type lithographic printing having a layer containing a compound having a support adsorptivity on the surface and the content of the compound being substantially the same in the plane of the layer containing the compound having a support adsorptivity It is the same as that described in the protective layer that the “plate original plate” may have.
  • the on-press development type lithographic printing plate dummy according to the present invention has characteristics such as on-press developability by having a sag shape at the end and a specific compound-containing layer on the polymer layer. It has a feature that it can exhibit good edge stain resistance even after long-term storage without being reduced.
  • the edge is not subjected to a hydrophilic treatment such as applying a coating solution containing a water-soluble compound, and good edge stains are obtained even after long-term storage. It has a feature that it can exhibit prevention.
  • the on-press development type lithographic printing plate dummy plate according to the present invention is good without being subjected to a hydrophilic treatment such as applying a coating solution containing a water-soluble compound on the edge. It has a feature that it can exhibit excellent edge stain resistance.
  • the on-press development type lithographic printing plate dummy plate according to the present invention is good without being subjected to a hydrophilic treatment such as applying a coating solution containing a water-soluble compound on the edge. It has a feature that it can exhibit excellent edge stain resistance.
  • the support adsorbability of the on-press development type lithographic printing plate dummy plate is increased.
  • the specific compound in the layer containing the compound is eluted by at least one selected from printing ink and fountain solution, and the end of the on-press development type lithographic printing plate precursor dummy and the on-press development type lithographic printing plate precursor By moving to the end portion, the end portion can be hydrophilized, and good edge stain resistance can be exhibited.
  • the molecular weight is a mass average molecular weight (Mw) in terms of polystyrene converted by a gel permeation chromatography (GPC) method, and the ratio of repeating units is a mole percentage.
  • Mw mass average molecular weight
  • GPC gel permeation chromatography
  • (A) Alkaline etching treatment An aqueous solution having a caustic soda concentration of 25 mass%, an aluminum ion concentration of 100 g / L, and a temperature of 60 ° C. is sprayed from a spray tube onto an aluminum plate having a thickness of 0.3 mm (material JIS 1052). It was. The etching amount of the surface of the aluminum plate subjected to the electrochemical roughening treatment was 3 g / m 2 .
  • Electrochemical surface roughening treatment Using an electrolytic solution (liquid temperature 35 ° C.) in which aluminum chloride is dissolved in a 1% by mass hydrochloric acid aqueous solution and aluminum ion concentration is 4.5 g / L, an aluminum plate is subjected to 60 Hz. Using an AC power source, electrochemical surface roughening was continuously performed using a flat cell electrolytic cell. A sine wave was used as the waveform of the AC power supply. In the electrochemical surface roughening treatment, the current density during the anode reaction of the aluminum plate at the peak of alternating current was 30 A / dm 2 .
  • the ratio of the total amount of electricity during the anode reaction of the aluminum plate to the total amount of electricity during the cathode reaction was 0.95.
  • the amount of electricity was 480 C / dm 2 in terms of the total amount of electricity at the time of anode of the aluminum plate.
  • the electrolytic solution was circulated using a pump to stir the electrolytic cell.
  • (D) Alkali etching treatment An aqueous solution having a caustic soda concentration of 5 mass%, an aluminum ion concentration of 5 g / L, and a temperature of 35 ° C. was sprayed from a spray tube onto the aluminum plate to carry out an etching treatment.
  • the etching amount of the aluminum plate subjected to the electrochemical surface roughening treatment was 0.05 g / m 2 .
  • the support (2) is prepared in the same manner as the production of the support (1) except that the anodic oxidation treatment time is adjusted so that the thickness of the anodized film is 750 nm. Produced. The average diameter of the micropores of the anodized film of the support (2) was 25 nm.
  • the support (3) was prepared in the same manner as the production of the support (1), except that the anodic oxidation treatment time was adjusted so that the thickness of the anodized film was 500 nm. Produced. The average diameter of the micropores of the anodized film of the support (3) was 25 nm.
  • the support (4) was produced in the same manner as the production of the support (1) except that (f) the anodizing treatment was changed as follows.
  • the average diameter of the micropores in the anodized film of the support (4) was 35 nm.
  • An image recording layer coating liquid (1) having the following composition is bar-coated on a support and oven-dried at 100 ° C. for 60 seconds to form an image recording layer (1) having a dry coating amount of 1.0 g / m 2. did.
  • the image recording layer coating solution (1) was prepared by mixing and stirring the following photosensitive solution (1) and microgel solution immediately before coating.
  • binder polymer (1) polymerization initiator (1), infrared absorber (1), TPB, low molecular weight hydrophilic compound (1) and fluorine-based surfactant (1) used in the photosensitive solution (1) Is shown below.
  • a method for preparing the microgel (1) used in the microgel solution is shown below.
  • ⁇ Preparation of polyvalent isocyanate compound (1)> In a suspension of 17.78 g (80 mmol) of isophorone diisocyanate and 7.35 g (20 mmol) of the following polyphenol compound (1) in ethyl acetate (25.31 g), bismuth tris (2-ethylhexanoate) (Neostan U -600, Nitto Kasei Co., Ltd.) 43 mg was added and stirred. When the exotherm had subsided, the reaction temperature was set to 50 ° C., and the mixture was stirred for 3 hours to obtain an ethyl acetate solution (50% by mass) of the polyvalent isocyanate compound (1).
  • An image recording layer coating liquid (2) having the following composition is bar-coated on the support and oven dried at 94 ° C. for 60 seconds to form an image recording layer (2) having a dry coating amount of 0.85 g / m 2. did.
  • the polymerizable compound 1 is dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • Graft copolymer 1 is a polymer grafted with poly (oxy-1,2-ethanediyl), ⁇ - (2-methyl-1-oxo-2-propenyl) - ⁇ -methoxy-, ethenylbenzene. This is a 25% dispersion in 80% n-propanol / 20% water solvent.
  • Mercapto-3-triazole is 3-mercapto-1H, 2,4-triazole available from PCAS (France).
  • Irgacure 250 is a 75% propylene carbonate solution of iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] hexafluorophosphate available from Ciba Specialty Chemicals.
  • Klucel 99M is a 1% aqueous solution of a hydroxypropyl cellulose thickener available from Hercules.
  • Byk 336 is a 25% xylene / methoxypropyl acetate solution of modified dimethylpolysiloxane copolymer available from Byk Chemie.
  • a specific compound-containing layer coating solution (1) having the following composition is bar-coated on the image recording layer and oven-dried at 120 ° C. for 60 seconds to form a specific compound-containing layer having a dry coating amount of 0.15 g / m 2. did.
  • CKS50 Polyvinyl alcohol
  • PVA-405 manufactured by Kuraray Co., Ltd., Saponification degree 81.5 mol%, polymerization degree 500
  • a method for preparing the inorganic layered compound dispersion (1) used in the specific compound-containing layer coating solution (1) is shown below.
  • the aspect ratio of the obtained dispersed particles was 100 or more.
  • a specific compound-containing layer coating solution (2) having the following composition is bar-coated on the image recording layer, and oven-dried at 120 ° C. for 60 seconds to contain a specific compound having a dry coating amount of 0.06 g / m 2. A layer was formed.
  • a lithographic printing plate precursor was prepared by combining the support, the image recording layer and the specific compound-containing layer as described in Table 1.
  • the specific compound-containing layer was formed using the specific compound-containing layer coating solution (1) in Examples 1 to 24 and Comparative Examples 1 and 2, and the specific compound-containing layer coating solution (2) in Example 25.
  • the planographic printing plate precursor of Comparative Example 2 was produced as follows. An undercoat layer coating solution (1) having the following composition was applied on the support (1) so that the dry coating amount was 20 mg / m 2, and an aqueous solution of sodium dihydrogen phosphate as a specific compound was not dried. The coating was performed using 2NL04 manufactured by Hyoshin Equipment Co., Ltd. as the coating apparatus.
  • the specific compound is specified at a width of 6 mm at a position 3 cm from the end so that the content of the specific compound is 150 mg / m 2.
  • An aqueous solution of the compound was applied. Thereafter, it was oven-dried at 100 ° C. for 60 seconds.
  • an image recording layer and a specific compound-containing layer were formed in combination as shown in Table 1 to prepare a lithographic printing plate precursor.
  • Undercoat layer compound (1) [the following structure] 0.18 g ⁇ Hydroxyethyliminodiacetic acid 0.05g ⁇ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.03g ⁇ Water 28.0g
  • the planographic printing plate precursor is cut using a rotary blade as shown in FIG. 2 while adjusting the gap between the upper cutting blade and the lower cutting blade, the amount of biting, and the blade edge angle to obtain a sagging amount of 50 ⁇ m and a sagging width of 150 ⁇ m. A sagging shape was formed.
  • the planographic printing plate precursor of Comparative Example 2 was cut at the center of the region where the aqueous solution of the specific compound having a width of 6 mm was applied to obtain a planographic printing plate precursor having a specific compound application region having a width of 3 mm at the end. It was.
  • the support (1) was 13%
  • the support (2) was 8%
  • the support (3) and ( 4) was 6%.
  • the lithographic printing plate precursor was exposed on a Luxcel PLATELTER T-6000III equipped with an infrared semiconductor laser under the conditions of an outer drum rotation speed of 1,000 rpm, a laser output of 70%, and a resolution of 2,000 dpi.
  • a chart including a solid image, a 50% halftone dot, and a non-image portion was used as the exposure image.
  • An image-exposed lithographic printing plate precursor is mounted on an offset rotary printing machine manufactured by Tokyo Machine Works, Ltd., as newspaper printing ink, Soiby KKST-S (red) manufactured by Inktec Co., Ltd., and as dampening water, Toyo Using Toyo ALKY made by Ink Co., Ltd., print on newspapers at a speed of 100,000 pages / hour, and print the 2,000th sheet with a water scale 1.3 times higher than the water scale for eliminating background stains. Sampling was performed, and the degree of linear stains caused by the edge of the lithographic printing plate precursor was observed and evaluated according to the following criteria. 5, 4, 3 are acceptable levels. 5: No linear stains are observed. 4: Discontinuous linear stains are slightly observed. 3: A continuous linear stain
  • planographic printing plate precursor was stored for 2 days in a humid heat environment at a temperature of 60 ° C./humidity of 60%, and then the edge stain resistance after forced aging was evaluated in the same manner as the edge stain resistance after the production. Storage for two days in a humid heat environment at a temperature of 60 ° C./humidity of 60% corresponds to 10 months of natural aging (temperature of 25 ° C./humidity of 50%).
  • the lithographic printing plate precursor subjected to image exposure in the same manner as in the evaluation of the anti-edge stain resistance is mounted on an offset rotary printing machine manufactured by Tokyo Machine Co., Ltd., and used as a newspaper printing ink, Soiby KKST- manufactured by Inktec Co., Ltd. S (Red), Sakata Inx Co., Ltd. Eco Seven N-1 was used as dampening water, printed on newspaper at a speed of 100,000 sheets / hour, 5,000, 10,000, 50,000, 100,000, The 000th printed material was sampled, and the image forming property in an area from the end of the planographic printing plate precursor to 1 mm inside was evaluated according to the following criteria. 5, 4, 3 are acceptable levels. 5: Images can be printed even after printing 100,000 sheets. 4: Images can be printed even after printing 50,000 sheets. 3: Images can be printed even after printing 10,000 sheets. 2: Images can be printed even after printing 5,000 sheets. 1: Images cannot be printed after printing 5000 sheets.
  • lithographic printing plate precursor subjected to image exposure in the same manner as in the evaluation of the anti-edge stain resistance is mounted on an offset rotary printing machine manufactured by Tokyo Machine Co., Ltd., and used as a newspaper printing ink, Soiby KKST- manufactured by Inktec Co., Ltd. S (Red), Sakata Inx Co., Ltd. Eco Seven N-1 was used as dampening water, and printing was performed on newsprint at a speed of 100,000 sheets / hour. Necessary until the on-press development of the unexposed part of the image recording layer on the printing machine is completed in the area from the edge of the lithographic printing plate precursor to 50 mm inward and no ink is transferred to the non-image part.
  • the number of newsprints was measured as the number of on-machine development, and evaluated according to the following criteria. 5, 4, 3, 2 are acceptable levels.
  • a lithographic printing plate precursor containing the specific compound according to the present invention in substantially the same amount in the plane of the specific compound-containing layer provided on the image recording layer is It can be seen that good edge stain resistance is exhibited even after long-term storage without degrading the properties such as property and on-press developability.
  • the planographic printing plate precursor of Comparative Example 1 that does not contain a specific compound clear linear edge stains are generated.
  • the planographic printing plate precursor of Comparative Example 2 having a hydrophilic treatment region at the end of the planographic printing plate precursor the image formability at the end is lowered. I understand that.
  • the second polymer layer coating solution (1) having the following composition was bar coated, followed by oven drying at 100 ° C. for 60 seconds, and a dry coating amount of 0.5 g / m. Two second polymer layers were formed.
  • a specific compound-containing layer coating solution (3) having the following composition is bar-coated on the second polymer layer, and oven-dried at 120 ° C. for 60 seconds to form a specific compound-containing layer having a dry coating amount of 0.15 g / m 2. Formed.
  • CKS50 manufactured by Nippon Synthetic Chemical Industry Co., Ltd., sulfonic acid modification, saponification degree 99 mol% or more, polymerization degree 300
  • PVA-405 manufactured by Kuraray Co., Ltd., Saponification degree 81.5 mol%, polymerization degree 500
  • a lithographic printing plate dummy plate was prepared by combining the support, the first polymer layer, the second polymer layer, and the specific compound-containing layer as described in Table 2.
  • the specific compound-containing layer was formed using the specific compound-containing layer coating solution (3).
  • the planographic printing plate dummy plate of Example 27 was produced as follows. On the support (1), the undercoat layer coating solution (1) having the above composition was bar-coated, followed by oven drying at 100 ° C. for 60 seconds to form a first polymer layer having a dry coating amount of 20 mg / m 2 .
  • the specific compound-containing layer coating solution (3) having the above composition is bar-coated and oven-dried at 120 ° C. for 60 seconds to form a specific compound-containing layer having a dry coating amount of 0.15 g / m 2. Then, a lithographic printing plate dummy plate was produced.
  • the planographic printing plate dummy plate of Comparative Example 4 was produced as follows. On the support (1), the undercoat layer coating solution (1) having the above composition was bar-coated, followed by oven drying at 100 ° C. for 60 seconds to form a first polymer layer having a dry coating amount of 20 mg / m 2 .
  • the specific compound-containing layer coating solution (3) having the above composition is bar-coated and oven-dried at 120 ° C. for 60 seconds to form a specific compound-containing layer having a dry coating amount of 0.15 g / m 2.
  • a lithographic printing plate dummy was formed.
  • [Cutting of lithographic printing plate dummy] A planographic printing plate dummy plate is cut using a rotary blade as shown in FIG. 2 by adjusting the gap between the upper cutting blade and the lower cutting blade, the amount of biting, and the edge angle, and a sagging amount of 50 ⁇ m and a sagging width of 150 ⁇ m. A sagging shape having was formed.
  • the support (1) was 13%.
  • planographic printing plate dummy evaluation of planographic printing plate dummy
  • the planographic printing plate dummy plate was evaluated for edge stain resistance and on-press developability after production and forced aging as follows. The evaluation results are shown in Table 2.
  • a lithographic printing plate dummy plate is mounted on an offset rotary printing machine manufactured by Tokyo Machine Works, Ltd., as newspaper printing ink, Soiby KKST-S (red) manufactured by Inktec Co., Ltd., and as dampening water, Toyo Ink ( Using Toyo ALKY, manufactured by Toyo Co., Ltd., printed on newsprint at a speed of 100,000 sheets / hour, and the 2,000th printed matter was sampled at a water scale 1.3 times higher than the water scale for eliminating soiling.
  • the degree of linear contamination due to the edge of the planographic printing plate dummy was observed and evaluated according to the following criteria. 5, 4, 3 are acceptable levels. 5: No linear stains are observed. 4: Discontinuous linear stains are slightly observed. 3: A continuous linear stain
  • the planographic printing plate dummy plate was stored for 2 days in a wet heat environment at a temperature of 60 ° C./humidity of 60%, and then the edge stain prevention property after forced aging was evaluated in the same manner as the edge stain prevention property after the production. Storage for two days in a humid heat environment at a temperature of 60 ° C./humidity of 60% corresponds to 10 months of natural aging (temperature of 25 ° C./humidity of 50%).
  • a lithographic printing plate dummy is mounted on an offset rotary printing machine manufactured by Tokyo Machine Works, Ltd., as a printing ink for newspapers, Soiby KKST-S (Red) manufactured by Inktec Co., Ltd., and Sakata Inx Co., Ltd. as a dampening solution.
  • Printing was performed on newsprint at a speed of 100,000 sheets / hour using Eco Seven N-1.
  • the number of newspapers required until the on-press development is completed and the ink is not transferred is measured as the on-press developed number. Evaluated by criteria. 5, 4, 3, 2 are acceptable levels.
  • On-machine development number is 25 or less.
  • 4: The number of on-press developed sheets is 26-30.
  • the number of on-press developed sheets is 31 to 35.
  • 2 The number of on-press developed sheets is 36 to 40 sheets.
  • the planographic printing plate dummy containing the specific compound according to the present invention in substantially the same amount in the plane of the specific compound-containing layer provided on the polymer layer is It can be seen that good edge stain resistance is exhibited even after long-term storage without degrading the characteristics. On the other hand, in the planographic printing plate dummy plates of Comparative Examples 3 and 4 that do not contain the specific compound, clear linear edge stains are generated.
  • Example 28 to 29 and Comparative Examples 5 to 6 [Preparation of lithographic printing plate dummy]
  • a lithographic printing plate dummy plate of Example 28 was prepared in the same manner as in Example 26 except that the support (1) was changed to the support (4).
  • a lithographic printing plate dummy plate of Example 29 was prepared in the same manner as in Example 27 except that the support (1) was changed to the support (4).
  • a lithographic printing plate dummy plate of Comparative Example 5 was prepared in the same manner as Comparative Example 3 except that the support (1) was changed to the support (4).
  • a lithographic printing plate dummy plate of Comparative Example 6 was prepared in the same manner as Comparative Example 4 except that the support (1) was changed to the support (4).
  • a planographic printing plate dummy plate is cut using a rotary blade as shown in FIG. 2 by adjusting the gap between the upper cutting blade and the lower cutting blade, the amount of biting, and the edge angle, and a sagging amount of 50 ⁇ m and a sagging width of 150 ⁇ m. A sagging shape having was formed.
  • the support (4) was 6%.
  • Example 30 [Preparation of lithographic printing plate precursor] A lithographic printing plate precursor of Example 30 was prepared in the same manner as in Example 3 except that the specific compound in the specific compound-containing layer was excluded (that is, the specific compound in the specific compound-containing layer coating solution (1) was excluded). did. A planographic printing plate precursor of Example 31 was prepared in the same manner as in Example 23 except that the specific compound in the specific compound-containing layer was excluded (that is, the specific compound in the specific compound-containing layer coating solution (1) was excluded). did.
  • planographic printing plate precursor is cut using a rotary blade as shown in FIG. 2 while adjusting the gap between the upper cutting blade and the lower cutting blade, the amount of biting, and the blade edge angle to obtain a sagging amount of 50 ⁇ m and a sagging width of 150 ⁇ m. A sagging shape was formed.
  • the support (1) was 13% and the support (4) was 6%.
  • Examples 32-35 and Comparative Examples 7-10 The lithographic printing plate precursors obtained in Examples 30 and 31 and the lithographic printing plate dummy plates obtained in Examples 26 to 29 and Comparative Examples 3 to 6 were combined as shown in Table 3 below, and the following evaluation was performed. It was.
  • lithographic printing plate precursor was exposed on a Luxcel PLATELTER T-6000III equipped with an infrared semiconductor laser under the conditions of an outer drum rotation speed of 1,000 rpm, a laser output of 70%, and a resolution of 2,000 dpi.
  • a chart including a solid image, a 50% halftone dot, and a non-image portion was used as the exposure image.
  • One exposed lithographic printing plate precursor and one unexposed lithographic printing plate dummy were mounted on the same plate cylinder of an offset rotary printing machine manufactured by Tokyo Machinery Co., Ltd.
  • an on-press development type lithographic printing plate precursor exhibiting good edge stain resistance even after long-term storage without deteriorating properties such as image forming property and on-press developability at the end, and machine A method for preparing a lithographic printing plate using the upper development type lithographic printing plate precursor can be provided.
  • an on-press development type lithographic printing plate precursor dummy plate and a printing method exhibiting good edge stain resistance even after long-term storage without deteriorating on-press developability and other characteristics are provided. can do.

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Abstract

Provided are: an on-press development type lithographic printing plate precursor which has an image-recording layer on an aluminum support having an anodized film, a sagging shape at one end portion thereof, and a layer on the image-recording layer, the layer containing a compound having support adsorbability, wherein the content of the compound is substantially uniform in the surface of the layer which contains the compound having support adsorbability; and a method for fabricating a lithographic printing plate using said lithographic printing plate precursor.

Description

機上現像型平版印刷版原版、平版印刷版の作製方法、機上現像型平版印刷版ダミー版、及び印刷方法On-press development type lithographic printing plate precursor, lithographic printing plate preparation method, on-press development type lithographic printing plate dummy plate, and printing method
　本発明は、機上現像型平版印刷版原版、平版印刷版の作製方法、機上現像型平版印刷版ダミー版、及び印刷方法に関する。 The present invention relates to an on-press development type lithographic printing plate precursor, a lithographic printing plate preparation method, an on-press development type lithographic printing plate dummy plate, and a printing method.
　一般に、平版印刷版は、印刷過程でインキを受容する親油性の画像部と湿し水を受容する親水性の非画像部とからなる。平版印刷は、水と油性インキとが互いに反発する性質を利用して、平版印刷版の親油性の画像部をインキ受容部、親水性の非画像部を湿し水受容部（インキ非受容部）として、平版印刷版の表面にインキの付着性の差異を生じさせ、画像部のみにインキを着肉させた後、紙等の被印刷体にインキを転写して印刷する方法である。 Generally, a lithographic printing plate is composed of an oleophilic image portion that receives ink during the printing process and a hydrophilic non-image portion that receives dampening water. Lithographic printing utilizes the property that water and oil-based ink repel each other, so that the oleophilic image area of the lithographic printing plate is dampened with the ink receiving area and the hydrophilic non-image area is dampened with the water receiving area (ink non-receiving area). ), A difference in ink adhesion is caused on the surface of the lithographic printing plate, the ink is applied only to the image area, and then the ink is transferred to a printing medium such as paper for printing.
　現在、平版印刷版原版から平版印刷版を作製する製版工程においては、ＣＴＰ（コンピュータ・トゥ・プレート）技術による画像露光が行われている。即ち、画像露光は、リスフィルムを介することなく、レーザーやレーザーダイオードを用いて直接平版印刷版原版に走査露光などにより行われる。 At present, in the plate making process for producing a lithographic printing plate from a lithographic printing plate precursor, image exposure is carried out by CTP (computer to plate) technology. That is, image exposure is performed by scanning exposure or the like directly on a lithographic printing plate precursor using a laser or a laser diode without using a lith film.
　一方、地球環境への関心の高まりから、平版印刷版原版の製版に関して、現像処理などの湿式処理に伴う廃液に関する環境問題がクローズアップされ、これに伴い、現像処理の簡易化又は無処理化が指向されている。簡易な現像処理の一つとして、「機上現像」と呼ばれる方法が提案されている。機上現像は、平版印刷版原版を画像露光後、従来の湿式現像処理を行わず、そのまま印刷機に取り付け、画像記録層の非画像部の除去を通常の印刷工程の初期段階で行う方法である。 On the other hand, due to the growing interest in the global environment, environmental issues related to waste liquids associated with wet processing such as development processing have been highlighted in relation to plate making of lithographic printing plate precursors, and as a result, development processing has been simplified or eliminated. It is oriented. As one simple development process, a method called “on-press development” has been proposed. On-press development is a method in which the lithographic printing plate precursor is subjected to image exposure and then subjected to the conventional wet development treatment, and is directly attached to the printing press, and the non-image portion of the image recording layer is removed at the initial stage of the normal printing process. is there.
　平版印刷版を用いて印刷する場合、通常の枚葉印刷機のように印刷版のサイズよりも小さい紙への印刷においては、印刷版の端部は紙面外の位置にあるので端部が印刷品質に影響することはない。しかし、新聞印刷のような輪転機を用いてロール状の紙に連続して印刷する場合には、印刷版の端部はロール紙面内にあるため、端部に付着したインキが紙に転写して線状の汚れ（エッジ汚れ）が発生し、印刷物の商品価値を著しく損ねることになる。 When printing on a planographic printing plate, when printing on paper smaller than the size of the printing plate as in a normal sheet-fed printing press, the edge of the printing plate is printed because it is located outside the paper. There is no impact on quality. However, when printing continuously on a roll of paper using a rotary press such as newspaper printing, the edge of the printing plate is within the roll paper surface, so the ink adhering to the edge is transferred to the paper. As a result, linear stains (edge stains) are generated, and the commercial value of the printed matter is significantly impaired.
　上記エッジ汚れの発生を抑制することを目的として、特許文献１には、支持体と画像記録層とを有する平版印刷版原版の対向する２つの側面の端部の画像記録層側版面に、親水化成分により処理されてなる親水化領域が形成され、上記平版印刷版原版の対向する上記２つの側面の端部から内部に３ｍｍまでの画像記録層側版面の領域Ａに含まれる親水化成分の単位面積当たりの含有量が、上記領域Ａ以外の領域における親水化成分の単位面積当たりの含有量より１０ｍｇ／ｍ２以上多い平版印刷版原版の積層体が提案されている。 For the purpose of suppressing the occurrence of the edge stains, Patent Document 1 discloses that hydrophilicity is provided on the image recording layer side plate surface at the ends of two opposing side surfaces of a lithographic printing plate precursor having a support and an image recording layer. Of the hydrophilic component contained in the region A of the image recording layer side plate surface up to 3 mm from the end of the two side surfaces facing each other of the lithographic printing plate precursor. A laminate of a lithographic printing plate precursor in which the content per unit area is 10 mg / m 2 or more higher than the content per unit area of the hydrophilizing component in the region other than the region A has been proposed.
日本国特開２０１７－１９２０６号公報Japanese Unexamined Patent Publication No. 2017-19206
　上記特許文献１に記載の平版印刷版原版においては、エッジ汚れの発生を抑制するために、上記親水化成分を含有する塗布液を塗布するなどの手段により、端部領域Ａにおける水溶性化合物の含有量を、端部領域Ａ以外の領域における親水化成分の含有量に比べて１０ｍｇ／ｍ２以上多くすることが特徴である。
　しかしながら、平版印刷版原版の端部領域に、親水化成分を含有する塗布液を塗布するなどの親水化処理を施すと、親水化処理を施した端部領域において画像形成性が低下するという現象が生じることが分かった。このことは、親水化処理を施すことにより、画像記録層の機械的強度が低下すること、及び、画像記録層と支持体との密着力が低下することに起因して、機上現像時に、端部領域における画像記録層が保持されず、非画像部と共に除去されることが原因と考えられる。 In the lithographic printing plate precursor described in Patent Document 1, in order to suppress the occurrence of edge stains, the water-soluble compound in the end region A is applied by means such as applying a coating solution containing the hydrophilic component. It is characterized in that the content is increased by 10 mg / m 2 or more compared to the content of the hydrophilic component in the region other than the end region A.
However, if a hydrophilic treatment such as applying a coating liquid containing a hydrophilic component is applied to the edge region of the lithographic printing plate precursor, the image forming property is lowered in the edge region subjected to the hydrophilic treatment. Was found to occur. This is because the mechanical strength of the image recording layer is lowered by applying a hydrophilic treatment, and the adhesion between the image recording layer and the support is lowered, and during on-press development, It is considered that the image recording layer in the edge region is not retained and is removed together with the non-image portion.
　本発明が解決しようとする課題は、端部の画像形成性、機上現像性などの特性を低下させることなく、長期保存後においても良好なエッジ汚れ防止性を示す機上現像型平版印刷版原版、及び機上現像型平版印刷版原版を用いた平版印刷版の作製方法を提供することである。
　また、本発明が解決しようとする課題は、機上現像性などの特性を低下させることなく、長期保存後においても良好なエッジ汚れ防止性を示す機上現像型平版印刷版原版ダミー版、及び印刷方法を提供することである。 The problem to be solved by the present invention is an on-press development type lithographic printing plate that exhibits good edge stain resistance even after long-term storage without deteriorating the properties such as image forming properties and on-press developability at the edges. It is to provide a method for preparing a lithographic printing plate using an original plate and an on-press development type lithographic printing plate precursor.
Further, the problem to be solved by the present invention is an on-press development type lithographic printing plate precursor dummy plate that exhibits good edge stain resistance even after long-term storage without degrading on-press developability and other properties, and It is to provide a printing method.
　上記課題を解決するための手段を以下に記載する。 Measures for solving the above problems are described below.
（１）　陽極酸化皮膜を有するアルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版であって、上記平版印刷版原版は端部にダレ形状を有し、上記画像記録層の上に支持体吸着性を有する化合物を含有する層を有し、上記化合物の含有量が上記支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版原版。
（２）　上記化合物の分子量が１，０００以下である（１）に記載の機上現像型平版印刷版原版。
（３）　上記支持体吸着性を有する化合物を含有する層が更に界面活性剤を含有する（１）又は（２）に記載の機上現像型平版印刷版原版。
（４）　上記支持体吸着性を有する化合物を含有する層が更に水溶性ポリマーを含有する（１）～（３）のいずれか１項に記載の機上現像型平版印刷版原版。
（５）　上記化合物がオキソ酸又はその塩である（１）～（４）のいずれか１項に記載の機上現像型平版印刷版原版。
（６）　上記化合物が下記式１で表わされる化合物である（１）～（５）のいずれか１項に記載の機上現像型平版印刷版原版。 (1) An on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, wherein the lithographic printing plate precursor has a sag shape at an end thereof, An on-press development type lithographic plate having a layer containing a compound having support adsorptivity on the surface, and the content of the compound being substantially the same in the plane of the layer containing the compound having support adsorbing property A printing plate master.
(2) The on-press development type lithographic printing plate precursor as described in (1), wherein the molecular weight of the compound is 1,000 or less.
(3) The on-press development type lithographic printing plate precursor as described in (1) or (2), wherein the layer containing the compound having support adsorptivity further contains a surfactant.
(4) The on-press development type lithographic printing plate precursor as described in any one of (1) to (3), wherein the layer containing the support-adsorbing compound further contains a water-soluble polymer.
(5) The on-press development type lithographic printing plate precursor as described in any one of (1) to (4), wherein the compound is oxo acid or a salt thereof.
(6) The on-press development type lithographic printing plate precursor as described in any one of (1) to (5), wherein the compound is a compound represented by the following formula 1.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式１中、ｎは、２～１０の整数を表し、Ｒ１、Ｒ２、Ｒ３は、それぞれ独立に、水素原子、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アルキル基又はアルキレンオキシド基を表す。
（７）　上記化合物がリン酸、ポリリン酸、ホスホン酸もしくはホスフィン酸又はこれらの塩である（１）～（６）のいずれか１項に記載の機上現像型平版印刷版原版。
（８）　上記化合物の含有量が２０～１５０ｍｇ／ｍ２である（１）～（７）のいずれか１項に記載の機上現像型平版印刷版原版。
（９）　上記ダレ形状が、ダレ量Ｘが２５～１５０μｍ、ダレ幅Ｙが７０～３００μｍである（１）～（８）のいずれか１項に記載の機上現像型平版印刷版原版。
（１０）　上記平版印刷版原版のダレ幅Ｙに相当する領域の上記陽極酸化皮膜の表面に存在するクラックの面積率が２０％以下である（９）に記載の機上現像型平版印刷版原版。
（１１）　上記クラックの面積率が１０％以下である（１０）に記載の機上現像型平版印刷版原版。
（１２）　上記画像記録層が、ポリマー粒子を含有する（１）～（１１）のいずれか１項に記載の機上現像型平版印刷版原版。
（１３）　上記ポリマー粒子が、スチレン化合物に由来するモノマー単位、及び／又は、（メタ）アクリロニトリル化合物に由来するモノマー単位を含むポリマーの粒子である（１２）に記載の機上現像型平版印刷版原版。
（１４）　上記画像記録層が、重合開始剤、赤外線吸収剤及び重合性化合物を含有する（１）～（１３）のいずれか１項に記載の機上現像型平版印刷版原版。
（１５）　（１）～（１４）のいずれか１項に記載の機上現像型平版印刷版原版を、赤外線レーザーにより画像露光する工程と、印刷機上で印刷インキ及び湿し水から選ばれる少なくとも１つにより、画像記録層の未露光部分を除去する工程とを含む平版印刷版の作製方法。 In Formula 1, n represents an integer of 2 to 10, and R1, R2, and R3 each independently represent a hydrogen atom, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an alkyl group, or an alkylene oxide group. .
(7) The on-press development type lithographic printing plate precursor as described in any one of (1) to (6), wherein the compound is phosphoric acid, polyphosphoric acid, phosphonic acid, phosphinic acid or a salt thereof.
(8) The on-press development type lithographic printing plate precursor as described in any one of (1) to (7), wherein the content of the compound is 20 to 150 mg / m 2 .
(9) The on-press development type lithographic printing plate precursor as described in any one of (1) to (8), wherein the sagging shape has a sagging amount X of 25 to 150 μm and a sagging width Y of 70 to 300 μm.
(10) The on-press development type lithographic printing plate precursor as described in (9), wherein the area ratio of cracks present on the surface of the anodic oxide film in the region corresponding to the sag width Y of the lithographic printing plate precursor is 20% or less .
(11) The on-press development type lithographic printing plate precursor as described in (10), wherein the crack has an area ratio of 10% or less.
(12) The on-press development type lithographic printing plate precursor as described in any one of (1) to (11), wherein the image recording layer contains polymer particles.
(13) The on-press development type lithographic printing plate according to (12), wherein the polymer particle is a polymer particle including a monomer unit derived from a styrene compound and / or a monomer unit derived from a (meth) acrylonitrile compound. Original edition.
(14) The on-press development type lithographic printing plate precursor as described in any one of (1) to (13), wherein the image recording layer contains a polymerization initiator, an infrared absorber and a polymerizable compound.
(15) The on-press development type lithographic printing plate precursor according to any one of (1) to (14) is selected from a step of image exposure with an infrared laser, and a printing ink and a fountain solution on the printing press. And a step of removing an unexposed portion of the image recording layer by at least one.
（１６）
　陽極酸化皮膜を有するアルミニウム支持体上にポリマー層を有する機上現像型平版印刷版ダミー版であって、上記平版印刷版ダミー版は端部にダレ形状を有し、上記ポリマー層の上に支持体吸着性を有する化合物を含有する層を有し、上記化合物の含有量が上記支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版ダミー版。
（１７）
　（１６）に記載の機上現像型平版印刷版ダミー版、及び、アルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版を機上現像する工程を含む印刷方法。
（１８）
　上記画像記録層が有機ホウ素含有アニオンを含む重合開始剤を含有する（１７）に記載の印刷方法。
（１９）
　上記重合開始剤が、有機ホウ素含有アニオン及びジアリールヨードニウムカチオンを含むヨードニウム化合物である（１８）に記載の印刷方法。
（２０）
　上記画像記録層が、ポリマー微粒子を含有する（１７）～（１９）のいずれか一項に記載の印刷方法。
（２１）
　上記ポリマー微粒子が、スチレン及びアクリロニトリルを含む共重合体の粒子である（２０）に記載の印刷方法。
（２２）
　上記ポリマー微粒子が、ミクロゲルである（２０）に記載の印刷方法。
（２３）
　上記機上現像型平版印刷版原版が、上記アルミニウム支持体と上記画像記録層の間に下塗り層を有する（１７）～（２２）のいずれか一項に記載の印刷方法。
（２４）
　上記機上現像型平版印刷版原版が、上記画像記録層の上に保護層を有する（１７）～（２３）のいずれか一項に記載の印刷方法。 (16)
An on-press development type lithographic printing plate dummy plate having a polymer layer on an aluminum support having an anodized film, wherein the lithographic printing plate dummy plate has a sagging shape at an end and is supported on the polymer layer An on-press development type lithographic printing plate dummy having a layer containing a compound having a body adsorptivity, wherein the content of the compound is substantially the same in the plane of the layer containing the compound having a support adsorptivity Edition.
(17)
A printing method comprising the on-press development of the on-press development type lithographic printing plate dummy plate according to (16) and the on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support.
(18)
The printing method according to (17), wherein the image recording layer contains a polymerization initiator containing an organic boron-containing anion.
(19)
The printing method according to (18), wherein the polymerization initiator is an iodonium compound containing an organic boron-containing anion and a diaryl iodonium cation.
(20)
The printing method according to any one of (17) to (19), wherein the image recording layer contains polymer fine particles.
(21)
The printing method according to (20), wherein the polymer fine particles are copolymer particles containing styrene and acrylonitrile.
(22)
The printing method according to (20), wherein the polymer fine particle is a microgel.
(23)
The printing method according to any one of (17) to (22), wherein the on-press development type lithographic printing plate precursor has an undercoat layer between the aluminum support and the image recording layer.
(24)
The printing method according to any one of (17) to (23), wherein the on-press development type lithographic printing plate precursor has a protective layer on the image recording layer.
　本発明によれば、端部の画像形成性、機上現像性などの特性を低下させることなく、長期保存後においても良好なエッジ汚れ防止性を示す機上現像型平版印刷版原版、及び機上現像型平版印刷版原版を用いた平版印刷版の作製方法を提供することができる。
　また、本発明によれば、機上現像性などの特性を低下させることなく、長期保存後においても良好なエッジ汚れ防止性を示す機上現像型平版印刷版原版ダミー版、及び印刷方法を提供することができる。 According to the present invention, an on-press development type lithographic printing plate precursor exhibiting good edge stain resistance even after long-term storage without deteriorating properties such as image forming property and on-press developability at the end, and machine A method for preparing a lithographic printing plate using the upper development type lithographic printing plate precursor can be provided.
In addition, according to the present invention, an on-press development type lithographic printing plate precursor dummy plate and a printing method exhibiting good edge stain resistance even after long-term storage without deteriorating on-press developability and other characteristics are provided. can do.
平版印刷版原版の端部の断面形状を示す模式図である。It is a schematic diagram which shows the cross-sectional shape of the edge part of a lithographic printing plate precursor. スリッター装置の裁断部の１例を示す概念図である。It is a conceptual diagram which shows an example of the cutting part of a slitter apparatus.
　以下に、発明を実施するための形態を詳細に記載する。
　本明細書において、式で表される化合物における基の表記に関して、置換あるいは無置換を記していない場合、当該基が更に置換基を有することが可能な場合には、他に特に規定がない限り、無置換の基のみならず置換基を有する基も包含する。例えば、式において、「Ｒはアルキル基、アリール基又は複素環基を表す」との記載があれば、「Ｒは無置換アルキル基、置換アルキル基、無置換アリール基、置換アリール基、無置換複素環基又は置換複素環基を表す」ことを意味する。
　本明細書において、「（メタ）アクリレート」の用語は「アクリレート及びメタクリレートの少なくともいずれか」を意味する。「（メタ）アクリロイル基」、「（メタ）アクリル酸」、「（メタ）アクリル樹脂」等も同様である。 Hereinafter, modes for carrying out the invention will be described in detail.
In this specification, regarding the notation of a group in a compound represented by the formula, if it is not substituted or unsubstituted, and the group can further have a substituent, unless otherwise specified, In addition to an unsubstituted group, a group having a substituent is also included. For example, in the formula, if there is a description that “R represents an alkyl group, an aryl group or a heterocyclic group”, “R is an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted group” Represents a heterocyclic group or a substituted heterocyclic group.
In this specification, the term “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acryloyl group”, “(meth) acrylic acid”, “(meth) acrylic resin” and the like.
［機上現像型平版印刷版原版］
　本発明に係る機上現像型平版印刷版原版は、陽極酸化皮膜を有するアルミニウム支持体と画像記録層とを少なくとも有し、平版印刷版原版の端部にダレ形状を有し、画像記録層の上に支持体吸着性を有する化合物を含有する層を有し、上記化合物の含有量が上記支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版原版である。 [On-press development type lithographic printing plate precursor]
The on-press development type lithographic printing plate precursor according to the present invention has at least an aluminum support having an anodized film and an image recording layer, has a sagging shape at the end of the lithographic printing plate precursor, An on-press development type lithographic plate having a layer containing a compound having support adsorptivity on the surface, and the content of the compound being substantially the same in the plane of the layer containing the compound having support adsorbing property It is a printing plate master.
〔陽極酸化皮膜を有するアルミニウム支持体〕
　機上現像型平版印刷版原版を構成する陽極酸化皮膜を有するアルミニウム支持体について記載する。 [Aluminum support with anodized film]
An aluminum support having an anodized film constituting the on-press development type lithographic printing plate precursor will be described.
　アルミニウム支持体に用いられるアルミニウム板は、寸度的に安定なアルミニウムを主成分とする金属、即ちアルミニウムまたはアルミニウム合金からなる。純アルミニウム板及びアルミニウムを主成分とし微量の異元素を含む合金板から選ばれることが好ましい。 The aluminum plate used for the aluminum support is made of a dimensionally stable aluminum-based metal, that is, aluminum or an aluminum alloy. It is preferably selected from a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements.
　アルミニウム合金に含まれる異元素には、ケイ素、鉄、マンガン、銅、マグネシウム、クロム、亜鉛、ビスマス、ニッケル、チタンなどがある。合金中の異元素の含有量は１０質量％以下である。純アルミニウム板が好適であるが、完全に純粋なアルミニウムは製錬技術上製造が困難であるので、僅かに異元素を含有する合金板でもよい。アルミニウム支持体に用いられるアルミニウム板は、その組成が特定されるものではなく、従来から公知のアルミニウム板、例えばＪＩＳ　Ａ　１０５０、ＪＩＳ　Ａ　１１００、ＪＩＳ　Ａ　３１０３、ＪＩＳ　Ａ　３００５などを適宜利用することが出来る。
　アルミニウム板の厚さは、０．１～０．６ｍｍ程度が好ましい。 Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. Content of the different element in an alloy is 10 mass% or less. A pure aluminum plate is suitable, but since completely pure aluminum is difficult to manufacture in terms of smelting technology, an alloy plate containing a slightly different element may be used. The composition of the aluminum plate used for the aluminum support is not specified, and conventionally known aluminum plates such as JIS A 1050, JIS A 1100, JIS A 3103, and JIS A 3005 can be used as appropriate. I can do it.
The thickness of the aluminum plate is preferably about 0.1 to 0.6 mm.
　陽極酸化皮膜は、陽極酸化処理によりアルミニウム板の表面に形成される、皮膜表面に略垂直であり、個々が均一に分布した極微細孔（マイクロポアともいう）を有する陽極酸化アルミニウム皮膜を意味する。マイクロポアは、陽極酸化皮膜表面から厚み方向に向かってのびている。 An anodized film means an anodized aluminum film that is formed on the surface of an aluminum plate by an anodizing treatment and that is substantially perpendicular to the surface of the film and has extremely fine pores (also referred to as micropores) that are uniformly distributed. . The micropores extend in the thickness direction from the surface of the anodized film.
〔アルミニウム支持体の製造方法〕
　アルミニウム支持体の製造方法は、特に限定されるものではない。アルミニウム支持体の製造方法の好ましい態様としては、アルミニウム板に粗面化処理を施す工程（粗面化処理工程）、粗面化処理されたアルミニウム板を陽極酸化する工程（陽極酸化処理工程）、陽極酸化処理工程で得られた陽極酸化皮膜を有するアルミニウム板を、酸水溶液又はアルカリ水溶液に接触させ、陽極酸化皮膜中のマイクロポアの径を拡大させる工程（ポアワイド処理工程）を含む方法が挙げられる。 [Method for producing aluminum support]
The method for producing the aluminum support is not particularly limited. As a preferable aspect of the manufacturing method of the aluminum support, a step of roughening the aluminum plate (roughening step), a step of anodizing the roughened aluminum plate (anodizing step), Examples include a method including a step (pore wide treatment step) in which an aluminum plate having an anodized film obtained in the anodizing treatment step is brought into contact with an acid aqueous solution or an alkaline aqueous solution to increase the diameter of micropores in the anodized film. .
　以下に、各工程を詳細に説明する。 Below, each process is explained in detail.
＜粗面化処理工程＞
　粗面化処理工程は、アルミニウム板の表面に、電気化学的粗面化処理を含む粗面化処理を施す工程である。粗面化処理工程は、後述する陽極酸化処理工程の前に実施されることが好ましいが、アルミニウム板の表面がすでに好ましい表面形状を有していれば、実施しなくてもよい。 <Roughening treatment process>
The roughening treatment step is a step of performing a roughening treatment including an electrochemical roughening treatment on the surface of the aluminum plate. The roughening treatment step is preferably performed before the anodizing step described later, but may not be performed if the surface of the aluminum plate already has a preferable surface shape.
　粗面化処理は、電気化学的粗面化処理のみを施してもよいが、電気化学的粗面化処理と機械的粗面化処理および／または化学的粗面化処理とを組み合わせて施してもよい。
　機械的粗面化処理と電気化学的粗面化処理とを組み合わせる場合には、機械的粗面化処理の後に、電気化学的粗面化処理を施すのが好ましい。 The surface roughening treatment may be performed only by electrochemical surface roughening treatment, but may be performed by combining electrochemical surface roughening treatment with mechanical surface roughening treatment and / or chemical surface roughening treatment. Also good.
When the mechanical surface roughening treatment and the electrochemical surface roughening treatment are combined, it is preferable to perform the electrochemical surface roughening treatment after the mechanical surface roughening treatment.
　電気化学的粗面化処理は、硝酸や塩酸の水溶液中で施すのが好ましい。 The electrochemical surface roughening treatment is preferably performed in an aqueous solution of nitric acid or hydrochloric acid.
　機械的粗面化処理は、一般的には、アルミニウム板の表面を表面粗さＲa：０．３５～１．０μｍとする目的で施される。
　機械的粗面化処理の諸条件は特に限定されないが、例えば、特公昭５０－４００４７号公報に記載されている方法に従って施すことができる。機械的粗面化処理は、パミストン懸濁液を使用したブラシグレイン処理により施したり、転写方式で施したりすることができる。
　また、化学的粗面化処理も特に限定されず、公知の方法に従って施すことができる。 The mechanical surface roughening treatment is generally performed for the purpose of setting the surface of the aluminum plate to a surface roughness Ra: 0.35 to 1.0 μm.
Various conditions for the mechanical surface-roughening treatment are not particularly limited, and for example, they can be applied according to the method described in JP-B-50-40047. The mechanical surface roughening treatment can be performed by brush grain processing using a pumiston suspension or can be performed by a transfer method.
Further, the chemical surface roughening treatment is not particularly limited, and can be performed according to a known method.
　機械的粗面化処理の後には、以下の化学エッチング処理を施すのが好ましい。
　機械的粗面化処理の後に施される化学エッチング処理は、アルミニウム板の表面の凹凸形状のエッジ部分をなだらかにし、印刷時のインキの引っかかりを防止し、平版印刷版の耐汚れ性を向上させるとともに、表面に残った研磨材粒子等の不要物を除去するために行われる。
　化学エッチング処理としては、酸によるエッチングやアルカリによるエッチングが知られているが、エッチング効率の点で特に優れている方法として、アルカリ溶液を用いる化学エッチング処理（以下、「アルカリエッチング処理」ともいう。）が挙げられる。 After the mechanical surface roughening treatment, the following chemical etching treatment is preferably performed.
The chemical etching process performed after the mechanical roughening process smoothes the uneven edges of the surface of the aluminum plate, prevents ink from being caught during printing, and improves the stain resistance of the lithographic printing plate At the same time, it is performed to remove unnecessary materials such as abrasive particles remaining on the surface.
As the chemical etching treatment, acid etching or alkali etching is known, but as a method that is particularly excellent in terms of etching efficiency, chemical etching treatment using an alkaline solution (hereinafter also referred to as “alkali etching treatment”). ).
　アルカリ溶液に用いられるアルカリ剤は、特に限定されないが、例えば、カセイソーダ、カセイカリ、メタケイ酸ソーダ、炭酸ソーダ、アルミン酸ソーダ、グルコン酸ソーダ等が好適に挙げられる。
　また、アルカリ剤は、アルミニウムイオンを含有してもよい。アルカリ溶液の濃度は、０．０１質量％以上であるのが好ましく、３質量％以上であるのがより好ましく、また、３０質量％以下であるのが好ましく、２５質量％以下であるのがより好ましい。
　更に、アルカリ溶液の温度は室温以上であるのが好ましく、３０℃以上であるのがより好ましく、８０℃以下であるのが好ましく、７５℃以下であるのがより好ましい。 The alkaline agent used in the alkaline solution is not particularly limited, and preferred examples include caustic soda, caustic potash, sodium metasilicate, sodium carbonate, sodium aluminate, and sodium gluconate.
Further, the alkaline agent may contain aluminum ions. The concentration of the alkaline solution is preferably 0.01% by mass or more, more preferably 3% by mass or more, more preferably 30% by mass or less, and more preferably 25% by mass or less. preferable.
Furthermore, the temperature of the alkaline solution is preferably room temperature or higher, more preferably 30 ° C. or higher, preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
　エッチング量は、０．１ｇ／ｍ２以上であるのが好ましく、１ｇ／ｍ２以上であるのがより好ましく、また、２０ｇ／ｍ２以下であるのが好ましく、１０ｇ／ｍ２以下であるのがより好ましい。
　また、処理時間は、エッチング量に対応して２秒～５分であるのが好ましく、生産性向上の点から２～１０秒であるのがより好ましい。 The etching amount is preferably 0.1 g / m 2 or more, more preferably 1 g / m 2 or more, more preferably 20 g / m 2 or less, and 10 g / m 2 or less. Is more preferable.
The treatment time is preferably 2 seconds to 5 minutes corresponding to the etching amount, and more preferably 2 to 10 seconds from the viewpoint of improving productivity.
　機械的粗面化処理後にアルカリエッチング処理を施した場合、アルカリエッチング処理により生じる生成物を除去するために、低温の酸性溶液を用いて化学エッチング処理（以下、「デスマット処理」ともいう。）を施すのが好ましい。
　酸性溶液に用いられる酸は、特に限定されないが、例えば、硫酸、硝酸、塩酸が挙げられる。酸性溶液の濃度は、１～５０質量％であるのが好ましい。また、酸性溶液の温度は、２０～８０℃であるのが好ましい。酸性溶液の濃度および温度がこの範囲であると、アルミニウム支持体を用いた平版印刷版の耐ポツ状汚れ性がより向上する。 When an alkali etching process is performed after the mechanical surface roughening process, a chemical etching process (hereinafter also referred to as “desmut process”) is performed using a low-temperature acidic solution in order to remove products generated by the alkali etching process. It is preferable to apply.
Although the acid used for an acidic solution is not specifically limited, For example, a sulfuric acid, nitric acid, and hydrochloric acid are mentioned. The concentration of the acidic solution is preferably 1 to 50% by mass. The temperature of the acidic solution is preferably 20 to 80 ° C. When the concentration and temperature of the acidic solution are within this range, the spot-like stain resistance of the lithographic printing plate using the aluminum support is further improved.
　上記粗面化処理は、所望により機械的粗面化処理および化学エッチング処理を施した後に、電気化学的粗面化処理を施す処理であるが、機械的粗面化処理を行わずに電気化学的粗面化処理を施す場合にも、電気化学的粗面化処理の前に、カセイソーダ等のアルカリ水溶液を用いて化学エッチング処理を施すことができる。これにより、アルミニウム板の表面近傍に存在する不純物等を除去することができる。 The above roughening treatment is a treatment in which an electrochemical roughening treatment is performed after a mechanical roughening treatment and a chemical etching treatment if desired, but the electrochemical roughening treatment is performed without performing the mechanical roughening treatment. Also in the case of performing the roughening treatment, the chemical etching treatment can be performed using an alkaline aqueous solution such as caustic soda before the electrochemical roughening treatment. Thereby, impurities existing in the vicinity of the surface of the aluminum plate can be removed.
　電気化学的粗面化処理は、アルミニウム板の表面に微細な凹凸（ピット）を付与することが容易であるため、印刷性の優れた平版印刷版を作るのに適している。
　電気化学的粗面化処理は、硝酸または塩酸を主体とする水溶液中で、直流または交流を用いて行われる。 The electrochemical roughening treatment is suitable for making a lithographic printing plate having excellent printability because it is easy to impart fine irregularities (pits) to the surface of the aluminum plate.
The electrochemical surface roughening treatment is performed using direct current or alternating current in an aqueous solution mainly composed of nitric acid or hydrochloric acid.
　また、電気化学的粗面化処理の後には、以下の化学エッチング処理を行うのが好ましい。電気化学的粗面化処理後のアルミニウム板の表面には、スマットや金属間化合物が存在する。電気化学的粗面化処理の後に行われる化学エッチング処理においては、特にスマットを効率よく除去するため、まず、アルカリ溶液を用いて化学エッチング処理（アルカリエッチング処理）をするのが好ましい。アルカリ溶液を用いた化学エッチング処理の諸条件は、処理温度は２０～８０℃であるのが好ましく、また、処理時間は１～６０秒であるのが好ましい。また、アルカリ溶液中にアルミニウムイオンを含有するのが好ましい。 Further, it is preferable to perform the following chemical etching treatment after the electrochemical surface roughening treatment. Smut and intermetallic compounds exist on the surface of the aluminum plate after the electrochemical roughening treatment. In the chemical etching process performed after the electrochemical surface roughening process, it is preferable to first perform a chemical etching process (alkali etching process) using an alkaline solution in order to efficiently remove smut. Regarding various conditions of the chemical etching treatment using an alkaline solution, the treatment temperature is preferably 20 to 80 ° C., and the treatment time is preferably 1 to 60 seconds. Moreover, it is preferable to contain aluminum ion in an alkaline solution.
　更に、電気化学的粗面化処理後にアルカリ溶液を用いる化学エッチング処理を行った後、それにより生じる生成物を除去するために、低温の酸性溶液を用いて化学エッチング処理（デスマット処理）を行うのが好ましい。
　また、電気化学的粗面化処理後にアルカリエッチング処理を行わない場合においても、スマットを効率よく除去するため、デスマット処理を行うのが好ましい。 Furthermore, after the electrochemical surface roughening treatment, a chemical etching treatment using an alkaline solution is performed, and then a chemical etching treatment (desmut treatment) is performed using a low-temperature acidic solution in order to remove the resulting products. Is preferred.
Even when the alkali etching treatment is not performed after the electrochemical surface roughening treatment, it is preferable to perform a desmut treatment in order to efficiently remove the smut.
　上記化学エッチング処理は、いずれも浸せき法、シャワー法、塗布法等により行うことができ、特に限定されない。 Any of the above chemical etching processes can be performed by a dipping method, a shower method, a coating method, or the like, and is not particularly limited.
＜陽極酸化処理工程＞
　陽極酸化処理工程は、上記粗面化処理が施されたアルミニウム板に陽極酸化処理を施すことにより、アルミニウム板表面に深さ方向（厚み方向）にのびるマイクロポアを有するアルミニウムの酸化皮膜を形成する工程である。この陽極酸化処理によりアルミニウム板の表面に、マイクロポアを有するアルミニウムの陽極酸化皮膜が形成される。 <Anodizing process>
In the anodizing step, an aluminum oxide film having micropores extending in the depth direction (thickness direction) is formed on the surface of the aluminum plate by anodizing the aluminum plate that has been subjected to the roughening treatment. It is a process. By this anodic oxidation treatment, an aluminum anodic oxide film having micropores is formed on the surface of the aluminum plate.
　陽極酸化処理は、この分野で従来から行われている方法で行うことができるが、上記マイクロポアを最終的に形成できるように適宜製造条件が設定される。具体的には、陽極酸化処理工程において形成されるマイクロポアの平均径（平均開口径）は、通常、４～１４ｎｍ程度であり、好ましくは５～１０ｎｍである。上記範囲内であれば、所定の形状を有するマイクロポアが形成しやすく、得られる平版印刷版原版および平版印刷版の性能もより優れる。 The anodizing treatment can be performed by a method conventionally used in this field, but manufacturing conditions are appropriately set so that the micropores can be finally formed. Specifically, the average diameter (average opening diameter) of the micropores formed in the anodizing treatment step is usually about 4 to 14 nm, preferably 5 to 10 nm. Within the above range, micropores having a predetermined shape can be easily formed, and the performance of the obtained lithographic printing plate precursor and lithographic printing plate is further improved.
　また、マイクロポアの深さは、通常、１０ｎｍ以上１００ｎｍ未満程度であり、好ましくは２０～６０ｎｍである。上記範囲内であれば、所定の形状を有するマイクロポアが形成しやすく、得られる平版印刷版原版および平版印刷版の性能もより優れる。 Further, the depth of the micropore is usually about 10 nm or more and less than 100 nm, preferably 20 to 60 nm. Within the above range, micropores having a predetermined shape can be easily formed, and the performance of the obtained lithographic printing plate precursor and lithographic printing plate is further improved.
　マイクロポアのポア密度は特に限定されないが、ポア密度が５０～４０００個／μｍ２であることが好ましく、１００～３０００個／μｍ２であることがより好ましい。上記範囲内であれば、得られる平版印刷版の耐刷性および放置払い性、並びに、平版印刷版原版の機上現像性に優れる。 The pore density of the micropores is not particularly limited, but the pore density is preferably 50 to 4000 / μm 2 , more preferably 100 to 3000 / μm 2 . Within the above range, the resulting lithographic printing plate is excellent in printing durability and neglectability and on-press developability of the lithographic printing plate precursor.
　陽極酸化処理工程においては、硫酸、リン酸、シュウ酸、等の水溶液を主に電解浴として用いることができる。場合によっては、クロム酸、スルファミン酸、ベンゼンスルフォン酸等またはこれらの二種以上を組み合わせた水溶液または非水溶液を用いることもできる。電解浴中でアルミニウム板に直流または交流を流すと、アルミニウム板表面に陽極酸化皮膜を形成することができる。なお、電解浴にはアルミニウムイオンが含まれていてもよい。アルミニウムイオンの含有量は特に限定されないが、１～１０ｇ／Ｌが好ましい。 In the anodizing treatment step, an aqueous solution of sulfuric acid, phosphoric acid, oxalic acid or the like can be mainly used as an electrolytic bath. Depending on the case, chromic acid, sulfamic acid, benzenesulfonic acid, etc., or an aqueous solution or a non-aqueous solution combining two or more of these may be used. When direct current or alternating current is passed through the aluminum plate in the electrolytic bath, an anodized film can be formed on the surface of the aluminum plate. The electrolytic bath may contain aluminum ions. The content of aluminum ions is not particularly limited, but is preferably 1 to 10 g / L.
　陽極酸化処理の条件は使用される電解液によって適宜設定されるが、一般的には、電解液の濃度が１～８０質量％（好ましくは５～２０質量％）、液温５～７０℃（好ましくは１０～６０℃）、電流密度０．５～６０Ａ／ｄｍ２（好ましくは５～５０Ａ／ｄｍ２）、電圧１～１００Ｖ（好ましくは５～５０Ｖ）、電解時間１～１００秒（好ましくは５～６０秒）の範囲が適当である。 The conditions of the anodizing treatment are appropriately set depending on the electrolytic solution used. In general, the concentration of the electrolytic solution is 1 to 80% by mass (preferably 5 to 20% by mass), and the liquid temperature is 5 to 70 ° C. ( Preferably 10 to 60 ° C.), current density 0.5 to 60 A / dm 2 (preferably 5 to 50 A / dm 2 ), voltage 1 to 100 V (preferably 5 to 50 V), electrolysis time 1 to 100 seconds (preferably The range of 5 to 60 seconds is appropriate.
　これらの陽極酸化処理のうちでも特に、英国特許第１，４１２，７６８号明細書に記載されている、硫酸中にて高電流密度で陽極酸化する方法が好ましい。 Among these anodizing treatments, the method of anodizing at a high current density in sulfuric acid described in British Patent 1,412,768 is particularly preferable.
＜ポアワイド処理工程＞
　ポアワイド処理工程は、上記陽極酸化処理工程により形成された陽極酸化皮膜に存在するマイクロポアの径（ポア径）を拡大させる処理（孔径拡大処理）である。このポアワイド処理により、マイクロポアの径が拡大され、より大きな平均径を有するマイクロポアを有する陽極酸化皮膜が形成される。ポアワイド処理後のマイクロポアの平均径は１０ｎｍ超１００ｎｍ以下が適当である。耐刷性、耐汚れ性、及び画像視認性のバランスの観点から、ポアワイド処理後のマイクロポアの平均径は１５～６０ｎｍが好ましく、２０～５０ｎｍがより好ましく、２４～４０ｎｍが更に好ましい。 <Pore wide processing process>
The pore wide treatment step is a treatment (pore diameter enlargement treatment) for enlarging the diameter (pore diameter) of the micropores present in the anodized film formed by the anodization treatment step. By this pore wide treatment, the diameter of the micropores is enlarged, and an anodized film having micropores having a larger average diameter is formed. The average diameter of the micropores after the pore wide treatment is suitably more than 10 nm and not more than 100 nm. From the viewpoint of the balance between printing durability, stain resistance, and image visibility, the average diameter of the micropores after pore-wide processing is preferably 15 to 60 nm, more preferably 20 to 50 nm, and still more preferably 24 to 40 nm.
　ポアワイド処理は、上記陽極酸化処理工程により得られたアルミニウム板を、酸水溶液またはアルカリ水溶液に接触させることにより行う。接触させる方法は、特に限定されず、例えば、浸せき法、スプレー法が挙げられる。中でも、浸せき法が好ましい。 The pore-wide treatment is performed by bringing the aluminum plate obtained by the anodizing treatment step into contact with an acid aqueous solution or an alkali aqueous solution. The method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred.
　ポアワイド処理工程においてアルカリ水溶液を使用する場合、水酸化ナトリウム、水酸化カリウム、および水酸化リチウムからなる群から選ばれる少なくとも一つのアルカリ水溶液を用いることが好ましい。アルカリ水溶液の濃度は０．１～５質量％であるのが好ましい。なお、アルカリ水溶液のｐＨを１１～１３に調整した後、１０～７０℃（好ましくは２０～５０℃）の条件下で、アルミニウム板をアルカリ水溶液に１～３００秒（好ましくは１～５０秒）接触させることが適当である。この際、アルカリ処理液中に炭酸塩、硼酸塩、燐酸塩等の多価弱酸の金属塩を含んでもよい。 When an alkaline aqueous solution is used in the pore-wide treatment step, it is preferable to use at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide, and lithium hydroxide. The concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass. After adjusting the pH of the alkaline aqueous solution to 11 to 13, the aluminum plate is placed in the alkaline aqueous solution for 1 to 300 seconds (preferably 1 to 50 seconds) under the condition of 10 to 70 ° C. (preferably 20 to 50 ° C.). It is appropriate to make it contact. At this time, the alkali treatment liquid may contain a metal salt of a polyvalent weak acid such as carbonate, borate or phosphate.
　ポアワイド処理工程において酸水溶液を使用する場合、硫酸、リン酸、硝酸、塩酸等の無機酸またはこれらの混合物の水溶液を用いることが好ましい。酸水溶液の濃度は、１～８０質量％が好ましく、より好ましくは５～５０質量％である。なお、酸水溶液の液温５～７０℃（好ましくは１０～６０℃）の条件下で、アルミニウム板を酸水溶液に１～３００秒（好ましくは１～１５０秒）接触させることが適当である。なお、アルカリ水溶液または酸水溶液中にはアルミニウムイオンが含まれていてもよい。アルミニウムイオンの含有量は特に限定されないが、１～１０ｇ／Ｌが好ましい。 When an aqueous acid solution is used in the pore-wide treatment step, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or a mixture thereof. The concentration of the acid aqueous solution is preferably 1 to 80% by mass, more preferably 5 to 50% by mass. It is appropriate that the aluminum plate is brought into contact with the acid aqueous solution for 1 to 300 seconds (preferably 1 to 150 seconds) under the condition that the aqueous solution of the acid aqueous solution is 5 to 70 ° C. (preferably 10 to 60 ° C.). The alkaline aqueous solution or the acidic aqueous solution may contain aluminum ions. The content of aluminum ions is not particularly limited, but is preferably 1 to 10 g / L.
＜端部ポアワイド処理工程＞
　ポアワイド処理工程は支持体上の一部の領域（端部）でのみ実施されることも好ましい。上記のようにポアワイド処理を支持体の全面ではなく、一部の領域で実施することにより、耐キズ性の低下を防止することができる。 <End pore wide treatment process>
It is also preferable that the pore-wide treatment step is performed only in a partial region (end portion) on the support. As described above, the pore-wide treatment is performed not on the entire surface of the support but on a part of the support, thereby preventing the scratch resistance from being lowered.
　一部の領域でのみポアワイド処理を実施する方法としては、ダイコート方、ディップコート方、エアーナイフコート法、カーテンコート法、ローラーコート法、ワイヤーバーコード法、グラビアコート法、スライドコート法、インクジェットコート法、ディスペンサーコート法、スプレー法等の公知の方法を利用することができるが、酸水溶液またはアルカリ水溶液を支持体上の一部に塗布する必要がある点から、インクジェットコート法、又は、ディスペンサーコート法が好ましい。また、塗布する領域は裁断後の平版印刷原版の対向する２辺にあたることが好ましい。 Pore wide treatment can be performed only in certain areas as die coating method, dip coating method, air knife coating method, curtain coating method, roller coating method, wire barcode method, gravure coating method, slide coating method, inkjet coating method. Although known methods such as a method, a dispenser coating method, and a spray method can be used, an inkjet coating method or a dispenser coating is necessary because an acid aqueous solution or an alkaline aqueous solution needs to be applied to a part of the support. The method is preferred. Moreover, it is preferable that the area | region to apply | coat corresponds to 2 sides which the lithographic printing original plate after a cutting | disconnection opposes.
　酸水溶液またはアルカリ水溶液は、支持体の端部から塗布してもよいし、支持体の端部以外の位置に塗布してもよく、これらの塗布する位置を組み合わせてもよい。また、支持体の端部から塗布する場合と、支持体の端部以外の位置に塗布する場合のどちらの場合でも、一定の幅を持った帯状に塗布することが好ましい。好ましい塗布幅は１～５０ｍｍである。塗布幅の塗布領域上を裁断し、裁断後の端部より１ｃｍ以内に塗布領域が存在することが好ましい。裁断は、塗布領域上の１箇所を裁断してもよいし、同一塗布領域上の２箇所で裁断していてもよい。 The acid aqueous solution or the alkaline aqueous solution may be applied from the end of the support, may be applied to a position other than the end of the support, or a combination of these application positions. Moreover, it is preferable to apply | coat to the band shape with a fixed width | variety in the case of apply | coating from the edge part of a support body, and the case where it apply | coats to positions other than the edge part of a support body. A preferable coating width is 1 to 50 mm. It is preferable that the coating region having a coating width is cut and the coating region is present within 1 cm from the end after cutting. The cutting may be performed at one place on the application area or at two places on the same application area.
＜親水化処理工程＞
　アルミニウム支持体の製造方法は、上記ポアワイド処理工程の後、親水化処理を施す親水化処理工程を有していてもよい。親水化処理としては、特開２００５－２５４６３８号公報の段落０１０９～０１１４に開示される公知の方法が使用できる。 <Hydrophilic treatment process>
The manufacturing method of an aluminum support body may have the hydrophilic treatment process which performs a hydrophilic treatment after the said pore wide process process. As the hydrophilization treatment, a known method disclosed in paragraphs 0109 to 0114 of JP-A-2005-254638 can be used.
　ケイ酸ソーダ、ケイ酸カリ等のアルカリ金属ケイ酸塩の水溶液に浸漬させる方法、親水性ビニルポリマーまたは親水性化合物を塗布して親水性の下塗層を形成させる方法等により、親水化処理を行うのが好ましい。 Hydrophilic treatment is performed by a method of immersing in an aqueous solution of an alkali metal silicate such as sodium silicate or potassium silicate, or a method of forming a hydrophilic undercoat layer by applying a hydrophilic vinyl polymer or a hydrophilic compound. It is preferred to do so.
　ケイ酸ソーダ、ケイ酸カリ等のアルカリ金属ケイ酸塩の水溶液による親水化処理は、米国特許第２，７１４，０６６号明細書および米国特許第３，１８１，４６１号明細書に記載されている方法および手順に従って行うことができる。 Hydrophilization treatment with an aqueous solution of an alkali metal silicate such as sodium silicate and potassium silicate is described in US Pat. No. 2,714,066 and US Pat. No. 3,181,461. It can be performed according to methods and procedures.
　アルミニウム支持体は、必要に応じて、画像記録層とは反対側の面に、特開平５－４５８８５号公報に記載の有機高分子化合物又は特開平６－３５１７４号公報に記載のケイ素のアルコキシ化合物などを含むバックコート層を有していてもよい。 If necessary, the aluminum support may be formed on the surface opposite to the image recording layer by an organic polymer compound described in JP-A-5-45885 or an alkoxy compound of silicon described in JP-A-6-35174. You may have the backcoat layer containing these.
〔画像記録層〕
　機上現像型平版印刷版原版を構成する画像記録層について記載する。画像記録層は、その非画像部が、印刷機上で印刷インキ及び湿し水から選ばれる少なくとも１つにより除去される性質を有する層である。画像記録層としては、機上現像型平版印刷版原版を構成する公知の画像記録層を用いることができる。 (Image recording layer)
The image recording layer constituting the on-press development type lithographic printing plate precursor will be described. The image recording layer is a layer having a property that the non-image portion is removed on the printing machine by at least one selected from printing ink and fountain solution. As the image recording layer, a known image recording layer constituting the on-press development type lithographic printing plate precursor can be used.
　１つの態様によれば、画像記録層は、ポリマー粒子を含有することが好ましい。 According to one aspect, the image recording layer preferably contains polymer particles.
＜ポリマー粒子＞
　ポリマー粒子は、機上現像性の向上に寄与する。ポリマー粒子は、熱が加えられたときに画像記録層を疎水性に変換できるポリマー粒子であることが好ましい。ポリマー粒子は、疎水性熱可塑性ポリマー粒子、熱反応性ポリマー粒子、重合性基を有するポリマー粒子、疎水性化合物を内包しているマイクロカプセル、及び、ミクロゲル（架橋ポリマー粒子）から選ばれる少なくとも１つであることが好ましい。 <Polymer particles>
The polymer particles contribute to improvement of on-press developability. The polymer particles are preferably polymer particles that can convert the image recording layer to hydrophobic when heat is applied. The polymer particles are at least one selected from hydrophobic thermoplastic polymer particles, heat-reactive polymer particles, polymer particles having a polymerizable group, microcapsules containing a hydrophobic compound, and microgel (crosslinked polymer particles). It is preferable that
　疎水性熱可塑性ポリマー粒子としては、１９９２年１月のＲｅｓｅａｒｃｈ　Ｄｉｓｃｌｏｓｕｒｅ　Ｎｏ．３３３０３、特開平９－１２３３８７号公報、同９－１３１８５０号公報、同９－１７１２４９号公報、同９－１７１２５０号公報及び欧州特許第９３１６４７号明細書などに記載の疎水性熱可塑性ポリマー粒子が好適に挙げられる。
　疎水性熱可塑性ポリマー粒子を構成するポリマーの具体例としては、エチレン、スチレン、塩化ビニル、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチル、塩化ビニリデン、アクリロニトリル、ビニルカルバゾール、ポリアルキレン構造を有するアクリレート又はメタクリレートなどのモノマーのホモポリマーもしくはコポリマー又はそれらの混合物が挙げられる。好ましくは、ポリスチレン、スチレン及びアクリロニトリルを含む共重合体、ポリメタクリル酸メチルが挙げられる。疎水性熱可塑性ポリマー粒子の平均粒径は０．０１～２．０μｍが好ましい。 Hydrophobic thermoplastic polymer particles include Research Disclosure No. 1 of January 1992. 33303, hydrophobic thermoplastic polymer particles described in JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250 and European Patent No. 931647 are suitable. It is mentioned in.
Specific examples of the polymer constituting the hydrophobic thermoplastic polymer particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, polyalkylene structure And homopolymers or copolymers of monomers such as acrylates or methacrylates, or mixtures thereof. Preferably, polystyrene, a copolymer containing styrene and acrylonitrile, and polymethyl methacrylate are used. The average particle size of the hydrophobic thermoplastic polymer particles is preferably 0.01 to 2.0 μm.
　熱反応性ポリマー粒子としては、熱反応性基を有するポリマー粒子が挙げられる。熱反応性基を有するポリマー粒子は、熱反応による架橋及びその際の官能基変化により疎水化領域を形成する。 Examples of the thermally reactive polymer particles include polymer particles having a thermally reactive group. The polymer particles having a thermoreactive group form a hydrophobized region by crosslinking by a thermal reaction and a functional group change at that time.
　熱反応性基を有するポリマー粒子における熱反応性基としては、化学結合が形成されるならば、どのような反応を行う官能基でもよく、重合性基が好ましい。その例としては、ラジカル重合反応を行うエチレン性不飽和基（例えば、アクリロイル基、メタクリロイル基、ビニル基、アリル基など）、カチオン重合性基（例えば、ビニル基、ビニルオキシ基、エポキシ基、オキセタニル基など）、付加反応を行うイソシアナト基又はそのブロック体、エポキシ基、ビニルオキシ基及びこれらの反応相手である活性水素原子を有する官能基（例えば、アミノ基、ヒドロキシ基、カルボキシ基など）、縮合反応を行うカルボキシ基及び反応相手であるヒドロキシ基又はアミノ基、開環付加反応を行う酸無水物及び反応相手であるアミノ基又はヒドロキシ基などが好適に挙げられる。 The thermoreactive group in the polymer particles having a thermoreactive group may be any functional group that performs any reaction as long as a chemical bond is formed, and is preferably a polymerizable group. Examples include ethylenically unsaturated groups that undergo radical polymerization reactions (eg, acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, etc.), cationic polymerizable groups (eg, vinyl groups, vinyloxy groups, epoxy groups, oxetanyl groups). Etc.), isocyanato group that performs an addition reaction or a block thereof, an epoxy group, a vinyloxy group, and a functional group having an active hydrogen atom that is a reaction partner thereof (for example, an amino group, a hydroxy group, a carboxy group, etc.), a condensation reaction Preferred examples include a carboxyl group to be performed and a hydroxy group or amino group which is a reaction partner, an acid anhydride which performs a ring-opening addition reaction, and an amino group or hydroxy group which is a reaction partner.
　マイクロカプセルとしては、例えば、特開２００１－２７７７４０号公報及び特開２００１－２７７７４２号公報に記載のごとく、画像記録層の構成成分の全て又は一部をマイクロカプセルに内包させたものが挙げられる。画像記録層の構成成分は、マイクロカプセル外にも含有させることもできる。マイクロカプセルを含有する画像記録層としては、疎水性の構成成分をマイクロカプセルに内包し、親水性の構成成分をマイクロカプセル外に含有することが好ましい態様である。 Examples of the microcapsule include those in which all or part of the constituent components of the image recording layer are encapsulated in the microcapsule as described in JP-A Nos. 2001-277740 and 2001-277742. The constituent components of the image recording layer can also be contained outside the microcapsules. The image recording layer containing microcapsules is preferably a mode in which hydrophobic constituent components are encapsulated in microcapsules and hydrophilic constituent components are contained outside the microcapsules.
　ミクロゲル（架橋ポリマー粒子）は、その内部及び表面の少なくとも一方に、画像記録層の構成成分の一部を含有することができる。特に、ラジカル重合性基をその表面に有することによって反応性ミクロゲルとした態様が画像形成感度や耐刷性の観点から好ましい。 The microgel (crosslinked polymer particles) can contain a part of the constituent components of the image recording layer in at least one of the inside and the surface thereof. In particular, an embodiment in which a reactive microgel is formed by having a radical polymerizable group on the surface thereof is preferable from the viewpoint of image forming sensitivity and printing durability.
　画像記録層の構成成分をマイクロカプセル化又はミクロゲル化するためには、公知の方法を用いることができる。
　マイクロカプセルやミクロゲルの平均粒径は、０．０１～３．０μｍが好ましく、０．０５～２．０μｍがより好ましく、０．１０～１．０μｍが特に好ましい。この範囲内で良好な解像度と経時安定性が得られる。 In order to microencapsulate or microgel the constituent components of the image recording layer, a known method can be used.
The average particle size of the microcapsules or microgel is preferably 0.01 to 3.0 μm, more preferably 0.05 to 2.0 μm, and particularly preferably 0.10 to 1.0 μm. Within this range, good resolution and stability over time can be obtained.
　ポリマー粒子としては、機上現像性への寄与の観点から、スチレン化合物に由来するモノマー単位、及び／又は、（メタ）アクリロニトリル化合物に由来するモノマー単位を含むポリマーの粒子が好ましい。また、ポリ（エチレングリコール）アルキルエーテルメタクリレート化合物に由来するモノマー単位を更に含むポリマーの粒子が好ましい。 The polymer particles are preferably polymer particles containing a monomer unit derived from a styrene compound and / or a monomer unit derived from a (meth) acrylonitrile compound from the viewpoint of contribution to on-press developability. Also preferred are polymer particles further comprising monomer units derived from poly (ethylene glycol) alkyl ether methacrylate compounds.
　ポリマー粒子は、１種単独で用いてもよいし、２種以上を併用してもよい。
　ポリマー粒子の含有量は、画像記録層の全固形分中、５～９０質量％が好ましく、５～８０質量％がより好ましく、１０～７５質量％が更に好ましい。 The polymer particles may be used alone or in combination of two or more.
The content of polymer particles is preferably 5 to 90% by mass, more preferably 5 to 80% by mass, and still more preferably 10 to 75% by mass in the total solid content of the image recording layer.
　もう１つの態様によれば、画像記録層は、重合開始剤、赤外線吸収剤、重合性化合物を含有することが好ましい。 According to another aspect, the image recording layer preferably contains a polymerization initiator, an infrared absorber, and a polymerizable compound.
＜重合開始剤＞
　重合開始剤は、光、熱あるいはその両方のエネルギーによりラジカルやカチオン等の重合開始種を発生する化合物であり、公知の熱重合開始剤、結合解離エネルギーの小さな結合を有する化合物、光重合開始剤などから適宜選択して用いることができる。
　重合開始剤としては、赤外線感光性重合開始剤が好ましい。また、重合開始剤としては、ラジカル重合開始剤が好ましい。
　ラジカル重合開始剤としては、例えば、有機ハロゲン化物、カルボニル化合物、アゾ化合物、有機過酸化物、メタロセン化合物、アジド化合物、ヘキサアリールビイミダゾール化合物、ジスルホン化合物、オキシムエステル化合物、及び、オニウム塩化合物が挙げられる。 <Polymerization initiator>
The polymerization initiator is a compound that generates polymerization initiation species such as radicals and cations by energy of light, heat, or both, and is a known thermal polymerization initiator, a compound having a bond with a small bond dissociation energy, a photopolymerization initiator. It can select suitably from etc. and can be used.
As a polymerization initiator, an infrared photosensitive polymerization initiator is preferable. Moreover, as a polymerization initiator, a radical polymerization initiator is preferable.
Examples of the radical polymerization initiator include organic halides, carbonyl compounds, azo compounds, organic peroxides, metallocene compounds, azide compounds, hexaarylbiimidazole compounds, disulfone compounds, oxime ester compounds, and onium salt compounds. It is done.
　有機ハロゲン化物としては、例えば、特開２００８－１９５０１８号公報の段落００２２～００２３に記載の化合物が好ましい。
　カルボニル化合物としては、例えば、特開２００８－１９５０１８号公報の段落００２４に記載の化合物が好ましい。
　アゾ化合物としては、例えば、特開平８－１０８６２１号公報に記載のアゾ化合物等が挙げられる。
　有機過酸化物としては、例えば、特開２００８－１９５０１８号公報の段落００２５に記載の化合物が好ましい。
　メタロセン化合物としては、例えば、特開２００８－１９５０１８号公報の段落００２６に記載の化合物が好ましい。
　アジド化合物としては、例えば、２，６－ビス（４－アジドベンジリデン）－４－メチルシクロヘキサノン等の化合物が挙げられる。
　ヘキサアリールビイミダゾール化合物としては、例えば、特開２００８－１９５０１８号公報の段落００２７に記載の化合物が好ましい。
　ジスルホン化合物としては、例えば、特開昭６１－１６６５４４号、特開２００２－３２８４６５号の各公報に記載の化合物が挙げられる。
　オキシムエステル化合物としては、例えば、特開２００８－１９５０１８号公報の段落００２８～００３０に記載の化合物が好ましい。 As the organic halide, for example, compounds described in paragraphs 0022 to 0023 of JP-A-2008-195018 are preferable.
As the carbonyl compound, for example, compounds described in paragraph 0024 of JP-A-2008-195018 are preferable.
Examples of the azo compound include azo compounds described in JP-A-8-108621.
As the organic peroxide, for example, compounds described in paragraph 0025 of JP-A-2008-195018 are preferable.
As the metallocene compound, for example, a compound described in paragraph 0026 of JP-A-2008-195018 is preferable.
Examples of the azide compound include compounds such as 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
As the hexaarylbiimidazole compound, for example, a compound described in paragraph 0027 of JP-A-2008-195018 is preferable.
Examples of the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2002-328465.
As the oxime ester compound, for example, compounds described in paragraphs 0028 to 0030 of JP-A-2008-195018 are preferable.
　重合開始剤の中でも、より好ましいものとして、ヨードニウム塩、スルホニウム塩及びアジニウム塩等のオニウム塩が挙げられる。ヨードニウム塩及びスルホニウム塩が特に好ましい。ヨードニウム塩及びスルホニウム塩の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Among polymerization initiators, more preferred are onium salts such as iodonium salts, sulfonium salts, and azinium salts. Iodonium salts and sulfonium salts are particularly preferred. Specific examples of iodonium salts and sulfonium salts are shown below, but the present invention is not limited thereto.
　ヨードニウム塩の例としては、ジフェニルヨードニウム塩が好ましく、特に、電子供与性基を置換基として有する、例えば、アルキル基又はアルコキシル基で置換されたジフェニルヨードニウム塩が好ましく、また、非対称のジフェニルヨードニウム塩が好ましい。具体例としては、ジフェニルヨードニウム＝ヘキサフルオロホスファート、４－メトキシフェニル－４－（２－メチルプロピル）フェニルヨードニウム＝ヘキサフルオロホスファート、４－（２－メチルプロピル）フェニル－ｐ－トリルヨードニウム＝ヘキサフルオロホスファート、４－ヘキシルオキシフェニル－２，４，６－トリメトキシフェニルヨードニウム＝ヘキサフルオロホスファート、４－ヘキシルオキシフェニル－２，４－ジエトキシフェニルヨードニウム＝テトラフルオロボラート、４－オクチルオキシフェニル－２，４，６－トリメトキシフェニルヨードニウム＝１－ペルフルオロブタンスルホナート、４－オクチルオキシフェニル－２，４，６－トリメトキシフェニルヨードニウム＝ヘキサフルオロホスファート、ビス（４－ｔ－ブチルフェニル）ヨードニウム＝ヘキサフルオロホスファートが挙げられる。 As an example of the iodonium salt, a diphenyl iodonium salt is preferable, and a diphenyl iodonium salt having an electron donating group as a substituent, for example, substituted with an alkyl group or an alkoxyl group is preferable, and an asymmetric diphenyl iodonium salt is also preferable. preferable. Specific examples include diphenyliodonium = hexafluorophosphate, 4-methoxyphenyl-4- (2-methylpropyl) phenyliodonium = hexafluorophosphate, 4- (2-methylpropyl) phenyl-p-tolyliodonium = hexa Fluorophosphate, 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium = hexafluorophosphate, 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium = tetrafluoroborate, 4-octyloxy Phenyl-2,4,6-trimethoxyphenyliodonium = 1-perfluorobutanesulfonate, 4-octyloxyphenyl-2,4,6-trimethoxyphenyliodonium = hexafluorophosphate, bis ( -t- butylphenyl) iodonium hexafluorophosphate and the like.
　スルホニウム塩の例としては、トリアリールスルホニウム塩が好ましく、特に電子求引性基を置換基として有する、例えば、芳香環上の基の少なくとも一部がハロゲン原子で置換されたトリアリールスルホニウム塩が好ましく、芳香環上のハロゲン原子の総置換数が４以上であるトリアリールスルホニウム塩が更に好ましい。具体例としては、トリフェニルスルホニウム＝ヘキサフルオロホスファート、トリフェニルスルホニウム＝ベンゾイルホルマート、ビス（４－クロロフェニル）フェニルスルホニウム＝ベンゾイルホルマート、ビス（４－クロロフェニル）－４－メチルフェニルスルホニウム＝テトラフルオロボラート、トリス（４－クロロフェニル）スルホニウム＝３，５－ビス（メトキシカルボニル）ベンゼンスルホナート、トリス（４－クロロフェニル）スルホニウム＝ヘキサフルオロホスファート、トリス（２，４－ジクロロフェニル）スルホニウム＝ヘキサフルオロホスファートが挙げられる。 As an example of the sulfonium salt, a triarylsulfonium salt is preferable, and in particular, a triarylsulfonium salt having an electron withdrawing group as a substituent, for example, at least a part of the group on the aromatic ring is substituted with a halogen atom is preferable. Further, a triarylsulfonium salt in which the total number of halogen atoms on the aromatic ring is 4 or more is more preferable. Specific examples include triphenylsulfonium = hexafluorophosphate, triphenylsulfonium = benzoylformate, bis (4-chlorophenyl) phenylsulfonium = benzoylformate, bis (4-chlorophenyl) -4-methylphenylsulfonium = tetrafluoro. Borate, tris (4-chlorophenyl) sulfonium = 3,5-bis (methoxycarbonyl) benzenesulfonate, tris (4-chlorophenyl) sulfonium = hexafluorophosphate, tris (2,4-dichlorophenyl) sulfonium = hexafluorophos Fart.
　重合開始剤としては、以下の５種類の重合開始剤も用いることができる。（ｉ）アルキル又はアリールアート錯体：酸化的に炭素－ヘテロ結合が解裂し、活性ラジカルを生成すると考えられる。具体的には、ボレート化合物等が挙げられる。（ｉｉ）アミノ酢酸化合物：酸化により窒素に隣接した炭素上のＣ－Ｘ結合が解裂し、活性ラジカルを生成するものと考えられる。Ｘとしては、水素原子、カルボキシ基、トリメチルシリル基又はベンジル基が好ましい。具体的には、Ｎ－フェニルグリシン類（フェニル基に置換基を有していてもよい。）、Ｎ－フェニルイミノジ酢酸（フェニル基に置換基を有していてもよい。）等が挙げられる。（ｉｉｉ）含硫黄化合物：上述のアミノ酢酸化合物の窒素原子を硫黄原子に置き換えたものが、同様の作用により活性ラジカルを生成し得る。具体的には、フェニルチオ酢酸（フェニル基に置換基を有していてもよい。）等が挙げられる。（ｉｖ）含錫化合物：上述のアミノ酢酸化合物の窒素原子を錫原子に置き換えたものが、同様の作用により活性ラジカルを生成し得る。（ｖ）スルフィン酸塩類：酸化により活性ラジカルを生成し得る。具体的は、アリールスルフィン駿ナトリウム等が挙げられる。 As the polymerization initiator, the following five kinds of polymerization initiators can also be used. (I) Alkyl or aryl art complex: It is considered that a carbon-hetero bond is oxidatively cleaved to generate an active radical. Specific examples include borate compounds. (Ii) Aminoacetic acid compound: It is considered that the C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical. X is preferably a hydrogen atom, a carboxy group, a trimethylsilyl group or a benzyl group. Specific examples include N-phenylglycines (which may have a substituent on the phenyl group), N-phenyliminodiacetic acid (which may have a substituent on the phenyl group), and the like. It is done. (Iii) Sulfur-containing compound: A compound obtained by replacing the nitrogen atom of the above-mentioned aminoacetic acid compound with a sulfur atom can generate an active radical by the same action. Specific examples include phenylthioacetic acid (which may have a substituent on the phenyl group). (Iv) Tin-containing compound: A compound in which the nitrogen atom of the above-mentioned aminoacetic acid compound is replaced with a tin atom can generate an active radical by the same action. (V) Sulfinic acid salts: An active radical can be generated by oxidation. Specific examples include arylsulfin sodium.
　これら５種類の重合開始剤の中で、ボレート化合物が好ましい。ボレート化合物としては、テトラアリールボレート化合物又はモノアルキルトリアリールボレート化合物が好ましく、化合物安定性の観点から、テトラアリールボレート化合物がより好ましい。
　ボレート化合物が有する対カチオンとしては、アルカリ金属イオン又はテトラアルキルアンモニウムイオンが好ましく、ナトリウムイオン、カリウムイオン又はテトラブチルアンモニウムイオンがより好ましい。 Of these five types of polymerization initiators, borate compounds are preferred. As the borate compound, a tetraaryl borate compound or a monoalkyltriaryl borate compound is preferable, and from the viewpoint of compound stability, a tetraaryl borate compound is more preferable.
The counter cation possessed by the borate compound is preferably an alkali metal ion or a tetraalkylammonium ion, more preferably a sodium ion, a potassium ion or a tetrabutylammonium ion.
　ボレート化合物の具体としては、以下に示す化合物が挙げられる。ここで、Ｘｃ ＋は一価のカチオンを表し、アルカリ金属イオン又はテトラアルキルアンモニウムイオンが好ましく、アルカリ金属イオン又はテトラブチルアンモニウムイオンがより好ましい。また、Ｂｕはｎ－ブチル基を表す。 Specific examples of the borate compound include the following compounds. Here, X c + represents a monovalent cation, preferably an alkali metal ion or a tetraalkylammonium ion, and more preferably an alkali metal ion or a tetrabutylammonium ion. Bu represents an n-butyl group.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　重合開始剤は、１種単独で用いてもよいし、２種以上を併用してもよい。
　重合開始剤の含有量は、画像記録層の全固形分中、０．０１～５０質量％が好ましく、０．０５～３０質量％がより好ましく、０．１～２０質量％が更に好ましい。 A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
The content of the polymerization initiator is preferably 0.01 to 50% by mass, more preferably 0.05 to 30% by mass, and still more preferably 0.1 to 20% by mass in the total solid content of the image recording layer.
＜赤外線吸収剤＞
　赤外線吸収剤は、赤外線により励起して重合開始剤等に電子移動及び／又はエネルギー移動する機能を有する。また、吸収した赤外線を熱に変換する機能を有する。赤外線吸収剤は、７５０～１，４００ｎｍの波長域に極大吸収を有することが好ましい。赤外線吸収剤としては、染料又は顔料が挙げられ、染料が好ましく用いられる。 <Infrared absorber>
The infrared absorber has a function of being excited by infrared rays and transferring electrons and / or energy to a polymerization initiator or the like. Moreover, it has the function to convert the absorbed infrared rays into heat. The infrared absorber preferably has a maximum absorption in a wavelength region of 750 to 1,400 nm. Examples of the infrared absorber include dyes and pigments, and dyes are preferably used.
　染料としては、市販の染料、及び、「染料便覧」（有機合成化学協会編集、昭和４５年刊）等の文献に記載されている公知の染料が利用できる。具体的には、アゾ染料、金属錯塩アゾ染料、ピラゾロンアゾ染料、ナフトキノン染料、アントラキノン染料、フタロシアニン染料、カルボニウム染料、キノンイミン染料、メチン染料、シアニン染料、スクアリリウム色素、ピリリウム塩、金属チオレート錯体等の染料が挙げられる。
　染料のうち、シアニン色素、スクアリリウム色素、ピリリウム塩が好ましく、シアニン色素がより好ましく、インドレニンシアニン色素が特に好ましい。 As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes Is mentioned.
Of the dyes, cyanine dyes, squarylium dyes, and pyrylium salts are preferred, cyanine dyes are more preferred, and indolenine cyanine dyes are particularly preferred.
　シアニン色素としては、下記式（ａ）で表されるシアニン色素が挙げられる。 Examples of the cyanine dye include cyanine dyes represented by the following formula (a).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（ａ）中、Ｘ１は、水素原子、ハロゲン原子、－Ｎ（Ｒ９）（Ｒ１０）、－Ｘ２－Ｌ１又は以下に示す基を表す。ここで、Ｒ９及びＲ１０は、同じでも異なってもよく、それぞれ独立に炭素数６～１０の芳香族炭化水素基、炭素数１～８のアルキル基又は水素原子を表すか、あるいは、Ｒ９とＲ１０とが互いに結合して環を形成してもよい。炭素数６～１０の芳香族炭化水素基又は炭素数１～８のアルキル基は置換基を有していてもよい。Ｒ９とＲ１０は共にフェニル基が好ましい。Ｘ２は酸素原子又は硫黄原子を表し、Ｌ１は、炭素数１～１２の炭化水素基又はヘテロ原子を含む炭素数１～１２の炭化水素基を表す。ここでヘテロ原子とは、Ｎ、Ｓ、Ｏ、ハロゲン原子、Ｓｅを表す。以下に示す基において、Ｘａ－は後述するＺａ－と同義であり、Ｒａは、水素原子、又はアルキル基、アリール基、置換又は無置換のアミノ基及びハロゲン原子から選択される置換基を表す。 In formula (a), X 1 represents a hydrogen atom, a halogen atom, —N (R 9 ) (R 10 ), —X 2 —L 1 or a group shown below. Here, R 9 and R 10 may be the same or different and each independently represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a hydrogen atom, 9 and R 10 may be bonded to each other to form a ring. The aromatic hydrocarbon group having 6 to 10 carbon atoms or the alkyl group having 1 to 8 carbon atoms may have a substituent. Both R 9 and R 10 are preferably phenyl groups. X 2 represents an oxygen atom or a sulfur atom, and L 1 represents a hydrocarbon group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom. Here, the hetero atom represents N, S, O, a halogen atom, or Se. In the group shown below, Xa - has Za described later - is synonymous with, Ra represents a hydrogen atom, or an alkyl group, an aryl group, a substituted or unsubstituted amino group and a substituent selected from halogen atoms.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　式（ａ）中、Ｒ１及びＲ２は、それぞれ独立に、炭素数１～１２の炭化水素基を表す。画像記録層塗布液の保存安定性から、Ｒ１及びＲ２は、炭素数２以上の炭化水素基であることが好ましく、更に、Ｒ１及びＲ２とは互いに結合して、５員環または６員環を形成していることが特に好ましい。 In the formula (a), R 1 and R 2 each independently represents a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the image recording layer coating solution, R 1 and R 2 are preferably hydrocarbon groups having 2 or more carbon atoms, and R 1 and R 2 are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.
　式（ａ）中、Ａｒ１、Ａｒ２は、同じでも異なっていてもよく、それぞれ芳香族炭化水素基を表す。芳香族炭化水素基は置換基を有していてもよい。好ましい芳香族炭化水素基としては、ベンゼン環基及びナフタレン環基が挙げられる。また、好ましい置換基としては、炭素数１２以下の炭化水素基、ハロゲン原子、炭素数１２以下のアルコキシ基が挙げられる。Ｙ１、Ｙ２は、同じでも異なっていてもよく、それぞれ硫黄原子又は炭素数１２以下のジアルキルメチレン基を表す。Ｒ３、Ｒ４は、同じでも異なっていてもよく、それぞれ炭素数２０以下の炭化水素基を表す。炭素数２０以下の炭化水素基は置換基を有していてもよい。好ましい置換基としては、炭素数１２以下のアルコキシ基、カルボキシ基、スルホ基が挙げられる。Ｒ５、Ｒ６、Ｒ７およびＲ８は、同じでも異なっていてもよく、それぞれ水素原子又は炭素数１２以下の炭化水素基を表す。原料の入手容易性から、好ましくは水素原子である。また、Ｚａ－は、対アニオンを表す。ただし、式（ａ）で表されるシアニン色素が、その構造内にアニオン性の置換基を有し、電荷の中和が必要ない場合にはＺａ－は必要ない。Ｚａ－は、画像記録層塗布液の保存安定性から、ハロゲン化物イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、又はスルホン酸イオンが好ましく、過塩素酸イオン、ヘキサフルオロホスフェートイオン、又はアリールスルホン酸イオンがより好ましい。 In the formula (a), Ar 1 and Ar 2 may be the same or different and each represents an aromatic hydrocarbon group. The aromatic hydrocarbon group may have a substituent. Preferable aromatic hydrocarbon groups include a benzene ring group and a naphthalene ring group. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y 1 and Y 2 may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R 3 and R 4 may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms. The hydrocarbon group having 20 or less carbon atoms may have a substituent. Preferable substituents include an alkoxy group having 12 or less carbon atoms, a carboxy group, and a sulfo group. R 5 , R 6 , R 7 and R 8 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. In view of easy availability of the raw material, a hydrogen atom is preferred. Za − represents a counter anion. However, Za − is not necessary when the cyanine dye represented by the formula (a) has an anionic substituent in its structure and neutralization of charge is not necessary. Za − is preferably a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, or a sulfonate ion in view of storage stability of the image recording layer coating solution, and is a perchlorate ion or a hexafluorophosphate ion. Or an aryl sulfonate ion is more preferable.
　式（ａ）で表されるシアニン色素において、Ｘ１がジフェニルアミノ基であることがより好ましい。また、Ｘ１がジフェニルアミノ基であり、Ｙ１及びＹ２が共にジメチルメチレン基であることが更に好ましい。 In the cyanine dye represented by the formula (a), X 1 is more preferably a diphenylamino group. More preferably, X 1 is a diphenylamino group, and Y 1 and Y 2 are both dimethylmethylene groups.
　シアニン色素の具体例としては、特開２００１－１３３９６９号公報の段落００１７～００１９に記載の化合物、特開２００２－０２３３６０号公報の段落００１６～００２１、特開２００２－０４０６３８号公報の段落００１２～００３７に記載の化合物、好ましくは特開２００２－２７８０５７号公報の段落００３４～００４１、特開２００８－１９５０１８公報の段落００８０～００８６に記載の化合物、特に好ましくは特開２００７－９０８５０号公報の段落００３５～００４３に記載の化合物が挙げられる。
　また、特開平５－５００５号公報の段落０００８～０００９、特開２００１－２２２１０１号公報の段落００２２～００２５に記載の化合物も好ましく使用することができる。
　顔料としては、特開２００８－１９５０１８号公報の段落００７２～００７６に記載の化合物が好ましい。 Specific examples of cyanine dyes include compounds described in paragraphs 0017 to 0019 of JP-A-2001-133969, paragraphs 0016 to 0021 of JP-A-2002-023360, paragraphs 0012 to 0037 of JP-A-2002-040638. Compounds described in JP-A-2002-278057, preferably in compounds described in JP-A-2002-195018, paragraphs 0080-0086, particularly preferably in JP-A-2007-90850 And the compound described in 0043.
Further, compounds described in paragraphs 0008 to 0009 of JP-A-5-5005 and paragraphs 0022 to 0025 of JP-A-2001-222101 can also be preferably used.
As the pigment, compounds described in paragraphs 0072 to 0076 of JP-A-2008-195018 are preferable.
　赤外線吸収剤は、１種単独で使用してもよいし、２種以上を併用してもよい。
　赤外線吸収剤の含有量は、画像記録層の全固形分中、０．０５～３０質量％が好ましく、０．１～２０質量％がより好ましく、０．２～１０質量％が更に好ましい。 An infrared absorber may be used individually by 1 type, and may use 2 or more types together.
The content of the infrared absorber is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.2 to 10% by mass in the total solid content of the image recording layer.
＜重合性化合物＞
　重合性化合物は、例えば、ラジカル重合性化合物であっても、カチオン重合性化合物であってもよいが、少なくとも１個のエチレン性不飽和結合を有する付加重合性化合物（エチレン性不飽和化合物）であることが好ましい。エチレン性不飽和化合物としては、末端エチレン性不飽和結合を少なくとも１個有する化合物が好ましく、末端エチレン性不飽和結合を２個以上有する化合物がより好ましい。重合性化合物は、例えばモノマー、プレポリマー、即ち、２量体、３量体若しくはオリゴマー、又は、それらの混合物などの化学的形態を持つことができる。 <Polymerizable compound>
The polymerizable compound may be, for example, a radical polymerizable compound or a cationic polymerizable compound, but is an addition polymerizable compound having at least one ethylenically unsaturated bond (ethylenically unsaturated compound). Preferably there is. As the ethylenically unsaturated compound, a compound having at least one terminal ethylenically unsaturated bond is preferable, and a compound having two or more terminal ethylenically unsaturated bonds is more preferable. The polymerizable compound can have a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer or an oligomer, or a mixture thereof.
　モノマーの例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸）や、そのエステル類、アミド類が挙げられる。好ましくは、不飽和カルボン酸と多価アルコール化合物とのエステル類、不飽和カルボン酸と多価アミン化合物とのアミド類が用いられる。また、ヒドロキシ基、アミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステル類あるいはアミド類と、単官能若しくは多官能イソシアネート類あるいはエポキシ類との付加反応物、及び単官能もしくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基、エポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル類あるいはアミド類と単官能又は多官能のアルコール類、アミン類、チオール類との付加反応物、更にハロゲン原子、トシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル類あるいはアミド類と単官能又は多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸を、不飽和ホスホン酸、スチレン、ビニルエーテル等に置き換えた化合物群を使用することもできる。これら化合物は、特表２００６－５０８３８０号公報、特開２００２－２８７３４４号公報、特開２００８－２５６８５０号公報、特開２００１－３４２２２２号公報、特開平９－１７９２９６号公報、特開平９－１７９２９７号公報、特開平９－１７９２９８号公報、特開２００４－２９４９３５号公報、特開２００６－２４３４９３号公報、特開２００２－２７５１２９号公報、特開２００３－６４１３０号公報、特開２００３－２８０１８７号公報、特開平１０－３３３３２１号公報等に記載されている。 Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), esters thereof, and amides. Preferably, esters of unsaturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyvalent amine compound are used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. In addition, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and an addition reaction product of a monofunctional or polyfunctional alcohol, amine or thiol, further a halogen atom, A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, a compound group in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene, vinyl ether, or the like can be used. These compounds are disclosed in JP-T-2006-508380, JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, JP-A-9-179297. JP, 9-179298, JP 2004-294935, JP 2006-243493, JP 2002-275129, JP 2003-64130, JP 2003-280187, It is described in JP-A-10-333321.
　多価アルコール化合物と不飽和カルボン酸とのエステルのモノマーの具体例としては、アクリル酸エステルとして、エチレングリコールジアクリレート、１，３－ブタンジオールジアクリレート、テトラメチレングリコールジアクリレート、プロピレングリコールジアクリレート、トリメチロールプロパントリアクリレート、ヘキサンジオールジアクリレート、テトラエチレングリコールジアクリレート、ペンタエリスリトールテトラアクリレート、ソルビトールトリアクリレート、イソシアヌル酸エチレンオキシド（ＥＯ）変性トリアクリレート、ポリエステルアクリレートオリゴマー等が挙げられる。メタクリル酸エステルとして、テトラメチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート、エチレングリコールジメタクリレート、ペンタエリスリトールトリメタクリレート、ビス〔ｐ－（３－メタクリルオキシ－２－ヒドロキシプロポキシ）フェニル〕ジメチルメタン、ビス〔ｐ－（メタクリルオキシエトキシ）フェニル〕ジメチルメタン等が挙げられる。また、多価アミン化合物と不飽和カルボン酸とのアミドのモノマーの具体例としては、メチレンビスアクリルアミド、メチレンビスメタクリルアミド、１，６－ヘキサメチレンビスアクリルアミド、１，６－ヘキサメチレンビスメタクリルアミド、ジエチレントリアミントリスアクリルアミド、キシリレンビスアクリルアミド、キシリレンビスメタクリルアミド等が挙げられる。 Specific examples of monomers of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) -modified triacrylate, and polyester acrylate oligomer. Methacrylic acid esters include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] Examples thereof include dimethylmethane and bis [p- (methacryloxyethoxy) phenyl] dimethylmethane. Specific examples of amide monomers of polyamine compounds and unsaturated carboxylic acids include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1,6-hexamethylene bismethacrylamide, Examples include diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
　また、イソシアネートとヒドロキシ基の付加反応を用いて製造されるウレタン系付加重合性化合物も好適であり、その具体例としては、例えば、特公昭４８－４１７０８号公報に記載されている、１分子に２個以上のイソシアネート基を有するポリイソシアネート化合物に下記式（Ｍ）で表されるヒドロキシ基を含有するビニルモノマーを付加させて得られる１分子中に２個以上の重合性ビニル基を含有するビニルウレタン化合物等が挙げられる。
　ＣＨ２＝Ｃ（ＲＭ４）ＣＯＯＣＨ２ＣＨ（ＲＭ５）ＯＨ　　　　（Ｍ）
　式（Ｍ）中、ＲＭ４及びＲＭ５は、それぞれ独立に、水素原子又はメチル基を表す。 Also suitable are urethane-based addition-polymerizable compounds produced by the addition reaction of isocyanate and hydroxy groups. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. Vinyl containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxy group represented by the following formula (M) to a polyisocyanate compound having two or more isocyanate groups A urethane compound etc. are mentioned.
CH 2 ═C (R M4 ) COOCH 2 CH (R M5 ) OH (M)
In formula (M), R M4 and R M5 each independently represent a hydrogen atom or a methyl group.
　また、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報、特開２００３－３４４９９７号公報、特開２００６－６５２１０号公報に記載のウレタンアクリレート類、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報、特開２０００－２５０２１１号公報、特開２００７－９４１３８号公報に記載のエチレンオキサイド系骨格を有するウレタン化合物類、米国特許第７１５３６３２号明細書、特表平８－５０５９５８号公報、特開２００７－２９３２２１号公報、特開２００７－２９３２２３号公報に記載の親水基を有するウレタン化合物類も好適である。 Further, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-A-2003-344997, JP-A-2006-65210, Ethylene described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, JP-B-62-39418, JP-A-2000-250211, and JP-A-2007-94138 Urethane compounds having an oxide skeleton, urethane compounds having a hydrophilic group described in US Pat. No. 7,153,632, JP-A-8-505958, JP-A-2007-293221, and JP-A-2007-293223 Are also suitable.
　重合性化合物の構造、単独使用か併用か、添加量等の使用方法の詳細は、平版印刷版原版の最終的な用途等を考慮して任意に設定できる。
　重合性化合物の含有量は、画像記録層の全固形分中、１～５０質量％が好ましく、３～３０質量％がより好ましく、５～２０質量％が更に好ましい。 Details of the method of use such as the structure of the polymerizable compound, whether it is used alone or in combination, and the amount added can be arbitrarily set in consideration of the final use of the lithographic printing plate precursor.
The content of the polymerizable compound is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, and still more preferably 5 to 20% by mass in the total solid content of the image recording layer.
　画像記録層は、バインダーポリマー、連鎖移動剤、低分子親水性化合物、感脂化剤、その他の成分を含有することができる。 The image recording layer can contain a binder polymer, a chain transfer agent, a low molecular weight hydrophilic compound, a sensitizer, and other components.
＜バインダーポリマー＞
　バインダーポリマーとしては、皮膜性を有するポリマーが好ましく、（メタ）アクリル樹脂、ポリビニルアセタール樹脂、ポリウレタン樹脂などが好ましく挙げられる。 <Binder polymer>
As the binder polymer, a polymer having a film property is preferable, and (meth) acrylic resin, polyvinyl acetal resin, polyurethane resin, and the like are preferable.
　機上現像型平版印刷版原版の画像記録層に用いられるバインダーポリマー（以下、機上現像用バインダーポリマーともいう）について、詳細に記載する。
　機上現像用バインダーポリマーとしては、アルキレンオキサイド鎖を有するバインダーポリマーが好ましい。アルキレンオキサイド鎖を有するバインダーポリマーは、ポリ（アルキレンオキサイド）部位を主鎖に有していても側鎖に有していてもよい。また、ポリ（アルキレンオキサイド）を側鎖に有するグラフトポリマーでも、ポリ（アルキレンオキサイド）含有繰返し単位で構成されるブロックと（アルキレンオキサイド）非含有繰返し単位で構成されるブロックとのブロックコポリマーでもよい。
　ポリ（アルキレンオキサイド）部位を主鎖に有する場合は、ポリウレタン樹脂が好ましい。ポリ（アルキレンオキサイド）部位を側鎖に有する場合の主鎖のポリマーとしては、（メタ）アクリル樹脂、ポリビニルアセタール樹脂、ポリウレタン樹脂、ポリウレア樹脂、ポリイミド樹脂、ポリアミド樹脂、エポキシ樹脂、ポリスチレン樹脂、ノボラック型フェノール樹脂、ポリエステル樹脂、合成ゴム、天然ゴムが挙げられ、特に（メタ）アクリル樹脂が好ましい。 The binder polymer used for the image recording layer of the on-press development type lithographic printing plate precursor (hereinafter also referred to as on-press development binder polymer) will be described in detail.
The binder polymer for on-press development is preferably a binder polymer having an alkylene oxide chain. The binder polymer having an alkylene oxide chain may have a poly (alkylene oxide) moiety in the main chain or a side chain. Further, it may be a graft polymer having poly (alkylene oxide) in the side chain, or a block copolymer of a block composed of poly (alkylene oxide) -containing repeating units and a block composed of (alkylene oxide) -free repeating units.
A polyurethane resin is preferred when it has a poly (alkylene oxide) moiety in the main chain. As the main chain polymer in the case of having a poly (alkylene oxide) moiety in the side chain, (meth) acrylic resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, polystyrene resin, novolak type Examples thereof include phenol resin, polyester resin, synthetic rubber, and natural rubber, and (meth) acrylic resin is particularly preferable.
　アルキレンオキサイドとしては炭素数が２～６のアルキレンオキサイドが好ましく、エチレンオキサイド又はプロピレンオキサイドが特に好ましい。
　ポリ（アルキレンオキサイド）部位におけるアルキレンオキサイドの繰返し数は２～１２０が好ましく、２～７０がより好ましく、２～５０が更に好ましい。
　アルキレンオキサイドの繰返し数が１２０以下であれば、摩耗による耐刷性、インキ受容性による耐刷性の両方が低下することがなく好ましい。 The alkylene oxide is preferably an alkylene oxide having 2 to 6 carbon atoms, particularly preferably ethylene oxide or propylene oxide.
The repeating number of alkylene oxide at the poly (alkylene oxide) site is preferably 2 to 120, more preferably 2 to 70, and still more preferably 2 to 50.
If the number of alkylene oxide repeats is 120 or less, both the printing durability due to wear and the printing durability due to ink acceptance are not deteriorated.
　ポリ（アルキレンオキサイド）部位は、バインダーポリマーの側鎖として、下記式（ＡＯ）で表される構造で含有されることが好ましく、（メタ）アクリル樹脂の側鎖として、下記式（ＡＯ）で表される構造で含有されることがより好ましい。 The poly (alkylene oxide) moiety is preferably contained as a side chain of the binder polymer in a structure represented by the following formula (AO), and represented by the following formula (AO) as a side chain of the (meth) acrylic resin. More preferably, it is contained in the structure.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（ＡＯ）中、ｙは２～１２０を表し、Ｒ１は水素原子又はアルキル基を表し、Ｒ２は水素原子又は一価の有機基を表す。
　一価の有機基としては、炭素数１～６のアルキル基が好ましい。具体的には、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｎ－ヘキシル基、イソヘキシル基、１，１－ジメチルブチル基、２，２－ジメチルブチル基、シクロペンチル基及びシクロヘキシル基が挙げられる。
　式（ＡＯ）において、ｙは２～７０が好ましく、２～５０がより好ましい。Ｒ１は水素原子又はメチル基が好ましく、水素原子が特に好ましい。Ｒ２は水素原子又はメチル基が特に好ましい。 In the formula (AO), y represents 2 to 120, R 1 represents a hydrogen atom or an alkyl group, and R 2 represents a hydrogen atom or a monovalent organic group.
As the monovalent organic group, an alkyl group having 1 to 6 carbon atoms is preferable. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n- Examples include a hexyl group, an isohexyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a cyclopentyl group, and a cyclohexyl group.
In the formula (AO), y is preferably 2 to 70, more preferably 2 to 50. R 1 is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. R 2 is particularly preferably a hydrogen atom or a methyl group.
　バインダーポリマーは、画像部の皮膜強度を向上するために、架橋性を有していてもよい。ポリマーに架橋性を持たせるためには、エチレン性不飽和結合などの架橋性官能基を高分子の主鎖中又は側鎖中に導入すればよい。架橋性官能基は、共重合により導入してもよいし、ポリマー反応により導入してもよい。
　分子の主鎖中にエチレン性不飽和結合を有するポリマーの例としては、ポリ－１，４－ブタジエン、ポリ－１，４－イソプレンなどが挙げられる。
　分子の側鎖中にエチレン性不飽和結合を有するポリマーの例としては、アクリル酸又はメタクリル酸のエステル又はアミドのポリマーであって、エステル又はアミドの残基（－ＣＯＯＲ又は－ＣＯＮＨＲのＲ）がエチレン性不飽和結合を有するポリマーを挙げることができる。 The binder polymer may have crosslinkability in order to improve the film strength of the image area. In order to impart crosslinkability to the polymer, a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or side chain of the polymer. The crosslinkable functional group may be introduced by copolymerization or may be introduced by a polymer reaction.
Examples of the polymer having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene and poly-1,4-isoprene.
Examples of polymers having ethylenically unsaturated bonds in the side chain of the molecule are polymers of esters or amides of acrylic acid or methacrylic acid, where the ester or amide residue (R of —COOR or —CONHR) is Mention may be made of polymers having an ethylenically unsaturated bond.
　エチレン性不飽和結合を有する残基（上記Ｒ）の例としては、－（ＣＨ２）ｎＣＲ１Ａ＝ＣＲ２ＡＲ３Ａ、－（ＣＨ２Ｏ）ｎＣＨ２ＣＲ１Ａ＝ＣＲ２ＡＲ３Ａ、－（ＣＨ２ＣＨ２Ｏ）ｎＣＨ２ＣＲ１Ａ＝ＣＲ２ＡＲ３Ａ、－（ＣＨ２）ｎＮＨ－ＣＯ－Ｏ－ＣＨ２ＣＲ１Ａ＝ＣＲ２ＡＲ３Ａ、－（ＣＨ２）ｎ－Ｏ－ＣＯ－ＣＲ１Ａ＝ＣＲ２ＡＲ３Ａ及び－（ＣＨ２ＣＨ２Ｏ）２－ＸＡ（式中、ＲＡ１～ＲＡ３はそれぞれ独立に、水素原子、ハロゲン原子、炭素数１～２０のアルキル基、アリール基、アルコキシ基又はアリールオキシ基を表し、ＲＡ１とＲＡ２又はＲＡ３とは互いに結合して環を形成してもよい。ｎは、１～１０の整数を表す。ＸＡは、ジシクロペンタジエニル残基を表す。）を挙げることができる。 Examples of residues having an ethylenically unsaturated bond (R above) include — (CH 2 ) n CR 1A = CR 2A R 3A , — (CH 2 O) n CH 2 CR 1A = CR 2A R 3A , − (CH 2 CH 2 O) n CH 2 CR 1A = CR 2A R 3A ,-(CH 2 ) n NH-CO-O-CH 2 CR 1A = CR 2A R 3A ,-(CH 2 ) n -O-CO —CR 1A = CR 2A R 3A and — (CH 2 CH 2 O) 2 —X A (wherein R A1 to R A3 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, Represents an aryl group, an alkoxy group or an aryloxy group, and R A1 and R A2 or R A3 may combine with each other to form a ring, n represents an integer of 1 to 10. X A represents di Represents a cyclopentadienyl residue. It can be mentioned.
　エステル残基の具体例としては、－ＣＨ２ＣＨ＝ＣＨ２、－ＣＨ２ＣＨ２Ｏ－ＣＨ２ＣＨ＝ＣＨ２、－ＣＨ２Ｃ（ＣＨ３）＝ＣＨ２、－ＣＨ２ＣＨ＝ＣＨ－Ｃ６Ｈ５、－ＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ－Ｃ６Ｈ５、－ＣＨ２ＣＨ２－ＮＨＣＯＯ－ＣＨ２ＣＨ＝ＣＨ２及び－ＣＨ２ＣＨ２Ｏ－Ｘ（式中、Ｘはジシクロペンタジエニル残基を表す。）が挙げられる。
　アミド残基の具体例としては、－ＣＨ２ＣＨ＝ＣＨ２、－ＣＨ２ＣＨ２－Ｙ（式中、Ｙはシクロヘキセン残基を表す。）及び－ＣＨ２ＣＨ２－ＯＣＯ－ＣＨ＝ＣＨ２が挙げられる。 Specific examples of the ester residue include —CH 2 CH═CH 2 , —CH 2 CH 2 O—CH 2 CH═CH 2 , —CH 2 C (CH 3 ) ═CH 2 , —CH 2 CH═CH— C 6 H 5 , —CH 2 CH 2 OCOCH═CH—C 6 H 5 , —CH 2 CH 2 —NHCOO—CH 2 CH═CH 2 and —CH 2 CH 2 O—X wherein X is dicyclo Represents a pentadienyl residue.).
Specific examples of the amide residue include —CH 2 CH═CH 2 , —CH 2 CH 2 —Y (wherein Y represents a cyclohexene residue) and —CH 2 CH 2 —OCO—CH═CH 2. Is mentioned.
　架橋性を有するバインダーポリマーは、例えば、その架橋性官能基にフリーラジカル（重合開始ラジカル又は重合性化合物の重合過程の生長ラジカル）が付加し、ポリマー間で直接に又は重合性化合物の重合連鎖を介して付加重合して、ポリマー分子間に架橋が形成されて硬化する。または、ポリマー中の原子（例えば、官能性架橋基に隣接する炭素原子上の水素原子）がフリーラジカルにより引き抜かれてポリマーラジカルが生成し、それが互いに結合することによって、ポリマー分子間に架橋が形成されて硬化する。 The binder polymer having crosslinkability, for example, has a free radical (polymerization initiation radical or a growth radical in the polymerization process of the polymerizable compound) added to the crosslinkable functional group, and the polymerization chain of the polymerizable compound is formed directly between the polymers. Through addition polymerization, a cross-link is formed between the polymer molecules and cured. Alternatively, atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group) are abstracted by free radicals to form polymer radicals that are bonded to each other so that crosslinking between the polymer molecules occurs. Forms and cures.
　バインダーポリマー中の架橋性基の含有量（ヨウ素滴定によるラジカル重合可能な不飽和二重結合の含有量）は、良好な感度と良好な保存安定性の観点から、バインダーポリマー１ｇ当たり、０．１～１０．０ｍｍｏｌが好ましく、１．０～７．０ｍｍｏｌがより好ましく、２．０～５．５ｍｍｏｌが更に好ましい。 The content of the crosslinkable group in the binder polymer (content of unsaturated double bond capable of radical polymerization by iodine titration) is 0.1 per 1 g of the binder polymer from the viewpoint of good sensitivity and good storage stability. ˜10.0 mmol is preferable, 1.0 to 7.0 mmol is more preferable, and 2.0 to 5.5 mmol is more preferable.
　以下にバインダーポリマーの具体例１～１１を示すが、本発明はこれらに限定されるものではない。下記例示化合物中、各繰返し単位に併記される数値（主鎖繰返し単位に併記される数値）は、繰返し単位のモル百分率を表す。側鎖の繰返し単位に併記される数値は、繰返し部位の繰返し数を示す。また、Ｍｅはメチル基を表し、Ｅｔはエチル基を表し、Ｐｈはフェニル基を表す。 Specific examples 1 to 11 of the binder polymer are shown below, but the present invention is not limited thereto. In the following exemplary compounds, a numerical value written together with each repeating unit (a numerical value written together with the main chain repeating unit) represents a mole percentage of the repeating unit. The numerical value written together with the repeating unit of the side chain indicates the number of repeating sites. Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　バインダーポリマーの分子量は、ＧＰＣ法によるポリスチレン換算値として重量平均分子量（Ｍｗ）が、２，０００以上であり、５，０００以上が好ましく、１０，０００～３００，０００がより好ましい。 As for the molecular weight of the binder polymer, the weight average molecular weight (Mw) is 2,000 or more, preferably 5,000 or more, more preferably 10,000 to 300,000 as a polystyrene conversion value by GPC method.
　必要に応じて、特開２００８－１９５０１８号公報に記載のポリアクリル酸、ポリビニルアルコールなどの親水性ポリマーを併用することができる。また、親油的なポリマーと親水的なポリマーとを併用することもできる。 If necessary, hydrophilic polymers such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination. Further, a lipophilic polymer and a hydrophilic polymer can be used in combination.
　バインダーポリマーは、１種単独で使用してよいし、２種以上を併用してもよい。
　バインダーポリマーの含有量は、画像記録層の全固形分中、１～９０質量％が好ましく、５～８０質量％がより好ましい。 A binder polymer may be used individually by 1 type and may use 2 or more types together.
The content of the binder polymer is preferably 1 to 90% by mass and more preferably 5 to 80% by mass in the total solid content of the image recording layer.
＜連鎖移動剤＞
　連鎖移動剤は、平版印刷版原版から作製される平版印刷版における耐刷性の向上に寄与する。
　連鎖移動剤としては、チオール化合物が好ましく、沸点（揮発し難さ）の観点で炭素数７以上のチオールがより好ましく、芳香環上にメルカプト基を有する化合物（芳香族チオール化合物）が更に好ましい。チオール化合物は単官能チオール化合物であることが好ましい。 <Chain transfer agent>
The chain transfer agent contributes to improvement in printing durability in a lithographic printing plate produced from a lithographic printing plate precursor.
The chain transfer agent is preferably a thiol compound, more preferably a thiol having 7 or more carbon atoms from the viewpoint of boiling point (difficult to volatilize), and still more preferably a compound having a mercapto group on the aromatic ring (aromatic thiol compound). The thiol compound is preferably a monofunctional thiol compound.
　連鎖移動剤の具体例としては、下記の化合物が挙げられる。 Specific examples of the chain transfer agent include the following compounds.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　連鎖移動剤は、１種単独で使用してもよいし、２種以上を併用してもよい。
　連鎖移動剤の含有量は、画像記録層の全固形分中、０．０１～５０質量％が好ましく、０．０５～４０質量％がより好ましく、０．１～３０質量％が更に好ましい。 A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
The content of the chain transfer agent is preferably from 0.01 to 50 mass%, more preferably from 0.05 to 40 mass%, still more preferably from 0.1 to 30 mass%, based on the total solid content of the image recording layer.
＜低分子親水性化合物＞
　低分子親水性化合物は、平版印刷版原版から作製される平版印刷版の耐刷性を低下させることなく、平版印刷版原版の機上現像性の向上に寄与する。低分子親水性化合物は、分子量１，０００未満の化合物が好ましく、分子量８００未満の化合物がより好ましく、分子量５００未満の化合物が更に好ましい。
　低分子親水性化合物としては、例えば、水溶性有機化合物としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール等のグリコール類及びそのエーテル又はエステル誘導体類、グリセリン、ペンタエリスリトール、トリス（２－ヒドロキシエチル）イソシアヌレート等のポリオール類、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン等の有機アミン類及びその塩、アルキルスルホン酸、トルエンスルホン酸、ベンゼンスルホン酸等の有機スルホン酸類及びその塩、アルキルスルファミン酸等の有機スルファミン酸類及びその塩、アルキル硫酸、アルキルエーテル硫酸等の有機硫酸類及びその塩、フェニルホスホン酸等の有機ホスホン酸類及びその塩、酒石酸、シュウ酸、クエン酸、リンゴ酸、乳酸、グルコン酸、アミノ酸類等の有機カルボン酸類及びその塩、ベタイン類等が挙げられる。 <Low molecular hydrophilic compound>
The low molecular weight hydrophilic compound contributes to the improvement of the on-press developability of the lithographic printing plate precursor without reducing the printing durability of the lithographic printing plate prepared from the lithographic printing plate precursor. The low molecular weight hydrophilic compound is preferably a compound having a molecular weight of less than 1,000, more preferably a compound having a molecular weight of less than 800, and still more preferably a compound having a molecular weight of less than 500.
As the low molecular weight hydrophilic compound, for example, as the water-soluble organic compound, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like glycols and ether or ester derivatives thereof, glycerin, Polyols such as pentaerythritol and tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkylsulfonic acid, toluenesulfonic acid and benzenesulfonic acid Acids and salts thereof, organic sulfamic acids such as alkylsulfamic acid and salts thereof, organic sulfuric acids such as alkylsulfuric acid and alkylethersulfuric acid and salts thereof, phenylphosphonic acid Organic phosphonic acids and salts thereof, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, organic carboxylic acids and salts thereof such as amino acids, betaines, and the like.
　低分子親水性化合物は、ポリオール類、有機硫酸塩類、有機スルホン酸塩類及びベタイン類から選ばれる少なくとも１つが好ましい。 The low molecular weight hydrophilic compound is preferably at least one selected from polyols, organic sulfates, organic sulfonates, and betaines.
　有機スルホン酸塩類の具体例としては、ｎ－ブチルスルホン酸ナトリウム、ｎ－ヘキシルスルホン酸ナトリウム、２－エチルヘキシルスルホン酸ナトリウム、シクロヘキシルスルホン酸ナトリウム、ｎ－オクチルスルホン酸ナトリウムなどのアルキルスルホン酸塩；５，８，１１－トリオキサペンタデカン－１－スルホン酸ナトリウム、５，８，１１－トリオキサヘプタデカン－１－スルホン酸ナトリウム、１３－エチル－５，８，１１－トリオキサヘプタデカン－１－スルホン酸ナトリウム、５，８，１１，１４－テトラオキサテトラコサン－１－スルホン酸ナトリウムなどのエチレンオキシド鎖を含むアルキルスルホン酸塩；ベンゼンスルホン酸ナトリウム、ｐ－トルエンスルホン酸ナトリウム、ｐ－ヒドロキシベンゼンスルホン酸ナトリウム、ｐ－スチレンスルホン酸ナトリウム、イソフタル酸ジメチル－５－スルホン酸ナトリウム、１－ナフチルスルホン酸ナトリウム、４－ヒドロキシナフチルスルホン酸ナトリウム、１，５－ナフタレンジスルホン酸ジナトリウム、１，３，６－ナフタレントリスルホン酸トリナトリウムなどのアリールスルホン酸塩、特開２００７－２７６４５４号公報の段落００２６～００３１及び特開２００９－１５４５２５号公報の段落００２０～００４７に記載の化合物等が挙げられる。塩は、カリウム塩、リチウム塩でもよい。 Specific examples of the organic sulfonates include alkyl sulfonates such as sodium n-butyl sulfonate, sodium n-hexyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium cyclohexyl sulfonate, sodium n-octyl sulfonate; 5 , 8,11-Trioxapentadecane-1-sulfonic acid sodium salt, 5,8,11-trioxaheptadecane-1-sulfonic acid sodium salt, 13-ethyl-5,8,11-trioxaheptadecane-1-sulfone Alkyl sulfonates containing ethylene oxide chains such as sodium acid, sodium 5,8,11,14-tetraoxatetracosane-1-sulfonate; sodium benzenesulfonate, sodium p-toluenesulfonate, p-hydroxybenzenesulfonic acid Na Sodium, sodium p-styrenesulfonate, sodium dimethyl-5-sulfonate isophthalate, sodium 1-naphthylsulfonate, sodium 4-hydroxynaphthylsulfonate, disodium 1,5-naphthalenedisulfonate, 1,3,6- Examples thereof include aryl sulfonates such as trisodium naphthalene trisulfonate, compounds described in paragraphs 0026 to 0031 of JP-A-2007-276454 and paragraphs 0020 to 0047 of JP-A-2009-154525. The salt may be a potassium salt or a lithium salt.
　有機硫酸塩類としては、ポリエチレンオキシドのアルキル、アルケニル、アルキニル、アリール又は複素環モノエーテルの硫酸塩が挙げられる。エチレンオキシド単位の数は１～４が好ましく、塩はナトリウム塩、カリウム塩又はリチウム塩が好ましい。具体例としては、特開２００７－２７６４５４号公報の段落００３４～００３８に記載の化合物が挙げられる。 Examples of organic sulfates include polyethylene oxide alkyl, alkenyl, alkynyl, aryl, or heterocyclic monoether sulfates. The number of ethylene oxide units is preferably 1 to 4, and the salt is preferably a sodium salt, potassium salt or lithium salt. Specific examples include the compounds described in paragraphs 0034 to 0038 of JP-A-2007-276454.
　ベタイン類としては、窒素原子への炭化水素置換基の炭素数が１～５である化合物が好ましく、具体例としては、トリメチルアンモニウムアセタート、ジメチルプロピルアンモニウムアセタート、３－ヒドロキシ－４－トリメチルアンモニオブチラート、４－（１－ピリジニオ）ブチラート、１－ヒドロキシエチル－１－イミダゾリオアセタート、トリメチルアンモニウムメタンスルホナート、ジメチルプロピルアンモニウムメタンスルホナート、３－トリメチルアンモニオ－１－プロパンスルホナート、３－（１－ピリジニオ）－１－プロパンスルホナート等が挙げられる。 The betaines are preferably compounds in which the hydrocarbon substituent on the nitrogen atom has 1 to 5 carbon atoms. Specific examples include trimethylammonium acetate, dimethylpropylammonium acetate, 3-hydroxy-4-trimethylammonium. Obtylate, 4- (1-pyridinio) butyrate, 1-hydroxyethyl-1-imidazolioacetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonio-1-propanesulfonate, 3 -(1-pyridinio) -1-propanesulfonate and the like.
　低分子親水性化合物は疎水性部分の構造が小さく、界面活性作用がほとんどないため、湿し水が画像記録層露光部（画像部）へ浸透して画像部の疎水性や皮膜強度を低下させることがなく、画像記録層のインキ受容性や耐刷性を良好に維持することができる。 Since low molecular weight hydrophilic compounds have a small hydrophobic part structure and almost no surface activity, the dampening solution penetrates into the exposed part of the image recording layer (image part) and reduces the hydrophobicity and film strength of the image part. The ink receptivity and printing durability of the image recording layer can be maintained satisfactorily.
　低分子親水性化合物は、１種単独で使用してもよいし、２種以上を併用してもよい。
　低分子親水性化合物の含有量は、画像記録層の全固形分中、０．５～２０質量％が好ましく、１～１５質量％がより好ましく、２～１０質量％が更に好ましい。 A low molecular weight hydrophilic compound may be used individually by 1 type, and may use 2 or more types together.
The content of the low molecular weight hydrophilic compound is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 2 to 10% by mass in the total solid content of the image recording layer.
＜感脂化剤＞
　感脂化剤は、平版印刷版原版から作製される平版印刷版におけるインキの着肉性（以下、単に「着肉性」ともいう）の向上に寄与する。感脂化剤としては、ホスホニウム化合物、含窒素低分子化合物、アンモニウム基含有ポリマーなどが挙げられる。特に、平版印刷版原版が保護層に無機層状化合物を含有する場合、これらの化合物は、無機層状化合物の表面被覆剤として機能し、無機層状化合物による印刷途中の着肉性低下を抑制する機能を有する。
　感脂化剤としては、ホスホニウム化合物と、含窒素低分子化合物と、アンモニウム基含有ポリマーとを併用することが好ましく、ホスホニウム化合物と、第四級アンモニウム塩類と、アンモニウム基含有ポリマーとを併用することがより好ましい。 <Grease sensitizer>
The oil-sensitizing agent contributes to the improvement of ink inking property (hereinafter also simply referred to as “inking property”) in a lithographic printing plate produced from a lithographic printing plate precursor. Examples of the sensitizer include phosphonium compounds, nitrogen-containing low molecular weight compounds, and ammonium group-containing polymers. In particular, when the lithographic printing plate precursor contains an inorganic layered compound in the protective layer, these compounds function as a surface coating agent for the inorganic layered compound and have a function of suppressing deterioration of the inking during printing by the inorganic layered compound. Have.
As the sensitizer, it is preferable to use a phosphonium compound, a nitrogen-containing low molecular weight compound, and an ammonium group-containing polymer in combination, and use a phosphonium compound, a quaternary ammonium salt, and an ammonium group-containing polymer in combination. Is more preferable.
　ホスホニウム化合物としては、特開２００６－２９７９０７号公報及び特開２００７－５０６６０号公報に記載のホスホニウム化合物が挙げられる。具体例としては、テトラブチルホスホニウムヨージド、ブチルトリフェニルホスホニウムブロミド、テトラフェニルホスホニウムブロミド、１，４－ビス（トリフェニルホスホニオ）ブタン＝ジ（ヘキサフルオロホスファート）、１，７－ビス（トリフェニルホスホニオ）ヘプタン＝スルファート、１，９－ビス（トリフェニルホスホニオ）ノナン＝ナフタレン－２，７－ジスルホナート等が挙げられる。 Examples of the phosphonium compound include phosphonium compounds described in JP-A-2006-297907 and JP-A-2007-50660. Specific examples include tetrabutylphosphonium iodide, butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, 1,4-bis (triphenylphosphonio) butanedi (hexafluorophosphate), 1,7-bis (tri Phenylphosphonio) heptane = sulfate, 1,9-bis (triphenylphosphonio) nonane = naphthalene-2,7-disulfonate, and the like.
　含窒素低分子化合物としては、アミン塩類、第四級アンモニウム塩類が挙げられる。また、イミダゾリニウム塩類、ベンゾイミダゾリニウム塩類、ピリジニウム塩類、キノリニウム塩類も挙げられる。中でも、第四級アンモニウム塩類及びピリジニウム塩類が好ましい。具体例としては、テトラメチルアンモニウム＝ヘキサフルオロホスファート、テトラブチルアンモニウム＝ヘキサフルオロホスファート、ドデシルトリメチルアンモニウム＝ｐ－トルエンスルホナート、ベンジルトリエチルアンモニウム＝ヘキサフルオロホスファート、ベンジルジメチルオクチルアンモニウム＝ヘキサフルオロホスファート、ベンジルジメチルドデシルアンモニウム＝ヘキサフルオロホスファート、特開２００８－２８４８５８号公報の段落００２１～００３７、特開２００９－９０６４５号公報の段落００３０～００５７に記載の化合物等が挙げられる。 Examples of nitrogen-containing low molecular weight compounds include amine salts and quaternary ammonium salts. Also included are imidazolinium salts, benzimidazolinium salts, pyridinium salts, and quinolinium salts. Of these, quaternary ammonium salts and pyridinium salts are preferred. Specific examples include tetramethylammonium = hexafluorophosphate, tetrabutylammonium = hexafluorophosphate, dodecyltrimethylammonium = p-toluenesulfonate, benzyltriethylammonium = hexafluorophosphate, benzyldimethyloctylammonium = hexafluorophosphate. And the compounds described in paragraphs 0021 to 0037 of JP2008-284858A, paragraphs 0030 to 0057 of JP2009-90645A, and the like.
　アンモニウム基含有ポリマーとしては、その構造中にアンモニウム基を有すればよく、側鎖にアンモニウム基を有する（メタ）アクリレートを共重合成分として５～８０モル％含有するポリマーが好ましい。具体例としては、特開２００９－２０８４５８号公報の段落００８９～０１０５に記載のポリマーが挙げられる。 The ammonium group-containing polymer may have an ammonium group in its structure, and a polymer containing 5 to 80 mol% of (meth) acrylate having an ammonium group in the side chain as a copolymerization component is preferable. Specific examples include the polymers described in paragraphs 0089 to 0105 of JP2009-208458A.
　アンモニウム基含有ポリマーは、特開２００９－２０８４５８号公報に記載の測定方法に従って求められる還元比粘度（単位：ｍｌ／ｇ）の値が、５～１２０の範囲のものが好ましく、１０～１１０の範囲のものがより好ましく、１５～１００の範囲のものが特に好ましい。上記還元比粘度を重量平均分子量（Ｍｗ）に換算した場合、１０，０００～１５０，００００が好ましく、１７，０００～１４０，０００がより好ましく、２０，０００～１３０，０００が特に好ましい。 The ammonium group-containing polymer preferably has a reduced specific viscosity (unit: ml / g) determined in accordance with the measurement method described in JP-A-2009-208458, in the range of 5 to 120, and in the range of 10 to 110. Are more preferable, and those in the range of 15 to 100 are particularly preferable. When the reduced specific viscosity is converted into a weight average molecular weight (Mw), it is preferably 10,000 to 150,000, more preferably 17,000 to 140,000, and particularly preferably 20,000 to 130,000.
　以下に、アンモニウム基含有ポリマーの具体例を示す。
（１）２－（トリメチルアンモニオ）エチルメタクリレート＝ｐ－トルエンスルホナート／３，６－ジオキサヘプチルメタクリレート共重合体（モル比１０／９０、Ｍｗ４．５万）
（２）２－（トリメチルアンモニオ）エチルメタクリレート＝ヘキサフルオロホスファート／３，６－ジオキサヘプチルメタクリレート共重合体（モル比２０／８０、Ｍｗ６．０万）
（３）２－（エチルジメチルアンモニオ）エチルメタクリレート＝ｐ－トルエンスルホナート／ヘキシルメタクリレート共重合体（モル比３０／７０、Ｍｗ４．５万）
（４）２－（トリメチルアンモニオ）エチルメタクリレート＝ヘキサフルオロホスファート／２－エチルヘキシルメタクリレート共重合体（モル比２０／８０、Ｍｗ６．０万）
（５）２－（トリメチルアンモニオ）エチルメタクリレート＝メチルスルファート／ヘキシルメタクリレート共重合体（モル比４０／６０、Ｍｗ７．０万）
（６）２－（ブチルジメチルアンモニオ）エチルメタクリレート＝ヘキサフルオロホスファート／３，６－ジオキサヘプチルメタクリレート共重合体（モル比２５／７５、Ｍｗ６．５万）
（７）２－（ブチルジメチルアンモニオ）エチルアクリレート＝ヘキサフルオロホスファート／３，６－ジオキサヘプチルメタクリレート共重合体（モル比２０／８０、Ｍｗ６．５万）
（８）２－（ブチルジメチルアンモニオ）エチルメタクリレート＝１３－エチル－５，８，１１－トリオキサ－１－ヘプタデカンスルホナート／３，６－ジオキサヘプチルメタクリレート共重合体（モル比２０／８０、Ｍｗ７．５万）
（９）２－（ブチルジメチルアンモニオ）エチルメタクリレート＝ヘキサフルオロホスファート／３，６－ジオキサヘプチルメタクリレート／２－ヒドロキシ－３－メタクロイルオキシプロピルメタクリレート共重合体（モル比１５／８０／５、Ｍｗ６．５万） Specific examples of the ammonium group-containing polymer are shown below.
(1) 2- (Trimethylammonio) ethyl methacrylate = p-toluenesulfonate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 10/90, Mw 45,000)
(2) 2- (Trimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80, Mw 60,000)
(3) 2- (Ethyldimethylammonio) ethyl methacrylate = p-toluenesulfonate / hexyl methacrylate copolymer (molar ratio 30/70, Mw 45,000)
(4) 2- (Trimethylammonio) ethyl methacrylate = hexafluorophosphate / 2-ethylhexyl methacrylate copolymer (molar ratio 20/80, Mw 60,000)
(5) 2- (Trimethylammonio) ethyl methacrylate = methyl sulfate / hexyl methacrylate copolymer (molar ratio 40/60, Mw 7 million)
(6) 2- (butyldimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 25/75, Mw 650,000)
(7) 2- (Butyldimethylammonio) ethyl acrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80, Mw 650,000)
(8) 2- (Butyldimethylammonio) ethyl methacrylate = 13-ethyl-5,8,11-trioxa-1-heptadecanesulfonate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80 , Mw75,000)
(9) 2- (Butyldimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate / 2-hydroxy-3-methacryloyloxypropyl methacrylate copolymer (molar ratio 15/80/5 , Mw 650,000)
　感脂化剤の含有量は、画像記録層の全固形分中、０．０１～３０質量％が好ましく、０．１～１５質量％がより好ましく、１～１０質量％が更に好ましい。 The content of the sensitizing agent is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, and still more preferably 1 to 10% by mass in the total solid content of the image recording layer.
＜その他の成分＞
　画像記録層は、その他の成分として、界面活性剤、重合禁止剤、高級脂肪酸誘導体、可塑剤、無機粒子、無機層状化合物等を含有することができる。具体的には、特開２００８－２８４８１７号公報の段落０１１４～０１５９に記載の各成分を用いることができる。 <Other ingredients>
The image recording layer can contain a surfactant, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, inorganic particles, an inorganic layered compound, and the like as other components. Specifically, each component described in paragraphs 0114 to 0159 of JP-A-2008-284817 can be used.
　画像記録層の一つの形態によれば、画像記録層は、赤外線吸収剤、重合性化合物、重合開始剤、並びに、バインダーポリマー及びポリマー粒子の少なくとも１つを含有する。画像記録層は、更に、連鎖移動剤を含有することが好ましい。画像記録層のもう一つの形態によれば、画像記録層は、赤外線吸収剤、熱融着性粒子、及び、バインダーポリマーを含有する。 According to one form of the image recording layer, the image recording layer contains an infrared absorber, a polymerizable compound, a polymerization initiator, and at least one of a binder polymer and polymer particles. The image recording layer preferably further contains a chain transfer agent. According to another form of the image recording layer, the image recording layer contains an infrared absorber, heat-fusible particles, and a binder polymer.
＜画像記録層の形成＞
　画像記録層は、例えば、特開２００８－１９５０１８号公報の段落０１４２～０１４３に記載のように、必要な上記各成分を適宜公知の溶剤に分散又は溶解して塗布液を調製し、塗布液を支持体にバーコーター塗布など公知の方法で塗布、乾燥することにより形成することができる。塗布、乾燥後における画像記録層の塗布量（固形分）は、用途によって異なるが、良好な感度と画像記録層の良好な皮膜特性が得る観点から、０．３～３．０ｇ／ｍ２程度が好ましい。 <Formation of image recording layer>
For example, as described in paragraphs 0142 to 0143 of JP-A-2008-195018, the image recording layer is prepared by appropriately dispersing or dissolving each of the above-described components in a known solvent to prepare a coating solution. It can be formed by coating and drying on a support by a known method such as bar coater coating. The coating amount (solid content) of the image recording layer after coating and drying varies depending on the application, but from the viewpoint of obtaining good sensitivity and good film properties of the image recording layer, it is about 0.3 to 3.0 g / m 2. Is preferred.
〔支持体吸着性を有する化合物を含有する層〕
　機上現像型平版印刷版原版を構成する支持体吸着性を有する化合物を含有する層について記載する。 [Layer containing a compound having support adsorptivity]
It describes about the layer containing the compound which has a support body adsorptivity which comprises an on-press development type lithographic printing plate precursor.
　支持体吸着性を有する化合物（以下、特定化合物ともいう）を含有する層（以下、特定化合物含有層ともいう）は、支持体吸着性を有する化合物を含有する。端部の画像形成性、機上現像性などの特性を低下させることなく、エッジ汚れ防止性を有効に発現させる観点から、特定化合物含有層は印刷機上で印刷インキ及び湿し水から選ばれる少なくとも１つにより除去される性質を有する層であることが好ましい。特定化合物含有層は、特定化合物を容易に溶出させるために、水溶性であることがより好ましい。 The layer (hereinafter also referred to as a specific compound-containing layer) containing a compound having support adsorptivity (hereinafter also referred to as a specific compound) contains a compound having support adsorbability. The specific compound-containing layer is selected from printing ink and fountain solution on the printing press from the viewpoint of effectively exhibiting edge stain resistance without deteriorating the properties such as image forming property and on-press developability at the edge. A layer having the property of being removed by at least one is preferable. The specific compound-containing layer is more preferably water-soluble in order to easily elute the specific compound.
　特定化合物含有層は、特定化合物を含有する連続した層である形態のみならず、特定化合物が非連続に島状に点在するような形態も包含する。 The specific compound-containing layer includes not only a continuous layer containing the specific compound but also a form in which the specific compound is scattered discontinuously in an island shape.
　特定化合物含有層は、画像記録層の上に存在すればよい。即ち、画像記録層よりも支持体から遠い位置に存在すればよい。例えば、画像記録層に接してその上に存在することが好ましい。 The specific compound-containing layer may be present on the image recording layer. In other words, it suffices to be located farther from the support than the image recording layer. For example, it is preferably in contact with the image recording layer.
＜支持体吸着性を有する化合物＞
　特定化合物含有層が含有する支持体吸着性を有する化合物（特定化合物）は、支持体吸着性を有することが、１つの特徴である。ここで、「支持体吸着性」とは、アルミニウム支持体が有する陽極酸化皮膜に対する吸着性を意味する。陽極酸化皮膜に対する吸着性の有無は、以下の方法により、容易に判定することができる。
　即ち、試験化合物を易溶性溶媒（例えば、水）に溶解した溶液を調製する。この溶液を乾燥後の塗布量が３０ｍｇ／ｍ２となるように陽極酸化皮膜を有するアルミニウム支持体上に塗布し乾燥させる。次に試験化合物を塗布したアルミニウム支持体を、上記易溶性溶媒を用いて洗浄と乾燥を５回繰り返した後、洗浄除去されなかった試験化合物の残存量を測定する。残存量の測定は、残存する試験化合物量を直接定量してもよいし、洗浄液中に溶解した試験化合物量を定量し、この値を用いて残存する試験化合物量を算出してもよい。試験化合物の定量は、例えば蛍光Ｘ線測定、反射分光吸光度測定などで実施することができる。
　残存量が、１ｍｇ／ｍ２以上であれば、試験化合物は、支持体吸着性を有すると判定される。 <Compound having support adsorptivity>
One feature of the compound having a support adsorbing property (specific compound) contained in the specific compound-containing layer is that it has a support adsorbing property. Here, “support adsorptive” means the adsorptivity to the anodized film of the aluminum support. The presence or absence of adsorptivity to the anodized film can be easily determined by the following method.
That is, a solution in which a test compound is dissolved in a readily soluble solvent (for example, water) is prepared. This solution is applied on an aluminum support having an anodized film and dried so that the coating amount after drying is 30 mg / m 2 . Next, the aluminum support on which the test compound is applied is washed and dried five times using the above-mentioned easily soluble solvent, and then the residual amount of the test compound that has not been removed by washing is measured. For the measurement of the remaining amount, the amount of the remaining test compound may be directly quantified, or the amount of the test compound dissolved in the cleaning solution may be quantified, and the amount of the remaining test compound may be calculated using this value. The quantification of the test compound can be performed, for example, by fluorescent X-ray measurement, reflection spectral absorbance measurement, or the like.
If the residual amount is 1 mg / m 2 or more, the test compound is determined to have support adsorbability.
　特定化合物は、支持体吸着性を有するために、アルミニウム支持体が有する陽極酸化皮膜に対して吸着性を示す基を有することが好ましい。アルミニウム支持体が有する陽極酸化皮膜に対して吸着性を示す基としては、陽極酸化皮膜の表面に存在する物質（例えば、金属、金属酸化物）又は官能基（例えば、水酸基）と、化学結合（例えば、イオン結合、水素結合、配位結合）を形成することができる官能基が挙げられる。このような官能基は当業界でよく知られている。
　このような官能基の中で、酸基が好ましい。酸基は、酸解離定数（ｐＫａ）が７以下であることが好ましい。酸基の例としては、フェノール性水酸基、カルボキシル基、－ＳＯ３Ｈ、－ＯＳＯ３Ｈ、－ＰＯ３Ｈ２、－ＯＰＯ３Ｈ２、－ＣＯＮＨＳＯ２－、－ＳＯ２ＮＨＳＯ２－、－ＣＯＣＨ２ＣＯＣＨ３などが挙げられる。特に、－ＯＰＯ３Ｈ２及び－ＰＯ３Ｈ２が好ましい。酸基は、塩を形成していてもよい。酸基が形成する塩としては、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩などが挙げられる。 The specific compound preferably has a group exhibiting adsorptivity to the anodized film of the aluminum support in order to have support adsorbability. Examples of the group exhibiting adsorptivity to the anodized film of the aluminum support include a substance (for example, metal, metal oxide) or a functional group (for example, hydroxyl group) present on the surface of the anodized film, and a chemical bond ( For example, the functional group which can form an ionic bond, a hydrogen bond, and a coordination bond is mentioned. Such functional groups are well known in the art.
Of these functional groups, acid groups are preferred. The acid group preferably has an acid dissociation constant (pKa) of 7 or less. Examples of acid groups include phenolic hydroxyl groups, carboxyl groups, —SO 3 H, —OSO 3 H, —PO 3 H 2 , —OPO 3 H 2 , —CONHSO 2 —, —SO 2 NHSO 2 —, —COCH 2 COCH 3 and the like. In particular, —OPO 3 H 2 and —PO 3 H 2 are preferable. The acid group may form a salt. Examples of the salt formed by the acid group include alkali metal salts, alkaline earth metal salts, and ammonium salts.
　特定化合物の分子量は、１，０００以下であることが好ましい。分子量が１，０００以下であることにより、機上現像時に特定化合物が特定化合物含有層から平版印刷版原版の端部における陽極酸化皮膜の表面に移動しやすく、優れたエッジ汚れ防止効果が得られると考えられる。分子量は、好ましくは５０～１，０００、より好ましくは５０～８００、更に好ましくは５０～６００である。 The molecular weight of the specific compound is preferably 1,000 or less. When the molecular weight is 1,000 or less, the specific compound easily moves from the specific compound-containing layer to the surface of the anodized film at the edge of the lithographic printing plate precursor during on-press development, and an excellent edge stain prevention effect is obtained. it is conceivable that. The molecular weight is preferably 50 to 1,000, more preferably 50 to 800, and still more preferably 50 to 600.
　特定化合物としては、オキソ酸を用いることができる。オキソ酸は、同じ原子にヒドロキシル基（－ＯＨ）とオキソ基（＝Ｏ）が結合し、且つそのヒドロキシル基が酸性プロトンを与える化合物を指す。オキソ酸は塩の形で用いてもよい。塩としては、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩などが挙げられる。 Oxo acid can be used as the specific compound. Oxo acid refers to a compound in which a hydroxyl group (—OH) and an oxo group (═O) are bonded to the same atom, and the hydroxyl group gives an acidic proton. Oxo acids may be used in the form of salts. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts and the like.
　特定化合物としては、下記式１で表される化合物も用いることができる。 As the specific compound, a compound represented by the following formula 1 can also be used.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式１中、ｎは、２～１０の整数を表し、Ｒ１、Ｒ２、Ｒ３は、それぞれ独立に、水素原子、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アルキル基又はアルキレンオキシド基を表す。 In Formula 1, n represents an integer of 2 to 10, and R1, R2, and R3 each independently represent a hydrogen atom, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an alkyl group, or an alkylene oxide group. .
　式１におけるアルキル基は、炭素数１～１０のアルキル基が好ましく、炭素数１～５のアルキル基がより好ましく、炭素数１～３のアルキル基が更に好ましい。式１におけるアルキレンオキシド基は、炭素数２又は３のアルキレンオキシド単位を１～１０個有するアルキレンオキシド基が好ましく、炭素数２又は３のアルキレンオキシド単位を１～５個有するアルキレンオキシド基がより好ましく、炭素数２又は３のアルキレンオキシド単位を１～３個有するアルキレンオキシド基が更に好ましい。 The alkyl group in Formula 1 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. The alkylene oxide group in Formula 1 is preferably an alkylene oxide group having 1 to 10 alkylene oxide units having 2 or 3 carbon atoms, more preferably an alkylene oxide group having 1 to 5 alkylene oxide units having 2 or 3 carbon atoms. An alkylene oxide group having 1 to 3 alkylene oxide units having 2 or 3 carbon atoms is more preferable.
　特定化合物の具体例としては、リン酸、ポリリン酸、メタリン酸、第一リン酸アンモニウム、第二リン酸アンモニウム、リン酸二水素ナトリウム、リン酸一水素ナトリウム、第一リン酸カリウム、第二リン酸カリウム、トリポリリン酸ナトリウム、ピロリン酸カリウム、ヘキサメタリン酸ナトリウム、ホスフィン酸、エチルホスホン酸、プロピルホスホン酸、ｉ－プロピルホスホン酸、ブチルホスホン酸、ヘキシルホスホン酸、オクチルホスホン酸、ドデシルホスホン酸、オクタデシルホスホン酸、２－ヒドロキシエチルホスホン酸及びこれらのナトリウム塩又はカリウム塩、メチルホスホン酸メチル、エチルホスホン酸メチル、２－ヒドロキシエチルホスホン酸メチルなどのアルキルホスホン酸モノアルキルエステル及びこれらのナトリウム塩又はカリウム塩、メチレンジホスホン酸、エチレンジホスホン酸等のアルキレンジホスホン酸及びこれらのナトリウム塩又はカリウム塩、ヒドロキシエチリデンジホスホン酸、ポリビニルホスホン酸、ｐ－トルエンスルホン酸、ｐ－トルエンスルホン酸ナトリウム、スルホフタル酸、クエン酸などが挙げられる。 Specific examples of specific compounds include phosphoric acid, polyphosphoric acid, metaphosphoric acid, primary ammonium phosphate, secondary ammonium phosphate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, primary potassium phosphate, secondary phosphorus Potassium acid, sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, phosphinic acid, ethylphosphonic acid, propylphosphonic acid, i-propylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, dodecylphosphonic acid, octadecylphosphonic acid Acids, 2-hydroxyethylphosphonic acids and sodium or potassium salts thereof, alkylphosphonic acid monoalkyl esters such as methylphosphonic acid methyl, ethylphosphonic acid methyl, methyl 2-hydroxyethylphosphonic acid and their sodium Or potassium salts, alkylene diphosphonic acids such as methylene diphosphonic acid, ethylene diphosphonic acid and their sodium or potassium salts, hydroxyethylidene diphosphonic acid, polyvinyl phosphonic acid, p-toluenesulfonic acid, p-toluenesulfone Examples include sodium acid, sulfophthalic acid, and citric acid.
　特定化合物としては、陽極酸化皮膜への吸着性の観点から、リン酸、ポリリン酸、ホスホン酸及びホスフィン酸並びにこれらの塩が特に好ましい。 As the specific compound, phosphoric acid, polyphosphoric acid, phosphonic acid, phosphinic acid and salts thereof are particularly preferable from the viewpoint of adsorptivity to the anodized film.
　特定化合物は、１種単独で使用してもよいし、２種以上を併用してもよい。
　特定化合物含有層における特定化合物の含有量は、２０～１５０ｍｇ／ｍ２が好ましく、３０～１００ｍｇ／ｍ２がより好ましく、５０～１００ｍｇ／ｍ２が更に好ましい。
　本発明の平版印刷版原版においては、特定化合物の含有量が特定化合物含有層の面内において実質的に同じであることが特徴の１つである。ここで、「特定化合物の含有量が特定化合物含有層の面内において実質的に同じである」とは、特定化合物が特定化合物含有層の面内においてほぼ均一に存在し、平版印刷版原版の中央部と端部において、特定化合物の含有量に実質的な差がないことを意味する。即ち、特定化合物含有層を塗布した際に通常発生し得る特定化合物含有層の面内における特定化合物の含有量差以外には、含有量差がないことを意味する。
　従って、本発明は、平版印刷版原版の端部のみに、意図的に特定化合物を適用して、端部における特定化合物の含有量を端部以外の領域における特定化合物の含有量より多くする状態を形成することとは異なる。 A specific compound may be used individually by 1 type, and may use 2 or more types together.
The content of the specific compound in a specific compound-containing layer is preferably 20 ~ 150mg / m 2, more preferably 30 ~ 100mg / m 2, more preferably 50 ~ 100mg / m 2.
One feature of the lithographic printing plate precursor according to the invention is that the content of the specific compound is substantially the same in the plane of the specific compound-containing layer. Here, “the content of the specific compound is substantially the same in the plane of the specific compound-containing layer” means that the specific compound exists almost uniformly in the plane of the specific compound-containing layer, and the lithographic printing plate precursor It means that there is no substantial difference in the content of the specific compound between the central part and the end part. That is, it means that there is no content difference other than the content difference of the specific compound in the plane of the specific compound-containing layer that can be normally generated when the specific compound-containing layer is applied.
Therefore, the present invention is a state in which the specific compound is intentionally applied only to the edge of the lithographic printing plate precursor so that the content of the specific compound in the edge is greater than the content of the specific compound in the region other than the edge. Is different from forming
　特定化合物含有層は、界面活性剤を含有することが好ましい。界面活性剤は、特定化合物含有層塗布液の表面張力を調整し、均一な塗布面状を与える効果を有する。
　界面活性剤としては、アニオン性界面活性剤、非イオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤が挙げられる。アニオン性界面活性剤、非イオン性界面活性剤が好ましい。アニオン性界面活性剤としては、特開２０１４－１０４６３１号公報の段落番号〔００２２〕にアニオン型界面活性剤として記載されている化合物が挙げられる。非イオン性界面活性剤としては、特開２０１４－１０４６３１号公報の段落番号〔００３１〕に非イオン型界面活性剤として記載されている化合物が挙げられる。界面活性剤は、必要に応じて、２種類以上を混合して使用することもできる。
　特定化合物含有層における界面活性剤の含有量は、５～５０ｍｇ／ｍ２が好ましく、５～２０ｍｇ／ｍ２がより好ましく、８～１５ｍｇ／ｍ２が更に好ましい。 The specific compound-containing layer preferably contains a surfactant. The surfactant has the effect of adjusting the surface tension of the specific compound-containing layer coating solution to give a uniform coated surface.
Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Anionic surfactants and nonionic surfactants are preferred. Examples of the anionic surfactant include compounds described as paragraphs [0022] in JP-A-2014-104631 as an anionic surfactant. Examples of the nonionic surfactant include compounds described as a nonionic surfactant in paragraph [0031] of JP-A-2014-104631. Two or more kinds of surfactants can be mixed and used as necessary.
The content of the surfactant in the particular compounds containing layer is preferably 5 ~ 50mg / m 2, more preferably 5 ~ 20mg / m 2, more preferably 8 ~ 15mg / m 2.
　特定化合物含有層は、水溶性ポリマーを含有することが好ましい。水溶性ポリマーは、特定化合物含有層のバインダーとして機能する。また、水溶性ポリマーは機上現像時、湿し水などの作用により溶解し、特定化合物を溶出させる効果もある。
　水溶性ポリマーとしては、平版印刷版原版の保護層（オーバーコート層と呼ばれることもある。）に用いられる水溶性ポリマーを好適に用いることができる。具体的には、例えば、ポリビニルアルコール、変性ポリビニルアルコール、ポリビニルピロリドン、水溶性セルロース誘導体、ポリ（メタ）アクリロニトリル等が挙げられる。水溶性ポリマーは、必要に応じて、２種類以上を混合して使用することもできる。
　特定化合物含有層における水溶性ポリマーの含有量は、３０～３００ｍｇ／ｍ２が好ましく、３０～１５０ｍｇ／ｍ２がより好ましく、５０～１２０ｍｇ／ｍ２が更に好ましい。 The specific compound-containing layer preferably contains a water-soluble polymer. The water-soluble polymer functions as a binder for the specific compound-containing layer. Further, the water-soluble polymer is dissolved by the action of dampening water during on-press development and has an effect of eluting the specific compound.
As the water-soluble polymer, a water-soluble polymer used for a protective layer (sometimes referred to as an overcoat layer) of a lithographic printing plate precursor can be suitably used. Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like. Two or more types of water-soluble polymers can be used as needed.
The content of the water-soluble polymer in the particular compounds containing layer is preferably 30 ~ 300mg / m 2, more preferably 30 ~ 150mg / m 2, more preferably 50 ~ 120mg / m 2.
＜特定化合物含有層の形成＞
　特定化合物含有層は、例えば、必要な各成分を適宜水などの溶剤に溶解して塗布液を調製し、塗布液を画像記録層上に公知の方法で塗布、乾燥することにより形成することができる。
　特定化合物含有層は保護層と一体化し、１つの層として画像記録層の上に形成することもできる。このような形態については、後述する保護層において説明する。 <Formation of specific compound-containing layer>
The specific compound-containing layer can be formed, for example, by dissolving each necessary component in a solvent such as water as appropriate to prepare a coating solution, and coating and drying the coating solution on the image recording layer by a known method. it can.
The specific compound-containing layer can be integrated with the protective layer and formed on the image recording layer as one layer. Such a form is demonstrated in the protective layer mentioned later.
　本発明に係る機上現像型平版印刷版原版は、画像記録層と支持体との間に下塗り層（中間層と呼ばれることもある。）を有することができる。 The on-press development type lithographic printing plate precursor according to the present invention may have an undercoat layer (sometimes referred to as an intermediate layer) between the image recording layer and the support.
〔下塗り層〕
　下塗り層は、露光部においては支持体と画像記録層との密着を強化し、未露光部においては画像記録層の支持体からのはく離を生じやすくさせるため、耐刷性を損なわずに現像性を向上させることに寄与する。また、赤外線レーザー露光の場合に、下塗り層が断熱層として機能することにより、露光により発生した熱が支持体に拡散して感度が低下するのを防ぐ効果も有する。 (Undercoat layer)
The undercoat layer enhances the adhesion between the support and the image recording layer in the exposed area, and easily peels off the image recording layer from the support in the unexposed area. It contributes to improving. In addition, in the case of infrared laser exposure, the undercoat layer functions as a heat insulating layer, and thus has an effect of preventing the heat generated by the exposure from diffusing to the support and lowering the sensitivity.
　下塗り層に用いられる化合物としては、支持体表面に吸着可能な吸着性基及び親水性基を有するポリマーが挙げられる。画像記録層との密着性を向上させるために吸着性基及び親水性基を有し、更に架橋性基を有するポリマーが好ましい。下塗り層に用いられる化合物は、低分子化合物でもポリマーであってもよい。下塗り層に用いられる化合物は、必要に応じて、２種以上を混合して使用してもよい。 Examples of the compound used for the undercoat layer include polymers having an adsorptive group and a hydrophilic group that can be adsorbed on the surface of the support. In order to improve the adhesion to the image recording layer, a polymer having an adsorptive group and a hydrophilic group and further having a crosslinkable group is preferable. The compound used for the undercoat layer may be a low molecular compound or a polymer. The compounds used for the undercoat layer may be used as a mixture of two or more if necessary.
　下塗り層に用いられる化合物がポリマーである場合、吸着性基を有するモノマー、親水性基を有するモノマー及び架橋性基を有するモノマーの共重合体が好ましい。
　支持体表面に吸着可能な吸着性基としては、フェノール性ヒドロキシ基、カルボキシ基、－ＰＯ３Ｈ２、－ＯＰＯ３Ｈ２、－ＣＯＮＨＳＯ２－、－ＳＯ２ＮＨＳＯ２－、－ＣＯＣＨ２ＣＯＣＨ３が好ましい。親水性基としては、スルホ基又はその塩、カルボキシ基の塩が好ましい。架橋性基としては、アクリル基、メタクリル基、アクリルアミド基、メタクリルアミド基、アリル基などが好ましい。
　ポリマーは、ポリマーの極性置換基と、当該極性置換基と対荷電を有する置換基及びエチレン性不飽和結合を有する化合物との塩形成で導入された架橋性基を有してもよいし、上記以外のモノマー、好ましくは親水性モノマーが更に共重合されていてもよい。 When the compound used for the undercoat layer is a polymer, a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group is preferable.
Examples of the adsorptive group that can be adsorbed on the support surface include a phenolic hydroxy group, a carboxy group, —PO 3 H 2 , —OPO 3 H 2 , —CONHSO 2 —, —SO 2 NHSO 2 —, —COCH 2 COCH 3 Is preferred. As the hydrophilic group, a sulfo group or a salt thereof, or a salt of a carboxy group is preferable. As the crosslinkable group, an acryl group, a methacryl group, an acrylamide group, a methacrylamide group, an allyl group, and the like are preferable.
The polymer may have a crosslinkable group introduced by salt formation between a polar substituent of the polymer, a substituent having a counter charge with the polar substituent, and a compound having an ethylenically unsaturated bond, Other monomers, preferably hydrophilic monomers, may be further copolymerized.
　具体的には、特開平１０－２８２６７９号公報に記載されている付加重合可能なエチレン性二重結合反応基を有しているシランカップリング剤、特開平２－３０４４４１号公報記載のエチレン性二重結合反応基を有しているリン化合物が好適に挙げられる。特開２００５－２３８８１６号、特開２００５－１２５７４９号、特開２００６－２３９８６７号、特開２００６－２１５２６３号の各公報に記載の架橋性基（好ましくは、エチレン性不飽和結合基）、支持体表面と相互作用する官能基及び親水性基を有する低分子又は高分子化合物も好ましく用いられる。
　より好ましいものとして、特開２００５－１２５７４９号及び特開２００６－１８８０３８号公報に記載の支持体表面に吸着可能な吸着性基、親水性基及び架橋性基を有する高分子ポリマーが挙げられる。 Specifically, a silane coupling agent having an ethylenic double bond reactive group capable of addition polymerization described in JP-A No. 10-282679 and an ethylenic compound described in JP-A No. 2-304441. The phosphorus compound which has a heavy bond reactive group is mentioned suitably. Crosslinkable groups (preferably ethylenically unsaturated bond groups) described in JP-A-2005-238816, JP-A-2005-12549, JP-A-2006-239867, and JP-A-2006-215263, a support A low molecular or high molecular compound having a functional group interacting with the surface and a hydrophilic group is also preferably used.
More preferable are polymer polymers having an adsorbable group, a hydrophilic group and a crosslinkable group which can be adsorbed on the surface of the support described in JP-A Nos. 2005-125749 and 2006-188038.
　下塗り層に用いられるポリマー中のエチレン性不飽和結合基の含有量は、ポリマー１ｇ当たり、好ましくは０．１～１０．０ｍｍｏｌ、より好ましくは０．２～５．５ｍｍｏｌである。
　下塗り層に用いられるポリマーの質量平均分子量（Ｍｗ）は、５，０００以上が好ましく、１万～３０万がより好ましい。 The content of the ethylenically unsaturated bond group in the polymer used for the undercoat layer is preferably 0.1 to 10.0 mmol, more preferably 0.2 to 5.5 mmol per 1 g of the polymer.
The polymer used for the undercoat layer preferably has a mass average molecular weight (Mw) of 5,000 or more, more preferably 10,000 to 300,000.
　下塗り層は、上記下塗り層用化合物の他に、経時による汚れ防止のため、キレート剤、第二級又は第三級アミン、重合禁止剤、アミノ基又は重合禁止能を有する官能基と支持体表面と相互作用する基とを有する化合物（例えば、１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）、２，３，５，６－テトラヒドロキシ－ｐ－キノン、クロラニル、スルホフタル酸、ヒドロキシエチルエチレンジアミン三酢酸、ジヒドロキシエチルエチレンジアミン二酢酸、ヒドロキシエチルイミノ二酢酸など）等を含有してもよい。 In addition to the above compound for the undercoat layer, the undercoat layer is a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group, or a functional group having a polymerization inhibitory ability and a support surface in order to prevent contamination with time. Having a group that interacts with (eg, 1,4-diazabicyclo [2.2.2] octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil, sulfophthalic acid, hydroxy Ethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, and the like).
　下塗り層は、例えば、必要な各成分を適宜溶剤に溶解又は分散して塗布液を調製し、塗布液を支持体上に公知の方法で塗布、乾燥することにより形成することができる。下塗り層の塗布量（固形分）は、０．１～１００ｍｇ／ｍ２が好ましく、１～３０ｍｇ／ｍ２がより好ましい。 The undercoat layer can be formed, for example, by dissolving or dispersing necessary components in a solvent as appropriate to prepare a coating solution, and coating and drying the coating solution on a support by a known method. The coating amount (solid content) of the undercoat layer is preferably 0.1 ~ 100mg / m 2, and more preferably 1 ~ 30mg / m 2.
　本発明に係る機上現像型平版印刷版原版は、特定化合物含有層の上に保護層（オーバーコート層と呼ばれることもある。）を有することができる。あるいは、特定化合物含有層と保護層を一体化し、１つの層として画像記録層の上に形成してもよい。 The on-press development type lithographic printing plate precursor according to the invention may have a protective layer (sometimes referred to as an overcoat layer) on the specific compound-containing layer. Alternatively, the specific compound-containing layer and the protective layer may be integrated and formed on the image recording layer as one layer.
〔保護層〕
　保護層は酸素遮断により画像形成阻害反応を抑制する機能の他、画像記録層における傷の発生防止及び高照度レーザー露光時のアブレーション防止の機能を有する。 [Protective layer]
In addition to the function of suppressing the image formation inhibition reaction by blocking oxygen, the protective layer has a function of preventing scratches in the image recording layer and preventing ablation during high-illuminance laser exposure.
　このような特性の保護層については、例えば、米国特許第３，４５８，３１１号明細書及び特公昭５５－４９７２９号公報に記載されている。保護層に用いられる酸素低透過性のポリマーとしては、水溶性ポリマー、水不溶性ポリマーのいずれをも適宜選択して使用することができ、必要に応じて、２種類以上を混合して使用することもできる。具体的には、例えば、ポリビニルアルコール、変性ポリビニルアルコール、ポリビニルピロリドン、水溶性セルロース誘導体、ポリ（メタ）アクリロニトリル等が挙げられる。
　変性ポリビニルアルコールとしてはカルボキシ基又はスルホ基を有する酸変性ポリビニルアルコールが好ましく用いられる。具体的には、特開２００５－２５０２１６号公報及び特開２００６－２５９１３７号公報に記載の変性ポリビニルアルコールが挙げられる。 The protective layer having such characteristics is described in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729. As the polymer having low oxygen permeability used for the protective layer, either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and if necessary, two or more types may be mixed and used. You can also. Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like.
As the modified polyvinyl alcohol, acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used. Specific examples include modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137.
　保護層は、酸素遮断性を高めるために無機層状化合物を含有することが好ましい。無機層状化合物は、薄い平板状の形状を有する粒子であり、例えば、天然雲母、合成雲母等の雲母群、式：３ＭｇＯ・４ＳｉＯ・Ｈ２Ｏで表されるタルク、テニオライト、モンモリロナイト、サポナイト、ヘクトライト、リン酸ジルコニウム等が挙げられる。
　好ましく用いられる無機層状化合物は雲母化合物である。雲母化合物としては、例えば、式：Ａ（Ｂ，Ｃ）２－５Ｄ４Ｏ１０（ＯＨ，Ｆ，Ｏ）２〔ただし、Ａは、Ｋ、Ｎａ、Ｃａのいずれか、Ｂ及びＣは、Ｆｅ（ＩＩ）、Ｆｅ（ＩＩＩ）、Ｍｎ、Ａｌ、Ｍｇ、Ｖのいずれかであり、Ｄは、Ｓｉ又はＡｌである。〕で表される天然雲母、合成雲母等の雲母群が挙げられる。 The protective layer preferably contains an inorganic layered compound in order to enhance oxygen barrier properties. The inorganic layered compound is a particle having a thin flat plate shape, for example, mica group such as natural mica and synthetic mica, talc, teniolite, montmorillonite, saponite, hector represented by the formula: 3MgO · 4SiO · H 2 O Light, zirconium phosphate, etc. are mentioned.
The inorganic layered compound preferably used is a mica compound. As the mica compound, for example, the formula: A (B, C) 2-5 D 4 O 10 (OH, F, O) 2 [where A is any of K, Na, Ca, and B and C are One of Fe (II), Fe (III), Mn, Al, Mg, and V, and D is Si or Al. ] Mica groups such as natural mica and synthetic mica represented by
　雲母群においては、天然雲母としては白雲母、ソーダ雲母、金雲母、黒雲母及び鱗雲母が挙げられる。合成雲母としてはフッ素金雲母ＫＭｇ３（ＡｌＳｉ３Ｏ１０）Ｆ２、カリ四ケイ素雲母ＫＭｇ２．５Ｓｉ４Ｏ１０）Ｆ２等の非膨潤性雲母、及び、ＮａテトラシリリックマイカＮａＭｇ２．５（Ｓｉ４Ｏ１０）Ｆ２、Ｎａ又はＬｉテニオライト（Ｎａ，Ｌｉ）Ｍｇ２Ｌｉ（Ｓｉ４Ｏ１０）Ｆ２、モンモリロナイト系のＮａ又はＬｉヘクトライト（Ｎａ，Ｌｉ）１／８Ｍｇ２／５Ｌｉ１／８（Ｓｉ４Ｏ１０）Ｆ２等の膨潤性雲母等が挙げられる。更に合成スメクタイトも有用である。 In the mica group, natural mica includes muscovite, soda mica, phlogopite, biotite, and sericite. As the synthetic mica, non-swelling mica such as fluor-phlogopite mica KMg 3 (AlSi 3 O 10 ) F 2 , potassium tetrasilicon mica KMg 2.5 Si 4 O 10 ) F 2 , and Na tetrasilicic mica NaMg2 . 5 (Si 4 O 10 ) F 2 , Na or Li Teniolite (Na, Li) Mg 2 Li (Si 4 O 10 ) F 2 , Montmorillonite Na or Li Hectorite (Na, Li) 1/8 Mg 2 / Examples include swellable mica such as 5 Li 1/8 (Si 4 O 10 ) F 2 . Synthetic smectite is also useful.
　雲母化合物の中でも、フッ素系の膨潤性雲母が特に有用である。即ち、膨潤性合成雲母は、１０～１５Å程度の厚さの単位結晶格子層からなる積層構造を有し、格子内金属原子置換が他の粘土鉱物より著しく大きい。その結果、格子層は正電荷不足を生じ、それを補償するために層間にＬｉ＋、Ｎａ＋、Ｃａ２＋、Ｍｇ２＋等の陽イオンを吸着している。これらの層間に介在している陽イオンは交換性陽イオンと呼ばれ、いろいろな陽イオンと交換し得る。特に、層間の陽イオンがＬｉ＋、Ｎａ＋の場合、イオン半径が小さいため層状結晶格子間の結合が弱く、水により大きく膨潤する。その状態でシェアーをかけると容易に劈開し、水中で安定したゾルを形成する。膨潤性合成雲母はこの傾向が強く、特に好ましく用いられる。 Of the mica compounds, fluorine-based swellable mica is particularly useful. That is, the swellable synthetic mica has a laminated structure composed of unit crystal lattice layers with a thickness of about 10 to 15 mm, and the substitution of metal atoms in the lattice is significantly larger than other clay minerals. As a result, the lattice layer is deficient in positive charge, and in order to compensate for this, cations such as Li + , Na + , Ca 2+ , and Mg 2+ are adsorbed between the layers. The cations present between these layers are called exchangeable cations and can be exchanged with various cations. In particular, when the cation between layers is Li + or Na + , the bond between the layered crystal lattices is weak because the ionic radius is small, and the layer swells greatly with water. If shear is applied in this state, it will easily cleave and form a stable sol in water. Swelling synthetic mica has a strong tendency and is particularly preferably used.
　雲母化合物の形状としては、拡散制御の観点からは、厚さは薄ければ薄いほどよく、平面サイズは塗布面の平滑性や活性光線の透過性を阻害しない限りにおいて大きい程よい。従って、アスペクト比は、好ましくは２０以上であり、より好ましくは１００以上、特に好ましくは２００以上である。アスペクト比は粒子の厚さに対する長径の比であり、例えば、粒子の顕微鏡写真による投影図から測定することができる。アスペクト比が大きい程、得られる効果が大きい。 As the shape of the mica compound, from the viewpoint of diffusion control, the thinner the better, the better the plane size, as long as the smoothness of the coated surface and the transmittance of actinic rays are not impaired. Accordingly, the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more. The aspect ratio is the ratio of the major axis to the thickness of the particle, and can be measured, for example, from a projection drawing of a particle by a micrograph. The larger the aspect ratio, the greater the effect that can be obtained.
　雲母化合物の粒子径は、その平均長径が、好ましくは０．３～２０μｍ、より好ましくは０．５～１０μｍ、特に好ましくは１～５μｍである。粒子の平均の厚さは、好ましくは０．１μｍ以下、より好ましくは０．０５μｍ以下、特に好ましくは０．０１μｍ以下である。具体的には、例えば、代表的化合物である膨潤性合成雲母の場合、好ましい態様としては、厚さが１～５０ｎｍ程度、面サイズ（長径）が１～２０μｍ程度である。 The average major axis of the mica compound is preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 1 to 5 μm. The average thickness of the particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, in the case of swellable synthetic mica, which is a representative compound, preferred embodiments have a thickness of about 1 to 50 nm and a surface size (major axis) of about 1 to 20 μm.
　無機層状化合物の含有量は、保護層の全固形分に対して、０～６０質量％が好ましく、３～５０質量％がより好ましい。複数種の無機層状化合物を併用する場合でも、無機層状化合物の合計量が上記の含有量であることが好ましい。上記範囲で酸素遮断性が向上し、良好な感度が得られる。また、着肉性の低下を防止できる。 The content of the inorganic stratiform compound is preferably 0 to 60% by mass and more preferably 3 to 50% by mass with respect to the total solid content of the protective layer. Even when a plurality of types of inorganic layered compounds are used in combination, the total amount of the inorganic layered compounds is preferably the above content. Within the above range, the oxygen barrier property is improved and good sensitivity is obtained. Further, it is possible to prevent a decrease in inking property.
　保護層は可撓性付与のための可塑剤、塗布性を向上させための界面活性剤、表面の滑り性を制御するための無機微粒子など公知の添加物を含有してもよい。また、画像記録層において記載した感脂化剤を保護層に含有させてもよい。 The protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coating properties, and inorganic fine particles for controlling the slipperiness of the surface. Further, the protective layer may contain the sensitizer described in the image recording layer.
　保護層は、例えば、必要な各成分を適宜溶剤に溶解又は分散して塗布液を調製し、塗布液を画像記録層上に公知の方法で塗布、乾燥することにより形成することができる。保護層の塗布量（固形分）は、０．０１～１０ｇ／ｍ２が好ましく、０．０２～３ｇ／ｍ２がより好ましく、０．０２～１ｇ／ｍ２が特に好ましい。 The protective layer can be formed, for example, by dissolving or dispersing necessary components in a solvent as appropriate to prepare a coating solution, and coating and drying the coating solution on the image recording layer by a known method. The coating amount of the protective layer (solid content) is preferably 0.01 ~ 10g / m 2, more preferably 0.02 ~ 3g / m 2, particularly preferably 0.02 ~ 1g / m 2.
　上述のように、特定化合物含有層と保護層を一体化し、１つの層として画像記録層の上に形成してもよい。この場合、特定化合物含有層は、例えば、特定化合物含有層及び保護層に必要な各成分を適宜溶剤に溶解又は分散して塗布液を調製し、塗布液を画像記録層上に公知の方法で塗布、乾燥することにより形成することができる。 As described above, the specific compound-containing layer and the protective layer may be integrated and formed on the image recording layer as one layer. In this case, the specific compound-containing layer is prepared, for example, by appropriately dissolving or dispersing each component necessary for the specific compound-containing layer and the protective layer in a solvent to prepare a coating solution, and then applying the coating solution on the image recording layer by a known method. It can be formed by coating and drying.
〔平版印刷版原版の端部ダレ形状〕
　本発明に係る機上現像型平版印刷版原版は、端部に、ダレ形状を有する。ダレ形状は、ダレ量Ｘが２５～１５０μｍ、ダレ幅Ｙが７０～３００μｍであることが好ましい。 [Edge sag shape of planographic printing plate precursor]
The on-press development type lithographic printing plate precursor according to the invention has a sagging shape at the end. The sagging shape preferably has a sagging amount X of 25 to 150 μm and a sagging width Y of 70 to 300 μm.
　図１は、平版印刷版原版の端部の断面形状を模式的に示す図である。
　図１において、平版印刷版原版１はその端部にダレ２を有している。平版印刷版原版１の端面１ｃの上端（ダレ２と端面１ｃとの境界点）と、特定化合物含有層面（更に保護層が形成されている場合には保護層面）１ａの延長線との距離Ｘを「ダレ量」といい、平版印刷版原版１の特定化合物含有層面１ａがダレ始める点と端面１ｃの延長線上との距離Ｙを「ダレ幅」という。 FIG. 1 is a diagram schematically showing a cross-sectional shape of an end portion of a lithographic printing plate precursor.
In FIG. 1, a planographic printing plate precursor 1 has a sag 2 at its end. The distance X between the upper end of the end face 1c of the lithographic printing plate precursor 1 (boundary point between the sag 2 and the end face 1c) and the extended line of the specific compound-containing layer face (protective layer face if a protective layer is further formed) 1a Is referred to as “sag amount”, and the distance Y between the point at which the specific compound-containing layer surface 1a of the planographic printing plate precursor 1 begins to sag and the extension line of the end surface 1c is referred to as “sag width”.
　端部のダレ量は３５μｍ以上がより好ましく、４０μｍ以上が更に好ましい。ダレ量の上限は、端部表面状態の悪化による機上現像性の劣化を防止する観点から１５０μｍが好ましい。機上現像性が劣化すると残存する画像記録層にインキが付着しエッジ汚れ発生の原因となる。ダレ量が少な過ぎると、端部に付着したインキがブランケットに転写しやすくなりエッジ汚れ発生の原因となる場合がある。ダレ量の範囲が２５～１５０μｍの場合、ダレ幅が小さいと、端部におけるクラックの発生が増大し、そこに印刷インキが溜まることによりエッジ汚れの原因となる。このような観点から、ダレ幅は７０～３００μｍの範囲が好ましく、８０～２５０μｍの範囲がより好ましい。なお、上記ダレ量とダレ幅の範囲は、平版印刷版原版１の支持体面１ｂのエッジ形状には関わらない。
　通常、平版印刷版原版１の端部において、画像記録層と支持体との境界Ｂ、及び、支持体面１ｂも、特定化合物含有層面１ａと同様に、ダレが発生している。 The sagging amount at the end is more preferably 35 μm or more, and further preferably 40 μm or more. The upper limit of the sagging amount is preferably 150 μm from the viewpoint of preventing deterioration of on-press developability due to deterioration of the end surface condition. When the on-machine developability deteriorates, ink adheres to the remaining image recording layer and causes edge smearing. If the amount of sag is too small, the ink adhering to the end portion is easily transferred to the blanket, which may cause edge smearing. When the range of the amount of sag is 25 to 150 μm, if the sag width is small, the occurrence of cracks at the end increases, and printing ink accumulates there, causing edge smearing. From such a viewpoint, the sagging width is preferably in the range of 70 to 300 μm, and more preferably in the range of 80 to 250 μm. The range of the sag amount and the sag width is not related to the edge shape of the support surface 1b of the planographic printing plate precursor 1.
Usually, at the edge of the lithographic printing plate precursor 1, the boundary B between the image recording layer and the support and the support surface 1b are also sagging as in the case of the specific compound-containing layer surface 1a.
　上記ダレ形状を有する端部の形成は、例えば、平版印刷版原版の裁断条件を調整することにより行うことができる。
　具体的には、平版印刷版原版の裁断時に使用するスリッター装置における上側裁断刃と下側裁断刃の隙間、噛み込み量、刃先角度などを調整することにより行うことができる。
　例えば、図２は、スリッター装置の裁断部を示す概念図である。スリッター装置には、上下一対の裁断刃１０、２０が左右に配置されている。裁断刃１０、２０は円板上の丸刃からなり、上側裁断刃１０ａ及び１０ｂは回転軸１１に、下側裁断刃２０ａ及び２０ｂは回転軸２１に、それぞれ同軸上に支持されている。上側裁断刃１０ａ及び１０ｂと下側裁断刃２０ａ及び２０ｂとは、相反する方向に回転される。平版印刷版原版３０は、上側裁断刃１０ａ、１０ｂと下側裁断刃２０ａ，２０ｂとの間を通されて所定の幅に裁断される。スリッター装置の裁断部の上側裁断刃１０ａと下側裁断刃２０ａとの隙間及び上側裁断刃１０ｂと下側裁断刃２０ｂとの隙間を調整することによりダレ形状を有する端部を形成することができる。 The end portion having the sagging shape can be formed, for example, by adjusting the cutting conditions of the planographic printing plate precursor.
Specifically, it can be performed by adjusting the gap between the upper cutting blade and the lower cutting blade, the biting amount, the blade edge angle, etc. in the slitter apparatus used when cutting the lithographic printing plate precursor.
For example, FIG. 2 is a conceptual diagram showing a cutting unit of a slitter device. In the slitter device, a pair of upper and lower cutting blades 10 and 20 are arranged on the left and right. The cutting blades 10 and 20 are round blades on a circular plate, and the upper cutting blades 10a and 10b are supported on the rotating shaft 11 and the lower cutting blades 20a and 20b are supported on the rotating shaft 21 on the same axis. The upper cutting blades 10a and 10b and the lower cutting blades 20a and 20b are rotated in opposite directions. The planographic printing plate precursor 30 is cut into a predetermined width by passing between the upper cutting blades 10a and 10b and the lower cutting blades 20a and 20b. By adjusting the gap between the upper cutting blade 10a and the lower cutting blade 20a and the gap between the upper cutting blade 10b and the lower cutting blade 20b in the cutting portion of the slitter device, an end portion having a sagging shape can be formed. .
　本発明に係る機上現像型平版印刷版原版においては、エッジ汚れを更に抑制する観点から、ダレ幅Ｙに相当する領域における、陽極酸化皮膜の表面に存在するクラックの面積率が２０％以下であることが好ましい。
　ここで、ダレ幅Ｙに相当する領域とは、上記図１における特定化合物含有層面（更に保護層が形成されている場合には保護層面）１ａの延長線と端面１ｃの延長線との交点から１ａの延長線が特定化合物含有層面（更に保護層が形成されている場合には保護層面）の接するまでの領域を意味する。 In the on-press development type lithographic printing plate precursor according to the present invention, from the viewpoint of further suppressing edge contamination, the area ratio of cracks existing on the surface of the anodized film in the region corresponding to the sagging width Y is 20% or less. Preferably there is.
Here, the region corresponding to the sagging width Y is from the intersection of the extension line of the specific compound-containing layer surface in FIG. 1 (the protective layer surface when a protective layer is further formed) 1a and the extended line of the end surface 1c. The extension line of 1a means the region until the specific compound-containing layer surface (or the protective layer surface when a protective layer is formed) is in contact.
　陽極酸化皮膜の表面に存在するクラックの面積率は、以下の方法で算出される。
　平版印刷版原版の構成層（下塗り層、画像記録層、特定化合物含有層、保護層）を、ヤマト科学（株）製ＰｌａｓｍａＲｅａｃｔｏｒＰＲ３００を用いて除去する。露出したアルミニウム支持体の陽極酸化皮膜の表面を、Ｐｔ-Ｐｄ膜を３ｎｍ蒸着して導電処理して試料を作成する。この試料を、（株）日立ハイテクノロジーズ製Ｓ-４８００型電界放出形走査電子顕微鏡（ＦＥ-ＳＥＭ）を用いて、加速電圧３０ｋＶでＳＥＭ観察を行い、観察倍率１，５００倍で端部から中央部に向かって連続写真を取得し、１５０×５０μｍの画像を得る。この画像に対して、画像処理ソフトにより、クラック部と陽極酸化皮膜層表面の輝度差を利用してクラック形状を抽出、２値化処理を行い、１５０×５０μｍ範囲におけるクラックの割合を算出し、クラックの面積率とする。 The area ratio of cracks existing on the surface of the anodized film is calculated by the following method.
The constituent layers (undercoat layer, image recording layer, specific compound-containing layer, protective layer) of the lithographic printing plate precursor are removed using PlasmaReactor PR300 manufactured by Yamato Scientific Co., Ltd. A sample is prepared by conducting a conductive treatment on the exposed surface of the anodized film of the aluminum support by depositing a Pt—Pd film by 3 nm. This sample was observed with an S-4800 field emission scanning electron microscope (FE-SEM) manufactured by Hitachi High-Technologies Corporation at an accelerating voltage of 30 kV. A continuous photograph is acquired toward the part, and an image of 150 × 50 μm is obtained. For this image, the image processing software extracts the crack shape using the luminance difference between the crack portion and the surface of the anodized film layer, performs binarization processing, calculates the ratio of cracks in the 150 × 50 μm range, The area ratio of cracks.
　クラックの面積率は、エッジ汚れの発生を防止する観点から、１０％以下が特に好ましい。 The area ratio of cracks is particularly preferably 10% or less from the viewpoint of preventing the occurrence of edge contamination.
　ダレ幅Ｙに相当する領域における、陽極酸化皮膜の表面に存在するクラックの面積率を１０％以下に調整するためには、上記陽極酸化皮膜の陽極酸化皮膜量を０．５～５．０ｇ／ｍ２の範囲に制御することが好ましい。陽極酸化皮膜量は、エッジ汚れを更に抑制する観点から、０．８～１．２ｇ／ｍ２の範囲に制御することがより好ましい。 In order to adjust the area ratio of cracks existing on the surface of the anodized film in the region corresponding to the sagging width Y to 10% or less, the amount of the anodized film of the anodized film is set to 0.5 to 5.0 g / it is preferably controlled in the range of m 2. The amount of the anodized film is more preferably controlled in the range of 0.8 to 1.2 g / m 2 from the viewpoint of further suppressing edge contamination.
　陽極酸化皮膜の陽極酸化皮膜量は、以下の方法で算出される。
　平版印刷版原版の構成層（下塗り層、画像記録層、特定化合物含有層、保護層）を、ヤマト科学（株）製ＰｌａｓｍａＲｅａｃｔｏｒ　ＰＲ３００を用いて除去する。露出したアルミニウム支持体の陽極酸化皮膜の表面を、蛍光Ｘ線分析装置（（株）リガク製ＺＳＸ　ＰｒｉｍｕｓＩＩ）で測定し、別途作成した検量線を用いて陽極酸化皮膜の陽極酸化皮膜量（ｇ／ｍ２）を算出する。検量線は蛍光Ｘ線分析装置から得られるコンプトン散乱線強度とメイソン法で算出した陽極酸化皮膜量の関係から作成した。メイソン法の測定精度を上げるため、メイソン液は全て新液を用いた。蛍光Ｘ線分析の条件は以下のとおりである。Ｘ線管球：Ｒｈ、測定スペクトル：ＲｈＬα、管電圧：５０ｋＶ、管電流：６０ｍＡ、スリット：Ｓ２、分光結晶：Ｇｅ、検出器：ＰＣ、分析面積：３０ｍｍφ、ピーク位置（２θ）：８９．５１０ｄｅｇ．、バックグランド（２θ）：８７．０００ｄｅｇ．及び９２．０００ｄｅｇ．、積算時間：６０秒／ｓａｍｐｌｅ The amount of the anodized film of the anodized film is calculated by the following method.
The constituent layers (undercoat layer, image recording layer, specific compound-containing layer, protective layer) of the lithographic printing plate precursor are removed using PlasmaReactor PR300 manufactured by Yamato Scientific Co., Ltd. The surface of the anodized film of the exposed aluminum support was measured with a fluorescent X-ray analyzer (ZSX Primus II, manufactured by Rigaku Corporation), and an anodized film amount (g / g) of the anodized film was prepared using a separately prepared calibration curve. m 2 ) is calculated. The calibration curve was created from the relationship between the Compton scattered radiation intensity obtained from the fluorescent X-ray analyzer and the amount of the anodized film calculated by the Mason method. In order to improve the measurement accuracy of the Mason method, all new Mason solutions were used. The conditions for the fluorescent X-ray analysis are as follows. X-ray tube: Rh, measurement spectrum: RhLα, tube voltage: 50 kV, tube current: 60 mA, slit: S2, spectral crystal: Ge, detector: PC, analysis area: 30 mmφ, peak position (2θ): 89.510 deg . , Background (2θ): 87.000 deg. And 92.000 deg. , Integration time: 60 seconds / sample
　陽極酸化皮膜の陽極酸化皮膜量を制御するには、例えば、陽極酸化処理における電解時間を調整する方法が挙げられる。 In order to control the amount of the anodized film of the anodized film, for example, there is a method of adjusting the electrolysis time in the anodizing process.
　ダレ幅Ｙに相当する領域における、陽極酸化皮膜の表面に存在するクラックの面積率を１０％以下に調整するためには、上記陽極酸化皮膜の表面に存在するマイクロポアの平均径を５～３５ｎｍの範囲に制御することが好ましい。 In order to adjust the area ratio of cracks existing on the surface of the anodized film in the region corresponding to the sagging width Y to 10% or less, the average diameter of the micropores existing on the surface of the anodized film is 5 to 35 nm. It is preferable to control within the range.
　陽極酸化皮膜のマイクロポアの平均径は、以下の方法で算出される。
　平版印刷版原版の構成層（下塗り層、画像記録層、特定化合物含有層、保護層）を、ヤマト科学（株）製ＰｌａｓｍａＲｅａｃｔｏｒＰＲ３００を用いて除去する。露出したアルミニウム支持体の陽極酸化皮膜の表面を、カーボン又はＰｔ-Ｐｄ膜を３ｎｍ蒸着して導電処理して試料を作成する。この試料を、（株）日立ハイテクノロジーズ製Ｓ-４８００型電界放出形走査電子顕微鏡（ＦＥ-ＳＥＭ）を用いて、観察倍率１５０，０００倍で端部から中央部に向かって連続写真を取得し、４００×６００ｎｍの画像を４枚得る。この４枚の画像に存在するマイクロポア９０個の直径を測定し、平均してマイクロポアの平均径とする。なお、マイクロポアの形状が円形でない場合には、マイクロポアの投影面積と同じ投影面積を持つ円を想定し、その円の直径をマイクロポアの直径とする。 The average pore diameter of the anodized film is calculated by the following method.
The constituent layers (undercoat layer, image recording layer, specific compound-containing layer, protective layer) of the lithographic printing plate precursor are removed using PlasmaReactor PR300 manufactured by Yamato Scientific Co., Ltd. A carbon or Pt—Pd film is vapor-deposited by 3 nm on the exposed surface of the anodized film of the aluminum support, and a sample is prepared. Using this sample, S-4800 field emission scanning electron microscope (FE-SEM) manufactured by Hitachi High-Technologies Corporation, continuous photographs were taken from the end to the center at an observation magnification of 150,000 times. 4 images of 400 × 600 nm are obtained. The diameters of 90 micropores present in the four images are measured and averaged to obtain the average diameter of the micropores. If the shape of the micropore is not circular, a circle having the same projected area as the projected area of the micropore is assumed, and the diameter of the circle is the diameter of the micropore.
　陽極酸化皮膜のマイクロポアの平均径を制御するには、例えば、ポアワイド処理における処理時間を調整する方法が挙げられる。 In order to control the average diameter of the micropores of the anodized film, for example, there is a method of adjusting the processing time in the pore wide processing.
　本発明に係る機上現像型平版印刷版原版は、端部にダレ形状を有することと、画像記録層の上に特定化合物含有層を有することにより、端部の画像形成性、機上現像性などの特性を低下させることなく、長期保存後においても良好なエッジ汚れ防止性を示すことができるという特徴を有する。
　更に、本発明に係る機上現像型平版印刷版原版においては、端部に、水溶性化合物を含有する塗布液を塗布するなどの親水化処理を施すことなく、長期保存後においても良好なエッジ汚れ防止性を示すことができるという特徴を有する。
　その理由は明らかではないが、以下の通りと推測される。
　本発明に係る機上現像型平版印刷版原版は、画像記録層の上に特定化合物含有層を有する。長期保存下において、画像形成層における重合性化合物が、活性種により暗重合を行ったとしても、特定化合物含有層に含まれる特定化合物は、画像記録層とは異なる層に存在しており、画像記録層の影響を受けにくくなっている。そのため、上記特定化合物は、印刷インキ及び湿し水から選ばれる少なくとも１つにより溶出し、機上現像型平版印刷版原版の端部に移動することで、端部を親水化させることができ、エッジ汚れ防止性がより向上するものと推測される。
　また、後述の機上現像型平版印刷版ダミー版は、通常、画像記録層を有していないため、長期保存下においても、良好なエッジ汚れ防止性を示すものと推測される。 The on-press development type lithographic printing plate precursor according to the present invention has a sag shape at the end portion and a specific compound-containing layer on the image recording layer, so that the image forming property at the end portion and the on-press developability are obtained. It has a feature that it can exhibit good edge stain resistance even after long-term storage without deteriorating the characteristics such as.
Furthermore, in the on-press development type lithographic printing plate precursor according to the present invention, a good edge can be obtained even after long-term storage without applying a hydrophilic treatment such as applying a coating solution containing a water-soluble compound to the edges. It has a feature that it can exhibit antifouling properties.
The reason is not clear, but is presumed as follows.
The on-press development type lithographic printing plate precursor according to the invention has a specific compound-containing layer on the image recording layer. Even if the polymerizable compound in the image forming layer undergoes dark polymerization with active species under long-term storage, the specific compound contained in the specific compound-containing layer is present in a layer different from the image recording layer. It is less affected by the recording layer. Therefore, the specific compound is eluted with at least one selected from printing ink and fountain solution, and can be made hydrophilic by moving to the end of the on-press development type lithographic printing plate precursor, It is presumed that the edge dirt prevention property is further improved.
In addition, the on-press development type lithographic printing plate dummy plate described later usually has no image recording layer, and thus is presumed to exhibit good edge stain resistance even under long-term storage.
［平版印刷版の作製方法］
　本発明に係る平版印刷版の作製方法は、本発明に係る平版印刷版原版を画像露光する工程（露光工程）、及び、画像露光後の平版印刷版原版を印刷機上で印刷インキ及び湿し水の少なくとも一方により、画像記録層の未露光部を除去する工程（機上現像工程）を含む。 [Preparation method of lithographic printing plate]
The method for producing a lithographic printing plate according to the present invention comprises a step of exposing an image of the lithographic printing plate precursor according to the present invention (exposure step), and printing ink and dampening of the lithographic printing plate precursor after image exposure on a printing machine. A step (on-press development step) of removing an unexposed portion of the image recording layer with at least one of water.
〔露光工程〕
　画像露光は、デジタルデータを赤外線レーザー等により走査露光する方法により行うことが好ましい。
　露光光源の波長は、７５０～１，４００ｎｍが好ましく用いられる。７５０～１，４００ｎｍの光源としては、赤外線を放射する固体レーザー及び半導体レーザーが好適である。露光機構は内面ドラム方式、外面ドラム方式、フラットベッド方式等のいずれでもよい。
　露光工程はプレートセッターなどにより公知の方法で行うことができる。また、露光装置を備えた印刷機を用いて、平版印刷版原版を印刷機に装着した後、印刷機上で露光を行ってもよい。 [Exposure process]
Image exposure is preferably performed by a method of scanning exposure of digital data with an infrared laser or the like.
The wavelength of the exposure light source is preferably 750 to 1,400 nm. As the light source of 750 to 1,400 nm, a solid laser or semiconductor laser that emits infrared light is suitable. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
The exposure step can be performed by a known method using a plate setter or the like. Alternatively, the exposure may be performed on the printing machine after the planographic printing plate precursor is mounted on the printing machine using a printing machine equipped with an exposure device.
〔機上現像工程〕
　機上現像工程においては、画像露光後の平版印刷版原版に何らの現像処理を施すことなく、印刷機上において印刷インキ及び湿し水を供給して印刷を開始すると、印刷途上の初期の段階で平版印刷版原版の未露光部分が除去され、それに伴って親水性支持体表面が露出し非画像部が形成される。印刷インキ及び湿し水としては、公知の平版印刷用の印刷インキ及び湿し水が用いられる。最初に平版印刷版原版表面に供給されるのは、印刷インキでも湿し水でもよいが、湿し水が除去された画像記録層成分によって汚染されることを防止する点で、最初に印刷インキを供給することが好ましい。
　このようにして、平版印刷版原版はオフセット印刷機上で機上現像され、そのまま多数枚の印刷に用いられる。 [On-press development process]
In the on-press development process, when printing is started by supplying printing ink and fountain solution on the printing press without performing any development processing on the lithographic printing plate precursor after image exposure, an initial stage of printing Thus, the unexposed portion of the lithographic printing plate precursor is removed, and accordingly, the hydrophilic support surface is exposed to form a non-image portion. As the printing ink and fountain solution, known lithographic printing ink and fountain solution are used. The lithographic printing plate precursor may be initially supplied with the printing ink or fountain solution, but the printing ink is first used in order to prevent the fountain solution from being contaminated by the removed image recording layer components. Is preferably supplied.
In this way, the lithographic printing plate precursor is subjected to on-press development on an offset printing machine and used as it is for printing a large number of sheets.
　本発明に係る平版印刷版の作製方法は、上記工程以外に、公知の他の工程を含んでいてもよい。他の工程としては、例えば、各工程の前に平版印刷版原版の位置や向き等を確認する検版工程や、機上現像工程の後に、印刷画像を確認する確認工程等が挙げられる。 The method for producing a lithographic printing plate according to the present invention may include other known steps in addition to the above steps. Examples of other processes include a plate inspection process for confirming the position and orientation of the lithographic printing plate precursor before each process, a confirmation process for confirming a printed image after the on-machine development process, and the like.
　［機上現像型平版印刷版ダミー版］
　カラーの新聞印刷のような多色印刷の分野において、一部の紙面を２色又は１色で印刷を行う必要がある場合等には、印刷機の版胴の印刷を必要としない部分に、印刷版の代りにダミー版を取り付けて印刷を行うことがある。このようなダミー版は、捨版、水版、ブランク版と称されることもある。
　本発明は、ダミー版、具体的には機上現像型平版印刷版ダミー版にも関する。 [On-press development type lithographic printing plate dummy]
In the field of multi-color printing such as color newspaper printing, when it is necessary to print a part of the paper surface with two colors or one color, etc. In some cases, a dummy plate is attached instead of the printing plate for printing. Such a dummy version is sometimes called a discarded version, a water version, or a blank version.
The present invention also relates to a dummy plate, specifically an on-press development type lithographic printing plate dummy plate.
　本発明に係る機上現像型平版印刷版ダミー版は、陽極酸化皮膜を有するアルミニウム支持体上にポリマー層を有する機上現像型平版印刷版ダミー版であって、上記平版印刷版ダミー版は端部にダレ形状を有し、上記ポリマー層の上に支持体吸着性を有する化合物を含有する層を有し、上記化合物の含有量が上記支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版ダミー版である。 An on-press development type lithographic printing plate dummy plate according to the present invention is an on-press development type lithographic printing plate dummy plate having a polymer layer on an aluminum support having an anodized film, and the lithographic printing plate dummy plate has an end face. In the plane of the layer having a sagging shape in the part, and having a layer containing a compound having a support adsorptivity on the polymer layer, the content of the compound having a compound having the support adsorbing property Is an on-press development type lithographic printing plate dummy plate which is substantially the same as in FIG.
〔陽極酸化皮膜を有するアルミニウム支持体〕
　機上現像型平版印刷版原版ダミー版を構成する陽極酸化皮膜を有するアルミニウム支持体は、特に限定されないが、上記機上現像型平版印刷版原版を構成する陽極酸化皮膜を有するアルミニウム支持体と同様のものが挙げられる。 [Aluminum support with anodized film]
The aluminum support having an anodic oxide film constituting the on-press development type lithographic printing plate precursor dummy is not particularly limited, but is the same as the aluminum support having the anodic oxide film constituting the on-press development type lithographic printing plate precursor. Can be mentioned.
〔ポリマー層〕
　機上現像型平版印刷版ダミー版を構成するポリマー層は、陽極酸化皮膜を有するアルミニウム支持体上に存在する。
　ポリマー層は、バインダーポリマーを含有することが好ましい。ポリマー層のバインダーポリマーとしては、被膜形成性を有するポリマーが好適である。ポリマー層に含有されるバインダーポリマーとしては、例えば、ポリビニルアルコール、変性ポリビニルアルコール、ポリビニルピロリドン、水溶性セルロース誘導体、ポリ（メタ）アクリロニトリル等が挙げられる。
　変性ポリビニルアルコールとしては、カルボキシ基又はスルホ基を有する酸変性ポリビニルアルコールが好ましく用いられる。具体的には、特開２００５－２５０２１６号及び特開２００６－２５９１３７号の各公報に記載の変性ポリビニルアルコールが挙げられる。 (Polymer layer)
The polymer layer constituting the on-press development type lithographic printing plate dummy is present on an aluminum support having an anodized film.
The polymer layer preferably contains a binder polymer. As the binder polymer of the polymer layer, a polymer having a film-forming property is suitable. Examples of the binder polymer contained in the polymer layer include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile and the like.
As the modified polyvinyl alcohol, acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used. Specific examples include modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137.
　ポリマー層のバインダーポリマーとしては、支持体吸着性基を有する繰り返し単位と親水性基を有する繰り返し単位とを含む水溶性高分子化合物が特に好ましい。これにより、平版印刷版ダミー版自体の機上現像性が向上し、また、エッジ汚れが抑制される。エッジ汚れとは、新聞印刷のように輪転機を用いてロール状の印刷用紙に連続して印刷を行う場合、平版印刷版ダミー版の端部が印刷用紙面内にあるため、端部に付着したインキが印刷用紙に転写されて線状の汚れを生じる現象のことである。 As the binder polymer of the polymer layer, a water-soluble polymer compound containing a repeating unit having a support-adsorbing group and a repeating unit having a hydrophilic group is particularly preferable. As a result, the on-press developability of the lithographic printing plate dummy itself is improved, and edge contamination is suppressed. Edge smear refers to the edge of a lithographic printing plate dummy when it is printed continuously on a roll-like printing paper using a rotary press, such as newspaper printing, so it adheres to the edge. This is a phenomenon in which the used ink is transferred to the printing paper and causes linear stains.
　以下に、支持体吸着性基を有する繰り返し単位と親水性基を有する繰り返し単位とを含む水溶性高分子化合物について詳述する。 Hereinafter, the water-soluble polymer compound containing a repeating unit having a support adsorptive group and a repeating unit having a hydrophilic group will be described in detail.
（支持体吸着性基）
　支持体吸着性基としては、例えば、陽極酸化処理又は親水化処理を施した支持体上に存在する金属、金属酸化物、ヒドロキシ基等とイオン結合形成、水素結合形成、極性相互作用などの相互作用が可能な基が挙げられる。
　支持体吸着性基の具体例を以下に挙げる。 (Support adsorbing group)
Examples of the support adsorptive group include ionic bond formation, hydrogen bond formation, and polar interaction with metals, metal oxides, hydroxy groups, etc. present on the support subjected to anodization treatment or hydrophilization treatment. Examples include groups capable of acting.
Specific examples of the support-adsorptive group are listed below.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式中、Ｍ１及びＭ２はそれぞれ独立に、水素原子、アルカリ金属もしくはアルカリ土類金属に含まれる金属原子又はアンモニウム基を表す。耐汚れ性の観点から、支持体吸着性基は、ホスホン酸基、リン酸基、カルボン酸基及びこれらの塩から選ばれる少なくとも１つの基であることが好ましい。支持体吸着性基は、ホスホン酸基もしくはその塩（構造１）、リン酸エステル基もしくはその塩（構造２）、カルボン酸基もしくはその塩であることがより好ましく、リン酸エステル基もしくはその塩又はホスホン酸基もしくはその塩であることが更に好ましい。
　支持体吸着性基を有する繰り返し単位は、具体的には下記一般式（Ｂ１）で表されることが好ましい。 In the formula, M 1 and M 2 each independently represent a hydrogen atom, a metal atom contained in an alkali metal or alkaline earth metal, or an ammonium group. From the viewpoint of stain resistance, the support adsorptive group is preferably at least one group selected from a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, and salts thereof. The support-adsorbing group is more preferably a phosphonic acid group or a salt thereof (structure 1), a phosphate ester group or a salt thereof (structure 2), a carboxylic acid group or a salt thereof, and a phosphate ester group or a salt thereof. Or it is still more preferable that it is a phosphonic acid group or its salt.
Specifically, the repeating unit having a support-adsorptive group is preferably represented by the following general formula (B1).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　式（Ｂ１）中、Ｒａ～Ｒｃは、それぞれ独立に、水素原子、炭素数１～６のアルキル基又はハロゲン原子を表す。Ｑは支持体吸着性基を表し、好ましい態様は上述したものと同じである。
　Ｌは、単結合又は２価の連結基を表す。２価の連結基は、１から６０個までの炭素原子、０個から１０個までの窒素原子、０個から５０個までの酸素原子、１個から１００個までの水素原子、及び０個から２０個までの硫黄原子から成り、より具体的には、下記の構造単位又はこれらが組み合わさって構成されるものを挙げることができる。 In formula (B1), R a to R c each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. Q represents a support-adsorptive group, and a preferred embodiment is the same as described above.
L represents a single bond or a divalent linking group. A divalent linking group can be from 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to It consists of up to 20 sulfur atoms, and more specifically, the following structural units or those constituted by a combination thereof can be mentioned.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　上記構造において、Ｒｄ及びＲｅは、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～２０のアリール基又はハロゲン原子を表す。ｎは１～４の整数を表す。 In the above structure, R d and R e each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom. n represents an integer of 1 to 4.
　以下に、支持体吸着性基を有する繰り返し単位の具体例を示すが、本発明はこれらに限定されるものではない。 Specific examples of the repeating unit having a support adsorptive group are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　上記高分子化合物は、支持体吸着性基を１種のみ有していても、２種以上有していてもよい。
　支持体吸着性基を有する繰り返し単位の含有量は、高分子化合物の全繰り返し単位に対して、２～８０モル％が好ましく、２～７０モル％がより好ましく、５～５０モル％が更に好ましく、１０～４０モル％が特に好ましい。 The polymer compound may have only one type of support adsorptive group or two or more types.
The content of the repeating unit having a support-adsorbing group is preferably 2 to 80 mol%, more preferably 2 to 70 mol%, still more preferably 5 to 50 mol%, based on all repeating units of the polymer compound. 10 to 40 mol% is particularly preferred.
（親水性基）
　上記高分子化合物は、アルミニウム支持体支持体表面の親水性を高めて、エッチ汚れを抑制するために、親水性基を有する繰り返し単位を有する。
　親水性基の具体例を以下に挙げる。 (Hydrophilic group)
The polymer compound has a repeating unit having a hydrophilic group in order to increase the hydrophilicity of the surface of the aluminum support and to suppress etch stains.
Specific examples of the hydrophilic group are given below.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　上式中、Ｍ１は水素原子、アルカリ金属もしくはアルカリ土類金属に含まれる金属原子又はアンモニウム基を表す。
　Ｘ＋は、－Ｎ＋Ｒ１Ｒ２－、－Ｓ＋Ｒ１－、－Ｉ＋－、－Ｐ＋Ｒ１Ｒ２－で示される基を表す。
　Ｒ１及びＲ２は、それぞれ独立に、水素原子、アルキル基、アリール基、アルケニル基又はアルキニル基を表し、Ｒ３はアルキレン基を表し、Ｒ４はアルキル基、アリール基、アルケニル基又はアルキニル基を表す。
　ｎは１～１００の整数を表す。Ｌは前述のＬと同義である。 In the above formula, M 1 represents a hydrogen atom, a metal atom contained in an alkali metal or alkaline earth metal, or an ammonium group.
X + represents a group represented by -N + R 1 R 2- , -S + R 1- , -I + -, -P + R 1 R 2- .
R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or an alkynyl group, R 3 represents an alkylene group, and R 4 represents an alkyl group, an aryl group, an alkenyl group or an alkynyl group. Represents.
n represents an integer of 1 to 100. L has the same meaning as L described above.
　親水性基としては、水との親和性が高くなる官能基であれば何れも好適に使用することができるが、スルホン酸（塩）基、アミド基、ポリアルキレンオキシド基、ヒドロキシル基、硫酸モノエステル（塩）基、スルホンアミド基、アミノ基、硫酸モノアミド（塩）基、ベタイン構造が好ましく、スルホン酸（塩）基、アミド基、ポリアルキレンオキシド基、ヒドロキシル基、硫酸モノエステル（塩）基、スルホンアミド基、アミノ基、硫酸モノアミド（塩）基、ベタイン構造がより好ましく、スルホン酸（塩）基、アミド基、ポリアルキレンオキシド基、ヒドロキシル基、ベタイン構造が特に好ましい。
　親水性基は、スルホン酸基及びその塩、アミド基並びにベタイン構造から選ばれる少なくとも１つの基又は構造であることが特に好ましい。 As the hydrophilic group, any functional group having high affinity with water can be suitably used. However, a sulfonic acid (salt) group, an amide group, a polyalkylene oxide group, a hydroxyl group, and a monosulfuric acid group can be used. Ester (salt) group, sulfonamide group, amino group, sulfuric monoamide (salt) group, betaine structure is preferable, sulfonic acid (salt) group, amide group, polyalkylene oxide group, hydroxyl group, sulfuric monoester (salt) group , Sulfonamido group, amino group, sulfuric monoamide (salt) group and betaine structure are more preferred, and sulfonic acid (salt) group, amide group, polyalkylene oxide group, hydroxyl group and betaine structure are particularly preferred.
The hydrophilic group is particularly preferably at least one group or structure selected from a sulfonic acid group and a salt thereof, an amide group, and a betaine structure.
　親水性基を有する繰り返し単位は、具体的には下記一般式（Ｂ２）で表されることが好ましい。 Specifically, the repeating unit having a hydrophilic group is preferably represented by the following general formula (B2).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式（Ｂ２）中、Ｒａ～Ｒｃは、それぞれ独立に、水素原子、炭素数１～６のアルキル基又はハロゲン原子を表す。Ｌは前述のＬと同義である。Ｗは親水性基を表し、好ましい態様は上述したものと同じである。 In formula (B2), R a to R c each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. L has the same meaning as L described above. W represents a hydrophilic group, and a preferred embodiment is the same as described above.
　以下に、親水性基を有する繰り返し単位の具体例を示すが、本発明はこれらに限定されるものではない。 Specific examples of the repeating unit having a hydrophilic group are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　上記高分子化合物は、親水性基を１種のみ有していても、２種以上有していてもよい。
　親水性基を有する繰り返し単位の含有量は、高分子化合物の全繰り返し単位に対して、３０～９８モル％が好ましく、４０～９０モル％がより好ましく、５０～９０モル％が更に好ましい。 The polymer compound may have only one kind of hydrophilic group or two or more kinds.
The content of the repeating unit having a hydrophilic group is preferably from 30 to 98 mol%, more preferably from 40 to 90 mol%, still more preferably from 50 to 90 mol%, based on all repeating units of the polymer compound.
（その他の繰り返し単位）
　上記高分子化合物は、上記支持体吸着性基を有する繰り返し単位及び親水性基を有する繰り返し単位以外に、他の繰り返し単位（以下、単に、「その他の繰り返し単位」ということもある。）を有する共重合体であってもよい。その他の繰り返し単位としては、既知の種々のモノマーに由来する繰り返し単位を挙げることができる。 (Other repeat units)
In addition to the repeating unit having a support-adsorptive group and the repeating unit having a hydrophilic group, the polymer compound has another repeating unit (hereinafter sometimes simply referred to as “other repeating unit”). A copolymer may also be used. Examples of other repeating units include repeating units derived from various known monomers.
　上記高分子化合物は、例えば、支持体吸着性基を有する繰り返し単位、親水性基を有する繰り返し単位の他に、（メタ）アクリル酸アルキル又はアラルキルエステルに対応する繰り返し単位、（メタ）アクリルアミド又はその誘導体に対応する繰り返し単位、α-ヒドロキシメチルアクリレートに対応する繰り返し単位、スチレン誘導体に対応する繰り返し単位を有していてもよい。
　（メタ）アクリル酸アルキルエステルのアルキル基は、好ましくは炭素数１～５のアルキル基、炭素数２～８の前述の置換基を有するアルキル基であり、メチル基がより好ましい。（メタ）アクリル酸アラルキルエステルとしては、（メタ）アクリル酸ベンジル等が挙げられる。
　（メタ）アクリルアミド誘導体としては、Ｎ－イソプロピルアクリルアミド、Ｎ－フェニルメタクリルアミド、Ｎ－（４－メトキシカルボニルフェニル）メタアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、モルホリノアクリルアミド等が挙げられる。
　α－ヒドロキシメチルアクリレートとしては、α－ヒドロキシメチルアクリル酸エチル、α－ヒドロキシメチルアクリル酸シクロヘキシル等が挙げられる。
　スチレン誘導体としては、スチレン、４－ｔｅｒｔブチルスチレン等が挙げられる。 The polymer compound includes, for example, a repeating unit having a support-adsorbing group, a repeating unit having a hydrophilic group, a repeating unit corresponding to an alkyl (meth) acrylate or an aralkyl ester, (meth) acrylamide or the like. It may have a repeating unit corresponding to the derivative, a repeating unit corresponding to α-hydroxymethyl acrylate, and a repeating unit corresponding to the styrene derivative.
The alkyl group of the (meth) acrylic acid alkyl ester is preferably an alkyl group having 1 to 5 carbon atoms and an alkyl group having the aforementioned substituent having 2 to 8 carbon atoms, and a methyl group is more preferable. Examples of the (meth) acrylic acid aralkyl ester include benzyl (meth) acrylate.
Examples of (meth) acrylamide derivatives include N-isopropylacrylamide, N-phenylmethacrylamide, N- (4-methoxycarbonylphenyl) methacrylamide, N, N-dimethylacrylamide, morpholinoacrylamide and the like.
Examples of α-hydroxymethyl acrylate include ethyl α-hydroxymethyl acrylate and cyclohexyl α-hydroxymethyl acrylate.
Examples of the styrene derivative include styrene and 4-tertbutylstyrene.
　その他の繰り返し単位の含有量は、上記高分子化合物の全繰り返し単位に対して、４０モル％以下が好ましく、３０モル％がより好ましく、２０モル％以下が更に好ましい。 The content of other repeating units is preferably 40 mol% or less, more preferably 30 mol%, still more preferably 20 mol% or less, based on all repeating units of the polymer compound.
　上記高分子化合物は、上記支持体吸着性基としてホスホン酸基、リン酸基、カルボン酸基及びこれらの塩から選ばれる少なくとも１つの基を有する繰り返し単位と、上記親水性基としてスルホン酸基及びその塩、アミド基並びにベタイン構造から選ばれる少なくとも１つの基又は構造を有する繰り返し単位とを含む共重合体であることが特に好ましい。 The polymer compound includes a repeating unit having at least one group selected from a phosphonic acid group, a phosphoric acid group, a carboxylic acid group and a salt thereof as the support adsorptive group, a sulfonic acid group as the hydrophilic group, and Particularly preferred is a copolymer comprising a salt, an amide group and a repeating unit having at least one group or structure selected from betaine structures.
　ポリマー層に含有されるバインダーポリマーは、１種類を単独で使用してもよいし、２種類以上を混合して使用してもよい。
　ポリマー層は、１層であってもよく、２層以上存在しても良い。
　ポリマー層におけるバインダーポリマーの含有量は、ポリマー層の全固形分に対して、１０～１００質量％が好ましく、３０～９５質量％がより好ましく、４０～９０質量％が更に好ましい。 The binder polymer contained in the polymer layer may be used alone or in combination of two or more.
The polymer layer may be a single layer or two or more layers.
The content of the binder polymer in the polymer layer is preferably 10 to 100% by mass, more preferably 30 to 95% by mass, and still more preferably 40 to 90% by mass with respect to the total solid content of the polymer layer.
〔下塗り層〕
　本発明に係る機上現像型平版印刷版ダミー版は、ポリマー層と支持体との間に下塗り層（中間層と呼ばれることもある。）を有することができる。
　下塗り層としては、特に限定されないが、上記機上現像型平版印刷版原版が、画像記録層と支持体との間に有しても良い上記下塗り層（中間層と呼ばれることもある。）を挙げることができる。上記下塗り層がポリマーを含有することにより、下塗り層はポリマー層に該当する。 (Undercoat layer)
The on-press development type lithographic printing plate dummy according to the present invention may have an undercoat layer (sometimes referred to as an intermediate layer) between the polymer layer and the support.
The undercoat layer is not particularly limited, but the above-described undercoat layer (sometimes referred to as an intermediate layer) that the on-press development type lithographic printing plate precursor may have between the image recording layer and the support. Can be mentioned. When the undercoat layer contains a polymer, the undercoat layer corresponds to the polymer layer.
〔支持体吸着性を有する化合物を含有する層〕
　本発明に係る機上現像型平版印刷版ダミー版は、上記ポリマー層の上に支持体吸着性を有する化合物を含有する層を有する。
　機上現像型平版印刷版ダミー版を構成する支持体吸着性を有する化合物を含有する層は、上記機上現像型平版印刷版原版を構成する支持体吸着性を有する化合物を含有する層と同様である。 [Layer containing a compound having support adsorptivity]
The on-press development type lithographic printing plate dummy according to the present invention has a layer containing a compound having support adsorptivity on the polymer layer.
The layer containing the compound having support adsorptivity constituting the on-press development type lithographic printing plate dummy plate is the same as the layer containing the compound having support adsorbing property constituting the on-press development type lithographic printing plate precursor. It is.
〔保護層〕
　本発明に係る機上現像型平版印刷版ダミー版は、支持体吸着性を有する化合物を含有する層（特定化合物含有層）の上に保護層（オーバーコート層と呼ばれることもある。）を有することができる。あるいは、支持体吸着性を有する化合物を含有する層と保護層を一体化し、１つの層として支持体吸着性を有する化合物を含有する層の上に形成してもよい。
　機上現像型平版印刷版ダミー版が有しても良い保護層は、上記機上現像型平版印刷版原版が有しても良い保護層と同様である。
　上述のように、支持体吸着性を有する化合物を含有する層と保護層を一体化し、１つの層としてポリマー層の上に形成してもよい。この場合、支持体吸着性を有する化合物を含有する層は、例えば、支持体吸着性を有する化合物を含有する層及び保護層に必要な各成分を適宜溶剤に溶解又は分散して塗布液を調製し、塗布液を画像記録層上に公知の方法で塗布、乾燥することにより形成することができる。 [Protective layer]
The on-press development type lithographic printing plate dummy according to the present invention has a protective layer (sometimes referred to as an overcoat layer) on a layer containing a compound having a support adsorptivity (a specific compound-containing layer). be able to. Alternatively, a layer containing a compound having support adsorptivity and a protective layer may be integrated and formed as a single layer on a layer containing a compound having support adsorbability.
The protective layer that the on-press development type lithographic printing plate dummy plate may have is the same as the protective layer that the on-press development type lithographic printing plate precursor may have.
As described above, the layer containing the compound having support adsorptivity and the protective layer may be integrated and formed on the polymer layer as one layer. In this case, the layer containing the compound having support adsorptivity is prepared by, for example, appropriately dissolving or dispersing each component necessary for the layer containing the compound having support adsorptivity and the protective layer in a solvent. The coating liquid can be formed on the image recording layer by coating and drying by a known method.
〔機上現像型平版印刷版ダミー版の端部ダレ形状〕
　本発明に係る機上現像型平版印刷版ダミー版は、端部に、ダレ形状を有する。
　上記ダレ形状としては、上記機上現像型平版印刷版原版が、端部に有する、ダレ形状として記載したダレ形状と同様である。 [End sag shape of on-press development type lithographic printing plate dummy]
The on-press development type lithographic printing plate dummy according to the present invention has a sagging shape at the end.
The sag shape is the same as the sag shape described as the sag shape of the on-press development type lithographic printing plate precursor at the end.
〔印刷方法〕
　本発明に係る印刷方法は、上記機上現像型平版印刷版ダミー版、及び、アルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版を機上現像する工程を含む。
　より具体的には、本発明に係る印刷方法は、印刷機の同一の版胴上に取り付けられた、上記機上現像型平版印刷版ダミー版、及び、アルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版を機上現像する工程を含む。 [Printing method]
The printing method according to the present invention includes a step of on-machine development of the on-press development type lithographic printing plate dummy plate and the on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support.
More specifically, the printing method according to the present invention includes the on-press development type lithographic printing plate dummy plate mounted on the same plate cylinder of a printing press, and an image recording layer on the aluminum support. A step of on-press development of the on-press development type lithographic printing plate precursor;
　本発明の係る印刷方法においては、例えば、印刷機の同一の版胴上に、上記機上現像型平版印刷版ダミー版及び上記機上現像型平版印刷版原版を取り付ける。印刷機としては、例えば、新聞用オフセット輪転印刷機（（株）東京機械製作所製や三菱重工業（株）製など）が用いられる。
　その後、通常の方法で、印刷を行う。即ち、湿し水と印刷インキとを供給すると、供給された湿し水及び／又は印刷インキによって、機上現像型平版印刷版ダミー版及び機上現像型平版印刷版原版の構成層が溶解又は分散して除去され、その部分に親水性のアルミニウム支持体表面又は親水性の下塗り層成分が表面に吸着したアルミニウム支持体が露出する。その結果、湿し水は露出した親水性の表面に付着し、印刷インキの付着は阻止される。
　ここで、最初に機上現像型平版印刷版ダミー版及び機上現像型平版印刷版原版の表面に供給されるのは、湿し水でもよく印刷インキでもよいが、湿し水を浸透させ構成層の機上現像性を促進するために、最初に湿し水を供給することが好ましい。 In the printing method according to the present invention, for example, the on-press development type lithographic printing plate dummy plate and the on-press development type lithographic printing plate precursor are mounted on the same plate cylinder of a printing press. As the printing machine, for example, a newspaper offset rotary printing machine (manufactured by Tokyo Machine Works, Ltd. or Mitsubishi Heavy Industries, Ltd.) is used.
Thereafter, printing is performed by a normal method. That is, when dampening water and printing ink are supplied, the constituent layers of the on-press development type lithographic printing plate dummy plate and on-press development type lithographic printing plate precursor are dissolved or dissolved by the supplied dampening water and / or printing ink. Dispersed and removed, the surface of the hydrophilic aluminum support or the aluminum support with the hydrophilic undercoat layer component adsorbed on the surface is exposed at the portion. As a result, the fountain solution adheres to the exposed hydrophilic surface and the printing ink is prevented from adhering.
Here, the surface of the on-press development type lithographic printing plate dummy plate and on-press development type lithographic printing plate precursor may be supplied with dampening water or printing ink. In order to promote the on-press developability of the layer, it is preferable to supply fountain solution first.
　上記機上現像型平版印刷版原版は、印刷機の版胴上に取り付けられる前に、常法に従って画像露光される。画像露光は、デジタルデータを赤外線レーザー等により走査露光する方法により行うことが好ましい。
　露光光源の波長は、７５０～１，４００ｎｍが好ましく用いられる。７５０～１，４００ｎｍの光源としては、赤外線を放射する固体レーザー及び半導体レーザーが好適である。露光機構は内面ドラム方式、外面ドラム方式、フラットベッド方式等のいずれでもよい。
　画像露光はプレートセッターなどにより公知の方法で行うことができる。また、露光装置を備えた印刷機を用いて、上記機上現像型平版印刷版原版を印刷機に装着した後、印刷機上で露光を行ってもよい。 The on-press development type lithographic printing plate precursor is subjected to image exposure according to a conventional method before being mounted on a plate cylinder of a printing press. Image exposure is preferably performed by a method of scanning exposure of digital data with an infrared laser or the like.
The wavelength of the exposure light source is preferably 750 to 1,400 nm. As the light source of 750 to 1,400 nm, a solid laser or semiconductor laser that emits infrared light is suitable. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
Image exposure can be performed by a known method using a plate setter or the like. Moreover, after mounting the on-press development type lithographic printing plate precursor on a printing machine using a printing machine equipped with an exposure device, exposure may be performed on the printing machine.
　上記印刷方法に用いられる機上現像型平版印刷版原版は、アルミニウム支持体上に画像記録層を有する。
　アルミニウム支持体としては、平版印刷版原版に用いられる公知のアルミニウム支持体（アルミニウム合金支持体を含む）が用いられる。なかでも、公知の方法で粗面化処理され、陽極酸化処理されたアルミニウム板が好ましく用いられる。
　アルミニウム支持体としては、特に限定されないが、上記「陽極酸化皮膜を有するアルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版であって、平版印刷版原版は端部にダレ形状を有し、画像記録層の上に支持体吸着性を有する化合物を含有する層を有し、化合物の含有量が支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版原版」における「陽極酸化皮膜を有するアルミニウム支持体」と同様のものを挙げることができる。 The on-press development type lithographic printing plate precursor used in the printing method has an image recording layer on an aluminum support.
As the aluminum support, known aluminum supports (including aluminum alloy supports) used for lithographic printing plate precursors are used. Among these, an aluminum plate that has been roughened and anodized by a known method is preferably used.
The aluminum support is not particularly limited, but the above-mentioned “on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, and the lithographic printing plate precursor has a sag shape at the end. And a layer containing a compound having support adsorptivity on the image recording layer, and the content of the compound is substantially the same in the plane of the layer containing the compound having support adsorptivity. The same thing as the “aluminum support having an anodized film” in “on-press development type lithographic printing plate precursor” can be mentioned.
　上記印刷方法に用いられる機上現像型平版印刷版原版における画像記録層としては、特に限定されないが、上記「陽極酸化皮膜を有するアルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版であって、平版印刷版原版は端部にダレ形状を有し、画像記録層の上に支持体吸着性を有する化合物を含有する層を有し、化合物の含有量が上記支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版原版」における画像記録層で記載したものと同様のものを挙げることができる。 The image recording layer in the on-press development type lithographic printing plate precursor used in the above printing method is not particularly limited, but the above-mentioned on-press development type lithographic printing plate having an image recording layer on an aluminum support having an anodized film. A lithographic printing plate precursor having a sagging shape at an end and a layer containing a compound having support adsorptivity on an image recording layer, wherein the content of the compound is the above support adsorbability Examples thereof include the same as those described in the image recording layer in the “on-press development type lithographic printing plate precursor which is substantially the same in the plane of the layer containing the compound having the above-mentioned”.
　上記印刷方法に用いられる機上現像型平版印刷版原版における画像記録層は、重合開始剤を含有することが好ましい。
　重合開始剤としては、特に限定されないが、上記「陽極酸化皮膜を有するアルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版であって、平版印刷版原版は端部にダレ形状を有し、画像記録層の上に支持体吸着性を有する化合物を含有する層を有し、化合物の含有量が前支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版原版」における画像記録層に含有されても良い重合開始剤にて記載したものと同様のものを挙げることができる The image recording layer in the on-press development type lithographic printing plate precursor used in the printing method preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited, but the above-mentioned “on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, and the lithographic printing plate precursor has a sag shape at the end. A layer containing a compound having support adsorptivity on the image recording layer, and the content of the compound is substantially the same in the plane of the layer containing the compound having pre-support adsorptivity. Examples of the polymerization initiator that may be contained in the image recording layer in the “on-press development type lithographic printing plate precursor” are the same as those described above.
　上記印刷方法に用いられる機上現像型平版印刷版原版における画像記録層は、有機ホウ素含有アニオンを含む重合開始剤を含有することも好ましい。 It is also preferred that the image recording layer in the on-press development type lithographic printing plate precursor used in the above printing method contains a polymerization initiator containing an organic boron-containing anion.
　有機ホウ素含有アニオンを含む重合開始剤において、有機ホウ素含有アニオンとしては、テトラアリールボレートアニオンが好ましい。
　テトラアリールボレートアニオンは、下記一般式（Ｉ）で表される。 In the polymerization initiator containing an organic boron-containing anion, the organic boron-containing anion is preferably a tetraarylborate anion.
The tetraarylborate anion is represented by the following general formula (I).
一般式（Ｉ）
Figure JPOXMLDOC01-appb-C000024
 Formula (I)
Figure JPOXMLDOC01-appb-C000024
　一般式（Ｉ）中、Ｒ１、Ｒ２、Ｒ３及びＲ４は、それぞれ独立に、炭素数６～２０のアリール基又は炭素数５～２０のヘテロアリール基を表す。アリール基及びヘテロアリール基は置換基を有していてもよい。置換基としては、ハロゲン原子、アルキル基、アルコキシ基、アリール基等が挙げられる。
　アリール基の具体例としては、フェニル基、トリル基、キシリル基、メシチル基、ジュリル基、メトキシフェニル基、ジメトキシフェニル基、クロロフェニル基、フルオロフェニル基、トリフルオロメチルフェニル基、ペンタフルオロフェニル基、ナフチル等が挙げられる。ヘテロアリール基の具体例としては、ピリジル基、ピリミジル基、フラニル基、ピロリル基、イミダゾリル基、トリアゾリル基、テトラゾリル基、インドリル基、キノリニル基、オキサジアゾリル基、ベンゾオキサゾリル基等が挙げられる。
　一般式（Ｉ）において、Ｒ１、Ｒ２、Ｒ３及びＲ４は、置換又は無置換のフェニル基であることが好ましい。Ｒ１、Ｒ２、Ｒ３及びＲ４の少なくとも３つが、同一の置換又は無置換のフェニル基であることがより好ましい。 In general formula (I), R 1 , R 2 , R 3 and R 4 each independently represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms. The aryl group and heteroaryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an aryl group.
Specific examples of the aryl group include phenyl group, tolyl group, xylyl group, mesityl group, duryl group, methoxyphenyl group, dimethoxyphenyl group, chlorophenyl group, fluorophenyl group, trifluoromethylphenyl group, pentafluorophenyl group, naphthyl group. Etc. Specific examples of the heteroaryl group include pyridyl group, pyrimidyl group, furanyl group, pyrrolyl group, imidazolyl group, triazolyl group, tetrazolyl group, indolyl group, quinolinyl group, oxadiazolyl group, and benzoxazolyl group.
In the general formula (I), R 1 , R 2 , R 3 and R 4 are preferably a substituted or unsubstituted phenyl group. More preferably, at least three of R 1 , R 2 , R 3 and R 4 are the same substituted or unsubstituted phenyl group.
　有機ホウ素含有アニオンを含む重合開始剤において、有機ホウ素含有アニオンの対イオンを形成するカチオンとしては、ヨードニウムカチオンが好ましく、特に、ジアリールヨードニウムカチオンが好ましい。ジアリールヨードニウムカチオンとしては、米国特許第７，５２４，６１４号明細書の構造（Ｉ）で表される化合物が好適である。 In the polymerization initiator containing an organic boron-containing anion, the cation forming the counter ion of the organic boron-containing anion is preferably an iodonium cation, and more preferably a diaryl iodonium cation. As the diaryliodonium cation, a compound represented by the structure (I) of US Pat. No. 7,524,614 is preferable.
　有機ホウ素含有アニオンを含む重合開始剤の中で、有機ホウ素含有アニオン及びジアリールヨードニウムカチオンを含むヨードニウム化合物が好ましい。
　有機ホウ素含有アニオン及びジアリールヨードニウムカチオンを含むヨードニウム化合物の具体例としては、４－オクチルオキシフェニルフェニルヨードニウムテトラフェニルボレート、［４－［（２－ヒドロキシテトラデシル）オキシ］フェニル］フェニルヨードニウムテトラフェニルボレート、ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムテトラフェニルボレート、４－メチルフェニル－４’－ヘキシルフェニルヨードニウムテトラフェニルボレート、４－メチルフェニル－４’－シクロヘキシルフェニルヨードニウムテトラフェニルボレート、ビス（ｔｅｒｔ－ブチルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、４－ヘキシルフェニルフェニルヨードニウムテトラフェニルボレート、４－シクロヘキシルフェニルフェニルヨードニウムテトラフェニルボレート、２－メチル－４－ｔｅｒｔ－ブチルフェニル－４’－メチルフェニルヨードニウムテトラフェニルボレート、４－メチルフェニル－４’－ドデシルフェニルヨードニウムテトラキス（４－フルオロフェニル）ボレート、ビス（ドデシルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、及びビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムテトラキス（１－イミダゾリル）ボレート等が挙げられるが、これらに限定されるものではない。これらの中で、ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムテトラフェニルボレート、４－メチルフェニル－４’－ヘキシルフェニルヨードニウムテトラフェニルボレート、２－メチル－４－ｔｅｒｔ－ブチルフェニル－４’－メチルフェニルヨードニウムテトラフェニルボレート、及び４－メチルフェニル－４’－シクロヘキシルフェニルヨードニウムテトラフェニルボレートが好ましい。 Among the polymerization initiators containing an organic boron-containing anion, an iodonium compound containing an organic boron-containing anion and a diaryl iodonium cation is preferable.
Specific examples of iodonium compounds containing an organic boron-containing anion and a diaryliodonium cation include 4-octyloxyphenylphenyliodonium tetraphenylborate, [4-[(2-hydroxytetradecyl) oxy] phenyl] phenyliodonium tetraphenylborate, Bis (4-tert-butylphenyl) iodonium tetraphenylborate, 4-methylphenyl-4′-hexylphenyliodonium tetraphenylborate, 4-methylphenyl-4′-cyclohexylphenyliodonium tetraphenylborate, bis (tert-butylphenyl) ) Iodonium tetrakis (pentafluorophenyl) borate, 4-hexylphenylphenyliodonium tetraphenylborate, 4-cyclohexyl Silphenylphenyliodonium tetraphenylborate, 2-methyl-4-tert-butylphenyl-4′-methylphenyliodonium tetraphenylborate, 4-methylphenyl-4′-dodecylphenyliodoniumtetrakis (4-fluorophenyl) borate, bis Examples thereof include (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate and bis (4-tert-butylphenyl) iodoniumtetrakis (1-imidazolyl) borate, but are not limited thereto. Among these, bis (4-tert-butylphenyl) iodonium tetraphenylborate, 4-methylphenyl-4′-hexylphenyliodonium tetraphenylborate, 2-methyl-4-tert-butylphenyl-4′-methylphenyl Iodonium tetraphenylborate and 4-methylphenyl-4′-cyclohexylphenyliodonium tetraphenylborate are preferred.
　有機ホウ素含有アニオンを含む重合開始剤は、１種類を単独で使用してもよいし、２種類以上を混合して使用してもよい。
　有機ホウ素含有アニオンを含む重合開始剤の含有量は、画像記録層の全固形分に対して０．１～５０質量％が好ましく、０．５～３０質量％がより好ましく、０．８～２０質量％が特に好ましい。 One kind of polymerization initiator containing an organic boron-containing anion may be used alone, or two or more kinds may be mixed and used.
The content of the polymerization initiator containing an organic boron-containing anion is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and more preferably 0.8 to 20% with respect to the total solid content of the image recording layer. Mass% is particularly preferred.
　上記印刷方法に用いられる機上現像型平版印刷版原版における画像記録層は、ポリマー粒子を含有することが好ましい。
　ポリマー粒子としては、特に限定されないが、上記「陽極酸化皮膜を有するアルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版であって、平版印刷版原版は端部にダレ形状を有し、画像記録層の上に支持体吸着性を有する化合物を含有する層を有し、化合物の含有量が支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版原版」における画像記録層に含有されても良いポリマー粒子にて記載したものと同様のものを挙げることができる The image recording layer in the on-press development type lithographic printing plate precursor used in the above printing method preferably contains polymer particles.
The polymer particles are not particularly limited, but the above-mentioned “on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, and the lithographic printing plate precursor has a sag shape at the end. And having a layer containing a compound having support adsorptivity on the image recording layer, and the content of the compound is substantially the same in the plane of the layer containing the compound having support adsorptivity Examples of the polymer particles that may be contained in the image recording layer in the “on-press development type lithographic printing plate precursor” are the same.
　上記ポリマー粒子は、スチレン及びアクリロニトリルを含む共重合体の粒子であることが好ましい。
　上記ポリマー粒子が、ミクロゲルであることが好ましい。 The polymer particles are preferably copolymer particles containing styrene and acrylonitrile.
The polymer particles are preferably a microgel.
　本発明の印刷方法に用いる機上現像型平版印刷版原版は、画像記録層と支持体との間に下塗り層（中間層と呼ばれることもある。）を有することができる。
　下塗り層は、上記「陽極酸化皮膜を有するアルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版であって、平版印刷版原版は端部にダレ形状を有し、画像記録層の上に支持体吸着性を有する化合物を含有する層を有し、化合物の含有量が支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版原版」が有しても良い下塗り層にて記載したものと同様である。 The on-press development type lithographic printing plate precursor used in the printing method of the present invention can have an undercoat layer (sometimes referred to as an intermediate layer) between the image recording layer and the support.
The undercoat layer is an “on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, wherein the lithographic printing plate precursor has a sag shape at the end, and the image recording layer An on-press development type lithographic printing having a layer containing a compound having a support adsorptivity on the surface and the content of the compound being substantially the same in the plane of the layer containing the compound having a support adsorptivity It is the same as that described in the undercoat layer that the “plate original plate” may have.
　本発明の印刷方法に用いられる機上現像型平版印刷版原版は、画像記録層の上に保護層（オーバーコート層と呼ばれることもある。）を有することができる。
　保護層は、上記「陽極酸化皮膜を有するアルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版であって、平版印刷版原版は端部にダレ形状を有し、画像記録層の上に支持体吸着性を有する化合物を含有する層を有し、化合物の含有量が支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版原版」が有しても良い保護層にて記載したものと同様である。 The on-press development type lithographic printing plate precursor used in the printing method of the present invention can have a protective layer (sometimes referred to as an overcoat layer) on the image recording layer.
The protective layer is the above-mentioned on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, and the lithographic printing plate precursor has a sagging shape at the end, and the image recording layer An on-press development type lithographic printing having a layer containing a compound having a support adsorptivity on the surface and the content of the compound being substantially the same in the plane of the layer containing the compound having a support adsorptivity It is the same as that described in the protective layer that the “plate original plate” may have.
　本発明に係る機上現像型平版印刷版ダミー版は、端部にダレ形状を有することと、ポリマー層の上に特定化合物含有層を有することにより、端部の機上現像性などの特性を低下させることなく、長期保存後においても良好なエッジ汚れ防止性を示すことができるという特徴を有する。
　本発明に係る機上現像型平版印刷版ダミー版においては、端部に、水溶性化合物を含有する塗布液を塗布するなどの親水化処理を施すことなく、長期保存後においても良好なエッジ汚れ防止性を示すことができるという特徴を有する。
　本発明に係る印刷方法において、本発明に係る機上現像型平版印刷版ダミー版においては、端部に、水溶性化合物を含有する塗布液を塗布するなどの親水化処理を施すことなく、良好なエッジ汚れ防止性を示すことができるという特徴を有する。
　本発明に係る印刷方法において、本発明に係る機上現像型平版印刷版ダミー版においては、端部に、水溶性化合物を含有する塗布液を塗布するなどの親水化処理を施すことなく、良好なエッジ汚れ防止性を示すことができるという特徴を有する。
　また、本発明に係る印刷方法における機上現像型平版印刷版ダミー版と機上現像型平版印刷版原版を機上現像する工程において、機上現像型平版印刷版ダミー版の支持体吸着性を有する化合物を含有する層における特定化合物が、印刷インキ及び湿し水から選ばれる少なくとも１つにより溶出し、機上現像型平版印刷版原ダミー版の端部及び機上現像型平版印刷版原版の端部に移動することで、端部を親水化させることができ、良好なエッジ汚れ防止性を示すことができるという特徴を有する。 The on-press development type lithographic printing plate dummy according to the present invention has characteristics such as on-press developability by having a sag shape at the end and a specific compound-containing layer on the polymer layer. It has a feature that it can exhibit good edge stain resistance even after long-term storage without being reduced.
In the on-press development type lithographic printing plate dummy plate according to the present invention, the edge is not subjected to a hydrophilic treatment such as applying a coating solution containing a water-soluble compound, and good edge stains are obtained even after long-term storage. It has a feature that it can exhibit prevention.
In the printing method according to the present invention, the on-press development type lithographic printing plate dummy plate according to the present invention is good without being subjected to a hydrophilic treatment such as applying a coating solution containing a water-soluble compound on the edge. It has a feature that it can exhibit excellent edge stain resistance.
In the printing method according to the present invention, the on-press development type lithographic printing plate dummy plate according to the present invention is good without being subjected to a hydrophilic treatment such as applying a coating solution containing a water-soluble compound on the edge. It has a feature that it can exhibit excellent edge stain resistance.
Further, in the step of on-machine development of the on-press development type lithographic printing plate dummy plate and the on-press development type lithographic printing plate precursor in the printing method according to the present invention, the support adsorbability of the on-press development type lithographic printing plate dummy plate is increased. The specific compound in the layer containing the compound is eluted by at least one selected from printing ink and fountain solution, and the end of the on-press development type lithographic printing plate precursor dummy and the on-press development type lithographic printing plate precursor By moving to the end portion, the end portion can be hydrophilized, and good edge stain resistance can be exhibited.
　以下、実施例により本発明を詳細に説明するが、本発明はこれらに限定されるものではない。なお、高分子化合物において、特別に規定したもの以外は、分子量はゲル浸透クロマトグラフィー（ＧＰＣ）法によるポリスチレン換算値とした質量平均分子量（Ｍｗ）であり、繰り返し単位の比率はモル百分率である。また、「部」、「％」は、特に断りのない限り、「質量部」、「質量％」を意味する。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In the polymer compound, unless otherwise specified, the molecular weight is a mass average molecular weight (Mw) in terms of polystyrene converted by a gel permeation chromatography (GPC) method, and the ratio of repeating units is a mole percentage. Further, “part” and “%” mean “part by mass” and “% by mass” unless otherwise specified.
［実施例１～２５及び比較例１～２］ [Examples 1 to 25 and Comparative Examples 1 and 2]
＜支持体（１）の作製＞ <Preparation of support (1)>
　アルミニウム板に、下記（ａ）～（ｇ）の各処理を順次施し、陽極酸化皮膜を有するアルミニウム支持体（支持体（１））を作製した。なお、全ての処理工程の間には水洗処理を施した。 The following treatments (a) to (g) were sequentially performed on the aluminum plate to produce an aluminum support (support (1)) having an anodized film. In addition, the water washing process was performed between all the process steps.
（ａ）アルカリエッチング処理
　厚さ０．３ｍｍのアルミニウム板（材質ＪＩＳ　１０５２）に、カセイソーダ濃度２５質量％、アルミニウムイオン濃度１００ｇ／Ｌ、温度６０℃の水溶液をスプレー管から吹き付けて、エッチング処理を行った。アルミニウム板の電気化学的粗面化処理を施す面のエッチング量は、３ｇ／ｍ2であった。 (A) Alkaline etching treatment An aqueous solution having a caustic soda concentration of 25 mass%, an aluminum ion concentration of 100 g / L, and a temperature of 60 ° C. is sprayed from a spray tube onto an aluminum plate having a thickness of 0.3 mm (material JIS 1052). It was. The etching amount of the surface of the aluminum plate subjected to the electrochemical roughening treatment was 3 g / m 2 .
（ｂ）デスマット処理
　アルミニウム板に、温度３５℃の硫酸水溶液（濃度３００ｇ／Ｌ）をスプレー管から５秒間吹き付けて、デスマット処理を行った。 (B) Desmut treatment A sulfuric acid aqueous solution (concentration: 300 g / L) having a temperature of 35 ° C. was sprayed on the aluminum plate from the spray tube for 5 seconds to perform desmut treatment.
（ｃ）電気化学的粗面化処理
　アルミニウム板を、１質量％塩酸水溶液に塩化アルミニウムを溶解させてアルミニウムイオン濃度を４．５ｇ／Ｌとした電解液（液温３５℃）を用い、６０Ｈｚの交流電源を用いて、フラットセル型の電解槽を用いて連続的に電気化学的粗面化処理を行った。交流電源の波形は、正弦波を用いた。電気化学的粗面化処理において、交流のピーク時におけるアルミニウム板のアノード反応時の電流密度は、３０Ａ／ｄｍ２であった。アルミニウム板のアノード反応時の電気量総和とカソード反応時の電気量総和との比は０．９５であった。電気量はアルミニウム板のアノード時の電気量総和で４８０Ｃ／ｄｍ２であった。電解液はポンプを用いて液を循環させることで、電解槽内の撹拌を行った。 (C) Electrochemical surface roughening treatment Using an electrolytic solution (liquid temperature 35 ° C.) in which aluminum chloride is dissolved in a 1% by mass hydrochloric acid aqueous solution and aluminum ion concentration is 4.5 g / L, an aluminum plate is subjected to 60 Hz. Using an AC power source, electrochemical surface roughening was continuously performed using a flat cell electrolytic cell. A sine wave was used as the waveform of the AC power supply. In the electrochemical surface roughening treatment, the current density during the anode reaction of the aluminum plate at the peak of alternating current was 30 A / dm 2 . The ratio of the total amount of electricity during the anode reaction of the aluminum plate to the total amount of electricity during the cathode reaction was 0.95. The amount of electricity was 480 C / dm 2 in terms of the total amount of electricity at the time of anode of the aluminum plate. The electrolytic solution was circulated using a pump to stir the electrolytic cell.
（ｄ）アルカリエッチング処理
　アルミニウム板に、カセイソーダ濃度５質量％、アルミニウムイオン濃度５ｇ／Ｌ、温度３５℃の水溶液をスプレー管から吹き付けて、エッチング処理を行った。アルミニウム板の電気化学的粗面化処理を施した面のエッチング量は、０．０５ｇ／ｍ２であった。 (D) Alkali etching treatment An aqueous solution having a caustic soda concentration of 5 mass%, an aluminum ion concentration of 5 g / L, and a temperature of 35 ° C. was sprayed from a spray tube onto the aluminum plate to carry out an etching treatment. The etching amount of the aluminum plate subjected to the electrochemical surface roughening treatment was 0.05 g / m 2 .
（ｅ）デスマット処理
　アルミニウム板に、硫酸濃度３００ｇ／Ｌ、アルミニウムイオン濃度５ｇ／Ｌ、液温３５℃の水溶液をスプレー管から５秒間吹き付けて、デスマット処理を行った。 (E) Desmutting treatment An aqueous solution having a sulfuric acid concentration of 300 g / L, an aluminum ion concentration of 5 g / L, and a liquid temperature of 35 ° C. was sprayed onto the aluminum plate from a spray tube for 5 seconds to perform desmutting treatment.
（ｆ）陽極酸化処理
　１５質量％硫酸（アルミニウムイオンを０．５質量％含む。）の電解液を用い、４０℃、電流密度１５Ａ／ｄｍ２の条件で厚さ１，０００ｎｍの直流陽極酸化皮膜を設けた。その後、スプレーによる水洗を行った。 (F) Anodizing treatment DC anodized film having a thickness of 1,000 nm using an electrolytic solution of 15% by mass sulfuric acid (containing 0.5% by mass of aluminum ions) under the conditions of 40 ° C. and current density of 15 A / dm 2. Was provided. Then, water washing by spraying was performed.
（ｇ）ポアワイド処理
　アルミニウム板を、ＮａＯＨ５％水溶液を用い３５℃で１５秒間アルカリ処理して支持体（１）を作製した。支持体（１）の陽極酸化皮膜のマイクロポアの平均径は２５ｎｍであった。陽極酸化皮膜のマイクロポアの平均径は先に記載した方法に従って算出した数値である（以下同様）。 (G) Pore-wide treatment An aluminum plate was alkali-treated at 35 ° C. for 15 seconds using a 5% NaOH aqueous solution to produce a support (1). The average diameter of the micropores of the anodized film of the support (1) was 25 nm. The average diameter of the micropores in the anodized film is a numerical value calculated according to the method described above (the same applies hereinafter).
＜支持体（２）の作製＞
　支持体（１）の作製において、陽極酸化処理の時間を調整して、陽極酸化皮膜の厚さを７５０ｎｍとする他は、支持体（１）の作製と同様にして、支持体（２）を作製した。支持体（２）の陽極酸化皮膜のマイクロポアの平均径は２５ｎｍであった。 <Preparation of support (2)>
In the production of the support (1), the support (2) is prepared in the same manner as the production of the support (1) except that the anodic oxidation treatment time is adjusted so that the thickness of the anodized film is 750 nm. Produced. The average diameter of the micropores of the anodized film of the support (2) was 25 nm.
＜支持体（３）の作製＞
　支持体（１）の作製において、陽極酸化処理の時間を調整して、陽極酸化皮膜の厚さを５００ｎｍとする他は、支持体（１）の作製と同様にして、支持体（３）を作製した。支持体（３）の陽極酸化皮膜のマイクロポアの平均径は２５ｎｍであった。 <Preparation of support (3)>
In the production of the support (1), the support (3) was prepared in the same manner as the production of the support (1), except that the anodic oxidation treatment time was adjusted so that the thickness of the anodized film was 500 nm. Produced. The average diameter of the micropores of the anodized film of the support (3) was 25 nm.
＜支持体（４）の作製＞
　支持体（１）の作製において、（ｆ）陽極酸化処理を以下のように変更する他は、支持体（１）の作製と同様にして、支持体（４）を作製した。支持体（４）の陽極酸化皮膜のマイクロポアの平均径は３５ｎｍであった。 <Preparation of support (4)>
In the production of the support (1), the support (4) was produced in the same manner as the production of the support (1) except that (f) the anodizing treatment was changed as follows. The average diameter of the micropores in the anodized film of the support (4) was 35 nm.
（ｆ）陽極酸化処理
　２２質量％リン酸水溶液の電解液を用い、３８℃、電流密度１５Ａ／ｄｍ２の条件で厚さ５００ｎｍの直流陽極酸化皮膜を設けた。その後、スプレーによる水洗を行った。 (F) Anodizing treatment A DC anodized film having a thickness of 500 nm was provided under the conditions of 38 ° C. and a current density of 15 A / dm 2 using an electrolytic solution of 22 mass% phosphoric acid aqueous solution. Then, water washing by spraying was performed.
＜画像記録層（１）の形成＞
　支持体上に、下記組成の画像記録層塗布液（１）をバー塗布し、１００℃で６０秒間オーブン乾燥して、乾燥塗布量が１．０ｇ／ｍ２の画像記録層（１）を形成した。
　画像記録層塗布液（１）は下記感光液（１）及びミクロゲル液を塗布直前に混合し攪拌することにより調製した。 <Formation of Image Recording Layer (1)>
An image recording layer coating liquid (1) having the following composition is bar-coated on a support and oven-dried at 100 ° C. for 60 seconds to form an image recording layer (1) having a dry coating amount of 1.0 g / m 2. did.
The image recording layer coating solution (1) was prepared by mixing and stirring the following photosensitive solution (1) and microgel solution immediately before coating.
＜感光液（１）＞
・バインダーポリマー（１）〔下記構造〕　　　　　　　０．２４０部
・重合開始剤（１）〔下記構造〕　　　　　　　　　　　０．２４５部
・赤外線吸収剤（１）〔下記構造〕　　　　　　　　　　０．０４６部
・ボレート化合物　　　　　　　　　　　　　　　　　　０．０１０部
　　ＴＰＢ〔下記構造〕
・重合性化合物　　　　　　　　　　　　　　　　　　　０．１９２部
　　トリス（アクリロイルオキシエチル）イソシアヌレート
　　（ＮＫエステル　Ａ－９３００、新中村化学（株）製）
・低分子親水性化合物　　　　　　　　　　　　　　　　０．０６２部
　　トリス（２－ヒドロキシエチル）イソシアヌレート
・低分子親水性化合物（１）〔下記構造〕　　　　　　　０．０５０部
・フッ素系界面活性剤（１）〔下記構造〕　　　　　　　０．００８部
・２－ブタノン　　　　　　　　　　　　　　　　　　　１．０９１部
・１－メトキシ－２－プロパノール　　　　　　　　　　８．６０９部 <Photosensitive solution (1)>
-Binder polymer (1) [following structure] 0.240 parts-Polymerization initiator (1) [following structure] 0.245 parts-Infrared absorber (1) [following structure] 0.046 parts-borate compound 0.010 TPB [The following structure]
Polymerizable compound 0.192 parts Tris (acryloyloxyethyl) isocyanurate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Low molecular weight hydrophilic compound 0.062 parts Tris (2-hydroxyethyl) isocyanurate Low molecular weight hydrophilic compound (1) [structure shown below] 0.050 part Fluorosurfactant (1) [structure shown below] 0 0.008 part 2-butanone 1.091 part 1-methoxy-2-propanol 8.609 part
＜ミクロゲル液＞
・ミクロゲル（１）　　　　　　　　　　　　　　　　　２．６４０部
・蒸留水　　　　　　　　　　　　　　　　　　　　　　２．４２５部 <Microgel solution>
-Microgel (1) 2.640 parts-Distilled water 2.425 parts
　上記感光液（１）に用いたバインダーポリマー（１）、重合開始剤（１）、赤外線吸収剤（１）、ＴＰＢ、低分子親水性化合物（１）及びフッ素系界面活性剤（１）の構造を以下に示す。 Structures of binder polymer (1), polymerization initiator (1), infrared absorber (1), TPB, low molecular weight hydrophilic compound (1) and fluorine-based surfactant (1) used in the photosensitive solution (1) Is shown below.
Figure JPOXMLDOC01-appb-C000025
 
Figure JPOXMLDOC01-appb-C000025
 
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　　上記ミクロゲル液に用いたミクロゲル（１）の調製法を以下に示す。
＜多価イソシアネート化合物（１）の調製＞
　イソホロンジイソシアネート１７．７８ｇ（８０ｍｍｏｌ）と下記多価フェノール化合物（１）７．３５ｇ（２０ｍｍｏｌ）との酢酸エチル（２５．３１ｇ）懸濁溶液に、ビスマストリス（２－エチルヘキサノエート）（ネオスタン　Ｕ－６００、日東化成（株）製）４３ｍｇを加えて攪拌した。発熱が収まった時点で反応温度を５０℃に設定し、３時間攪拌して多価イソシアネート化合物（１）の酢酸エチル溶液（５０質量％）を得た。 A method for preparing the microgel (1) used in the microgel solution is shown below.
<Preparation of polyvalent isocyanate compound (1)>
In a suspension of 17.78 g (80 mmol) of isophorone diisocyanate and 7.35 g (20 mmol) of the following polyphenol compound (1) in ethyl acetate (25.31 g), bismuth tris (2-ethylhexanoate) (Neostan U -600, Nitto Kasei Co., Ltd.) 43 mg was added and stirred. When the exotherm had subsided, the reaction temperature was set to 50 ° C., and the mixture was stirred for 3 hours to obtain an ethyl acetate solution (50% by mass) of the polyvalent isocyanate compound (1).
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
＜ミクロゲル（１）の調製＞
　下記油相成分及び水相成分を混合し、ホモジナイザーを用いて１２０００ｒｐｍで１０分間乳化した。得られた乳化物を４５℃で４時間攪拌後、１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン－オクチル酸塩（Ｕ－ＣＡＴ　ＳＡ１０２、サンアプロ（株）製）の１０質量％水溶液５．２０ｇを加え、室温で３０分攪拌し、４５℃で２４時間静置した。蒸留水で、固形分濃度を２０質量％になるように調整し、ミクロゲル（１）の水分散液が得られた。光散乱法により平均粒径を測定したところ、０．２８μｍであった。 <Preparation of microgel (1)>
The following oil phase component and aqueous phase component were mixed and emulsified at 12000 rpm for 10 minutes using a homogenizer. After the resulting emulsion was stirred at 45 ° C. for 4 hours, 10 masses of 1,8-diazabicyclo [5.4.0] undec-7-ene-octylate (U-CAT SA102, manufactured by San Apro Co., Ltd.) % Aqueous solution (5.20 g) was added, and the mixture was stirred at room temperature for 30 minutes and allowed to stand at 45 ° C. for 24 hours. Distilled water was used to adjust the solid content concentration to 20% by mass, and an aqueous dispersion of microgel (1) was obtained. When an average particle diameter was measured by a light scattering method, it was 0.28 μm.
（油相成分）
（成分１）酢酸エチル：１２．０ｇ
（成分２）トリメチロールプロパン（６モル）とキシレンジイソシアネート（１８モル）を付加させ、これにメチル辺末端ポリオキシエチレン（１モル、オキシエチレン単位の繰返し数：９０）を付加させた付加体（５０質量％酢酸エチル溶液、三井化学（株）製）：３．７６ｇ
（成分３）多価イソシアネート化合物（１）（５０質量％酢酸エチル溶液）：１５．０ｇ
（成分４）ジペンタエリスリトールペンタアクリレート（ＳＲ－３９９、サートマー社製）の６５質量％酢酸エチル溶液：１１．５４ｇ
（成分５）スルホン酸塩型界面活性剤（パイオニンＡ－４１－Ｃ、竹本油脂（株）製）の１０％酢酸エチル溶液：４．４２ｇ (Oil phase component)
(Component 1) Ethyl acetate: 12.0 g
(Component 2) An adduct obtained by adding trimethylolpropane (6 mol) and xylene diisocyanate (18 mol) and adding a methyl side terminal polyoxyethylene (1 mol, repeating number of oxyethylene units: 90) to this ( 50 mass% ethyl acetate solution, manufactured by Mitsui Chemicals, Inc.): 3.76 g
(Component 3) Polyvalent isocyanate compound (1) (50% by mass ethyl acetate solution): 15.0 g
(Component 4) 65 mass% ethyl acetate solution of dipentaerythritol pentaacrylate (SR-399, manufactured by Sartomer): 11.54 g
(Component 5) 10% ethyl acetate solution of a sulfonate type surfactant (Pionin A-41-C, Takemoto Yushi Co., Ltd.): 4.42 g
（水相成分）蒸留水：４６．８７ｇ (Aqueous phase component) Distilled water: 46.87 g
＜画像記録層（２）の形成＞
　支持体上に、下記組成の画像記録層塗布液（２）をバー塗布し、９４℃で６０秒間オーブン乾燥して、乾燥塗布量が０．８５ｇ／ｍ２の画像記録層（２）を形成した。 <Formation of image recording layer (2)>
An image recording layer coating liquid (2) having the following composition is bar-coated on the support and oven dried at 94 ° C. for 60 seconds to form an image recording layer (2) having a dry coating amount of 0.85 g / m 2. did.
（画像記録層塗布液（２））
・重合性化合物１＊１　　　　　　　　　　　　　　　　　０．３２５部
・グラフトコポリマー１＊２　　　　　　　　　　　　　　０．０６０部
・グラフトコポリマー２＊３　　　　　　　　　　　　　　０．１９８部
・メルカプト－３－トリアゾール＊４　　　　　　　　　　０．１８０部
・Ｉｒｇａｃｕｒｅ２５０＊５　　　　　　　　　　　　　０．０３２部
・赤外線吸収剤１〔下記構造〕　　　　　　　　　　　　０．００７部
・テトラフェニルホウ酸ナトリウム〔下記構造〕　　　　０．０４０部
・Ｋｌｕｃｅｌ　９９Ｍ＊６　　　　　　　　　　　　　　０．００７部
・Ｂｙｋ　３３６＊７　　　　　　　　　　　　　　　　　０．０１５部
・ｎ－プロパノール　　　　　　　　　　　　　　　　　７．４７０部
・水　　　　　　　　　　　　　　　　　　　　　　　　１．８６８部 (Image recording layer coating solution (2))
-Polymerizable compound 1 * 1 0.325 parts-Graft copolymer 1 * 2 0.060 parts-Graft copolymer 2 * 3 0.198 parts-Mercapto-3-triazole * 4 0.180 parts-Irgacure 250 * 5 0.032 Parts, infrared absorber 1 [following structure] 0.007 parts, sodium tetraphenylborate [following structure] 0.040 parts, Klucel 99M * 6 0.007 parts, Byk 336 * 7 0.015 parts, n-propanol 7.470 parts, water 1.868 parts
＊１：重合性化合物１は、ジペンタエリスリトールヘキサアクリレート（新中村化学工業（株）製）である。
＊２：グラフトコポリマー１は、ポリ（オキシ－１，２－エタンジイル），α－（２－メチル－１－オキソ－２－プロペニル）－ω－メトキシ－，エテニルベンゼンでグラフトされたポリマーであり、これを、８０％ｎ－プロパノール／２０％水の溶剤中２５％の分散物である。
＊３：グラフトコポリマー２は、ポリ（エチレングリコール）メチルエーテルメタクリレート／スチレン／アクリロニトリル＝１０：９：８１のグラフトコポリマーのポリマー粒子であり、これを、ｎ－プロパノール／水の質量比が８０／２０である溶媒中に、２４質量％含有している分散物である。ポリマー粒子の体積平均粒径は１９３ｎｍである。
＊４：メルカプト－３－トリアゾールは、ＰＣＡＳ社（フランス）から入手可能な３－メルカプト－１Ｈ，２，４－トリアゾールである。
＊５：Ｉｒｇａｃｕｒｅ　２５０は、Ｃｉｂａ　Ｓｐｅｃｉａｌｔｙ　Ｃｈｅｍｉｃａｌｓ社から入手可能な、ヨードニウム　（４－メチルフェニル）［４－（２－メチルプロピル）フェニル］ヘキサフルオロホスフェートの７５％プロピレンカーボネート溶液である。
＊６：Ｋｌｕｃｅｌ　９９Ｍは、Ｈｅｒｃｕｌｅｓ社から入手可能な、ヒドロキシプロピルセルロース増粘剤の１％水溶液である。
＊７：Ｂｙｋ　３３６は、Ｂｙｋ　Ｃｈｅｍｉｅ社から入手可能な、変性ジメチルポリシロキサンコポリマーの２５％キシレン／メトキシプロピルアセテート溶液である。 * 1: The polymerizable compound 1 is dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.).
* 2: Graft copolymer 1 is a polymer grafted with poly (oxy-1,2-ethanediyl), α- (2-methyl-1-oxo-2-propenyl) -ω-methoxy-, ethenylbenzene. This is a 25% dispersion in 80% n-propanol / 20% water solvent.
* 3: Graft copolymer 2 is a polymer particle of a graft copolymer of poly (ethylene glycol) methyl ether methacrylate / styrene / acrylonitrile = 10: 9: 81, and the mass ratio of n-propanol / water is 80/20. It is a dispersion containing 24% by mass in the solvent. The volume average particle diameter of the polymer particles is 193 nm.
* 4: Mercapto-3-triazole is 3-mercapto-1H, 2,4-triazole available from PCAS (France).
* 5: Irgacure 250 is a 75% propylene carbonate solution of iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] hexafluorophosphate available from Ciba Specialty Chemicals.
* 6: Klucel 99M is a 1% aqueous solution of a hydroxypropyl cellulose thickener available from Hercules.
* 7: Byk 336 is a 25% xylene / methoxypropyl acetate solution of modified dimethylpolysiloxane copolymer available from Byk Chemie.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
＜特定化合物含有層（１）の形成＞
　画像記録層上に、下記組成の特定化合物含有層塗布液（１）をバー塗布し、１２０℃で６０秒間オーブン乾燥して、乾燥塗布量が０．１５ｇ／ｍ２の特定化合物含有層を形成した。 <Formation of specific compound-containing layer (1)>
A specific compound-containing layer coating solution (1) having the following composition is bar-coated on the image recording layer and oven-dried at 120 ° C. for 60 seconds to form a specific compound-containing layer having a dry coating amount of 0.15 g / m 2. did.
＜特定化合物含有層塗布液（１）＞
・無機層状化合物分散液（１）〔下記〕　　　　　　　　１．５部
・ポリビニルアルコール（ＣＫＳ５０、日本合成化学工業（株）製、スルホン酸変性、けん化度９９モル％以上、重合度３００）６質量％水溶液
　　　　　　　　　　　　　　　　　　　　　　　　　　０．５５部
・ポリビニルアルコール（ＰＶＡ－４０５、（株）クラレ製、
けん化度８１．５モル％、重合度５００）６質量％水溶液
　　　　　　　　　　　　　　　　　　　　　　　　　　０．０３部
・界面活性剤（ポリオキシエチレンラウリルエーテル、エマレックス７１０、日本エマルジョン（株）製）１質量％水溶液　　　　　０．８６部
・特定化合物〔表１に記載の化合物〕　　　　　　〔表１に記載の量〕
・イオン交換水　　　　　　　　　　　　　　　　　　　６．０部 <Specific compound-containing layer coating solution (1)>
・ Inorganic layered compound dispersion (1) [below] 1.5 parts ・ Polyvinyl alcohol (CKS50, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., sulfonic acid modification, saponification degree 99 mol% or more, polymerization degree 300) 6 mass% aqueous solution 0.55 parts polyvinyl alcohol (PVA-405, manufactured by Kuraray Co., Ltd.,
Saponification degree 81.5 mol%, polymerization degree 500) 6% by weight aqueous solution 0.03 part. Surfactant (polyoxyethylene lauryl ether, Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 1% by weight aqueous solution 0.86 part Specific compounds [compounds listed in Table 1] [amounts listed in Table 1]
・ Ion exchange water 6.0 parts
　上記特定化合物含有層塗布液（１）に用いた無機層状化合物分散液（１）の調製法を以下に示す。
＜無機層状化合物分散液（１）の調製＞
　イオン交換水１９３．６ｇに合成雲母（ソマシフＭＥ－１００、コープケミカル（株）製）６．４ｇを添加し、ホモジナイザーを用いて平均粒径（レーザー散乱法）が３μｍになるまで分散した。得られた分散粒子のアスペクト比は１００以上であった。 A method for preparing the inorganic layered compound dispersion (1) used in the specific compound-containing layer coating solution (1) is shown below.
<Preparation of inorganic layered compound dispersion (1)>
6.4 g of synthetic mica (Somasif ME-100, manufactured by Co-op Chemical Co., Ltd.) was added to 193.6 g of ion-exchanged water, and dispersed using an homogenizer until the average particle size (laser scattering method) became 3 μm. The aspect ratio of the obtained dispersed particles was 100 or more.
＜特定化合物含有層（２）の形成＞
　画像記録層上に、下記組成の特定化合物含有層塗布液（２）をバー塗布し、１２０℃で６０秒間オーブン乾燥して、特定化合物の乾燥塗布量が０．０６ｇ／ｍ２の特定化合物含有層を形成した。 <Formation of specific compound-containing layer (2)>
A specific compound-containing layer coating solution (2) having the following composition is bar-coated on the image recording layer, and oven-dried at 120 ° C. for 60 seconds to contain a specific compound having a dry coating amount of 0.06 g / m 2. A layer was formed.
＜特定化合物含有層塗布液（２）＞
・界面活性剤（ポリオキシエチレンラウリルエーテル、エマレックス７１０、日本エマルジョン（株）製）１質量％水溶液　　　　　０．８６部
・特定化合物〔表１に記載の化合物〕　　　　　　〔表１に記載の量〕
・イオン交換水　　　　　　　　　　　　　　　　　　　６．０部 <Specific compound-containing layer coating solution (2)>
-Surfactant (polyoxyethylene lauryl ether, Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 1% by weight aqueous solution 0.86 parts-Specific compound [compound described in Table 1] [Amount described in Table 1]
・ Ion exchange water 6.0 parts
〔平版印刷版原版の作製〕
　上記支持体、画像記録層及び特定化合物含有層を表１に記載するように組み合わせて平版印刷版原版を作製した。特定化合物含有層は、実施例１～２４及び比較例１～２では、特定化合物含有層塗布液（１）を、実施例２５では、特定化合物含有層塗布液（２）を用いて形成した。
　比較例２の平版印刷版原版は、以下のようにして作製した。支持体（１）上に、下記組成の下塗り層塗布液（１）を乾燥塗布量が２０ｍｇ／ｍ２になるよう塗布した後、乾燥せずに、特定化合物としてリン酸二水素ナトリウムの水溶液を、塗布装置として兵神装置（株）製２ＮＬ０４を用いて塗布した。即ち、塗布装置のクリアランスを０．３ｍｍに固定し、送液量を調整することにより、特定化合物の含有量が１５０ｍｇ／ｍ２になるように、端部から３ｃｍの位置に６ｍｍの幅で特定化合物の水溶液を塗布した。その後、１００℃で６０秒間オーブン乾燥した。この下塗り層の上に、画像記録層及び特定化合物含有層を表１に記載のように組み合わせて形成し、平版印刷版原版を作製した。 [Preparation of lithographic printing plate precursor]
A lithographic printing plate precursor was prepared by combining the support, the image recording layer and the specific compound-containing layer as described in Table 1. The specific compound-containing layer was formed using the specific compound-containing layer coating solution (1) in Examples 1 to 24 and Comparative Examples 1 and 2, and the specific compound-containing layer coating solution (2) in Example 25.
The planographic printing plate precursor of Comparative Example 2 was produced as follows. An undercoat layer coating solution (1) having the following composition was applied on the support (1) so that the dry coating amount was 20 mg / m 2, and an aqueous solution of sodium dihydrogen phosphate as a specific compound was not dried. The coating was performed using 2NL04 manufactured by Hyoshin Equipment Co., Ltd. as the coating apparatus. In other words, by fixing the clearance of the coating device to 0.3 mm and adjusting the liquid feeding amount, the specific compound is specified at a width of 6 mm at a position 3 cm from the end so that the content of the specific compound is 150 mg / m 2. An aqueous solution of the compound was applied. Thereafter, it was oven-dried at 100 ° C. for 60 seconds. On this undercoat layer, an image recording layer and a specific compound-containing layer were formed in combination as shown in Table 1 to prepare a lithographic printing plate precursor.
＜下塗り層塗布液（１）＞
・下塗り層用化合物（１）〔下記構造〕　　　　　　　　０．１８ｇ
・ヒドロキシエチルイミノ二酢酸　　　　　　　　　　　０．０５ｇ
・界面活性剤（エマレックス７１０、日本エマルジョン（株）製）
　　　　　　　　　　　　　　　　　　　　　　　　　　０．０３ｇ
・水　　　　　　　　　　　　　　　　　　　　　　　　２８．０ｇ <Undercoat layer coating solution (1)>
・ Undercoat layer compound (1) [the following structure] 0.18 g
・ Hydroxyethyliminodiacetic acid 0.05g
・ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.)
0.03g
・ Water 28.0g
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
〔平版印刷版原版の裁断〕
　平版印刷版原版を、図２に示すような回転刃を用いて、上側裁断刃と下側裁断刃の隙間、噛み込み量及び刃先角度を調整して裁断し、ダレ量５０μｍ及びダレ幅１５０μｍを有するダレ形状を形成した。なお、比較例２の平版印刷版原版については、６ｍｍ幅の特定化合物の水溶液が塗布された領域の中心で裁断を行い、端部に３ｍｍ幅の特定化合物塗布領域を有する平版印刷版原版を得た。
　陽極酸化皮膜の表面に存在するクラックの面積率を先に記載した方法に従って算出したところ、支持体（１）は、１３％、支持体（２）は、８％、支持体（３）及び（４）は、６％であった。 [Cutting of lithographic printing plate precursor]
The planographic printing plate precursor is cut using a rotary blade as shown in FIG. 2 while adjusting the gap between the upper cutting blade and the lower cutting blade, the amount of biting, and the blade edge angle to obtain a sagging amount of 50 μm and a sagging width of 150 μm. A sagging shape was formed. The planographic printing plate precursor of Comparative Example 2 was cut at the center of the region where the aqueous solution of the specific compound having a width of 6 mm was applied to obtain a planographic printing plate precursor having a specific compound application region having a width of 3 mm at the end. It was.
When the area ratio of cracks existing on the surface of the anodized film was calculated according to the method described above, the support (1) was 13%, the support (2) was 8%, the support (3) and ( 4) was 6%.
〔平版印刷版原版の評価〕
　平版印刷版原版について、製造後及び強制経時後のエッジ汚れ防止性、端部の画像形成性、及び機上現像性を以下のように評価した。評価結果を表１に示す。 [Evaluation of planographic printing plate precursor]
The lithographic printing plate precursor was evaluated for edge stain prevention, edge image formation, and on-press development after production and forced aging as follows. The evaluation results are shown in Table 1.
＜製造後のエッジ汚れ防止性＞
　平版印刷版原版を、赤外線半導体レーザー搭載の富士フイルム（株）製Ｌｕｘｃｅｌ　ＰＬＡＴＥＳＥＴＴＥＲ　Ｔ－６０００ＩＩＩにて、外面ドラム回転数１，０００ｒｐｍ、レーザー出力７０％、解像度２，４０００ｄｐｉの条件で露光した。露光画像にはベタ画像、５０％網点、非画像部を含むチャートを用いた。
　画像露光した平版印刷版原版を、（株）東京機械製作所製オフセット輪転印刷機に装着し、新聞用印刷インキとして、インクテック（株）製　ソイビーＫＫＳＴ－Ｓ（紅）、湿し水として、東洋インキ（株）製東洋ＡＬＫＹを用いて、新聞用紙に１００，０００枚／時のスピードで印刷し、地汚れ解消の水目盛から１．３倍の水目盛で、２，０００枚目の印刷物をサンプリングし、平版印刷版原版の端部に起因する線状汚れの程度を観察し、下記の基準で評価した。５、４、３が許容レベルである。
５：線状汚れは全く認められない。
４：非連続の線状汚れがうっすらと認められる。
３：連続した線状汚れがうっすらと認められる。
２：非連続のはっきりした線状汚れが認められる。
１：連続したはっきりした線状汚れが認められる。 <Prevention of edge contamination after production>
The lithographic printing plate precursor was exposed on a Luxcel PLATELTER T-6000III equipped with an infrared semiconductor laser under the conditions of an outer drum rotation speed of 1,000 rpm, a laser output of 70%, and a resolution of 2,000 dpi. A chart including a solid image, a 50% halftone dot, and a non-image portion was used as the exposure image.
An image-exposed lithographic printing plate precursor is mounted on an offset rotary printing machine manufactured by Tokyo Machine Works, Ltd., as newspaper printing ink, Soiby KKST-S (red) manufactured by Inktec Co., Ltd., and as dampening water, Toyo Using Toyo ALKY made by Ink Co., Ltd., print on newspapers at a speed of 100,000 pages / hour, and print the 2,000th sheet with a water scale 1.3 times higher than the water scale for eliminating background stains. Sampling was performed, and the degree of linear stains caused by the edge of the lithographic printing plate precursor was observed and evaluated according to the following criteria. 5, 4, 3 are acceptable levels.
5: No linear stains are observed.
4: Discontinuous linear stains are slightly observed.
3: A continuous linear stain | pollution | contamination is recognized slightly.
2: Discontinuous and clear linear stains are observed.
1: Continuous and clear linear stains are observed.
＜強制経時後のエッジ汚れ防止性＞
　平版印刷版原版を、温度６０℃／湿度６０％の湿熱環境下に２日間保管した後、上記製造後のエッジ汚れ防止性と同様にして強制経時後のエッジ汚れ防止性を評価した。温度６０℃／湿度６０％の湿熱環境下２日間の保管は、自然経時（温度２５℃／湿度５０％）１０ヵ月間に相当する。 <Edge dirt prevention after forced aging>
The planographic printing plate precursor was stored for 2 days in a humid heat environment at a temperature of 60 ° C./humidity of 60%, and then the edge stain resistance after forced aging was evaluated in the same manner as the edge stain resistance after the production. Storage for two days in a humid heat environment at a temperature of 60 ° C./humidity of 60% corresponds to 10 months of natural aging (temperature of 25 ° C./humidity of 50%).
＜端部の画像形成性＞
　上記エッジ汚れ防止性の評価と同様にして画像露光した平版印刷版原版を、（株）東京機械製作所製オフセット輪転印刷機に装着し、新聞用印刷インキとして、インクテック（株）製ソイビーＫＫＳＴ－Ｓ（紅）、湿し水としてサカタインクス（株）製エコセブンＮ－１を用い、新聞用紙に１００，０００枚／時のスピードで印刷し、５,０００、１０,０００、５０,０００、１００,０００枚目の印刷物をサンプリングし、平版印刷版原版の端部から内側に１ｍｍまでの領域における画像形成性を以下の基準で評価した。５、４、３が許容レベルである。
５：１００,０００枚印刷後も画像が印刷できている。
４：５０,０００枚印刷後も画像が印刷できている。
３：１０,０００枚印刷後も画像が印刷できている。
２：５,０００枚印刷後も画像が印刷できている。
１：５,０００枚印刷後では画像が印刷できていない。 <Image Formability at Edge>
The lithographic printing plate precursor subjected to image exposure in the same manner as in the evaluation of the anti-edge stain resistance is mounted on an offset rotary printing machine manufactured by Tokyo Machine Co., Ltd., and used as a newspaper printing ink, Soiby KKST- manufactured by Inktec Co., Ltd. S (Red), Sakata Inx Co., Ltd. Eco Seven N-1 was used as dampening water, printed on newspaper at a speed of 100,000 sheets / hour, 5,000, 10,000, 50,000, 100,000, The 000th printed material was sampled, and the image forming property in an area from the end of the planographic printing plate precursor to 1 mm inside was evaluated according to the following criteria. 5, 4, 3 are acceptable levels.
5: Images can be printed even after printing 100,000 sheets.
4: Images can be printed even after printing 50,000 sheets.
3: Images can be printed even after printing 10,000 sheets.
2: Images can be printed even after printing 5,000 sheets.
1: Images cannot be printed after printing 5000 sheets.
＜機上現像性＞
　上記エッジ汚れ防止性の評価と同様にして画像露光した平版印刷版原版を、（株）東京機械製作所製オフセット輪転印刷機に装着し、新聞用印刷インキとして、インクテック（株）製ソイビーＫＫＳＴ－Ｓ（紅）、湿し水としてサカタインクス（株）製エコセブンＮ－１を用い、新聞用紙に１００，０００枚／時のスピードで印刷した。平版印刷版原版の端部から内側に５０ｍｍまでの領域において、画像記録層の未露光部の印刷機上での機上現像が完了し、非画像部にインキが転写しない状態になるまでに要した新聞用紙の枚数を機上現像枚数として計測し、以下の基準で評価した。５、４、３、２が許容レベルである。
５：機上現像枚数が２５枚以下である。
４：機上現像枚数が２６～３０枚である。
３：機上現像枚数が３１～３５枚である。
２：機上現像枚数が３６～４０枚である。
１：機上現像枚数が４１枚以上である。 <On-press developability>
The lithographic printing plate precursor subjected to image exposure in the same manner as in the evaluation of the anti-edge stain resistance is mounted on an offset rotary printing machine manufactured by Tokyo Machine Co., Ltd., and used as a newspaper printing ink, Soiby KKST- manufactured by Inktec Co., Ltd. S (Red), Sakata Inx Co., Ltd. Eco Seven N-1 was used as dampening water, and printing was performed on newsprint at a speed of 100,000 sheets / hour. Necessary until the on-press development of the unexposed part of the image recording layer on the printing machine is completed in the area from the edge of the lithographic printing plate precursor to 50 mm inward and no ink is transferred to the non-image part. The number of newsprints was measured as the number of on-machine development, and evaluated according to the following criteria. 5, 4, 3, 2 are acceptable levels.
5: On-machine development number is 25 or less.
4: The number of on-press developed sheets is 26-30.
3: The number of on-press developed sheets is 31 to 35.
2: The number of on-press developed sheets is 36 to 40 sheets.
1: The on-machine development number is 41 or more.
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
　表１に記載の結果から、本発明に係る特定化合物を、画像記録層上に設けられた特定化合物含有層の面内において実質的に同じ量含有する平版印刷版原版は、端部の画像形成性、機上現像性などの特性を低下させることなく、長期保存後においても良好なエッジ汚れ防止性を示すことがわかる。これに対して、特定化合物を含有しない比較例１の平版印刷版原版では、はっきりした線状のエッジ汚れが発生している。また、特開平２０１７-１９２０６号公報の実施例のように、平版印刷版原版の端部に親水化処理領域を有する比較例２の平版印刷版原版では、端部の画像形成性が低下していることがわかる。 From the results shown in Table 1, a lithographic printing plate precursor containing the specific compound according to the present invention in substantially the same amount in the plane of the specific compound-containing layer provided on the image recording layer is It can be seen that good edge stain resistance is exhibited even after long-term storage without degrading the properties such as property and on-press developability. On the other hand, in the planographic printing plate precursor of Comparative Example 1 that does not contain a specific compound, clear linear edge stains are generated. Further, as in the examples of JP-A-2017-19206, in the planographic printing plate precursor of Comparative Example 2 having a hydrophilic treatment region at the end of the planographic printing plate precursor, the image formability at the end is lowered. I understand that.
［実施例２６～２７及び比較例３～４］
＜第１ポリマー層（１）の形成＞
　支持体（１）上に、上記組成の下塗り層塗布液（１）をバー塗布した後、１００℃で６０秒オーブン乾燥し、乾燥塗布量２０ｍｇ／ｍ２の第１ポリマー層を形成した。 [Examples 26 to 27 and Comparative Examples 3 to 4]
<Formation of first polymer layer (1)>
On the support (1), the undercoat layer coating solution (1) having the above composition was bar-coated, followed by oven drying at 100 ° C. for 60 seconds to form a first polymer layer having a dry coating amount of 20 mg / m 2 .
＜第２ポリマー層（１）の形成＞
　第１ポリマー層（１）（下塗り層）上に、下記組成の第２ポリマー層用塗布液（１）をバー塗布した後、１００℃で６０秒オーブン乾燥し、乾燥塗布量０．５ｇ／ｍ２の第２ポリマー層を形成した。 <Formation of second polymer layer (1)>
On the first polymer layer (1) (undercoat layer), the second polymer layer coating solution (1) having the following composition was bar coated, followed by oven drying at 100 ° C. for 60 seconds, and a dry coating amount of 0.5 g / m. Two second polymer layers were formed.
（第２ポリマー層用塗布液（１））
・ポリビニルピロリドンＫ３０（富士フイルム和光純薬株式会社）
　　　　　　　　　　　　　　　　　　　　　　　　０．５００部
・フッ素系界面活性剤（１）（上記構造）　　　　　０．００４部
・１－メトキシ－２－プロパノール　　　　　　　１２．１０１部
・メタノール　　　　　　　　　　　　　　　　　　１．３４５部
・純水　　　　　　　　　　　　　　　　　　　　　０．０３６部 (Coating liquid for second polymer layer (1))
・ Polyvinylpyrrolidone K30 (Fujifilm Wako Pure Chemical Industries, Ltd.)
0.500 parts · Fluorosurfactant (1) (above structure) 0.004 parts · 1-methoxy-2-propanol 12.101 parts · Methanol 1.345 parts · Pure water 0.036 parts
＜特定化合物含有層（３）の形成＞
　第２ポリマー層上に、下記組成の特定化合物含有層塗布液（３）をバー塗布し、１２０℃で６０秒間オーブン乾燥して、乾燥塗布量が０．１５ｇ／ｍ２の特定化合物含有層を形成した。 <Formation of specific compound-containing layer (3)>
A specific compound-containing layer coating solution (3) having the following composition is bar-coated on the second polymer layer, and oven-dried at 120 ° C. for 60 seconds to form a specific compound-containing layer having a dry coating amount of 0.15 g / m 2. Formed.
＜特定化合物含有層塗布液（３）＞
・無機層状化合物分散液（１）〔上記〕　　　　　　　　１．５部
・ポリビニルアルコール（ＣＫＳ５０、日本合成化学工業（株）製、スルホン酸変性、けん化度９９モル％以上、重合度３００）６質量％水溶液
　　　　　　　　　　　　　　　　　　　　　　　　　　０．５５部
・ポリビニルアルコール（ＰＶＡ－４０５、（株）クラレ製、
けん化度８１．５モル％、重合度５００）６質量％水溶液
　　　　　　　　　　　　　　　　　　　　　　　　　　０．０３部
・界面活性剤（ポリオキシエチレンラウリルエーテル、エマレックス７１０、日本エマルジョン（株）製）１質量％水溶液　　　　　０．８６部
・特定化合物〔表２に記載の化合物〕　　　　　　〔表２に記載の量〕
・イオン交換水　　　　　　　　　　　　　　　　　　　６．０部 <Specific compound-containing layer coating solution (3)>
-Inorganic layered compound dispersion (1) [above] 1.5 parts-Polyvinyl alcohol (CKS50, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., sulfonic acid modification, saponification degree 99 mol% or more, polymerization degree 300) 6% by mass aqueous solution 0.55 parts polyvinyl alcohol (PVA-405, manufactured by Kuraray Co., Ltd.,
Saponification degree 81.5 mol%, polymerization degree 500) 6% by weight aqueous solution 0.03 part. Surfactant (polyoxyethylene lauryl ether, Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 1% by weight aqueous solution 0.86 part Specific compounds [compounds listed in Table 2] [amounts listed in Table 2]
・ Ion exchange water 6.0 parts
〔平版印刷版ダミー版の作製〕
　上記支持体、第１ポリマー層、第２ポリマー層及び特定化合物含有層を表２に記載するように組み合わせて平版印刷版ダミー版を作製した。特定化合物含有層は、実施例２６～２７及び比較例３～４では、特定化合物含有層塗布液（３）を用いて形成した。
　実施例２７の平版印刷版ダミー版は、以下のようにして作製した。支持体（１）上に、上記組成の下塗り層塗布液（１）をバー塗布した後、１００℃で６０秒オーブン乾燥し、乾燥塗布量２０ｍｇ／ｍ２の第１ポリマー層を形成した。第１ポリマー層上に、上記組成の特定化合物含有層塗布液（３）をバー塗布し、１２０℃で６０秒間オーブン乾燥して、乾燥塗布量が０．１５ｇ／ｍ２の特定化合物含有層を形成し、平版印刷版ダミー版を作製した。
　比較例４の平版印刷版ダミー版は、以下のようにして作製した。支持体（１）上に、上記組成の下塗り層塗布液（１）をバー塗布した後、１００℃で６０秒オーブン乾燥し、乾燥塗布量２０ｍｇ／ｍ２の第１ポリマー層を形成した。第１ポリマー層上に、上記組成の特定化合物含有層塗布液（３）をバー塗布し、１２０℃で６０秒間オーブン乾燥して、乾燥塗布量が０．１５ｇ／ｍ２の特定化合物含有層を形成し、平版印刷版ダミー版を作成した。 [Preparation of lithographic printing plate dummy]
A lithographic printing plate dummy plate was prepared by combining the support, the first polymer layer, the second polymer layer, and the specific compound-containing layer as described in Table 2. In Examples 26 to 27 and Comparative Examples 3 to 4, the specific compound-containing layer was formed using the specific compound-containing layer coating solution (3).
The planographic printing plate dummy plate of Example 27 was produced as follows. On the support (1), the undercoat layer coating solution (1) having the above composition was bar-coated, followed by oven drying at 100 ° C. for 60 seconds to form a first polymer layer having a dry coating amount of 20 mg / m 2 . On the first polymer layer, the specific compound-containing layer coating solution (3) having the above composition is bar-coated and oven-dried at 120 ° C. for 60 seconds to form a specific compound-containing layer having a dry coating amount of 0.15 g / m 2. Then, a lithographic printing plate dummy plate was produced.
The planographic printing plate dummy plate of Comparative Example 4 was produced as follows. On the support (1), the undercoat layer coating solution (1) having the above composition was bar-coated, followed by oven drying at 100 ° C. for 60 seconds to form a first polymer layer having a dry coating amount of 20 mg / m 2 . On the first polymer layer, the specific compound-containing layer coating solution (3) having the above composition is bar-coated and oven-dried at 120 ° C. for 60 seconds to form a specific compound-containing layer having a dry coating amount of 0.15 g / m 2. A lithographic printing plate dummy was formed.
〔平版印刷版ダミー版の裁断〕
　平版印刷版ダミー版を、図２に示すような回転刃を用いて、上側裁断刃と下側裁断刃の隙間、噛み込み量及び刃先角度を調整して裁断し、ダレ量５０μｍ及びダレ幅１５０μｍを有するダレ形状を形成した。
　陽極酸化皮膜の表面に存在するクラックの面積率を先に記載した方法に従って算出したところ、支持体（１）は、１３％であった。 [Cutting of lithographic printing plate dummy]
A planographic printing plate dummy plate is cut using a rotary blade as shown in FIG. 2 by adjusting the gap between the upper cutting blade and the lower cutting blade, the amount of biting, and the edge angle, and a sagging amount of 50 μm and a sagging width of 150 μm. A sagging shape having was formed.
When the area ratio of the cracks existing on the surface of the anodized film was calculated according to the method described above, the support (1) was 13%.
〔平版印刷版ダミー版の評価〕
　平版印刷版ダミー版について、製造後及び強制経時後のエッジ汚れ防止性、及び機上現像性を以下のように評価した。評価結果を表２に示す。 [Evaluation of planographic printing plate dummy]
The planographic printing plate dummy plate was evaluated for edge stain resistance and on-press developability after production and forced aging as follows. The evaluation results are shown in Table 2.
＜製造後のエッジ汚れ防止性＞
　平版印刷版ダミー版を、（株）東京機械製作所製オフセット輪転印刷機に装着し、新聞用印刷インキとして、インクテック（株）製　ソイビーＫＫＳＴ－Ｓ（紅）、湿し水として、東洋インキ（株）製東洋ＡＬＫＹを用いて、新聞用紙に１００，０００枚／時のスピードで印刷し、地汚れ解消の水目盛から１．３倍の水目盛で、２，０００枚目の印刷物をサンプリングし、平版印刷版ダミー版の端部に起因する線状汚れの程度を観察し、下記の基準で評価した。５、４、３が許容レベルである。
５：線状汚れは全く認められない。
４：非連続の線状汚れがうっすらと認められる。
３：連続した線状汚れがうっすらと認められる。
２：非連続のはっきりした線状汚れが認められる。
１：連続したはっきりした線状汚れが認められる。 <Prevention of edge contamination after production>
A lithographic printing plate dummy plate is mounted on an offset rotary printing machine manufactured by Tokyo Machine Works, Ltd., as newspaper printing ink, Soiby KKST-S (red) manufactured by Inktec Co., Ltd., and as dampening water, Toyo Ink ( Using Toyo ALKY, manufactured by Toyo Co., Ltd., printed on newsprint at a speed of 100,000 sheets / hour, and the 2,000th printed matter was sampled at a water scale 1.3 times higher than the water scale for eliminating soiling. The degree of linear contamination due to the edge of the planographic printing plate dummy was observed and evaluated according to the following criteria. 5, 4, 3 are acceptable levels.
5: No linear stains are observed.
4: Discontinuous linear stains are slightly observed.
3: A continuous linear stain | pollution | contamination is recognized slightly.
2: Discontinuous and clear linear stains are observed.
1: Continuous and clear linear stains are observed.
＜強制経時後のエッジ汚れ防止性＞
　平版印刷版ダミー版を、温度６０℃／湿度６０％の湿熱環境下に２日間保管した後、上記製造後のエッジ汚れ防止性と同様にして強制経時後のエッジ汚れ防止性を評価した。温度６０℃／湿度６０％の湿熱環境下２日間の保管は、自然経時（温度２５℃／湿度５０％）１０ヵ月間に相当する。 <Edge dirt prevention after forced aging>
The planographic printing plate dummy plate was stored for 2 days in a wet heat environment at a temperature of 60 ° C./humidity of 60%, and then the edge stain prevention property after forced aging was evaluated in the same manner as the edge stain prevention property after the production. Storage for two days in a humid heat environment at a temperature of 60 ° C./humidity of 60% corresponds to 10 months of natural aging (temperature of 25 ° C./humidity of 50%).
＜機上現像性＞
　平版印刷版ダミー版を、（株）東京機械製作所製オフセット輪転印刷機に装着し、新聞用印刷インキとして、インクテック（株）製ソイビーＫＫＳＴ－Ｓ（紅）、湿し水としてサカタインクス（株）製エコセブンＮ－１を用い、新聞用紙に１００，０００枚／時のスピードで印刷した。平版印刷版ダミー版の端部から内側に５０ｍｍまでの領域において、機上現像が完了し、インキが転写しない状態になるまでに要した新聞用紙の枚数を機上現像枚数として計測し、以下の基準で評価した。５、４、３、２が許容レベルである。
５：機上現像枚数が２５枚以下である。
４：機上現像枚数が２６～３０枚である。
３：機上現像枚数が３１～３５枚である。
２：機上現像枚数が３６～４０枚である。
１：機上現像枚数が４１枚以上である。 <On-press developability>
A lithographic printing plate dummy is mounted on an offset rotary printing machine manufactured by Tokyo Machine Works, Ltd., as a printing ink for newspapers, Soiby KKST-S (Red) manufactured by Inktec Co., Ltd., and Sakata Inx Co., Ltd. as a dampening solution. Printing was performed on newsprint at a speed of 100,000 sheets / hour using Eco Seven N-1. In the area up to 50 mm inward from the edge of the lithographic printing plate dummy plate, the number of newspapers required until the on-press development is completed and the ink is not transferred is measured as the on-press developed number. Evaluated by criteria. 5, 4, 3, 2 are acceptable levels.
5: On-machine development number is 25 or less.
4: The number of on-press developed sheets is 26-30.
3: The number of on-press developed sheets is 31 to 35.
2: The number of on-press developed sheets is 36 to 40 sheets.
1: The on-machine development number is 41 or more.
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　表２に記載の結果から、本発明に係る特定化合物を、ポリマー層上に設けられた特定化合物含有層の面内において実質的に同じ量含有する平版印刷版ダミー版は、機上現像性の特性を低下させることなく、長期保存後においても良好なエッジ汚れ防止性を示すことがわかる。これに対して、特定化合物を含有しない比較例３、４の平版印刷版ダミー版では、はっきりした線状のエッジ汚れが発生している。 From the results shown in Table 2, the planographic printing plate dummy containing the specific compound according to the present invention in substantially the same amount in the plane of the specific compound-containing layer provided on the polymer layer is It can be seen that good edge stain resistance is exhibited even after long-term storage without degrading the characteristics. On the other hand, in the planographic printing plate dummy plates of Comparative Examples 3 and 4 that do not contain the specific compound, clear linear edge stains are generated.
［実施例２８～２９及び比較例５～６］
〔平版印刷版ダミー版の作製〕
　支持体（１）を支持体（４）に変更した以外は、実施例２６と同様にして、実施例２８の平版印刷版ダミー版を作成した。
　支持体（１）を支持体（４）に変更した以外は、実施例２７と同様にして、実施例２９の平版印刷版ダミー版を作成した。
　支持体（１）を支持体（４）に変更した以外は、比較例３と同様にして、比較例５の平版印刷版ダミー版を作成した。
　支持体（１）を支持体（４）に変更した以外は、比較例４と同様にして、比較例６の平版印刷版ダミー版を作成した。 [Examples 28 to 29 and Comparative Examples 5 to 6]
[Preparation of lithographic printing plate dummy]
A lithographic printing plate dummy plate of Example 28 was prepared in the same manner as in Example 26 except that the support (1) was changed to the support (4).
A lithographic printing plate dummy plate of Example 29 was prepared in the same manner as in Example 27 except that the support (1) was changed to the support (4).
A lithographic printing plate dummy plate of Comparative Example 5 was prepared in the same manner as Comparative Example 3 except that the support (1) was changed to the support (4).
A lithographic printing plate dummy plate of Comparative Example 6 was prepared in the same manner as Comparative Example 4 except that the support (1) was changed to the support (4).
〔平版印刷版ダミー版の裁断〕
　平版印刷版ダミー版を、図２に示すような回転刃を用いて、上側裁断刃と下側裁断刃の隙間、噛み込み量及び刃先角度を調整して裁断し、ダレ量５０μｍ及びダレ幅１５０μｍを有するダレ形状を形成した。
　陽極酸化皮膜の表面に存在するクラックの面積率を先に記載した方法に従って算出したところ、支持体（４）は、６％であった。 [Cutting of lithographic printing plate dummy]
A planographic printing plate dummy plate is cut using a rotary blade as shown in FIG. 2 by adjusting the gap between the upper cutting blade and the lower cutting blade, the amount of biting, and the edge angle, and a sagging amount of 50 μm and a sagging width of 150 μm. A sagging shape having was formed.
When the area ratio of cracks existing on the surface of the anodized film was calculated according to the method described above, the support (4) was 6%.
［実施例３０～３１］
〔平版印刷版原版の作製〕
　特定化合物含有層における特定化合物を除いた（即ち、特定化合物含有層塗布液（１）における特定化合物を除いた）以外は、実施例３と同様にして、実施例３０の平版印刷版原版を作成した。
　特定化合物含有層における特定化合物を除いた（即ち、特定化合物含有層塗布液（１）における特定化合物を除いた）以外は、実施例２３と同様にして、実施例３１の平版印刷版原版を作成した。 [Examples 30 to 31]
[Preparation of lithographic printing plate precursor]
A lithographic printing plate precursor of Example 30 was prepared in the same manner as in Example 3 except that the specific compound in the specific compound-containing layer was excluded (that is, the specific compound in the specific compound-containing layer coating solution (1) was excluded). did.
A planographic printing plate precursor of Example 31 was prepared in the same manner as in Example 23 except that the specific compound in the specific compound-containing layer was excluded (that is, the specific compound in the specific compound-containing layer coating solution (1) was excluded). did.
〔平版印刷版原版の裁断〕
　平版印刷版原版を、図２に示すような回転刃を用いて、上側裁断刃と下側裁断刃の隙間、噛み込み量及び刃先角度を調整して裁断し、ダレ量５０μｍ及びダレ幅１５０μｍを有するダレ形状を形成した。
　陽極酸化皮膜の表面に存在するクラックの面積率を先に記載した方法に従って算出したところ、支持体（１）は、１３％で、支持体（４）は、６％であった。 [Cutting of lithographic printing plate precursor]
The planographic printing plate precursor is cut using a rotary blade as shown in FIG. 2 while adjusting the gap between the upper cutting blade and the lower cutting blade, the amount of biting, and the blade edge angle to obtain a sagging amount of 50 μm and a sagging width of 150 μm. A sagging shape was formed.
When the area ratio of the cracks existing on the surface of the anodized film was calculated according to the method described above, the support (1) was 13% and the support (4) was 6%.
［実施例３２～３５及び比較例７～１０］
　実施例３０、３１で得られた平版印刷版原版と実施例２６～２９、比較例３～６で得られた平版印刷版ダミー版を下記表３に示すように組み合わせて、以下の評価を行った。 [Examples 32-35 and Comparative Examples 7-10]
The lithographic printing plate precursors obtained in Examples 30 and 31 and the lithographic printing plate dummy plates obtained in Examples 26 to 29 and Comparative Examples 3 to 6 were combined as shown in Table 3 below, and the following evaluation was performed. It was.
＜平版印刷版原版と平版印刷版ダミー版のエッジ汚れ防止性＞
　平版印刷版原版を、赤外線半導体レーザー搭載の富士フイルム（株）製Ｌｕｘｃｅｌ　ＰＬＡＴＥＳＥＴＴＥＲ　Ｔ－６０００ＩＩＩにて、外面ドラム回転数１，０００ｒｐｍ、レーザー出力７０％、解像度２，４０００ｄｐｉの条件で露光した。露光画像にはベタ画像、５０％網点、非画像部を含むチャートを用いた。
　画像露光した平版印刷版原版１枚と露光していない平版印刷版ダミー版１枚を、（株）東京機械製作所製オフセット輪転印刷機の同一の版胴上に装着し、新聞用印刷インキとして、インクテック（株）製　ソイビーＫＫＳＴ－Ｓ（紅）、湿し水として、東洋インキ（株）製東洋ＡＬＫＹを用いて、新聞用紙に１００，０００枚／時のスピードで印刷し、地汚れ解消の水目盛から１．３倍の水目盛で、２，０００枚目の印刷物をサンプリングし、隣り合っている平版印刷版原版の端部と平版印刷版ダミー版の端部に起因する線状汚れの程度を観察し、下記の基準で評価した。５、４、３が許容レベルである。
５：線状汚れは全く認められない。
４：非連続の線状汚れがうっすらと認められる。
３：連続した線状汚れがうっすらと認められる。
２：非連続のはっきりした線状汚れが認められる。
１：連続したはっきりした線状汚れが認められる。 <Edge stain resistance of lithographic printing plate precursor and lithographic printing plate dummy>
The lithographic printing plate precursor was exposed on a Luxcel PLATELTER T-6000III equipped with an infrared semiconductor laser under the conditions of an outer drum rotation speed of 1,000 rpm, a laser output of 70%, and a resolution of 2,000 dpi. A chart including a solid image, a 50% halftone dot, and a non-image portion was used as the exposure image.
One exposed lithographic printing plate precursor and one unexposed lithographic printing plate dummy were mounted on the same plate cylinder of an offset rotary printing machine manufactured by Tokyo Machinery Co., Ltd. Ink Tech Co., Ltd., Soybee KKST-S (Red), Toyo Ink Co., Ltd., Toyo ALKY as dampening water, printed on newsprint at a speed of 100,000 sheets / hour to eliminate background stains Sample the 2,000th printed matter at a water scale 1.3 times higher than the water scale, and remove the linear stains caused by the edges of the adjacent lithographic printing plate precursor and the lithographic printing plate dummy. The degree was observed and evaluated according to the following criteria. 5, 4, 3 are acceptable levels.
5: No linear stains are observed.
4: Discontinuous linear stains are slightly observed.
3: A continuous linear stain | pollution | contamination is recognized slightly.
2: Discontinuous and clear linear stains are observed.
1: Continuous and clear linear stains are observed.
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
　表３に記載の結果から、本発明に係る特定化合物を、ポリマー層上に設けられた特定化合物含有層の面内において実質的に同じ量含有する平版印刷版ダミー版を用いた場合は、平版印刷版ダミー版について良好なエッジ汚れ防止性が得られると共に、平版印刷版原版についても良好なエッジ汚れ防止性が得られることがわかる。 From the results shown in Table 3, when a lithographic printing plate dummy plate containing substantially the same amount of the specific compound according to the present invention in the plane of the specific compound-containing layer provided on the polymer layer is used, It can be seen that a good edge stain prevention property can be obtained for the printing plate dummy plate, and a good edge stain prevention property can also be obtained for the planographic printing plate precursor.
　本発明によれば、端部の画像形成性、機上現像性などの特性を低下させることなく、長期保存後においても良好なエッジ汚れ防止性を示す機上現像型平版印刷版原版、及び機上現像型平版印刷版原版を用いた平版印刷版の作製方法を提供することができる。
　また、本発明によれば、機上現像性などの特性を低下させることなく、長期保存後においても良好なエッジ汚れ防止性を示す機上現像型平版印刷版原版ダミー版、及び印刷方法を提供することができる。 According to the present invention, an on-press development type lithographic printing plate precursor exhibiting good edge stain resistance even after long-term storage without deteriorating properties such as image forming property and on-press developability at the end, and machine A method for preparing a lithographic printing plate using the upper development type lithographic printing plate precursor can be provided.
In addition, according to the present invention, an on-press development type lithographic printing plate precursor dummy plate and a printing method exhibiting good edge stain resistance even after long-term storage without deteriorating on-press developability and other characteristics are provided. can do.
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、２０１８年１月３１日出願の日本特許出願（特願２０１８－１５０６３）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on Jan. 31, 2018 (Japanese Patent Application No. 2018-15063), the contents of which are incorporated herein by reference.
　１　平版印刷版原版
　１ａ　特定化合物含有層面
　１ｂ　支持体面
　１ｃ　端面
　２　ダレ
　Ｘ　ダレ量
　Ｙ　ダレ幅
　Ｂ　画像記録層面と支持体との境界
　１０　裁断刃
　１０ａ　上側裁断刃
　１０ｂ　上側裁断刃
　１１　回転軸
　２０　裁断刃
　２０ａ　下側裁断刃
　２０ｂ　下側裁断刃
　２１　回転軸
　３０　平版印刷版原版
  DESCRIPTION OF SYMBOLS 1 Planographic printing plate precursor 1a Specific compound containing layer surface 1b Support surface 1c End surface 2 Sag X Sag amount Y Sag width B Boundary between image recording layer surface and support 10 Cutting blade 10a Upper cutting blade 10b Upper cutting blade 11 Rotating shaft 20 Cutting blade 20a Lower cutting blade 20b Lower cutting blade 21 Rotating shaft 30 Planographic printing plate precursor

Claims (24)

  1. 　陽極酸化皮膜を有するアルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版であって、前記平版印刷版原版は端部にダレ形状を有し、前記画像記録層の上に支持体吸着性を有する化合物を含有する層を有し、前記化合物の含有量が前記支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版原版。 An on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support having an anodized film, wherein the lithographic printing plate precursor has a sag shape at an end and is supported on the image recording layer An on-press development type lithographic printing plate precursor having a layer containing a compound having a body adsorptivity, wherein the content of the compound is substantially the same in the plane of the layer containing the compound having a support adsorptivity .
  2. 　前記化合物の分子量が１，０００以下である請求項１に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor according to claim 1, wherein the molecular weight of the compound is 1,000 or less.
  3. 　前記支持体吸着性を有する化合物を含有する層が更に界面活性剤を含有する請求項１又は２に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor according to claim 1 or 2, wherein the layer containing the compound having support adsorptivity further contains a surfactant.
  4. 　前記支持体吸着性を有する化合物を含有する層が更に水溶性ポリマーを含有する請求項１～３のいずれか１項に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor as claimed in any one of claims 1 to 3, wherein the layer containing the compound having support adsorptivity further contains a water-soluble polymer.
  5. 　前記化合物がオキソ酸又はその塩である請求項１～４のいずれか１項に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor as claimed in any one of claims 1 to 4, wherein the compound is an oxo acid or a salt thereof.
  6. 　前記化合物が下記式１で表わされる化合物である請求項１～５のいずれか１項に記載の機上現像型平版印刷版原版。
    Figure JPOXMLDOC01-appb-C000001
    　式１中、ｎは、２～１０の整数を表し、Ｒ１、Ｒ２、Ｒ３は、それぞれ独立に、水素原子、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アルキル基又はアルキレンオキシド基を表す。     6. The on-press development type lithographic printing plate precursor as claimed in claim 1, wherein the compound is a compound represented by the following formula 1.
    Figure JPOXMLDOC01-appb-C000001
    In Formula 1, n represents an integer of 2 to 10, and R1, R2, and R3 each independently represent a hydrogen atom, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an alkyl group, or an alkylene oxide group. .
  7. 　前記化合物がリン酸、ポリリン酸、ホスホン酸もしくはホスフィン酸又はこれらの塩である請求項１～６のいずれか１項に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor according to any one of claims 1 to 6, wherein the compound is phosphoric acid, polyphosphoric acid, phosphonic acid, phosphinic acid or a salt thereof.
  8. 　前記化合物の含有量が２０～１５０ｍｇ／ｍ２である請求項１～７のいずれか１項に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor as claimed in any one of claims 1 to 7, wherein the content of the compound is 20 to 150 mg / m 2 .
  9. 　前記ダレ形状が、ダレ量Ｘが２５～１５０μｍ、ダレ幅Ｙが７０～３００μｍである請求項１～８のいずれか１項に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor as claimed in any one of claims 1 to 8, wherein the sagging shape has a sagging amount X of 25 to 150 µm and a sagging width Y of 70 to 300 µm.
  10. 　前記平版印刷版原版のダレ幅Ｙに相当する領域の前記陽極酸化皮膜の表面に存在するクラックの面積率が２０％以下である請求項９に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor according to claim 9, wherein an area ratio of cracks existing on the surface of the anodic oxide film in a region corresponding to a sag width Y of the lithographic printing plate precursor is 20% or less.
  11. 　前記クラックの面積率が１０％以下である請求項１０に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor according to claim 10, wherein an area ratio of the cracks is 10% or less.
  12. 　前記画像記録層が、ポリマー粒子を含有する請求項１～１１のいずれか１項に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor according to any one of claims 1 to 11, wherein the image recording layer contains polymer particles.
  13. 　前記ポリマー粒子が、スチレン化合物に由来するモノマー単位、及び／又は、（メタ）アクリロニトリル化合物に由来するモノマー単位を含むポリマーの粒子である請求項１２に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor according to claim 12, wherein the polymer particles are polymer particles containing a monomer unit derived from a styrene compound and / or a monomer unit derived from a (meth) acrylonitrile compound.
  14. 　前記画像記録層が、重合開始剤、赤外線吸収剤及び重合性化合物を含有する請求項１～１３のいずれか１項に記載の機上現像型平版印刷版原版。 The on-press development type lithographic printing plate precursor according to any one of claims 1 to 13, wherein the image recording layer comprises a polymerization initiator, an infrared absorber and a polymerizable compound.
  15. 　請求項１～１４のいずれか１項に記載の機上現像型平版印刷版原版を、赤外線レーザーにより画像露光する工程と、印刷機上で印刷インキ及び湿し水から選ばれる少なくとも１つにより、画像記録層の未露光部分を除去する工程とを含む平版印刷版の作製方法。 The on-press development type lithographic printing plate precursor according to any one of claims 1 to 14, by image exposure with an infrared laser, and at least one selected from printing ink and fountain solution on the printing press, A method for producing a lithographic printing plate comprising a step of removing an unexposed portion of the image recording layer.
  16. 　陽極酸化皮膜を有するアルミニウム支持体上にポリマー層を有する機上現像型平版印刷版ダミー版であって、前記平版印刷版ダミー版は端部にダレ形状を有し、前記ポリマー層の上に支持体吸着性を有する化合物を含有する層を有し、前記化合物の含有量が前記支持体吸着性を有する化合物を含有する層の面内において実質的に同じである機上現像型平版印刷版ダミー版。 An on-press development type lithographic printing plate dummy plate having a polymer layer on an aluminum support having an anodized film, wherein the lithographic printing plate dummy plate has a sag shape at the end and is supported on the polymer layer An on-press development type lithographic printing plate dummy having a layer containing a compound having body adsorptivity, wherein the content of the compound is substantially the same in the plane of the layer containing the compound having support adsorptivity Edition.
  17. 　請求項１６に記載の機上現像型平版印刷版ダミー版、及び、アルミニウム支持体上に画像記録層を有する機上現像型平版印刷版原版を機上現像する工程を含む印刷方法。 A printing method comprising a step of on-machine development of the on-press development type lithographic printing plate dummy plate according to claim 16 and the on-press development type lithographic printing plate precursor having an image recording layer on an aluminum support.
  18. 　前記画像記録層が有機ホウ素含有アニオンを含む重合開始剤を含有する請求項１７に記載の印刷方法。 The printing method according to claim 17, wherein the image recording layer contains a polymerization initiator containing an organic boron-containing anion.
  19. 　前記重合開始剤が、有機ホウ素含有アニオン及びジアリールヨードニウムカチオンを含むヨードニウム化合物である請求項１８に記載の印刷方法。 The printing method according to claim 18, wherein the polymerization initiator is an iodonium compound containing an organic boron-containing anion and a diaryl iodonium cation.
  20. 　前記画像記録層が、ポリマー粒子を含有する請求項１７～１９のいずれか一項に記載の印刷方法。 The printing method according to any one of claims 17 to 19, wherein the image recording layer contains polymer particles.
  21. 　前記ポリマー粒子が、スチレン及びアクリロニトリルを含む共重合体の粒子である請求項２０に記載の印刷方法。 The printing method according to claim 20, wherein the polymer particles are copolymer particles containing styrene and acrylonitrile.
  22. 　前記ポリマー粒子が、ミクロゲルである請求項２０に記載の印刷方法。 The printing method according to claim 20, wherein the polymer particles are microgel.
  23. 　前記機上現像型平版印刷版原版が、前記アルミニウム支持体と前記画像記録層の間に下塗り層を有する請求項１７～２２のいずれか一項に記載の印刷方法。 The printing method according to any one of claims 17 to 22, wherein the on-press development type lithographic printing plate precursor has an undercoat layer between the aluminum support and the image recording layer.
  24. 　前記機上現像型平版印刷版原版が、前記画像記録層の上に保護層を有する請求項１７～２３のいずれか一項に記載の印刷方法。
          The printing method according to any one of claims 17 to 23, wherein the on-press development type lithographic printing plate precursor has a protective layer on the image recording layer.
PCT/JP2019/003499 2018-01-31 2019-01-31 On-press development type lithographic printing plate precursor, method for fabricating lithographic printing plate, on-press development type lithographic printing plate dummy plate, and printing method WO2019151447A1 (en)

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