WO2020262687A1 - Plaque originale d'impression planographique, procédé de fabrication de plaque d'impression planographique, et procédé d'impression planographique - Google Patents

Plaque originale d'impression planographique, procédé de fabrication de plaque d'impression planographique, et procédé d'impression planographique Download PDF

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Publication number
WO2020262687A1
WO2020262687A1 PCT/JP2020/025409 JP2020025409W WO2020262687A1 WO 2020262687 A1 WO2020262687 A1 WO 2020262687A1 JP 2020025409 W JP2020025409 W JP 2020025409W WO 2020262687 A1 WO2020262687 A1 WO 2020262687A1
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group
compound
printing plate
original plate
plate according
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PCT/JP2020/025409
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English (en)
Japanese (ja)
Inventor
俊佑 柳
洋平 石地
和朗 榎本
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富士フイルム株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/08—Developable by water or the fountain solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers

Definitions

  • This disclosure relates to a lithographic printing plate original plate, a method for producing a lithographic printing plate, and a lithographic printing method.
  • a lithographic printing plate comprises a lipophilic image portion that receives ink in the printing process and a hydrophilic non-image portion that receives dampening water.
  • the oil-based image part of the flat plate printing plate is the ink receiving part
  • the hydrophilic non-image part is the dampening water receiving part (that is, the ink non-receiving part). )
  • a lithographic printing plate original plate (also referred to as PS plate) in which a lipophilic photosensitive resin layer (also referred to as an image recording layer) is provided on a hydrophilic support has been widely used.
  • PS plate a lipophilic photosensitive resin layer
  • an image recording layer also referred to as an image recording layer
  • a flat plate printing plate is obtained by performing plate making by a method of dissolving and removing with a solvent to expose the surface of a hydrophilic support to form a non-image portion.
  • machine development is performed. That is, it is a method in which the lithographic printing plate original plate is exposed and then mounted on the printing machine as it is without the conventional development, and the unnecessary portion of the image recording layer is removed at the initial stage of the normal printing process.
  • Examples of the machine-developed planographic printing plate original plate are described in JP-A-2006-188038, for example, on the surface of a porous aluminum support, (1) a hydrophilic substituent and a sulfonic acid adsorbable on the surface of the support.
  • a layer containing a water-soluble polymer resin having a group, and (2) an oil-based ink and an aqueous component are supplied on a printing machine to remove an unexposed portion without going through any development processing step after exposure.
  • a lithographic printing plate original plate having a possible image recording layer
  • a lithographic printing plate original plate in which a sulfonic acid group remains in a layer containing a water-soluble polymer resin after contact with an oil-based ink and an aqueous component is disclosed.
  • Japanese Patent Application Laid-Open No. 08-190197 describes a photopolymerizable monomer having a long-chain alkyl group having 3 or more carbon atoms on a support having a hydrophilic surface, and photopolymerization.
  • a photosensitive lithographic printing plate having a photosensitive layer formed by applying a photosensitive composition containing an initiator and a water-insoluble particulate dispersion is disclosed.
  • Means for solving the above problems include the following forms. ⁇ 1> An aluminum support, an image recording layer, and a water-soluble resin layer are provided in this order.
  • the image recording layer has particles A containing a resin having an ethylenically unsaturated group and having an ethylenically unsaturated bond value of 0.10 mmol / g or more, and ethylenically unsaturated groups other than the particles A.
  • Containing compound B Planographic printing plate original plate.
  • Q represents a divalent linking group
  • W represents a divalent group having a hydrophilic structure or a divalent group having a hydrophobic structure
  • Y represents a monovalent group having a hydrophilic structure or It represents a monovalent group having a hydrophobic structure, either W or Y has a hydrophilic structure
  • * represents a binding site with another structure.
  • planographic printing plate original plate according to ⁇ 5> wherein the polyalkylene oxide structure includes a polypropylene oxide structure.
  • the polyalkylene oxide structure includes a polyethylene oxide structure and a polypropylene oxide structure.
  • planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 7>, wherein the resin having an ethylenically unsaturated group in the particles A is an addition polymerization type resin.
  • the resin having an ethylenically unsaturated group in the particles A has a structural unit formed of an aromatic vinyl compound.
  • the resin having an ethylenically unsaturated group in the particles A contains a structure obtained by at least reacting an isocyanate compound represented by the following formula (Iso) with water.
  • Iso isocyanate compound represented by the following formula (Iso) with water.
  • n represents an integer from 0 to 10.
  • the resin having an ethylenically unsaturated group in the particles A contains a structure obtained by at least reacting an isocyanate compound represented by the above formula (Iso) with water, and has a polyoxyalkylene structure.
  • the flat plate printing plate original plate according to ⁇ 10> which comprises a resin having a polyethylene oxide structure and a polypropylene oxide structure.
  • ⁇ 13> The planographic printing plate original plate according to ⁇ 12>, wherein the ethylenically unsaturated bond value of the image recording layer is 2.5 mmol / g or more.
  • the compound B contains a compound having a molecular weight of 2,500 or less, and the content of the compound having a molecular weight of 2,500 or less is 15% by mass to 80% by mass with respect to the total mass of the image recording layer.
  • ⁇ 1 The planographic printing plate original plate according to any one of> to ⁇ 13>.
  • ⁇ 15> The planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 14>, wherein the compound B contains a compound having an ethylenically unsaturated bond value of 5.0 mmol / g or more.
  • the compound having an ethylenically unsaturated bond value of 5.0 mmol / g or more has at least one structure selected from the group consisting of an adduct structure, a biuret structure, and an isocyanurate structure ⁇ 15> or ⁇ 16>
  • the original plate of the planographic printing plate ⁇ 18> The planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 14>, wherein the compound B contains a compound having one or two ethylenically unsaturated groups.
  • ⁇ 22> The planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 21>, wherein the layer on the aluminum support contains a hydroxycarboxylic acid or a salt thereof.
  • ⁇ 23> The planographic printing plate original plate according to ⁇ 22>, wherein the hydroxycarboxylic acid or a salt thereof contains a compound having two or more hydroxy groups.
  • ⁇ 24> The planographic printing plate original plate according to ⁇ 22> or ⁇ 23>, wherein the hydroxycarboxylic acid or a salt thereof contains a compound having three or more hydroxy groups.
  • ⁇ 25> The planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 24>, wherein the image recording layer further contains a polymerization initiator.
  • ⁇ 26> The lithographic printing plate original plate according to any one of ⁇ 1> to ⁇ 25>, wherein the image recording layer further contains an infrared absorber.
  • ⁇ 27> The image recording layer further contains an electron donating type polymerization initiator and an infrared absorber.
  • the infrared absorber has an organic anion having ⁇ d of 16 or more, ⁇ p of 16 to 32, and ⁇ h of 60% or less of ⁇ p in Hansen's solubility parameter ⁇ 26> or ⁇ 27.
  • the lithographic printing plate original plate described in. ⁇ 29> contains an electron-accepting polymerization initiator.
  • the electron-accepting polymerization initiator according to ⁇ 25>, wherein the electron-accepting polymerization initiator has an organic anion having a ⁇ d of 16 or more, a ⁇ p of 16 to 32, and a ⁇ h of 60% or less of the ⁇ p in the Hansen solubility parameter.
  • the above-mentioned polymerization initiator contains an electron-accepting polymerization initiator.
  • X represents a halogen atom and R 3 represents an aryl group.
  • ⁇ 31> The planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 30>, wherein the image recording layer further contains a color former.
  • ⁇ 32> The lithographic printing plate original plate according to ⁇ 31>, wherein the color former is an acid color former.
  • ⁇ 33> The lithographic printing plate original plate according to ⁇ 32>, wherein the acid color former is a leuco dye.
  • ⁇ 34> The planographic printing plate original plate according to ⁇ 33>, wherein the leuco dye is a leuco dye having a phthalide structure or a fluorine structure.
  • ⁇ 35> The planographic printing plate original plate according to ⁇ 34>, wherein the leuco dye having a phthalide structure or a fluorine structure is a compound represented by any of the following formulas (Le-1) to (Le-3).
  • ERG each independently represents an electron donating group
  • X 1 ⁇ X 4 are each independently a hydrogen atom, a halogen atom, or a dialkyl anilino
  • X 5 to X 10 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group
  • Y 1 and Y 2 each independently represent C or N
  • Y 1 represents a group. If it is N, then X 1 does not exist, if Y 2 is N, then X 4 does not exist, Ra 1 represents a hydrogen atom, an alkyl group or an alkoxy group, and Rb 1 to Rb 4 are.
  • ⁇ 36> The planographic plate according to ⁇ 34> or ⁇ 35>, wherein the leuco dye having the phthalide structure or the fluorine structure is a compound represented by any of the following formulas (Le-4) to (Le-6). Printed original plate.
  • ERG each independently represents an electron donating group
  • X 1 ⁇ X 4 are each independently a hydrogen atom, a halogen atom, or a dialkyl anilino Representing a group
  • Y 1 and Y 2 independently represent C or N, where X 1 does not exist when Y 1 is N and X 4 exists when Y 2 is N.
  • Ra 1 represents a hydrogen atom, an alkyl group, or an alkoxy group
  • Rb 1 to Rb 4 independently represent an alkyl group or an aryl group, respectively.
  • the leuco dye having the phthalide structure or the fluorine structure is any one of ⁇ 34> to ⁇ 36>, which is a compound represented by any of the following formulas (Le-7) to (Le-9).
  • X 1 ⁇ X 4 are each independently a hydrogen atom, a halogen atom, or a dialkyl anilino group
  • Y 1 and Y 2 are each independently , C or N, where X 1 does not exist when Y 1 is N, X 4 does not exist when Y 2 is N, and Ra 1 to Ra 4 are independent of each other.
  • Rb 1 to Rb 4 independently represent an alkyl group or an aryl group
  • Rc 1 and Rc 2 each independently represent an aryl group.
  • ⁇ 38> The lithographic printing plate original plate according to ⁇ 37>, wherein each of Ra 1 to Ra 4 is an alkoxy group independently.
  • ⁇ 39> The planographic printing plate original plate according to ⁇ 37>, wherein the leuco dye having the phthalide structure or the fluorine structure is a compound represented by the above formula (Le-8).
  • ⁇ 40> The planographic printing plate original plate according to ⁇ 39>, wherein X 1 to X 4 are hydrogen atoms and Y 1 and Y 2 are C in the formula (Le-8).
  • Rb 1 and Rb 2 are independently alkyl groups in the formula (Le-8).
  • ⁇ 42> The planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 41>, wherein the image recording layer further contains a binder resin having a structural unit formed of an aromatic vinyl compound.
  • ⁇ 43> The planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 41>, wherein the image recording layer further contains polyvinyl acetal as a binder resin.
  • ⁇ 44> The planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 43>, wherein the image recording layer further contains a fluoroaliphatic group-containing copolymer.
  • ⁇ 45> The lithographic printing plate according to ⁇ 44>, wherein the fluoroaliphatic group-containing copolymer has a structural unit formed of a compound represented by any of the following formulas (F1) and (F2). Original version.
  • R F1 independently represents a hydrogen atom or a methyl group
  • X independently represents an oxygen atom, a sulfur atom, or -N ( RF2 )-.
  • m represents an integer of 1 ⁇ 6
  • n represents an integer of 1 ⁇ 10
  • l represents an integer of 0 ⁇ 10
  • R F2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the fluoroaliphatic group-containing copolymer further has a structural unit formed by at least one compound selected from the group consisting of poly (oxyalkylene) acrylate and poly (oxyalkylene) methacrylate ⁇ 45.
  • the original plate of the lithographic printing plate described in. ⁇ 47> The planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 46>, wherein the water-soluble resin layer contains a hydrophobic resin.
  • ⁇ 48> The planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 47>, wherein the water-soluble resin layer contains a discoloring compound.
  • planographic printing plate original plate according to ⁇ 48> wherein the discoloring compound is an infrared absorber.
  • ⁇ 50> The lithographic printing plate original plate according to ⁇ 48> or ⁇ 49>, wherein the discoloring compound contains a decomposable compound that decomposes due to infrared exposure.
  • ⁇ 51> The planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 50>, wherein the thickness of the water-soluble resin layer is 20% or more with respect to the thickness of the image recording layer.
  • the aluminum support has an aluminum plate and an anodized film of aluminum arranged on the aluminum plate.
  • the anodized film is located closer to the image recording layer than the aluminum plate.
  • the anodized film has micropores extending in the depth direction from the surface on the image recording layer side.
  • the average diameter of the micropores on the surface of the anodized film is more than 10 nm and 100 nm or less.
  • the micropore communicates with the large-diameter hole extending from the surface of the anodized film to a depth of 10 nm to 1,000 nm and the bottom of the large-diameter hole, and has a depth of 20 nm to 2 from the communicating position. It is composed of a small-diameter hole that extends to the position of 000 nm.
  • the average diameter of the large-diameter pore portion on the surface of the anodized film is 15 nm to 100 nm.
  • ⁇ 54> The step of exposing the planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 53> like an image, and A step of supplying at least one selected from the group consisting of printing ink and dampening water to the lithographic printing plate original plate after exposure to remove the image recording layer of the non-image portion on the printing machine.
  • a method for producing a lithographic printing plate including.
  • ⁇ 55> The step of exposing the planographic printing plate original plate according to any one of ⁇ 1> to ⁇ 53> like an image, and At least one selected from the group consisting of printing ink and dampening water is supplied to the lithographic printing plate original plate after exposure, and the image recording layer of the non-image portion is removed on the printing machine to prepare a lithographic printing plate.
  • Process and The process of printing with the produced lithographic printing plate and Planographic printing methods including.
  • a lithographic printing plate original plate capable of obtaining a lithographic printing plate having high sensitivity and excellent printing resistance.
  • a method for producing a lithographic printing plate or a lithographic printing method having excellent printing resistance it is possible to provide a method for producing a lithographic printing plate or a lithographic printing method having excellent printing resistance.
  • FIG. 3 is a schematic cross-sectional view of another embodiment of an aluminum support. It is a graph which shows an example of the alternating current waveform diagram used for the electrochemical roughening process in the manufacturing method of an aluminum support. It is a side view which shows an example of the radial type cell in the electrochemical roughening treatment using alternating current in the manufacturing method of an aluminum support. It is the schematic of the anodizing treatment apparatus used for the anodizing treatment in the manufacturing method of the aluminum support which has an anodic oxide film.
  • the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • (meth) acrylic is a term used in a concept that includes both acrylic and methacrylic
  • "(meth) acryloyl” is a term that is used as a concept that includes both acryloyl and methacryloyl. is there.
  • each component in the composition or each structural unit in the polymer may be contained alone or in combination of two or more. ..
  • the amount of each component in the composition or each structural unit in the polymer includes a plurality of substances or structural units corresponding to each component or each structural unit in the polymer in the composition. In the case, unless otherwise specified, it means the total amount of the plurality of applicable substances present in the composition or the plurality of applicable constituent units present in the polymer. Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
  • weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure unless otherwise specified, columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all of which are trade names of tetrahydrofuran Co., Ltd.) were used. It is a molecular weight converted by detecting with a solvent THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analyzer and using polystyrene as a standard substance.
  • THF tetrahydrofuran
  • GPC gel permeation chromatography
  • the median diameter of the resin particles in the present disclosure refers to a value measured by the light scattering method unless otherwise specified, and the median diameter refers to the larger side and the smaller when the powder is divided into two from a certain particle size. Refers to diameters with the same number of sides.
  • the median diameter of the resin particles is measured by the light scattering method using LA-920 (HORIBA, Ltd.) according to the manual of the above-mentioned equipment.
  • the term "lithographic printing plate original” includes not only a lithographic printing plate original but also a discarded plate original. Further, the term “lithographic printing plate” includes not only a lithographic printing plate produced by subjecting a lithographic printing plate original plate through operations such as exposure and development as necessary, but also a discarded plate. In the case of a discarded original plate, exposure and development operations are not always necessary.
  • the discard plate is a planographic printing plate original plate for attaching to an unused plate cylinder when printing a part of the paper surface in a single color or two colors in, for example, color newspaper printing.
  • "*" in the chemical structural formula represents a bonding position with another structure.
  • the lithographic printing plate original plate according to the present disclosure has an aluminum support, an image recording layer, and a water-soluble resin layer in this order, and the image recording layer contains a resin having an ethylenically unsaturated group and has an ethylenically unsaturated bond.
  • particles A containing a resin having an ethylenically unsaturated group and having an ethylenically unsaturated bond value of 0.10 mmol / g or more are also referred to as “specific particles A” and are ethylenically contained in the specific particles A.
  • a resin having an unsaturated group is also referred to as "specific resin RA”.
  • the compound B having an ethylenically unsaturated group other than the particles A is also referred to as “specific compound B”.
  • the lithographic printing plate original plate according to the present disclosure is preferably a negative type lithographic printing plate original plate. Further, the lithographic printing plate original plate according to the present disclosure can be suitably used as an on-machine development type lithographic printing plate original plate.
  • the machine-developed lithographic printing plate original plate means a lithographic printing plate original plate that can be developed by the machine-developing method described later.
  • the ethylenically unsaturated bond value of the specific particle A in the present disclosure refers to the amount [mmol] of the ethylenically unsaturated group per 1 g of the specific particle A.
  • the ethylenically unsaturated bond value of the specific particle A in the present disclosure is based only on the amount of the ethylenically unsaturated group introduced into the specific particle A from the resin having an ethylenically unsaturated group (that is, the specific resin RA). Desired.
  • the amount of the ethylenically unsaturated bond group contained in this monomer is the ethylenically unsaturated of the resin particles A. It is not included in the amount of ethylenically unsaturated bond groups when determining the bond value.
  • the planographic printing plate original plate according to the present disclosure contains a specific particle A and a compound having an ethylenically unsaturated group other than the specific particle A (that is, the specific compound B) in the image recording layer.
  • the specific particles A are particles containing a resin having an ethylenically unsaturated group and having an ethylenically unsaturated bond value of 0.10 mmol / g or more.
  • the specific particle A is more ethylenic than the particles conventionally used in the image recording layer (for example, the particles used in JP-A-2006-188038 and JP-A-08-190197 described above). Resin particles having an unsaturated group. Therefore, in the image recording layer containing the specific particles A and the specific compound B, the polymerization reaction between the specific particles A and the polymerization reaction between the specific particles A and the specific compound B are promoted, and the image having high film strength is promoted. It is considered that a part is formed.
  • the image recording layer has a layer structure protected by a water-soluble resin layer
  • the water-soluble resin layer is used. Since oxygen blocking property is added, it is presumed that a lithographic printing plate having excellent sensitivity and excellent printing resistance can be obtained in combination with these.
  • the particles used in JP-A-2006-188038 and JP-A-08-190197 described above have no or few ethylenically unsaturated groups, and therefore have the above-mentioned "high sensitivity and high sensitivity". , A lithographic printing plate with excellent printing resistance can be obtained. ”It is considered that it is difficult to achieve the effect.
  • the lithographic printing plate original plate according to the present disclosure has an image recording layer containing specific particles A and specific compound B.
  • the image recording layer in the present disclosure is preferably a negative type image recording layer in which a cured portion is formed by the reaction with the specific particles A and the specific compound B.
  • the image recording layer in the present disclosure preferably has a non-cured portion (for example, an unexposed portion) that can be removed by at least one of dampening water and printing ink.
  • the image recording layer in the present disclosure preferably has an ethylenically unsaturated bond value of 1.5 mmol / g or more, preferably 2.0 mmol / g or more, from the viewpoint of improving sensitivity and obtaining excellent printing resistance. More preferably, it is more preferably 2.5 mmol / g or more, and particularly preferably 3.0 mmol / g or more.
  • the upper limit of the ethylenically unsaturated bond value of the image recording layer is not particularly limited, and is, for example, 10.0 mmol / g or less.
  • the image recording layer in the present disclosure preferably contains a polymerization initiator, an infrared absorber, and the like from the viewpoint of printing resistance and photosensitivity, and further components. May include.
  • the specific particles A in the present disclosure contain a resin having an ethylenically unsaturated group (that is, the specific resin RA) and have an ethylenically unsaturated bond value of 0.10 mmol / g or more.
  • the specific particle A preferably contains the specific resin RA in an amount of 80% by mass or more, preferably 90% by mass or more, based on the total mass of the specific particle A from the viewpoint of improving the sensitivity and obtaining excellent printing resistance. It is more preferably 95% by mass or more, and particularly preferably 100% by mass. That is, it is particularly preferable that the specific particles A are particles made of the specific resin RA.
  • the upper limit of the content of the specific resin RA is not particularly limited, and may be 100% by mass or less.
  • the ethylenically unsaturated bond value in the specific particle A refers to the amount [mmol] of the ethylenically unsaturated group per 1 g of the specific particle A.
  • the ethylenically unsaturated valency of the specific particles A is 0.10 mmol / g or more, preferably 0.5 mmol / g or more, and more preferably 1.00 mmol / g or more.
  • the ethylenically unsaturated bond value of the specific particle A is preferably 2.00 mmol / g or more, more preferably 2.2 mmol / g or more, and 2.4 mmol. / G or more is more preferable.
  • the upper limit of the ethylenically unsaturated valency of the specific particles A is, for example, 5.0 mmol / g.
  • the ethylenically unsaturated valency of the specific particles A can be determined by the following method.
  • thermo decomposition gas chromatography-mass spectrometry thermal decomposition gas chromatography-mass spectrometry
  • NMR nuclear magnetic resonance spectroscopy
  • FT-IR Fourier transform infrared red Using external spectroscopy
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the specific resin RA constituting the specific particles A is not particularly limited as long as it is a resin having an ethylenically unsaturated group in the molecule, and may be an addition polymerization type resin or a polycondensation type resin. A heavy addition type resin may be used, but an addition polymerization type resin is preferable from the viewpoint of obtaining excellent printing resistance.
  • the specific resin RA in the present disclosure preferably has a crosslinked structure from the viewpoint of increasing the hardness of the specific particles A.
  • the addition polymerization type resin as the specific resin RA is preferably a resin obtained by polymerizing an ethylenically unsaturated compound from the viewpoint of ease of production, and is monofunctional with a polyfunctional ethylenically unsaturated compound.
  • a resin obtained by copolymerizing with an ethylenically unsaturated compound is more preferable.
  • the specific resin RA has at least an ethylenically unsaturated group.
  • the specific resin RA is preferably a resin having a structural unit having an ethylenically unsaturated group from the viewpoint of achieving the ethylenically unsaturated bond value in the above-mentioned specific particles A.
  • the ethylenically unsaturated group contained in the specific resin RA is not particularly limited, and examples thereof include a (meth) acrylic group, an allyl group, a vinylphenyl group, a vinyl ether group, and a vinyl ester group.
  • a (meth) acrylic group is preferable from the viewpoint of reactivity, and more specifically, a (meth) acryloyl group and a (meth) acrylamide group are preferable, and a (meth) acryloyl group is preferable. Is the most preferable.
  • the specific resin RA may have only one type of ethylenically unsaturated group or two or more types.
  • Specific resin RA1- which is an addition polymerization type resin
  • specific resin RA1 also referred to as “specific resin RA1”
  • a method for introducing an ethylenically unsaturated group into the specific resin RA1 a method of using a polyfunctional monomer having two or more ethylenically unsaturated groups during resin synthesis and leaving an ethylenically unsaturated group after resin synthesis (1).
  • a method (2) of introducing an ethylenically unsaturated group by a polymer reaction after resin synthesis is preferable in the present disclosure.
  • the resin into which the ethylenically unsaturated group is introduced may be a resin having no ethylenically unsaturated group, or the amount of the ethylenically unsaturated group is less than the target amount. It may be a resin.
  • the structural unit having an ethylenically unsaturated group in the specific resin RA1 is not particularly limited, and examples thereof include a structural unit represented by the following formula D1.
  • L D1 represents a single bond or a divalent linking group
  • L D2 represents m + 1 valent connecting group
  • X D1 is -O- or -NR N - represents
  • R N represents a hydrogen atom or an alkyl
  • RD1 represents a hydrogen atom or a methyl group
  • RD represents an ethylenically unsaturated group
  • m represents an integer of 1 or more.
  • L D1 represents a divalent linking group, an alkylene group, an arylene group, or a divalent group in which two or more are bonded thereof
  • an alkylene group having 2 to 10 carbon atoms, or a phenylene group More preferred.
  • the LD1 is preferably a single bond.
  • the m + 1 valent linking group represented by L D2 is preferably a linking group containing any of the groups of the following formulas D2 to D6, and is any of the following formulas D2 to D6.
  • a linking group in which a group or a group of any of the following formulas D2 to D6 is bonded to one or more of the groups selected from the group consisting of an ester bond, an alkylene group, and an alkyleneoxy group is more preferable.
  • L D3 to L D7 represent divalent linking groups
  • L D5 and L D6 may be the same or different
  • X D5 is -O- or -NR N- .
  • R N represents a hydrogen atom or an alkyl group
  • R D in the formulas D1 represents the binding site to the wavy line part and the X D2 in the formula D1 Represents the binding site of.
  • LD3 is preferably an alkylene group, an arylene group, or a group in which two or more of these are bonded, and is an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a group in which two or more of these are bonded. Is more preferable.
  • LD4 is preferably an alkylene group, an arylene group, or a group in which two or more of these are bonded, and is an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a group in which two or more of these are bonded. Is more preferable.
  • LD5 is preferably an alkylene group, an arylene group, or a group in which two or more of these are bonded, and is an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a group in which two or more of these are bonded. Is more preferable.
  • X D5 is preferably —O— or —NH—.
  • LD6 is preferably an alkylene group, an arylene group, or a group in which two or more of these are bonded, and is an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a group in which two or more of these are bonded. Is more preferable.
  • LD7 is preferably an alkylene group, an arylene group, or a group in which two or more of these are bonded, and is an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a group in which two or more of these are bonded. Is more preferable.
  • X D1 is -NR N - when referring to, R N is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom. Further, X D1 is preferably —O—.
  • RD1 is preferably a methyl group.
  • at least one of m R D2 is preferably a methyl group.
  • m is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • the ethylenically unsaturated group represented by RD has the same meaning as the ethylenically unsaturated group possessed by the above-mentioned specific resin RA, and among them, the group represented by the following formula D7 is preferable. ..
  • X D2 is -O- or -NR N - represents, R N represents a hydrogen atom or an alkyl group.
  • R D2 represents a hydrogen atom or a methyl group.
  • m is synonymous with m in formula D1, and preferred embodiments are also the same. It is preferable that at least one of the m R D2s is a methyl group.
  • X D2 in the formula D7 is preferably —O— with X D1 .
  • the number of atoms between the ethylenically unsaturated group (for example, (meth) acryloxy group) and the main chain of the addition polymerization type resin is preferably 50 to 300, preferably 69 to 278. It is preferably 135 to 278, and more preferably 135 to 278.
  • the structural unit having an ethylenically unsaturated group (preferably the structural unit represented by the formula D1) is a specific resin RA1 by a method of introducing an ethylenically unsaturated group by a polymer reaction after resin synthesis. It is preferable to be introduced in.
  • a method for introducing an ethylenically unsaturated group by a polymer reaction after resin synthesis will be described.
  • the structural unit having an ethylenically unsaturated group is, for example, a reaction of a compound having an epoxy group and an ethylenically unsaturated group (for example, glycidyl methacrylate) with a polymer containing a structural unit having a carboxy group such as methacrylate. Reaction of a compound having an isocyanate group and an ethylenically unsaturated group (for example, 2-isocyanatoethyl methacrylate) with a polymer containing a structural unit having a group having an active hydrogen such as a hydroxy group and an amino group. It can be introduced into the specific resin RA1 by a method or the like.
  • the structural unit having a carboxy group or the structural unit having a group having an active hydrogen may remain in the specific resin RA1.
  • the structural unit having the carboxy group and the structural unit having the group having the active hydrogen are also generally referred to as "constituent units before the reaction", and these are after the ethylenically unsaturated group is introduced.
  • the structural unit of is also referred to as "constituent unit after reaction”.
  • the structural unit before the reaction corresponds to the structural unit having a hydrophilic structure described later
  • the structural unit having an ethylenically unsaturated group and the hydrophilic structure (here, a carboxy group) can be adjusted by adjusting the reaction rate. , Amino group, etc.) may be obtained together with the specific resin RA1.
  • the reaction rate is, for example, preferably 10% or more and 100% or less, and more preferably 30% or more and 70% or less.
  • the reaction rate is a value defined by the following formula R.
  • Formula R Reaction rate (number of moles of structural units after reaction in the obtained addition polymerization type resin / total number of moles of structural units before reaction in the obtained addition polymerization type resin) ⁇ 100
  • the structural unit having an ethylenically unsaturated group is specified by a method of reacting a polymer containing a structural unit having an epoxy group such as glycidyl (meth) acrylate with a compound having a carboxy group and an ethylenically unsaturated group. It may be introduced into the resin RA1.
  • the structural unit having an ethylenically unsaturated group is made into the specific resin RA1 by, for example, a method of reacting a basic compound with a polymer containing a structural unit having a partial structure represented by the following formula d1 or the following formula d2. It may be introduced.
  • an ethylenically unsaturated group is formed by the elimination reaction of the partial structure represented by the following formula d1 or the following formula d2, so that a structural unit having an ethylenically unsaturated group is introduced into the specific resin RA1. Will be done.
  • R d represents a hydrogen atom or an alkyl group
  • a d represents a halogen atom
  • X d is -O- or -NR N - represents
  • R N represents a hydrogen atom or an alkyl group
  • R d is preferably a hydrogen atom or a methyl group.
  • a d is a chlorine atom, a bromine atom, or preferably a iodine atom.
  • X d is preferably —O—.
  • X d is -NR N - when referring to, R N is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom.
  • the content of the structural unit having an ethylenically unsaturated group in the specific resin RA1 is 10 mass by mass with respect to the total mass of the specific resin RA1 (that is, the addition polymerization type resin) from the viewpoint of improving sensitivity and obtaining excellent printing resistance. It is preferably% to 70% by mass, more preferably 20% by mass to 70% by mass, further preferably 20% by mass to 60% by mass, and further preferably 20% by mass to 50% by mass. Especially preferable.
  • the specific resin RA1 preferably has a crosslinked structure in the molecule.
  • the crosslinked structure is not particularly limited, but is a specific resin as a structural unit formed by polymerizing a polyfunctional ethylenically unsaturated compound or a structural unit in which one or more reactive groups form a covalent bond in the resin. It is preferably introduced into RA1.
  • the functional number of the polyfunctional ethylenically unsaturated compound is preferably 2 to 15, more preferably 3 to 10, and 4 to 10 from the viewpoint of improving sensitivity and obtaining excellent printing resistance. It is more preferably present, and particularly preferably 5 to 10.
  • the structural unit having a crosslinked structure is preferably a bifunctional to 15-functional branched unit from the viewpoint of improving sensitivity and obtaining excellent printing resistance, and is preferably a trifunctional to 10-functional unit. It is more preferably a sex branching unit, further preferably a tetrafunctional to 10-functional bifurcation unit, and particularly preferably a pentafunctional to 10-functional bifurcation unit.
  • the n-functional branching unit refers to a branching unit in which n molecular chains appear, in other words, a structural unit having an n-functional bifurcation point (that is, a crosslinked structure).
  • the ethylenically unsaturated group in the polyfunctional ethylenically unsaturated compound is not particularly limited, and examples thereof include a (meth) acryloxy group, a (meth) acrylamide group, an aromatic vinyl group, and a maleimide group.
  • the polyfunctional ethylenically unsaturated compound is preferably a polyfunctional (meth) acrylate compound, a polyfunctional (meth) acrylamide compound, or a polyfunctional aromatic vinyl compound.
  • polyfunctional (meth) acrylate compound examples include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, 1,4-butanediol diacrylate, and 1,6.
  • -Hexanediol diacrylate polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane dimethyloldiacrylate, trimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol triacrylate, dipentaerythritol hexa.
  • examples thereof include acrylate and triacrylate of tris ( ⁇ -hydroxyethyl) isocyanurate.
  • the polyfunctional (meth) acrylamide compound include N, N'-methylenebisacrylamide, N- [tris (3-acrylamide propoxymethyl) methyl] acrylamide and the like.
  • the polyfunctional aromatic vinyl compound include divinylbenzene and the like.
  • the number of carbon atoms of the structural unit having a crosslinked structure is not particularly limited, but is preferably 8 to 100, and more preferably 8 to 70.
  • the structural unit having a crosslinked structure at least one selected from the group consisting of the structural units represented by the following BR-1 to BR-17 from the viewpoint of obtaining UV print resistance, improvement of sensitivity and excellent print resistance. Species building blocks are preferred. It is more preferable that the structural unit having a crosslinked structure includes at least one structural unit selected from the group consisting of the structural units represented by the following BR-1 to BR-10 or BR-13 to BR-17. At least one structural unit selected from the group consisting of the structural units represented by the following BR-1 to BR-7 or BR-13 to BR-17 is more preferable, and the structural unit represented by the following BR-1 is particularly preferable. preferable.
  • R BR independently represents a hydrogen atom or a methyl group
  • n represents an integer of 1 to 20.
  • the content of the structural unit having a crosslinked structure in the specific resin RA1 is 1% by mass to 30% by mass with respect to the total mass of the specific resin RA1 (that is, the addition polymerization type resin) from the viewpoint of improving the sensitivity and obtaining excellent printing resistance. It is preferably by mass%, more preferably 3% by mass to 20% by mass, further preferably 5% by mass to 15% by mass, and particularly preferably 5% by mass to 15% by mass.
  • the specific resin RA1 preferably has a hydrophilic structure in the molecule.
  • the specific resin RA1 preferably contains a structural unit having a hydrophilic structure from the viewpoint of easily controlling the amount of the hydrophilic structure introduced.
  • the specific resin RA1 has a hydrophilic structure, and in addition to improving sensitivity and obtaining excellent printing resistance, it has on-machine developability, on-machine development residue suppression property, and dispersion stability of specific particles A (particularly in water). From the viewpoint of dispersion stability), it is preferable to have an ionic group or an acid group, and it is more preferable to have an ionic group.
  • an ionic group refers to a group that can be dissociated into an anion or a cation at least in part in water.
  • the specific resin RA1 more preferably has a sulfonic acid base (salt of a sulfonic acid group) or a sulfonic acid group as a hydrophilic structure from the viewpoint of dispersion stability of the specific particles A in water.
  • the specific resin RA1 has a hydrophilic structure, and in addition to improving sensitivity and obtaining excellent printing resistance, it has on-machine developability, on-machine development residue suppression property, and dispersion stability of specific particles A (particularly organic).
  • the specific resin RA1 has an ion as a hydrophilic structure from the viewpoints of improving sensitivity and obtaining excellent printing resistance, as well as on-machine developability, on-machine development residue suppression property, and particle dispersion stability. It is particularly preferable to have a sex group or an acid group and a polyalkylene oxide structure.
  • the acid group is a sulfonic acid group, a carboxylic acid group, or a phosphoric acid group from the viewpoints of on-machine developability, on-machine development residue suppression property, and particle dispersion stability (particularly dispersion stability in water).
  • a sulfate monoester group is preferable, a sulfonic acid group or a carboxylic acid group is more preferable, and a carboxylic acid group is particularly preferable.
  • an ionic group a group that dissociates a counter ion to generate an anion from the viewpoints of on-machine developability, on-machine development residue suppression property, and particle dispersion stability (particularly dispersion stability in water).
  • anionic group a salt of an acid group is more preferable, specifically, a sulfonic acid base, a carboxylic acid base, or a sulfate monoester base is more preferable, and a carboxylic acid base is particularly preferable.
  • the counter cation in the salt of the acid group may be an inorganic cation or an organic cation, but is preferably an inorganic cation.
  • the counter cation may be not only a monovalent cation but also a multivalent cation, but a monovalent cation is preferable.
  • the inorganic cation alkali metal ion or alkaline earth metal ion is more preferable, alkali metal ion is more preferable, and specifically, lithium ion, sodium ion, or potassium ion is particularly preferable.
  • the organic cation include a quaternary ammonium cation and a cation obtained by alkylating a nitrogen atom of an aromatic nitrogen-containing heterocycle.
  • Examples of the quaternary ammonium cation include tetramethylammonium cation, tetraethylammonium cation and dimethylbenzylammonium cation.
  • Examples of the cation obtained by alkylating the nitrogen atom of the aromatic nitrogen-containing heterocycle include a pyridinium cation.
  • an alkali metal ion or a quaternary ammonium cation is preferable, and an alkali metal ion is particularly preferable.
  • the polyalkylene oxide structure may be a polyethylene oxide structure, a polypropylene oxide structure, or a poly (ethylene oxide / propylene oxide) structure from the viewpoint of the dispersion stability of the specific particles A, particularly the dispersion stability in an organic solvent. It is preferable to have. Further, from the viewpoint of on-machine developability and developing residue suppressing property during on-machine development, the polyalkylene oxide structure preferably contains a polypropylene oxide structure, and includes a polyethylene oxide structure and a polypropylene oxide structure. Is more preferable.
  • the number of alkylene oxide structures in the polyalkylene oxide structure is preferably 2 or more, more preferably 5 or more, from the viewpoint of the dispersion stability of the specific particles A, particularly the dispersion stability in an organic solvent. It is more preferably 5 to 200, and particularly preferably 8 to 150.
  • the polyester structure is not particularly limited, but a ring-opening polymer chain of lactone and a polycondensation chain of hydroxycarboxylic acid are preferably mentioned.
  • the number of hydroxycarboxylic acid structures (or ring-opening structures of lactones) in the polyester structure is preferably 2 or more, preferably 2 to 20, from the viewpoint of dispersion stability of particles, particularly dispersion stability in organic solvents. More preferably, it is more preferably 2 to 10, and particularly preferably 4 to 10.
  • the specific resin RA1 preferably has a structural unit represented by the following formula A-1 as a structural unit having an ionic group or an acid group having a hydrophilic structure.
  • X 1 represents -O- or -NR 3-
  • L 1 represents a divalent linking group having 1 to 20 carbon atoms
  • R 1 represents an ionic group or an acid group
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents a hydrogen atom, an alkyl group, or an aryl group.
  • the ionic group or acid group represented by R 1 is the same as the ionic group or acid group in the above-mentioned hydrophilic structure, and the preferred example is also the same.
  • X 1 is preferably —O—.
  • L 1 is preferably a divalent linking group having 2 to 10 carbon atoms, more preferably a divalent linking group having 2 to 8 carbon atoms, and having 2 to 8 carbon atoms. It is more preferably an alkylene group, and particularly preferably an alkylene group having 2 to 5 carbon atoms.
  • the divalent linking group is specifically an alkylene group or a group in which one or more alkylene groups are bonded to one or more of at least one structure selected from the group consisting of an ether bond and an ester bond. Is preferable, and it is more preferable that it is an alkylene group.
  • R 3 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and more preferably a hydrogen atom.
  • the addition polymerization type resin preferably has a structural unit represented by the following formula A-3 or A-4 as a structural unit having a polyalkylene oxide structure or a polyester structure having a hydrophilic structure, and the following formula A It is more preferable to have a structural unit represented by -3.
  • L 2 represents an ethylene group or a propylene group
  • L 3 represents an alkylene group having 2 to 10 carbon atoms
  • L 4 represents an alkylene group having 1 to 10 carbon atoms.
  • R 4 and R 6 independently represent a hydrogen atom, an alkyl group, or an aryl group
  • R 5 and R 7 each independently represent a hydrogen atom or a methyl group
  • m1 represents an integer of 2 to 200.
  • m2 represents an integer of 2 to 20.
  • L 2 is preferably an ethylene group or a 1,2-propylene group.
  • L 3 is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group.
  • L 4 is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 3 to 8 carbon atoms, an alkylene group having 4-6 carbon atoms Is more preferable.
  • R 4 and R 6 are preferably hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or phenyl groups, respectively, and are hydrogen atoms or 1 to 4 carbon atoms, respectively. It is preferably an alkyl group of 4, and more preferably a hydrogen atom or a methyl group.
  • m1 is preferably an integer of 5 to 200, and more preferably an integer of 8 to 150.
  • m2 is preferably an integer of 2 to 10, and more preferably an integer of 4 to 10.
  • the specific resin RA1 has a structural unit represented by the above formula A-1 and the above formula A-3 or the above formula A-4 from the viewpoints of on-machine developability, on-machine development residue suppression property, and particle dispersion stability. It is particularly preferable to have a structural unit represented by the above formula, and most preferably to have a structural unit represented by the above formula A-1 and a structural unit represented by the above formula A-3.
  • the specific resin RA1 preferably has a group represented by the following formula Z as a hydrophilic structure from the viewpoint of on-machine developability, on-machine development residue suppression property, and dispersion stability of the specific particles A.
  • * -Q-W-Y formula Z In formula Z, Q represents a divalent linking group, W represents a divalent group having a hydrophilic structure or a divalent group having a hydrophobic structure, and Y represents a monovalent group having a hydrophilic structure or It represents a monovalent group having a hydrophobic structure, and * represents a binding site with another structure.
  • Q is preferably a divalent linking group having 1 to 20 carbon atoms, and more preferably a divalent linking group having 1 to 10 carbon atoms.
  • the divalent linking group represented by Q is preferably an alkylene group, an arylene group, an ester bond, an amide bond, or a group in which two or more of these are combined, and is a phenylene group, an ester bond, or an amide bond. Is more preferable.
  • the divalent group having a hydrophilic structure represented by W is a polyalkyleneoxy group or a group in which -CH 2 CH 2 NR W- is bonded to one end of a polyalkyleneoxy group.
  • R W represents a hydrogen atom or an alkyl group.
  • each RWA independently has a linear, branched or cyclic alkylene group having 6 to 120 carbon atoms, a haloalkylene group having 6 to 120 carbon atoms, an arylene group having 6 to 120 carbon atoms, or 6 carbon atoms. Represents ⁇ 120 aralkylene groups.
  • R W is as defined above R W.
  • R W is as defined above R W.
  • RWB represents an alkyl group having 6 to 20 carbon atoms.
  • the content of the structural unit having a hydrophilic structure in the specific resin RA1 is the specific resin RA1 (that is, the addition polymerization type resin) from the viewpoint of on-machine developability, on-machine development mass suppression property, and dispersion stability of the specific particles A. It is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 20% by mass, and further preferably 5% by mass to 15% by mass, based on the total mass of 5% by mass. It is particularly preferably from 10% by mass.
  • the content of the structural unit having an ionic group in the specific resin RA1 is the on-machine developability, the on-machine development mass inhibitory property, and the dispersion stability of the specific particles A. From the above viewpoint, it is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 20% by mass, and 5% by mass with respect to the total mass of the specific resin RA1 (that is, the addition polymerization type resin). It is more preferably to 15% by mass, and particularly preferably to 5% by mass to 10% by mass.
  • the specific resin RA1 has a structural unit having an ethylenically unsaturated bond, a structural unit having a crosslinked structure, and a structural unit other than the structural unit having a hydrophilic structure (also referred to as other structural units) as described above. You may be.
  • the compound (that is, monomer) forming the other structural unit include an aromatic vinyl compound, a (meth) acrylate compound, a (meth) acrylonitrile compound, a (meth) acrylamide compound, an N-vinyl heterocyclic compound, a vinyl halide compound, and vinyl.
  • Monofunctional ethylenically unsaturated compounds such as ester compounds, vinyl ether compounds and ⁇ -olefin compounds are preferably mentioned.
  • Specific examples of the compound (that is, monomer) forming the other structural unit include styrene, methyl methacrylate, acrylonitrile, methacrylonitrile, N, N-dimethylacrylamide, 2-hydroxyethyl acrylate, and 2,3-dihydroxy.
  • propyl methacrylate, 2-ethylhexyl methacrylate, acryloyl morpholine, diacetone acrylamide, N-isopropylacrylamide, cyclohexyl methacrylate, acryloxymethylethylene carbonate, pt-butylstyrene, methacrylicamide, N-vinylpyrrolidone and the like can be mentioned. ..
  • the specific resin RA1 is a structural unit derived from an aromatic vinyl compound such as styrene, a structural unit derived from an acrylonitrile compound such as acrylonitrile, and a structural unit derived from an N-vinyl heterocyclic compound such as N-vinylpyrrolidone. It is more preferable to have at least one structural unit selected from the group consisting of (meth) acrylate compounds such as 2-hydroxyethyl acrylate, and to have a structural unit derived from acrylonitrile and a structural unit derived from styrene. Is particularly preferable.
  • the structural unit formed of the aromatic vinyl compound the structural unit represented by the following formula A1 is preferably mentioned.
  • R A1 and R A2 each independently represent a hydrogen atom or an alkyl group
  • Ar represents an aromatic ring group
  • R A3 represents a substituent
  • n represents the maximum number of substituents below integer Ar Represent.
  • RA1 and RA2 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and both are hydrogen atoms. Is even more preferable.
  • Ar is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
  • RA3 is preferably an alkyl group or an alkoxy group, more preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and it is a methyl group or a methoxy group. Is more preferable.
  • n is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • the aromatic vinyl compound for obtaining the above-mentioned structural unit may be a compound having a structure in which a vinyl group is bonded to an aromatic ring, and examples thereof include styrene compounds and vinylnaphthalene compounds. Styrene compounds are preferable, and styrene is preferable. More preferred. Examples of the styrene compound include styrene, p-methylstyrene, p-methoxystyrene, ⁇ -methylstyrene, p-methyl- ⁇ -methylstyrene, ⁇ -methylstyrene, p-methoxy- ⁇ -methylstyrene and the like. Styrene is preferred.
  • vinylnaphthalene compound examples include 1-vinylnaphthalene, methyl-1-vinylnaphthalene, ⁇ -methyl-1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene and the like.
  • -Vinylnaphthalene is preferably mentioned.
  • the structural unit formed by the acrylonitrile compound the structural unit represented by the following formula B1 is preferably mentioned.
  • RB1 represents a hydrogen atom or an alkyl group.
  • RB1 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
  • Examples of the acrylonitrile compound for obtaining the above-mentioned structural unit include (meth) acrylonitrile, and acrylonitrile is preferably mentioned.
  • the structural unit formed by the N-vinyl heterocyclic compound As the structural unit formed by the N-vinyl heterocyclic compound, the structural unit represented by the following formula C1 is preferably mentioned.
  • Ar N represents a heterocyclic structure containing a nitrogen atom, a nitrogen atom in Ar N is bonded to the carbon atoms indicated by *.
  • the heterocyclic structure represented by Ar N is preferably a pyrrolidone ring, a carbazole ring, a pyrrole ring, a phenothiazine ring, a succinimide ring, a phthalimide ring, a caprolactam ring, and an imidazolid ring, and is preferably a pyrrolidone ring. Is more preferable.
  • the heterocyclic structure represented by Ar N may have a known substituent.
  • N-vinyl heterocyclic compound for obtaining the above-mentioned structural unit examples include N-vinylpyrrolidone, N-vinylcarbazole, N-vinylpyrrole, N-vinylphenothiazine, N-vinylsuccinimide, N-vinylphthalimide, and N.
  • -Vinyl caprolactam and N-vinyl imidazole are mentioned, and N-vinylpyrrolidone is preferable.
  • the specific resin RA1 may or may not have other constituent units of one kind alone, two or more kinds, or not.
  • the content of other structural units in the specific resin RA1 is 10% by mass with respect to the total mass of the specific resin RA1 (that is, the addition polymerization type resin) from the viewpoint of improving printing resistance, sensitivity, on-machine developability, and the like. It is preferably ⁇ 70% by mass, more preferably 20% by mass to 70% by mass, further preferably 20% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass. preferable.
  • Specific examples of the specific resin RA1 include resins (1), (5), (7), (9) to (17) synthesized in [Example] described later, and the specific resin RA1 is these. It is not limited to.
  • the method for synthesizing the specific particles A containing the specific resin RA1 is not particularly limited as long as it is a method for synthesizing the particles containing the specific resin RA1 and capable of achieving the ethylenically unsaturated bond value described above.
  • an emulsion polymerization method or the like for example, an emulsion polymerization method or the like.
  • resin particle synthesis methods such as suspension polymerization method, dispersion polymerization method, phase inversion emulsification method, soap-free emulsification polymerization method, and microemulsion polymerization method are used.
  • the specific resin is specified from the viewpoint of ease of particle synthesis and synthetic margin, and from the viewpoint of controlling the dispersibility of the specific particle A (particularly the dispersibility in water), the particle size, etc., which will be described later.
  • a method for synthesizing the specific particles A containing RA1 it is preferable to use an emulsion polymerization method.
  • a method for synthesizing the specific particles A containing the specific resin RA1 for example, a method of using a polyfunctional monomer having two or more ethylenically unsaturated groups at the time of particle synthesis and leaving the ethylenically unsaturated groups after the particle synthesis (1).
  • a method (') and a method (2') of introducing an ethylenically unsaturated group by a polymer reaction after particle synthesis but the latter method (2') is preferable in the present disclosure.
  • the particles into which the ethylenically unsaturated group is introduced may be particles containing a resin having no ethylenically unsaturated group, or the ethylenically unsaturated group is the target. The particles may contain less resin than the amount.
  • the specific particle More ethylenically unsaturated groups can be introduced on the surface of A.
  • the above-mentioned structural unit having a carboxy group such as methacrylic acid or the above-mentioned structural unit having a group having active hydrogen the above-mentioned structural unit before the reaction.
  • a method of polymerizing by changing the ratio of the monomers used for synthesis, that is, a seed polymerization method may be applied so that a large amount of hydrogen is present near the surface of the particles.
  • the specific resin RA in the present disclosure is not limited to the addition polymerization type resin, and may be a polycondensation type resin or a heavy addition type resin.
  • the polycondensation type resin means a resin obtained by a polycondensation reaction
  • the polyaddition type resin means a resin obtained by a polyaddition reaction.
  • the polycondensation type resin include polyamide and polyester.
  • the heavy addition type resin include polyurethane, polyurea, polyurethane urea, and polycarbonate.
  • Specific resin RA2 (hereinafter, also referred to as specific resin RA2) other than the specific resin RA1 which is an addition polymerization type resin is more specifically a urea bond, a urethane bond, an amide bond, a carbonate bond, an ester bond, and an imide.
  • examples thereof include resins having at least one bond selected from the group consisting of bonds in the main chain and having an ethylenically unsaturated group, and are composed of urea bonds, urethane bonds, amide bonds, and ester bonds.
  • a resin having at least one bond selected from the group in the main chain and having an ethylenically unsaturated group is preferable, and at least one bond selected from the group consisting of urea bond and urethane bond is used.
  • a resin having a main chain and an ethylenically unsaturated group is more preferable.
  • the specific resin RA2 is preferably polyurea, polyurethane, polyurethane urea, polyamide, or polyester having an ethylenically unsaturated group, and is polyurea or polyurethane having an ethylenically unsaturated group. Is more preferable.
  • the specific resin RA2 preferably has a hydrophilic structure, and the hydrophilic structure is the same as that of the specific resin RA1 and the preferred embodiment is also the same.
  • the specific resin RA2 in the present disclosure is a urea bond, particularly from the viewpoints of printing resistance, inking property, special color inking property, UV plate skipping property, on-machine development property, and development residue suppression property during on-machine development. It is preferable that the resin contains. More specifically, the specific resin RA2 is a resin containing a urea bond, and more preferably contains a structure obtained by at least reacting an isocyanate compound represented by the following formula (Iso) with water. It is particularly preferable to include a structure obtained by at least reacting the isocyanate compound represented by the formula (Iso) with water, and to contain a resin having a polyethylene oxide structure and a polypropylene oxide structure as the polyoxyalkylene structure. Further, in the specific resin RA2, the particles containing the resin containing the urea bond are preferably microgels (that is, crosslinked resin particles).
  • n represents an integer from 0 to 10.
  • the resin containing the urea bond which is one of the specific resins RA2 has an ethylenically unsaturated group.
  • the ethylenically unsaturated group more preferably has a group represented by the following formula (PETA).
  • a compound having reactivity with the isocyanate group such as an alcohol compound or an amine compound (for example, a compound having active hydrogen) is added by adding the compound.
  • Structures such as alcohol compounds and amine compounds can also be introduced into the specific resin RA2.
  • a polyol compound or a polyamine compound is preferable, a polyol compound is more preferable, and at least one compound selected from the group consisting of propylene glycol, glycerin, and trimethylolpropane is further preferable.
  • Specific examples of the specific resin RA2 include the resins (2), (18) to (23) synthesized in [Example] described later, but the specific resin RA2 is not limited thereto.
  • Examples of the components other than the specific resin RA (hereinafter, also referred to as other components) contained in the specific particles A include a polymerization initiator residue and a low molecular weight surfactant.
  • the content of other components is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and 0 by mass, based on the total mass of the specific particles A. It is particularly preferably by mass%. That is, it is particularly preferable that the specific particles A are particles made of the specific resin RA without containing other components.
  • Specific examples of the specific particles A containing the specific resin RA1 include particles (1) (5), (7), (9) to (17) synthesized in [Example] described later. Particle A is not limited to these. Specific examples of the specific particles A containing the specific resin RA2 include particles (2), (18) to (22) synthesized in [Example] described later, but the specific particles A are limited to these. It's not something.
  • the specific particles A preferably have water dispersibility from the viewpoint of developability and on-machine developability.
  • water-dispersible particles means that 5.0 g of particles are mixed with 100 mL of water in an environment of 20 ° C., and the stirring speed is 300 rpm (revolutions per minute, the same applies hereinafter) for 10 minutes. Disperse by stirring with, and when left to stand in an environment of 20 ° C. for 1 hour, no precipitate is visually confirmed, or a small amount of precipitate is visually confirmed, but it can be easily redispersed. It means something that is in a state of being.
  • the specific particles A are preferably in a state where no precipitate is visually confirmed after standing for 1 hour, or a small amount of precipitate is visually confirmed, but can be easily redispersed, and visually. It is more preferable that no precipitate is confirmed and the dispersibility is good.
  • the specific particles A preferably have organic solvent dispersibility from the viewpoints of print resistance, developability, and developability.
  • These organic solvents may be used as a coating solvent described later to form an image recording layer in the lithographic printing plate original plate according to the present disclosure.
  • particles having organic solvent dispersibility means that 5.0 g of particles are mixed with at least one of 100 mL of the above organic solvent in an environment of 20 ° C. for 10 minutes at a stirring rate of 300 rpm. It is dispersed by stirring, and when it is allowed to stand in an environment of 20 ° C. for 1 hour, a small amount of precipitate is visually confirmed, but it is in a state where it can be easily redispersed.
  • the specific particles A in the present disclosure are particles having organic solvent dispersibility, coating can be performed in a state where the particles are well dispersed in the coating liquid at the time of forming the image recording layer.
  • the specific particles A are difficult to be coated in an aggregated state, so that the coating surface of the image recording layer is excellent, and the printing resistance, developability, and on-machine It is considered that the developability is easy to be excellent.
  • the SP value of the organic solvent preferable as the coating solvent is 9.3 to 18.0, more preferably 10.0 to 15.0, and further preferably 10.5 to 12.5. It is preferable that the specific particles A in the present disclosure can be dispersed in an organic solvent having the above SP value.
  • the SP values of typical organic solvents are as follows.
  • SP value 9.3
  • the SP value in the present disclosure shall be calculated by the Okitsu method ("Journal of the Adhesive Society of Japan" 29 (5) (1993) by Toshinao Okitsu). Specifically, the SP value is calculated by the following formula.
  • ⁇ F is a value described in the literature.
  • the SP value ( ⁇ ) ⁇ F (Molar Attraction Constants) / V (molar volume)
  • the unit of the SP value in the present disclosure is MPa 1/2 .
  • the SP value is obtained as a weighted average value according to the content mass ratio of each organic solvent.
  • the weighted average value is "X" obtained by the following mathematical formula 1.
  • the SP value of the organic solvent A containing two or more kinds of organic solvents is the SP value of the organic solvent of the i-type (i represents an integer of 1 or more) contained in Si in the following formula 1. It is X calculated by substituting and substituting the mass content of the i-type organic solvent in the entire organic solvent A into Wi.
  • the particle size of the specific particles is preferably 1,000 nm or less, and more preferably 50 nm to 300 nm, in terms of median diameter, from the viewpoint of improving sensitivity and obtaining excellent printing resistance.
  • the method for measuring the median diameter is as described above.
  • the coefficient of variation of the particle size of the specific particles A is preferably 100% or less, more preferably 40% or less, and even more preferably 25% or less.
  • the lower limit of the coefficient of variation is not particularly limited and may be 0%.
  • the coefficient of variation increases the content of the hydrophilic structure (particularly, the amount of the polyalkylene oxide structure) in the case of the specific resin RA1 by appropriately setting the reaction conditions such as the stirring speed and the temperature at the time of particle synthesis. It can be lowered by such things.
  • the coefficient of variation of the particle size of the specific particle A is measured by direct observation of the particle size by the following microscopy.
  • the center particle size is defined as the point where the number of large particles and the number of small particles are the same, as in the definition of median size, and the fluctuation width from the center particle size is used to determine the particles by microscopy. Find the fluctuation coefficient.
  • the specific particles A may be used alone or in combination of two or more.
  • the content of the specific particles A in the image recording layer of the flat plate printing plate original according to the present disclosure is 10% by mass to 70% by mass with respect to the total mass of the image recording layer from the viewpoint of improving sensitivity and obtaining excellent printing durability. It is preferably%, more preferably 20% by mass to 70% by mass, further preferably 20% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass.
  • the specific compound B in the present disclosure is a compound having an ethylenically unsaturated group other than the specific particles A.
  • the specific compound B excludes the binder resin described later even if it is a compound having an ethylenically unsaturated group other than the specific particles A.
  • the ethylenically unsaturated group contained in the specific compound B is the same as the ethylenically unsaturated group contained in the specific resin RA, and the preferred examples are also the same.
  • the molecular weight (weight average molecular weight when having a molecular weight distribution) of the specific compound B is preferably 2,500 or less, more preferably 50 to 2,500, and more preferably 70 to 2,000. Is more preferable. Further, it is also one of the preferable embodiments that the molecular weight of the specific compound B (in the case of having a molecular weight distribution, the weight average molecular weight) is 100 to 2,500.
  • the specific compound B is an addition-polymerizable compound having at least one ethylenically unsaturated group (that is, an ethylenically unsaturated compound).
  • the specific compound B preferably has two or more ethylenically unsaturated groups, and preferably has three or more ethylenically unsaturated groups.
  • the number of ethylenically unsaturated groups contained in the specific compound B is preferably 20 or less, for example.
  • the ethylenically unsaturated bond value of the specific compound B is preferably, for example, 1 mmol / g to 12 mmol / g, more preferably 5 mmol / g to 12 mmol / g, from the viewpoint of improving sensitivity and obtaining excellent printing resistance. More preferably, it is 7 mmol / g to 12 mmol / g.
  • the specific compound B has a chemical form such as, for example, a monomer, a prepolymer, that is, a dimer, a trimer or an oligomer, or a mixture thereof.
  • the specific compound B preferably contains an oligomer.
  • the oligomer represents a polymerizable compound having a molecular weight (weight average molecular weight when having a molecular weight distribution) of 600 to 10,000 and containing at least one ethylenically unsaturated group. From the viewpoint of excellent chemical resistance and ability to suppress on-machine developing residue, the molecular weight of the oligomer is preferably 1,000 to 5,000, more preferably 1,000 to 2,500.
  • the number of ethylenically unsaturated groups in one molecule of the oligomer is preferably 2 or more, more preferably 3 or more, and further preferably 6 or more. It is particularly preferably 10 or more.
  • the upper limit of the number of ethylenically unsaturated groups in the oligomer is not particularly limited, but is preferably 20 or less.
  • the oligomer preferably has 7 or more ethylenically unsaturated groups and a molecular weight of 1,000 to 10,000. It is more preferable that the number of ethylenically unsaturated groups is 7 to 20 and the molecular weight is 1,000 to 5,000 (more preferably 1,000 to 2,500).
  • the oligomer is preferably at least one selected from the group consisting of a compound having a urethane bond, a compound having an ester bond, and a compound having an epoxy residue, and a compound having a urethane bond.
  • the epoxy residue refers to a structure formed by an epoxy group, and means, for example, a structure similar to the structure obtained by the reaction of an acid group (carboxylic acid group or the like) with an epoxy group.
  • the compound having a urethane bond is not particularly limited, and examples thereof include a compound obtained by reacting a polyisocyanate compound with a compound having a hydroxy group and an ethylenically unsaturated group.
  • polyisocyanate compound examples include bifunctional to pentafunctional polyisocyanate compounds, and bifunctional or trifunctional polyisocyanate compounds are preferable.
  • polyisocyanate compound examples include 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,3-cyclopentanediisocyanate, and 9H-fluorene-.
  • a compound having one hydroxy group and one or more ethylenically unsaturated groups is preferable, and it has one hydroxy group and two or more ethylenically unsaturated groups.
  • Compounds are more preferred.
  • Compounds having a hydroxy group and an ethylenically unsaturated group include hydroxyethyl (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (dipentaerythritol penta (). Meta) acrylate and the like can be mentioned.
  • the compound having a urethane bond is preferably, for example, a compound having at least a group represented by the following formula (Ac-1) or formula (Ac-2), and is represented by the following formula (Ac-1). More preferably, it is a compound having at least a group.
  • L 1 ⁇ L 4 each independently represents a divalent hydrocarbon group having 2 to 20 carbon atoms, the wavy line portion coupled to other structures Represents a position.
  • L 1 ⁇ L 4 each independently preferably an alkylene group having 2 to 20 carbon atoms, an alkylene group having 2 to 10 carbon atoms It is more preferable to have an alkylene group having 4 to 8 carbon atoms.
  • the alkylene group may have a branched or ring structure, but is preferably a linear alkylene group.
  • the wavy line portion in the formula (Ac-1) or the formula (Ac-2) can be directly bonded to the wavy line portion in the group represented by the following formula (Ae-1) or the formula (Ae-2), respectively. preferable.
  • R independently represents an acryloyloxy group or a methacryloyloxy group
  • the wavy line portion is a wavy line in the formulas (Ac-1) and (Ac-2). Represents the connection position with the part.
  • a compound having a urethane bond a compound in which an ethylenically unsaturated group is introduced by a polymer reaction into a polyurethane oligomer obtained by a reaction of a polyisocyanate compound and a polyol compound may be used.
  • a compound having a urethane bond is obtained by reacting a polyurethane oligomer obtained by reacting a polyol compound having an acid group with a polyisocyanate compound with a compound having an epoxy group and an ethylenically unsaturated group. You may.
  • the number of ethylenically unsaturated groups in the compound having an ester bond is preferably 3 or more, and more preferably 6 or more.
  • ⁇ Compound with epoxy residue a compound containing a hydroxy group in the compound is preferable.
  • the number of ethylenically unsaturated groups in the compound having an epoxy residue is preferably 2 to 6, and more preferably 2 to 3.
  • the compound having the epoxy residue can be obtained, for example, by reacting a compound having an epoxy group with acrylic acid.
  • oligomer used as the specific compound B a commercially available product may be used, and UA-510H, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV- 6300B, UV7620EA (above, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), U-15HA (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), EBECRYL450, EBECRYL657, EBECRYL885, EBECRYL800, EBECRYL3416, EBECRYL860 (above, Diesel Ol) (Manufactured), etc., but is not limited to this.
  • the content of the oligomer in the image recording layer with respect to the total mass of the specific compound B is preferably 30% by mass to 100% by mass, preferably 50% by mass. It is more preferably% to 100% by mass, and even more preferably 80% by mass to 100% by mass.
  • the specific compound B may contain a compound having an ethylenically unsaturated bond value of 5.0 mmol / g or more (hereinafter, also referred to as specific compound B1).
  • the ethylenically unsaturated bond value of the specific compound B1 is preferably 5.5 mmol / g or more, and more preferably 6.0 mmol / g or more.
  • the upper limit of the ethylenically unsaturated bond value of the specific compound B1 is, for example, 10.0 mmol / g or less, and more preferably 8.5 mmol / g or less.
  • the ethylenically unsaturated bond value of the compound in the present disclosure is determined by the following method. First, for a compound having a predetermined sample amount (for example, 0.2 g), the structure of the compound is specified by using, for example, thermal decomposition GC / MS, FT-IR, NMR, TOF-SIMS, etc., and ethylenically unsaturated. Find the total amount (mmol) of the groups. The ethylenically unsaturated bond value of a compound is calculated by dividing the total amount (mmol) of the determined ethylenically unsaturated groups by the sample amount (g) of the compound.
  • a predetermined sample amount for example, 0.2 g
  • the structure of the compound is specified by using, for example, thermal decomposition GC / MS, FT-IR, NMR, TOF-SIMS, etc.
  • X represents an n-valent organic group having a hydrogen-bonding group
  • Y represents a monovalent group having two or more ethylenically unsaturated groups
  • n represents an integer of two or more.
  • the molecular weight of X / (molecular weight of Y ⁇ n) is 1 or less.
  • the hydrogen-bonding group in X of the formula (I) is not particularly limited as long as it is a hydrogen-bondable group, and whether it is a hydrogen-bond-donating group or a hydrogen-bond-accepting group, both of them. It may be.
  • the hydrogen-bonding group include a hydroxy group, a carboxy group, an amino group, a carbonyl group, a sulfonyl group, a urethane group, a urea group, an imide group, an amide group, a sulfonamide group and the like.
  • the hydrogen-bonding group is at least one group selected from the group consisting of a urethane group, a urea group, an imide group, an amide group, and a sulfonamide group from the viewpoint of on-machine developability and print resistance. It is more preferable to contain at least one group selected from the group consisting of a urethane group, a urea group, an imide group, and an amide group, and more preferably than the group consisting of a urethane group, a urea group, and an imide group. It is more preferably at least one selected group, and particularly preferably containing at least one group selected from the group consisting of urethane groups and urea groups.
  • X in the formula (I) is preferably an organic group having no ethylenically unsaturated bond. Further, X in the formula (I) is a monovalent to n-valent aliphatic hydrocarbon group, a monovalent to n-valent aromatic hydrocarbon group, a urethane bond, or a urea from the viewpoint of on-machine developability and printing resistance. It is preferably a group that combines two or more structures selected from the group consisting of a bond, a biuret bond, and an allophanate bond, and is preferably a monovalent to n-valent aliphatic hydrocarbon group and a monovalent to n-valent aromatic group. It is more preferable that the group is a combination of two or more structures selected from the group consisting of a hydrocarbon group, a urethane bond, a urea bond, and a biuret bond.
  • X in the formula (I) is a quantified product in which a polyfunctional isocyanate compound is increased in a large amount (including an adducted body of a polyfunctional alcohol compound such as a trimethylolpropane adduct) from the viewpoint of on-machine developability and print resistance.
  • the group is a group obtained by removing the terminal isocyanate group from the group, and is a group obtained by removing the terminal isocyanate group from a quantifier (including an adduct of a polyfunctional alcohol compound) in which a bifunctional isocyanate compound is abundant. Is more preferable, and a group in which the terminal isocyanate group is removed from a quantifier (including an adduct of a polyfunctional alcohol compound) in which hexamethylene diisocyanate is increased is particularly preferable.
  • the molecular weight of X in the formula (I) is preferably 100 to 1,000, more preferably 150 to 800, and particularly preferably 150 to 500, from the viewpoint of on-machine developability and print resistance.
  • the ethylenically unsaturated group in Y of the formula (I) is not particularly limited, and from the viewpoint of reactivity, on-machine developability, and print resistance, a vinylphenyl group, a vinyl ester group, a vinyl ether group, an allyl group, ( It is preferably at least one group selected from the group consisting of a meta) acryloxy group and a (meth) acrylamide group. From the same viewpoint as above, the ethylenically unsaturated group in Y of the formula (I) is at least one group selected from the group consisting of a vinylphenyl group, a (meth) acryloxy group, and a (meth) acrylamide group.
  • the ethylenically unsaturated group in Y of the formula (I) preferably contains a (meth) acryloxy group from the viewpoint of on-machine developability and print resistance.
  • Y in the formula (I) is preferably a group having three or more (meth) acryloxy groups, more preferably a group having five or more (meth) acryloxy groups, and five or more twelve. It is more preferable that the group has the following (meth) acryloxy group.
  • Y in the formula (I) may have a structure represented by the following formula (Y-1) or the formula (Y-2) from the viewpoint of on-machine developability and print resistance.
  • R independently represents an acrylic group or a methacrylic group, and the wavy line portion represents the bonding position with another structure.
  • R is preferably an acrylic group.
  • n Ys in the formula (I) are all the same group.
  • the molecular weight of Y in the formula (I) is preferably 200 or more and 1,000 or less, and more preferably 250 or more and 800 or less, from the viewpoint of on-machine developability and print resistance.
  • N in the formula (I) is an integer of 2 or more, and is more preferably 2 to 3 from the viewpoint of on-machine developability and print resistance.
  • the molecular weight of X / (molecular weight of Y ⁇ n) is 1 or less, preferably 0.01 to 0.8, preferably 0.1 to 0.5, from the viewpoint of on-machine developability and print resistance. More preferably.
  • the structure of the specific compound B1 preferably includes a structure in which the terminal isocyanate group of the quantifier (including the adduct) of the polyfunctional isocyanate compound is sealed with a compound having an ethylenically unsaturated group. .. Among them, as the quantifier of the polyfunctional isocyanate compound, the quantifier of the bifunctional isocyanate compound is preferable.
  • the specific compound B1 is a polyfunctional ethylene having a hydroxy group (also referred to as a hydroxyl group) at the end of the terminal isocyanate group of the multimerized product in which the polyfunctional isocyanate compound is increased in quantity. It is preferably a compound obtained by reacting a sex unsaturated compound.
  • the specific compound B1 is a polyfunctional ethylenic compound having a hydroxy group at the terminal isocyanate group of a multimeric compound (including an adduct compound of a polyfunctional alcohol compound) in which a difunctional isocyanate compound is increased in quantity.
  • the compound is obtained by reacting an unsaturated compound.
  • the specific compound B1 is a polyfunctional ethylenically non-polyfunctional compound having a hydroxy group at the terminal isocyanate group of the multimer (including the adduct of the polyfunctional alcohol compound) in which hexamethylene diisocyanate is increased. It is particularly preferable that the compound is obtained by reacting a saturated compound.
  • the polyfunctional isocyanate compound is not particularly limited, and known compounds can be used, and may be an aliphatic polyfunctional isocyanate compound or an aromatic polyfunctional isocyanate compound.
  • Specific examples of the polyfunctional isocyanate compound include 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and 1,3-.
  • Cyclopentane diisocyanate, 9H-fluorene-2,7-diisocyanate, 9H-fluoren-9-on-2,7-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylenediisocyanate, trilen-2 , 4-Diisocyanate, Trilen-2,6-Diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 2,2-bis (4-isocyanatophenyl) hexafluoropropane, 1,5-di Isocyanatonaphthalene, dimers of these polyisocyanates, trimmers (isocyanurate bonds) and the like are preferably mentioned.
  • a biuret compound obtained by reacting the above polyisocyanate compound with a known amine compound may be used.
  • the polyfunctional ethylenically unsaturated compound having a hydroxy group is preferably a trifunctional or higher functional ethylenically unsaturated compound having a hydroxy group, and is a pentafunctional or higher functional ethylenically unsaturated compound having a hydroxy group. Is more preferable.
  • the polyfunctional ethylenically unsaturated compound having a hydroxy group is preferably a polyfunctional (meth) acrylate compound having a hydroxy group.
  • the specific compound B1 preferably has at least one structure selected from the group consisting of an adduct structure, a biuret structure, and an isocyanurate structure from the viewpoint of on-machine developability and print resistance. From the same viewpoint as above, it is more preferable that the specific compound B1 has at least one structure selected from the group consisting of a trimethylolpropane adduct structure, a biuret structure, and an isocyanurate structure, and the trimethylolpropane adduct structure is formed. It is particularly preferable to have.
  • the specific compound B1 preferably has a structure represented by any of the following formulas (A-1) to (A-3), and the following formula (A-). It is more preferable to have the structure represented by 1).
  • RA1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the wavy line portion represents a bond position with another structure.
  • R A1 in the formula (A1) from the viewpoint of on-press development property and printing durability, a hydrogen atom, or preferably an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms It is more preferably present, more preferably a methyl group or an ethyl group, and particularly preferably an ethyl group.
  • the specific compound B1 is preferably a (meth) acrylate compound having a urethane group, that is, a urethane (meth) acrylate oligomer from the viewpoint of on-machine developability and print resistance.
  • the specific compound B1 may be an oligomer having a polyester bond (hereinafter, also referred to as a polyester (meth) acrylate oligomer) as long as the ethylenically unsaturated bond value is 5.0 mmol / g or more, or an epoxy residue may be used. It may be an oligomer having an oligomer (hereinafter, also referred to as an epoxy (meth) acrylate oligomer). Here, the epoxy residues in the epoxy (meth) acrylate oligomer are as described above.
  • the number of ethylenically unsaturated groups in the polyester (meth) acrylate oligomer which is the specific compound B1 is preferably 3 or more, and more preferably 6 or more.
  • the epoxy (meth) acrylate oligomer which is the specific compound B1 a compound containing a hydroxy group in the compound is preferable.
  • the number of ethylenically unsaturated groups in the epoxy (meth) acrylate oligomer is preferably 2 to 6, and more preferably 2 to 3.
  • the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting a compound having an epoxy group with acrylic acid.
  • the molecular weight (weight average molecular weight when having a molecular weight distribution) of the specific compound B1 may be more than 1,000, preferably 1,100 to 10,000, and more preferably 1,100 to 5,000. ..
  • Specific compound B1 a synthetic product or a commercially available product may be used.
  • Specific examples of the specific compound B1 include, for example, the following commercially available products, but the specific compound B1 used in the present disclosure is not limited thereto.
  • the content of the specific compound B1 in the image recording layer with respect to the total mass of the specific compound B is preferably 10% by mass to 100% by mass, preferably 50% by mass to 100% by mass. Is more preferable, and 80% by mass to 100% by mass is further preferable.
  • the specific compound B may further contain a compound other than the above-mentioned oligomer and the specific compound B1.
  • the compound other than the oligomer as the specific compound B is preferably a low molecular weight compound having a molecular weight (weight average molecular weight when having a molecular weight distribution) of less than 1,000 (preferably less than 800).
  • the low molecular weight compound as the specific compound B may be in a chemical form such as a monomer, a dimer, a trimer, or a mixture thereof.
  • the low molecular weight compound as the specific compound B is at least one compound selected from the group consisting of a compound having three or more ethylenically unsaturated groups and a compound having an isocyanul ring structure from the viewpoint of chemical resistance. It is preferable to have.
  • the low molecular weight compound as the specific compound B preferably has a molecular weight (weight average molecular weight in the case of having a molecular weight distribution) of 50 or more and less than 600, and is excellent in chemical resistance and suppression of on-machine developing residue. , 100 or more and less than 600, more preferably 300 or more and less than 600, and even more preferably 400 or more and less than 600.
  • the ratio of the oligomer to the low molecular weight compound is 10 on a mass basis from the viewpoint of chemical resistance and suppression of on-machine development residue. It is preferably 1/1 to 1/10, more preferably 10/1 to 3/7, and even more preferably 10/1 to 7/3.
  • Examples of the low molecular weight compound as the specific compound B include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof or amides thereof.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters of an unsaturated carboxylic acid and a polyhydric alcohol compound, and amides of an unsaturated carboxylic acid and a polyvalent amine compound are used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogen atom an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogen atom
  • Substituents of unsaturated carboxylic acid esters or amides having a releasable substituent such as a tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
  • JP-A-2006-508380 JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, JP-A-9-179297.
  • JP-A-9-179298 JP-A-2004-294935, JP-A-2006-243493, JP-A-2002-275129, JP-A-2003-64130, JP-A-2003-280187, It is described in Kaihei 10-333321.
  • the monomer of the ester of the polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, and propylene glycol diacrylate as acrylic acid esters.
  • EO ethylene oxide
  • methacrylic acid ester As methacrylic acid ester, tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropantrimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] There are dimethylmethane, bis [p- (methacrylicoxyethoxy) phenyl] dimethylmethane and the like.
  • amide monomer of the polyvalent amine compound and the unsaturated carboxylic acid examples include methylenebisacrylamide, methylenebismethacrylamide, 1,6-hexamethylenebisacrylamide, and 1,6-hexamethylenebismethacrylamide.
  • a urethane-based addition-polymerizable compound produced by using an addition reaction of isocyanate and a hydroxy group is also suitable, and specific examples thereof include, for example, 2 per molecule described in JP-A-48-41708.
  • a vinyl urethane compound 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. And so on.
  • Formula (M) CH 2 C ( R M4) COOCH 2 CH (R M5) OH
  • RM4 and RM5 each independently represent a hydrogen atom or a methyl group.
  • the specific compound B may contain, as a low molecular weight compound, a compound having one or two ethylenically unsaturated bond groups (hereinafter, also referred to as the specific compound B2).
  • a preferred embodiment of the ethylenically unsaturated group contained in the specific compound B2 is the same as that of the ethylenically unsaturated group in the specific compound B1.
  • the specific compound B2 is preferably a compound having two ethylenically unsaturated bonding groups (that is, a bifunctional polymerizable compound) from the viewpoint of suppressing a decrease in on-machine developability.
  • the specific compound B2 is preferably a methacrylate compound, that is, a compound having a methacryloxy group, from the viewpoint of on-machine developability and print resistance.
  • the specific compound B2 preferably contains an alkyleneoxy structure or a urethane bond from the viewpoint of on-machine developability.
  • the molecular weight (weight average molecular weight when having a molecular weight distribution) of the specific compound B2 is preferably 50 or more and less than 1,000, more preferably 200 to 900, and more preferably 250 to 800. More preferred.
  • specific compound B2 commercially available products shown below may be used, but the specific compound B2 used in the present disclosure is not limited thereto.
  • Specific examples of the specific compound B2 include BPE-80N (compound of (1) above) manufactured by Shin Nakamura Chemical Industry Co., Ltd., BPE-100, BPE-200, BPE-500, and CN104 manufactured by Sartmer Co., Ltd. Examples thereof include ethoxylated bisphenol A dimethacrylate such as the compound of 1).
  • Specific examples of the specific compound B2 include ethoxylated bisphenol A diacrylates such as A-BPE-10 (compound of (2) above) manufactured by Shin Nakamura Chemical Industry Co., Ltd. and A-BPE-4. ..
  • specific examples of the specific compound B2 include bifunctional methacrylate such as FST 510 manufactured by AZ Electronics.
  • FST 510 is a reaction product of 1 mol of 2,2,4-trimethylhexamethylene diisocyanate and 2 mol of hydroxyethyl methacrylate, and is a solution of the compound of the above (3) in an 82% by mass of methyl ethyl ketone. is there.
  • the content of the specific compound B2 in the image recording layer with respect to the total mass of the specific compound B is preferably 10% by mass to 100% by mass, preferably 50% by mass to 100% by mass. Is more preferable, and 80% by mass to 100% by mass is further preferable.
  • the content of the specific compound B is preferably 5% by mass to 75% by mass, more preferably 10% by mass to 70% by mass, and particularly preferably 15% by mass to 60% by mass with respect to the total mass of the image recording layer. is there.
  • the specific compound B preferably contains a compound having a molecular weight of 2,500 or less (more preferably 100 to 2,500) from the viewpoint of reactivity with the specific particles A.
  • a compound having a molecular weight of 2,500 or less (more preferably 100 to 2,500), which is a specific compound B, is used with respect to the total mass of the image recording layer from the viewpoint of improving sensitivity and obtaining excellent printing durability. It is preferably from 15% by mass to 80% by mass, more preferably from 15% by mass to 70% by mass, and even more preferably from 20% by mass to 65% by mass.
  • the ratio of the total amount of the specific particles A and the specific compound B to the image recording layer is preferably 40% by mass to 90% by mass, more preferably 50% by mass to 90% by mass, and 60% by mass to 80% by mass. Is more preferable.
  • the image recording layer in the present disclosure preferably contains a polymerization initiator.
  • the polymerizable initiator is not particularly limited, and examples thereof include an electron-accepting polymerization initiator and an electron-donating polymerization initiator. Above all, the polymerization initiator preferably contains at least an electron-accepting polymerization initiator.
  • the image recording layer preferably contains an electron-accepting polymerization initiator from the viewpoint of improving sensitivity and obtaining excellent printing resistance.
  • the electron-accepting polymerization initiator used in the present disclosure is a compound that generates a polymerization initiator such as a radical or a cation by energy of light, heat, or both, and is a known thermal polymerization initiator and has a small bond dissociation energy. A compound having a bond, a photopolymerization initiator and the like can be appropriately selected and used.
  • a radical polymerization initiator is preferable, and an onium compound is more preferable.
  • the electron-accepting polymerization initiator is preferably an infrared photosensitive polymerization initiator.
  • the electron-accepting polymerization initiator may be used alone or in combination of two or more.
  • Examples of the radical polymerization initiator include (a) an organic halide, (b) a carbonyl compound, (c) an azo compound, (d) an organic peroxide, (e) a metallocene compound, (f) an azide compound, and (g). ) Hexaaryl biimidazole compounds, (h) disulfone compounds, (i) oxime ester compounds, and (j) onium compounds.
  • preferred ones include (i) an oxime ester compound and (j) an onium compound from the viewpoint of curability.
  • the compounds described in paragraphs 0022 to 0023 of JP-A-2008-195018 are preferable.
  • B) As the carbonyl compound for example, the compound described in paragraph 0024 of JP-A-2008-195018 is preferable.
  • C) As the azo compound for example, the azo compound described in JP-A-8-108621 can be used.
  • D) As the organic peroxide for example, the compound described in paragraph 0025 of JP-A-2008-195018 is preferable.
  • the metallocene compound for example, the compound described in paragraph 0026 of JP-A-2008-195018 is preferable.
  • Examples of the (f) azide compound include compounds such as 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
  • Examples of the (h) disulfone compound include the compounds described in JP-A-61-166544 and JP-A-2002-328465.
  • Examples of the oxime ester compound for example, the compounds described in paragraphs 0028 to 0030 of JP-A-2008-195018 are preferable.
  • the electron-accepting polymerization initiator is particularly preferably a (j) onium compound.
  • the (j) onium compound will be described in detail.
  • an iodonium salt compound, a sulfonium salt compound, or an azinium salt compound is preferable, an iodonium salt compound or a sulfonium salt compound is more preferable, and an iodonium salt is preferable, from the viewpoint of improving sensitivity and obtaining excellent printing resistance.
  • Compounds are more preferred. Specific examples of these compounds are shown below, but the present disclosure is not limited thereto.
  • a diaryl iodonium salt compound is preferable, a diphenyl iodonium salt compound substituted with an electron donating group such as an alkyl group or an alkoxyl group is more preferable, and an asymmetric diphenyl iodonium salt compound is preferable.
  • a triarylsulfonium salt compound is preferable, and in particular, an electron-attracting group, for example, a triarylsulfonium salt compound in which at least a part of a group on the aromatic ring is substituted with a halogen atom is preferable, and aromatic.
  • a triarylsulfonium salt compound having a total number of halogen atoms substituted on the ring of 4 or more is more preferable.
  • triphenylsulfonium hexafluorophosphate
  • triphenylsulfonium benzoylformate
  • bis (4-chlorophenyl) phenylsulfonium benzoylformate
  • bis (4-chlorophenyl) -4-methylphenylsulfonium tetrafluoro.
  • Tris (4-chlorophenyl) Sulfonium 3,5-bis (methoxycarbonyl) Benzene Sulfonium
  • Tris (4-chlorophenyl) Sulfonium Hexafluorophosphate
  • Tris (2,4-dichlorophenyl) Sulfonium Hexafluorophos Examples include falt.
  • a sulfonamide anion or a sulfonimide anion is preferable, and a sulfonimide anion is more preferable.
  • a sulfonamide anion an aryl sulfonamide anion is preferable.
  • a bisaryl sulfonimide anion is preferable. Specific examples of the sulfonamide anion or the sulfonamide anion are shown below, but the present disclosure is not limited thereto. In the specific examples below, Ph represents a phenyl group, Me represents a methyl group, and Et represents an ethyl group.
  • the electron-accepting polymerization initiator may contain a compound represented by the following formula (II) from the viewpoint of developability and UV printing resistance in the obtained lithographic printing plate.
  • X represents a halogen atom and R 3 represents an aryl group.
  • X in the formula (II) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • a chlorine atom or a bromine atom is preferable because it has excellent sensitivity, and a bromine atom is particularly preferable.
  • R 3 from the viewpoint of excellent balance between sensitivity and storage stability, an aryl group substituted with an amide group.
  • electron-accepting polymerization initiator represented by the above formula (II) include compounds represented by the following formula, but the present disclosure is not limited thereto.
  • the minimum empty orbital (LUMO) of the electron-accepting polymerization initiator is preferably ⁇ 3.00 eV or less, and more preferably ⁇ 3.02 eV or less, from the viewpoint of improving sensitivity and obtaining excellent printing resistance. preferable.
  • the lower limit of LUMO of the electron-accepting polymerization initiator is preferably -3.80 eV or more, and more preferably -3.60 eV or more.
  • the content of the electron-accepting polymerization initiator is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, based on the total mass of the image recording layer. It is preferably 0.8% by mass to 20% by mass, and particularly preferably 0.8% by mass.
  • the polymerization initiator preferably further contains an electron donating type polymerization initiator from the viewpoint of contributing to chemical resistance and excellent printing resistance in the lithographic printing plate, and the electron donating type polymerization initiator and the above electron donating. More preferably, it contains both type polymerization initiators.
  • the electron donating type polymerization initiator include the following five types.
  • Alkyl or arylate complex It is considered that the carbon-heterobond is oxidatively cleaved to generate an active radical. Specific examples thereof include borate compounds.
  • (Ii) Amino acetic acid compound It is considered that the CX bond on the carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical.
  • X a hydrogen atom, a carboxy group, a trimethylsilyl group or a benzyl group is preferable. Specific examples thereof include N-phenylglycines (which may have a substituent on a phenyl group) and N-phenyliminodiacetic acid (which may have a substituent on a phenyl group). Be done.
  • Sulfur-containing compound The above-mentioned aminoacetic acid compound in which the nitrogen atom is replaced with a sulfur atom can generate an active radical by the same action.
  • Tin-containing compound The above-mentioned aminoacetic acid compound in which the nitrogen atom is replaced with a tin atom can generate an active radical by the same action.
  • Sulfinates Active radicals can be generated by oxidation. Specific examples thereof include sodium arylsulfinate and the like.
  • the image recording layer preferably contains a borate compound.
  • a borate compound a tetraaryl borate compound or a monoalkyl triaryl borate compound is preferable, a tetraaryl borate compound is more preferable, and a tetraphenyl borate compound is particularly preferable from the viewpoint of compound stability.
  • the counter cation contained in the borate compound is not particularly limited, but is preferably an alkali metal ion or a tetraalkylammonium ion, and more preferably a sodium ion, a potassium ion, or a tetrabutylammonium ion. Further, as the counter cation contained in the borate compound, onium ion in the above-mentioned electron-accepting polymerization initiator is also preferable.
  • sodium tetraphenylborate is preferably mentioned as the borate compound.
  • the maximum occupied orbital (HOMO) of the electron donating type polymerization initiator used in the present disclosure is preferably ⁇ 6.00 eV or more, preferably ⁇ 600 eV or more, from the viewpoint of improving sensitivity and obtaining excellent printing durability. It is more preferably .95 eV or more, and even more preferably ⁇ 5.93 eV or more.
  • the upper limit of HOMO of the electron donating polymerization initiator is preferably ⁇ 5.00 eV or less, and more preferably ⁇ 5.40 eV or less.
  • the highest occupied orbital (HOMO) and the lowest empty orbital (LUMO) are calculated by the following methods.
  • Quantum chemistry calculation software Gaussian09 is used, and structural optimization is performed by DFT (B3LYP / 6-31G (d)).
  • the MO energy Ebare (unit: hartree) obtained by the above MO energy calculation is converted into Escaled (unit: eV) used as the values of HOMO and LUMO in the present disclosure by the following formula.
  • Escaled 0.823168 x 27.2114 x Ebare-1.07634 Note that 27.2114 is simply a coefficient for converting heartree to eV, 0.823168 and ⁇ 1.07634 are adjustment coefficients, and HOMO and LUMO of the compound to be calculated are calculated values. Determine to suit.
  • Bu represents an n-butyl group and Z represents a counter cation.
  • the counter cation represented by Z + include Na + , K + , N + (Bu) 4, and the like.
  • the counter cation represented by Z + may be an onium ion in the electron-accepting polymerization initiator.
  • the electron donating type polymerization initiator only one kind may be added, or two or more kinds may be used in combination.
  • the content of the electron donating type polymerization initiator is preferably 0.01% by mass to 30% by mass, more preferably 0.05% by mass to 25% by mass, and 0.1% by mass, based on the total mass of the image recording layer. It is more preferably to 20% by mass.
  • the electron-accepting polymerization initiator and the electron-donating polymerization initiator form a salt.
  • the above-mentioned onium compound may be a salt of an onium ion and an anion (for example, tetraphenylborate anion) in the electron donating type polymerization initiator.
  • the iodonium borate compound in which the iodonium cation in the above-mentioned iodonium salt compound (for example, dip-tolyl iodonium cation) and the borate anion in the electron donating type polymerization initiator form a salt is formed.
  • Specific examples of the embodiment in which the electron-accepting polymerization initiator and the electron-donating polymerization initiator form a salt are shown below, but the present disclosure is not limited thereto.
  • the image recording layer contains onium ions and anions in the above-mentioned electron donating type polymerization initiator
  • the image recording layer is assumed to contain the electron accepting type polymerization initiator and the above-mentioned electron donating type polymerization initiator.
  • the image recording layer in the present disclosure preferably contains an infrared absorber.
  • the infrared absorber is not particularly limited, and examples thereof include pigments and dyes.
  • the dye used as the infrared absorber commercially available dyes and known dyes described in documents such as "Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used.
  • dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes.
  • azo dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes.
  • dyes particularly preferable ones include cyanine pigments, squarylium pigments, pyrylium salts, nickel thiolate complexes, and indolenin cyanine pigments.
  • the cyanine pigment is particularly preferable.
  • the infrared absorber is preferably a cationic polymethine dye having an oxygen or nitrogen atom at the meso position.
  • Preferred examples of the cationic polymethine dye include cyanine dye, pyrylium dye, thiopyrylium dye, and azurenium dye, and cyanine dye is preferable from the viewpoint of easy availability and solvent solubility during the introduction reaction.
  • the cyanine dye examples include the compounds described in paragraphs 0017 to 0019 of JP-A-2001-133939, paragraphs 0016 to 0021 of JP-A-2002-0233360, and paragraphs 0012 to 0037 of JP-A-2002-040638. Examples of the compounds described in. As a specific example of the cyanine dye, the compounds described in paragraphs 0034 to 0041 of JP-A-2002-278057 or paragraphs 0080-0086 of JP-A-2008-195018, and particularly preferably JP-A-2007-90850, are preferable.
  • infrared absorber Only one type of infrared absorber may be used, or two or more types may be used in combination. Further, a pigment and a dye may be used in combination as an infrared absorber.
  • the content of the infrared absorber in the image recording layer is preferably 0.1% by mass to 10.0% by mass, more preferably 0.5% by mass to 5.0% by mass, based on the total mass of the image recording layer. preferable.
  • the image recording layer in the present disclosure contains the electron-accepting polymerization initiator and the infrared absorber, and the electron-donating polymerization from the infrared absorber HOMO.
  • the value obtained by subtracting the HOMO of the initiator is preferably 0.70 eV or less, and more preferably 0.70 eV to ⁇ 0.10 eV.
  • a negative value means that the HOMO of the electron-donating polymerization initiator is higher than that of the infrared absorber.
  • ⁇ d in the solubility parameter of Hansen is 16 or more, ⁇ p is 16 to 32, and ⁇ h is 60 of ⁇ p. It is a preferred embodiment to have an organic anion of% or less.
  • the electron-accepting polymerization initiator in the present disclosure has ⁇ d of 16 or more, ⁇ p of 16 to 32, and ⁇ h in the solubility parameter of Hansen from the viewpoint of improving sensitivity and obtaining excellent printing resistance. It is a preferable embodiment to have an organic anion which is 60% or less of ⁇ p.
  • ⁇ d, ⁇ p, and ⁇ h in the Hansen solubility parameter in the present disclosure are the dispersion term ⁇ d [unit: MPa 0.5 ] and the polar term ⁇ p [unit: MPa 0.5 ] in the Hansen solubility parameter.
  • the hydrogen bond term ⁇ h [unit: MPa 0.5 ] is used.
  • the solubility parameter of Hansen is obtained by dividing the solubility parameter introduced by Hildebrand into three components, a dispersion term ⁇ d, a polar term ⁇ p, and a hydrogen bond term ⁇ h, and displaying them in a three-dimensional space. It was done.
  • Hansen's solubility parameters see Charles M. It is described in the document "Hansen Solubility Parameter; A Users Handbook (CRC Press, 2007)" by Hansen.
  • ⁇ d, ⁇ p, and ⁇ h in the Hansen solubility parameter of the organic anion are estimated from their chemical structures by using the computer software “Hansen Solubility Parameters in Practice (HSPiP ver. 4.1.07)”. It is the value that was set.
  • organic anion in which ⁇ d in the solubility parameter of Hansen is 16 or more, ⁇ p is 16 to 32, and ⁇ h is 60% or less of ⁇ p are preferably listed below. Needless to say, it is not limited to these.
  • the image recording layer in the present disclosure may contain a binder resin.
  • the binder resin is not particularly limited, and a known binder resin for the gallery recording layer in the lithographic printing plate original plate is used.
  • examples of the binder resin include acrylic resin, polyvinyl acetal resin, and polyurethane resin.
  • a binder resin having a structural unit formed of an aromatic vinyl compound is preferable, and a structural unit formed of an aromatic vinyl compound and a structural unit formed of a (meth) acrylonitrile compound are preferable.
  • the binder resin containing examples of the structural unit formed of the aromatic vinyl compound and the structural unit formed of the (meth) acrylonitrile compound include the structural units listed as other structural units in the specific resin RA1.
  • the binder resin used in the present disclosure preferably has a glass transition temperature (Tg) of 50 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoint of suppressing a decrease in on-machine developability over time. , 80 ° C. or higher is more preferable, and 90 ° C. or higher is particularly preferable.
  • the upper limit of the glass transition temperature of the binder resin is preferably 200 ° C., more preferably 120 ° C. or lower, from the viewpoint of easy water penetration into the image recording layer.
  • polyvinyl acetal is preferable from the viewpoint of further suppressing the decrease in on-machine developability with time.
  • Polyvinyl acetal is a resin obtained by acetalizing the hydroxy group of polyvinyl alcohol with an aldehyde.
  • polyvinyl butyral in which the hydroxy group of polyvinyl alcohol is acetalized (that is, butyralized) with butyraldehyde is preferable.
  • the polyvinyl acetal preferably contains a structural unit represented by the following (a) by acetalizing the hydroxy group of polyvinyl alcohol with an aldehyde.
  • R represents a residue of the aldehyde used for acetalization.
  • R include a hydrogen atom, an alkyl group and the like, as well as an ethylenically unsaturated group described later.
  • the content of the structural unit represented by (a) above (also referred to as the amount of ethylene groups in the main chain contained in the structural unit represented by (a) above, and also referred to as the degree of acetalization) is polyvinyl acetal. 50 mol% to 90 mol% is preferable, 55 mol% to 85 mol% is more preferable, and 55 mol% to 80 mol% is further more preferable with respect to the total structural unit (total ethylene group amount of the main chain).
  • the degree of acetalization is the amount of ethylene groups to which acetal groups are bonded (the amount of ethylene groups in the main chain included in the structural unit represented by (a) above) divided by the total amount of ethylene groups in the main chain. It is a value showing the molar fraction obtained by the above as a percentage. The same applies to the content of each structural unit of polyvinyl acetal, which will be described later.
  • the polyvinyl acetal preferably has an ethylenically unsaturated group from the viewpoint of improving printing resistance.
  • the ethylenically unsaturated group contained in the polyvinyl acetal is not particularly limited, and from the viewpoint of reactivity, on-machine developability, and print resistance, a vinylphenyl group (styryl group), a vinyl ester group, a vinyl ether group, It is more preferable that it is at least one group selected from the group consisting of an allyl group, a (meth) acryloxy group, and a (meth) acrylamide group, and a vinyl group, an allyl group, a (meth) acryloxy group and the like are preferable.
  • the polyvinyl acetal preferably contains a structural unit having an ethylenically unsaturated group.
  • the structural unit having an ethylenically unsaturated group may be a structural unit having an acetal ring described above, or a structural unit other than the structural unit having an acetal ring.
  • polyvinyl acetal is preferably a compound in which an ethylenically unsaturated group is introduced into the acetal ring. That is, it is preferable that R has an ethylenically unsaturated group in the structural unit represented by (a) above.
  • the structural unit having an ethylenically unsaturated group is a structural unit other than the structural unit having an acetal ring, for example, the structural unit having an acrylate group, specifically, the structural unit represented by the following (d). There may be.
  • the content of this structural unit is the same as that of all the structural units of polyvinyl acetal. It is preferably 1 mol% to 15 mol%, more preferably 1 mol% to 10 mol%.
  • the polyvinyl acetal preferably further contains a structural unit having a hydroxy group from the viewpoint of on-machine developability and the like. That is, the polyvinyl acetal preferably contains a structural unit derived from vinyl alcohol. Examples of the structural unit having a hydroxy group include the structural unit represented by the following (b).
  • the content (also referred to as the amount of hydroxyl groups) of the structural unit represented by (b) above is preferably 5 mol% to 50 mol%, preferably 10 mol%, based on all the structural units of polyvinyl acetal from the viewpoint of on-machine developability. It is more preferably from 40 mol%, still more preferably from 20 mol% to 40 mol%.
  • the polyvinyl acetal may further contain other structural units.
  • the other structural unit include a structural unit having an acetyl group, specifically, a structural unit represented by the following (c).
  • the content (also referred to as the amount of acetyl group) of the structural unit represented by the above (c) is preferably 0.5 mol% to 10 mol%, preferably 0.5 mol% to 8 mol%, based on all the structural units of polyvinyl acetal. Is more preferable, and 1 mol% to 3 mol% is further preferable.
  • the degree of acetalization, the amount of acrylate groups, the amount of hydroxyl groups, and the amount of acetyl groups can be determined as follows. That is, the mol content is calculated from the proton peak area ratios of the methyl or methylene moiety of acetal, the methyl moiety of the acrylate group, and the methyl moiety of the hydroxyl group and the acetyl group by 1 H NMR measurement.
  • the weight average molecular weight of the polyvinyl acetal is preferably 10,000 to 150,000.
  • polyvinyl acetals [P-1 to P-3] are listed below, but the polyvinyl acetals used in the present disclosure are not limited thereto.
  • “l” is 50 mol% to 90 mol%
  • “m” is 0.5 mol% to 10 mass%
  • "n” is 5 mol% to 50 mol%
  • “o” is 1 mol% to 1 mol%. It is 15 mol%.
  • polyvinyl acetal As the polyvinyl acetal, a commercially available product can be used. Commercially available products of polyvinyl acetal include Sekisui Chemical Co., Ltd.'s Eslek BL series (specifically, Eslek BL-10, BL-1, BL-5Z, BL-7Z, etc.) and Eslek BM series (specifically). Specifically, Eslek BM-1, BM-S (Z), BM-5, etc.), Eslek BH series (specifically, Eslek BH-S, BH-6, BH-3 (Z)), Eslek BX Examples include the series (Eslek BX-L, etc.) and the Eslek KS series (Eslek KS-10, etc.).
  • the image recording layer contains a binder resin. It is preferable not to use or to contain a small amount.
  • the content of the binder resin is preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total mass of the image recording layer, from the viewpoint of improving sensitivity and obtaining excellent printing resistance. Is more preferable, and 0% by mass is particularly preferable.
  • the image recording layer in the present disclosure preferably contains a color former.
  • a color former an acid color former is particularly preferable.
  • the "color former” means a compound having a property of developing or decoloring a color or decoloring by a stimulus such as light or acid and changing the color of the image recording layer.
  • the "acid color former” is a compound having a property of developing or decoloring and changing the color of the image recording layer by heating in a state of receiving an electron accepting compound (for example, a proton such as an acid). means.
  • the acid color former has a partial skeleton such as lactone, lactam, salton, spiropyrane, ester, and amide, and when it comes into contact with an electron-accepting compound, these partial skeletons are rapidly ring-opened or cleaved. Compounds are preferred.
  • acid color formers are 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide (also called crystal violet lactone), 3,3-bis (4-dimethylaminophenyl) phthalide, 3 -(4-Dimethylaminophenyl) -3- (4-diethylamino-2-methylphenyl) -6-dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3- (1,2-dimethylindole-3) -Il) phthalide, 3- (4-dimethylaminophenyl) -3- (2-methylindole-3-yl) phthalide, 3,3-bis (1,2-dimethylindole-3-yl) -5-dimethyl Aminophthalide, 3,3-bis (1,2-dimethylindole-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazole-3-
  • the acid color former used in the present disclosure is preferably at least one compound selected from the group consisting of a spiropyran compound, a spirooxazine compound, a spirolactone compound, and a spirolactam compound.
  • the hue of the dye after color development is preferably green, blue, or black.
  • the acid coloring agent is preferably a leuco dye from the viewpoint of color developing property and visibility of the exposed portion.
  • the leuco dye is not particularly limited as long as it has a leuco structure, but preferably has a spiro structure, and more preferably has a spirolactone ring structure.
  • the leuco dye is preferably a leuco dye having a phthalide structure or a fluorine structure from the viewpoint of color development and visibility of the exposed portion.
  • the leuco dye having the phthalide structure or the fluorine structure is a compound represented by any of the following formulas (Le-1) to (Le-3) from the viewpoint of color development and visibility of the exposed portion. It is more preferable that the compound is represented by the following formula (Le-2).
  • ERG each independently represents an electron donating group
  • X 1 ⁇ X 4 are each independently a hydrogen atom, a halogen atom, or a dialkyl anilino
  • X 5 to X 10 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group
  • Y 1 and Y 2 each independently represent C or N
  • Y 1 represents a group.
  • Ra 1 represents a hydrogen atom, an alkyl group, or an alkoxy group
  • Rb 1 to Rb 4 Represent each independently as an alkyl group or an aryl group.
  • the electron-donating groups in the ERGs of the formulas (Le-1) to (Le-3) include amino groups, alkylamino groups, arylamino groups, and dialkylamino groups from the viewpoint of color development and visibility of the exposed area.
  • a group, a monoalkyl monoarylamino group, a diarylamino group, an alkoxy group, an aryloxy group, or an alkyl group is preferable, and an amino group, an alkylamino group, an arylamino group, a dialkylamino group, a monoalkyl monoarylamino group, It is more preferably a diarylamino group, an alkoxy group, or an aryloxy group, further preferably a monoalkyl monoarylamino group, or a diarylamino group, and particularly preferably a monoalkyl monoarylamino group.
  • X 1 ⁇ X 4 in the formula (Le-1) ⁇ formula (Le-3) are each independently a chromogenic, and, from the viewpoint of visibility of the exposure unit, a hydrogen atom, or, be a chlorine atom It is preferably a hydrogen atom, more preferably a hydrogen atom.
  • X 5 to X 10 in the formula (Le-2) or the formula (Le-3) are independently each of a hydrogen atom, a halogen atom, an alkyl group, and an aryl group from the viewpoint of color development and visibility of the exposed part.
  • It is preferably a group, more preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and further preferably a hydrogen atom, a halogen atom, an alkyl group, or an aryl group.
  • a hydrogen atom is particularly preferable.
  • At least one of Y 1 and Y 2 in the formulas (Le-1) to (Le-3) is C from the viewpoint of color development and visibility of the exposed portion, and Y 1 and Y are Y. It is more preferable that both of 2 are C.
  • Ra 1 in the formulas (Le-1) to (Le-3) is preferably an alkyl group or an alkoxy group, and more preferably an alkoxy group, from the viewpoint of color development and visibility of the exposed portion. It is preferably a methoxy group, and particularly preferably a methoxy group.
  • Rb 1 to Rb 4 in the formulas (Le-1) to (Le-3) are preferably hydrogen atoms or alkyl groups independently from the viewpoint of color development and visibility of the exposed portion. It is more preferably an alkyl group and particularly preferably a methyl group.
  • the leuco dye having a phthalide structure or a fluorine structure is a compound represented by any of the following formulas (Le-4) to (Le-6) from the viewpoint of color development and visibility of the exposed portion. It is more preferable that the compound is represented by the following formula (Le-5).
  • ERG each independently represents an electron donating group
  • X 1 ⁇ X 4 are each independently a hydrogen atom, a halogen atom, or a dialkyl anilino Representing a group
  • Y 1 and Y 2 independently represent C or N, where X 1 does not exist when Y 1 is N and X 4 exists when Y 2 is N.
  • Ra 1 represents a hydrogen atom, an alkyl group, or an alkoxy group
  • Rb 1 to Rb 4 independently represent an alkyl group or an aryl group, respectively.
  • ERG, X 1 to X 4 , Y 1 , Y 2 , Ra 1 and Rb 1 to Rb 4 in the formulas (Le-4) to (Le-6) are the formulas (Le-1) to Rb 4 , respectively.
  • the leuco dye having the phthalide structure or the fluorine structure is a compound represented by any of the following formulas (Le-7) to (Le-9) from the viewpoint of color development and visibility of the exposed portion. Is more preferable, and a compound represented by the following formula (Le-8) is particularly preferable.
  • X 1 ⁇ X 4 are each independently a hydrogen atom, a halogen atom or a dialkyl anilino group
  • Y 1 and Y 2 are each independently Representing C or N, when Y 1 is N, X 1 does not exist, when Y 2 is N, X 4 does not exist
  • Ra 1 to Ra 4 are independently hydrogen.
  • Rb 1 to Rb 4 independently represent an alkyl group or an aryl group
  • Rc 1 and Rc 2 each independently represent an aryl group.
  • Ra 1 to Ra 4 in the formulas (Le-7) to (Le-9) are preferably alkyl groups or alkoxy groups independently from the viewpoint of color development and visibility of the exposed portion. It is more preferably an alkoxy group, and particularly preferably a methoxy group.
  • Rb 1 to Rb 4 in the formulas (Le-7) to (Le-9) are independently substituted with hydrogen atoms, alkyl groups, or alkoxy groups from the viewpoint of color development and visibility of the exposed portion. It is preferably an aryl group, more preferably an alkyl group, and particularly preferably a methyl group.
  • Rc 1 and Rc 2 in the formulas (Le-7) to (Le-9) are independently phenyl groups or alkylphenyl groups from the viewpoint of color development and visibility of the exposed portion. Is preferable, and a phenyl group is more preferable.
  • X 1 to X 4 are hydrogen atoms and Y 1 and Y 2 are C from the viewpoint of color development and visibility of the exposed portion.
  • Rb 1 and Rb 2 are independently alkyl groups or aryl groups substituted with an alkoxy group.
  • the alkyl group in the formulas (Le-1) to (Le-9) may be linear, have a branch, or have a ring structure. Further, the number of carbon atoms of the alkyl group in the formulas (Le-1) to (Le-9) is preferably 1 to 20, more preferably 1 to 8, and further preferably 1 to 4. It is preferably 1 or 2, and particularly preferably 1. The number of carbon atoms of the aryl group in the formulas (Le-1) to (Le-9) is preferably 6 to 20, more preferably 6 to 10, and particularly preferably 6 to 8.
  • each group such as a monovalent organic group, an alkyl group, an aryl group, a dialkylanilino group, an alkylamino group and an alkoxy group in the formulas (Le-1) to (Le-9) has a substituent.
  • substituents include alkyl groups, aryl groups, halogen atoms, amino groups, alkylamino groups, arylamino groups, dialkylamino groups, monoalkyl monoarylamino groups, diarylamino groups, hydroxy groups, alkoxy groups, allyloxy groups and acyl groups. Examples thereof include a group, an alkoxycarbonyl group, an aryloxycarbonyl group and a cyano group. Further, these substituents may be further substituted with these substituents.
  • leuco dye having a phthalide structure or a fluorine structure that are preferably used include the following compounds (S-1 to S-14).
  • acid color former products include ETAC, RED500, RED520, CVL, S-205, BLACK305, BLACK400, BLACK100, BLACK500, H-7001, GREEN300, NIRBLACK78, BLUE220, H-3035, BLUE203, ATP, H-1046, H-2114 (above, manufactured by Fukui Yamada Chemical Industry Co., Ltd.), ORANGE-DCF, Vermilion-DCF, PINK-DCF, RED-DCF, BLMB, CVL, GREEN-DCF, TH-107 (above, Hodogaya Chemical Co., Ltd.) ), ODB, ODB-2, ODB-4, ODB-250, ODB-BlackXV, Blue-63, Blue-502, GN-169, GN-2, Green-118, Red-40, Red-8 ( As mentioned above, Yamamoto Kasei Co., Ltd.), Crystal Violet lactone (Tokyo Kasei Kog),
  • ETAC, S-205, BLACK305, BLACK400, BLACK100, BLACK500, H-7001, GREEN300, NIRBLACK78, H-3035, ATP, H-1046, H-2114, GREEN-DCF, Blue-63. , GN-169, or crystal violet lactone is preferable because the film to be formed has a good visible light absorption rate.
  • color formers preferably acid color formers
  • the content of the color former is preferably 0.5% by mass to 10% by mass and 1% by mass to 5% by mass with respect to the total mass of the image recording layer. More preferred.
  • the image recording layer in the present disclosure may contain a chain transfer agent.
  • the chain transfer agent contributes to the improvement of printing durability in the lithographic printing plate.
  • a thiol compound is preferable, a thiol having 7 or more carbon atoms is more preferable from the viewpoint of boiling point (difficulty in volatilization), and a compound having a mercapto group on the aromatic ring (aromatic thiol compound) is further preferable.
  • the thiol compound is preferably a monofunctional thiol compound.
  • chain transfer agent examples include the following compounds.
  • the content of the chain transfer agent is preferably 0.01% by mass to 50% by mass, more preferably 0.05% by mass to 40% by mass, and 0.1% by mass to 30% by mass with respect to the total mass of the image recording layer. % Is more preferable.
  • the image recording layer may contain other resin particles different from the specific particles A.
  • the other resin particles are preferably resin particles that can convert the image recording layer into hydrophobic when heat is applied.
  • Other resin particles include hydrophobic thermoplastic resin particles, heat-reactive resin particles, resin particles having a polymerizable group other than specific particles A, microcapsules containing a hydrophobic compound, and microgels (that is, crosslinked resins). It is preferably at least one selected from the particles). Of these, resin particles and microgels having a polymerizable group other than the specific particles A are preferable.
  • hydrophobic thermoplastic resin particles Research Disclosure No. 1 of January 1992. 33303, JP-A-9-123387, 9-131850, 9-171249, 9-171250, European Patent No. 913647, and the like. Preferred. Specific examples of the resin constituting the hydrophobic thermoplastic resin particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinylcarbazole, and a polyalkylene structure. Examples thereof include homopolymers or copolymers of monomers such as acrylates or methacrylates having, or mixtures thereof.
  • a copolymer containing polystyrene, styrene and acrylonitrile, or polymethyl methacrylate may be mentioned.
  • the volume average particle diameter of the hydrophobic thermoplastic resin particles is preferably 0.01 ⁇ m to 2.0 ⁇ m.
  • heat-reactive resin particles examples include resin particles having a heat-reactive group.
  • the resin particles having a heat-reactive group form a hydrophobic region by cross-linking due to a heat reaction and changing the functional group at that time.
  • the thermally reactive group in the resin particles having a thermally reactive group may be a functional group that undergoes any reaction as long as a chemical bond is formed, and a polymerizable group is preferable.
  • a polymerizable group is preferable. Examples include ethylenically unsaturated groups (eg, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.) and cationically polymerizable groups (eg, vinyl group, vinyloxy group, epoxy group, oxetanyl group, etc.) that undergo a radical polymerization reaction.
  • an isocyanato group or a block thereof to carry out an addition reaction an epoxy group, a vinyloxy group and a functional group having an active hydrogen atom which is a reaction partner thereof (for example, an amino group, a hydroxy group, a carboxy group, etc.), a condensation reaction
  • a carboxy group to be carried out a hydroxy group or an amino group as a reaction partner, an acid anhydride for carrying out a ring-opening addition reaction, and an amino group or a hydroxy group to be a reaction partner.
  • microcapsules examples include those in which all or a part of the constituent components of the image recording layer are encapsulated in microcapsules, as described in JP-A-2001-277740 and JP-A-2001-277742.
  • the constituent components of the image recording layer can also be contained outside the microcapsules.
  • the hydrophobic constituents are encapsulated in the microcapsules and the hydrophilic constituents 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 mode in which a reactive microgel is formed by having a radically polymerizable group (more specifically, an ethylenically unsaturated group) on its surface is preferable from the viewpoint of image formation sensitivity and printing resistance.
  • a known method can be used for microencapsulating or microgelling the constituents of the image recording layer.
  • the average particle size of the microcapsules and the microgels is preferably 0.01 ⁇ m to 3.0 ⁇ m, more preferably 0.05 ⁇ m to 2.0 ⁇ m, and particularly preferably 0.10 ⁇ m to 1.0 ⁇ m, respectively. Good resolution and stability over time can be obtained within this range.
  • the content of the other resin particles is preferably 0% by mass to 30% by mass with respect to the total mass of the image recording layer.
  • the image recording layer in the present disclosure may contain a low molecular weight hydrophilic compound in order to improve on-machine developability while suppressing a decrease in printing resistance.
  • 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 further preferably a compound having a molecular weight of less than 500.
  • low-molecular-weight hydrophilic compounds include, as water-soluble organic compounds, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol, and ether or ester derivatives thereof, glycerin.
  • Pentaerythritol tris (2-hydroxyethyl) isocyanurate and other polyols, triethanolamine, diethanolamine, monoethanolamine and other organic amines and salts thereof, alkyl sulfonic acid, toluene sulfonic acid, benzene sulfonic acid and other organic Sulfonic acids and salts thereof, organic sulfamic acids such as alkylsulfamic acid and salts thereof, organic sulfates such as alkylsulfuric acid and alkylether sulfuric acid and salts thereof, organic phosphonic acids such as phenylphosphonic acid and salts thereof, tartaric acid, oxalic acid, Examples thereof include organic carboxylic acids such as citrate, malic acid, lactic acid, gluconic acid and amino acids, salts thereof, betaines and the like.
  • the low molecular weight hydrophilic compound it is preferable to contain 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, and sodium n-octyl sulfonate; 5 , 8,11-Trioxapentadecane-1-sulfonate, 5,8,11-trioxaheptadecane-1-sulfonate, 13-ethyl-5,8,11-trioxaheptadecane-1-sulfon Alkyl sulfonates containing ethylene oxide chains such as sodium acid, sodium 5,8,11,14-tetraoxatetracosan-1-sulfonate; sodium benzenesulfonate, sodium p-toluenesulfonate, p-hydroxybenzenesulfonic
  • organic sulfates include sulfates of alkyl, alkenyl, alkynyl, aryl or heterocyclic monoether of polyethylene oxide.
  • the number of ethylene oxide units is preferably 1 to 4, and the salt is preferably a sodium salt, a potassium salt or a lithium salt.
  • Specific examples include the compounds described in paragraphs 0034 to 0038 of JP-A-2007-276454.
  • betaines compounds having 1 to 5 carbon atoms of the hydrocarbon substituent on the nitrogen atom are preferable, and specific examples thereof include trimethylammonium acetate, dimethylpropylammonium acetate, and 3-hydroxy-4-trimethylammonium.
  • Obutyrate, 4- (1-pyridinio) butyrate, 1-hydroxyethyl-1-imidazolioacetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonio-1-propanesulfonate, 3 -(1-Pyridinio) -1-propanesulfonate and the like can be mentioned.
  • the low-molecular-weight hydrophilic compound Since the low-molecular-weight hydrophilic compound has a small structure of the hydrophobic part and has almost no surface-active action, it is difficult for dampening water to permeate the image part of the image recording layer and reduce the hydrophobicity and film strength of the image part. Therefore, by incorporating the low-molecular-weight hydrophilic compound in the image recording layer, the ink acceptability and printing resistance of the image recording layer can be maintained satisfactorily.
  • the low molecular weight hydrophilic compound may be used alone or in combination of two or more.
  • the content of the low molecular weight hydrophilic compound is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and 2% by mass to 10% by mass with respect to the total mass of the image recording layer. Is more preferable. Good on-machine developability and print resistance can be obtained in this range.
  • the image recording layer in the present disclosure may contain a fat-sensing agent such as a phosphonium compound, a nitrogen-containing low molecular weight compound, and an ammonium group-containing polymer in order to improve the incargability.
  • a fat-sensing agent such as a phosphonium compound, a nitrogen-containing low molecular weight compound, and an ammonium group-containing polymer in order to improve the incargability.
  • these compounds function as a surface coating agent for the inorganic layered compound, and it is possible to suppress a decrease in inking property during printing due to the inorganic layered compound.
  • the fat sensitive agent it is preferable to use a phosphonium compound, a nitrogen-containing low molecular weight compound, and an ammonium group-containing polymer in combination, and a phosphonium compound, a quaternary ammonium salt, and an ammonium group-containing polymer are used in combination. It is more preferable to do so.
  • Examples of the phosphonium compound include the 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) butane-di (hexafluorophosphine), and 1,7-bis (tri). Phenylphosphonio) heptane-sulfate, 1,9-bis (triphenylphosphonio) nonane-naphthalen-2,7-disulfonate and the like can be mentioned.
  • nitrogen-containing low molecular weight compounds examples include amine salts and quaternary ammonium salts.
  • imidazolinium salts, benzoimidazolinium salts, pyridinium salts, quinolinium salts and the like can also be mentioned. Of these, quaternary ammonium salts and pyridinium salts are preferable.
  • tetramethylammonium hexafluorophosphate
  • tetrabutylammonium hexafluorophosphate
  • dodecyltrimethylammonium p-toluenesulfonate
  • benzyltriethylammonium hexafluorophosphate
  • benzyldimethyloctylammonium hexafluorophos.
  • Examples thereof include fert, benzyldimethyldodecylammonium-hexafluorophosphate, compounds described in paragraphs 0021 to 0037 of JP-A-2008-284858 and paragraphs 0030 to 0057 of JP-A-2009-90645.
  • the ammonium group-containing polymer may have an ammonium group in its structure, and a polymer containing 5 mol% to 80 mol% of a (meth) acrylate having an ammonium group in the side chain as a copolymerization component is preferable.
  • Specific examples include the polymers described in paragraphs 0008-0105 of JP2009-208458A.
  • the ammonium salt-containing polymer preferably has a reduced specific viscosity (unit: ml / g) value in the range of 5 to 120, which is obtained according to the measurement method described in JP-A-2009-208458, and is in the range of 10 to 110. Is more preferable, and those in the range of 15 to 100 are particularly preferable.
  • Mw weight average molecular weight
  • the content of the oil-sensitive agent is preferably 0.01% by mass to 30.0% by mass, more preferably 0.1% by mass to 15.0% by mass, and 1% by mass with respect to the total mass of the image recording layer. % To 10% by mass is more preferable.
  • the image recording layer in the present disclosure can contain a dye having a large absorption in the visible light region as an image colorant.
  • a colorant By containing a colorant, it becomes easy to distinguish between the image portion and the non-image portion after image formation, and therefore it is preferable to include the colorant.
  • oil yellow # 101, oil yellow # 103, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 Orient Chemical Industry Co., Ltd., Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Ethyl Violet 6HNAPS, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI52015) and Examples of the dyes described in JP-A-62-293247. Further, pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide can also be preferably used.
  • the amount of the colorant added is preferably 0.005% by mass to 10% by mass with respect to the total mass of the image recording layer.
  • the image recording layer in the present disclosure preferably contains a fluorine-containing copolymer, and more preferably a fluorine-containing copolymer having a structural unit formed of a fluorine-containing monomer.
  • fluorine-containing copolymers fluoroaliphatic group-containing copolymers are preferable.
  • a fluorine-containing copolymer preferably a fluoroaliphatic group-containing copolymer
  • the image recording layer containing a fluorine-containing copolymer (preferably a fluoroaliphatic group-containing copolymer) has a high gradation, and is highly sensitive to laser light, for example, due to scattered light, reflected light, or the like.
  • a lithographic printing plate having good fog and excellent printing resistance can be obtained.
  • the fluoroaliphatic group-containing copolymer preferably has a structural unit formed of a fluoroaliphatic group-containing monomer, and among them, a compound represented by any of the following formulas (F1) and (F2). It is preferable to have a structural unit formed by.
  • R F1 independently represents a hydrogen atom or a methyl group
  • X independently represents an oxygen atom, a sulfur atom, or -N ( RF2 )-.
  • m represents an integer of 1 ⁇ 6
  • n represents an integer of 1 ⁇ 10
  • l represents an integer of 0 ⁇ 10
  • R F2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms represented by RF2 in the formulas (F1) and (F2) is preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, preferably a hydrogen atom or a methyl group. Is more preferable. It is preferable that X in the formulas (F1) and (F2) is an oxygen atom.
  • the m in the formula (F1) is preferably 1 or 2, and more preferably 2.
  • N in the formula (F1) is preferably 2, 4, 6, 8, or 10, and more preferably 4 or 6.
  • the l in the formula (F2) is preferably 0.
  • fluoroaliphatic group-containing monomer containing the compound represented by any of the formulas (F1) and (F2) and the fluorine-containing monomer are shown below, but the fluoroaliphatic group-containing monomer and the fluorine-containing monomer are shown below. , Not limited to these.
  • the fluorine-containing copolymer is composed of at least one compound selected from the group consisting of poly (oxyalkylene) acrylate and poly (oxyalkylene) methacrylate, in addition to the structural unit formed of the fluorine-containing monomer. It is preferable to have more units. Further, the fluoroaliphatic group-containing copolymer is composed of a poly (oxyalkylene) acrylate and a poly (oxy) in addition to a structural unit formed from a compound represented by any of the above formulas (F1) and (F2). It is preferable to further have a structural unit formed by at least one compound selected from the group consisting of alkylene) methacrylate.
  • the polyoxyalkylene group in the poly (oxyalkylene) acrylate and the poly (oxyalkylene) methacrylate can be represented by- (OR F3 ) x- , RF3 represents an alkyl group, and x is an integer of 2 or more. Represent.
  • the RF3 is preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Examples of the linear or branched alkylene group having a carbon number of 2 ⁇ 4, -CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, or -CH (CH 3 ) CH (CH 3 )-preferably.
  • x is preferably an integer of 2 to 100.
  • x "OR F3 " may be the same or different. That is, the polyoxyalkylene group may be one in which two or more kinds of "OR F3 " are regularly or irregularly bonded.
  • the polyoxyalkylene group may be one in which linear or branched oxypropylene units and oxyethylene units are regularly or irregularly bonded. More specifically, the polyoxyalkylene group may be a combination of a linear or branched block of oxypropylene units and a block of oxyethylene units.
  • the polyoxyalkylene group may contain one or more linking groups (for example, -CONH-Ph-NHCO-, -S-, etc., where Ph represents a phenylene group). ..
  • the molecular weight of the polyoxyalkylene group is preferably 250 to 3,000.
  • poly (oxyalkylene) acrylate and the poly (oxyalkylene) methacrylate a commercially available product or a synthetic product may be used.
  • the poly (oxyalkylene) acrylate and the poly (oxyalkylene) methacrylate react, for example, with a hydroxypoly (oxyalkylene) compound with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride, anhydrous acrylic acid, or the like by a known method. It can be synthesized by letting it.
  • hydroxypoly (oxyalkylene) compound a commercially available product may be used, for example, ADEKA (registered trademark) Pluronic manufactured by ADEKA Corporation, ADEKA polyether manufactured by ADEKA Corporation, and Union Carbide Corporation. Examples thereof include Carbowax (registered trademark), Triton manufactured by Dow Chemical Corporation, and PEG manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • ADEKA registered trademark
  • ADEKA polyether manufactured by ADEKA Corporation ADEKA Corporation
  • Union Carbide Corporation examples thereof include Carbowax (registered trademark), Triton manufactured by Dow Chemical Corporation, and PEG manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • poly (oxyalkylene) acrylate and the poly (oxyalkylene) methacrylate poly (oxyalkylene) diacrylate or the like synthesized by a known method may be used.
  • the image recording layer in the present disclosure may contain, as other components, a surfactant, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, inorganic particles, an inorganic layered compound and the like. Specifically, the description in paragraphs 0114 to 0159 of JP-A-2008-284817 can be referred to.
  • the planographic printing plate original plate according to the present disclosure preferably has a water-soluble resin layer (sometimes called a protective layer, an overcoat layer, etc.) on the image recording layer.
  • a water-soluble resin layer sometimes called a protective layer, an overcoat layer, etc.
  • the water-soluble resin layer has a function of suppressing an image formation inhibition reaction in the image recording layer, a function of preventing scratches in the image recording layer, and a function of preventing ablation during high-intensity laser exposure.
  • Have. Water-soluble resin layers exhibiting the above functions are described, for example, in US Pat. Nos. 3,458,311 and JP-A-55-49729.
  • the water-soluble resin used for the water-soluble resin layer is preferably a resin that exhibits low oxygen permeability after the layer is formed.
  • the water-soluble resin is a solution in which 1 g or more of the resin is dissolved in 100 g of pure water at 70 ° C. and 1 g of the resin is dissolved in 100 g of pure water at 70 ° C. and cooled to 25 ° C. A resin that does not precipitate even if.
  • the water-soluble resin used for the water-soluble resin layer include polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, water-soluble cellulose derivative, polyethylene glycol, poly (meth) acrylonitrile, and the like.
  • modified polyvinyl alcohol an acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used. More specifically, the modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137 can be mentioned.
  • the water-soluble resin layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol having a saponification degree of 50% or more.
  • the saponification degree is preferably 60% or more, more preferably 70% or more, still more preferably 85% or more.
  • the upper limit of the saponification degree is not particularly limited, and may be 100% or less.
  • the degree of saponification is measured according to the method described in JIS K 6726: 1994.
  • an aspect containing polyvinyl alcohol and polyethylene glycol is also preferably mentioned.
  • the content of the water-soluble resin is preferably 1% by mass to 99% by mass, more preferably 3% by mass to 97% by mass, and 5% by mass to the total mass of the water-soluble resin layer. It is more preferably 95% by mass.
  • the content of the water-soluble resin is preferably 30% by mass to 95% by mass, preferably 50% by mass to 95% by mass, based on the total mass of the water-soluble resin layer from the viewpoint of developability. Is more preferable, and 60% by mass to 95% by mass is further preferable.
  • the water-soluble resin layer may contain an inorganic layered compound in order to enhance oxygen blocking property.
  • Inorganic laminar compound is a particle having a thin tabular shape, for example, natural mica, micas such as synthetic mica, wherein: talc represented by 3MgO ⁇ 4SiO ⁇ H 2 O, teniolite, montmorillonite, saponite, hectorite Examples include light, zirconium phosphate and the like.
  • synthetic smectite is also useful.
  • the inorganic layered compound preferably used is a mica compound.
  • Examples of the mica compound include formula: A (B, C) 2-5 D 4 O 10 (OH, F, O) 2 [However, A is any of K, Na, Ca, and B and C are It is any of Fe (II), Fe (III), Mn, Al, Mg, and V, and D is Si or Al. ] Can be mentioned as a group of mica such as natural mica and synthetic mica.
  • natural mica includes muscovite, paragonite, phlogopite, biotite and lepidolite.
  • Synthetic mica includes non-swelling mica such as phlogopite fluorine KMg 3 (AlSi 3 O 10 ) F 2 , potassium tetrasilicon mica KMg 2.5 Si 4 O 10 ) F 2 , and Na tetrasilic mica Namg 2 .5 (Si 4 O 10 ) F 2 , Na or Li teniolite (Na, Li) Mg 2 Li (Si 4 O 10 ) F 2 , montmorillonite-based Na or Li hectrite (Na, Li) 1/8 Mg 2 / 5 Li 1/8 (Si 4 O 10 ) F 2 and other swelling mica can be mentioned.
  • the lattice layer causes a positive charge shortage, and in order to compensate for this, cations such as Li + , Na + , Ca 2+ , and Mg 2+ are adsorbed between the layers.
  • the cations intervening 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 cations swell greatly with water.
  • Swellable synthetic mica has this 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 particles, which can be measured, for example, from a micrograph projection of the particles. The larger the aspect ratio, the greater the effect obtained.
  • the average major axis of the mica compound is preferably 0.3 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 10 ⁇ m, and particularly preferably 1 ⁇ m 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.
  • the preferred embodiment is such that the thickness is about 1 nm to 50 nm and the surface size (major axis) is about 1 ⁇ m to 20 ⁇ m.
  • the content of the inorganic layered compound is preferably 1% by mass to 60% by mass, preferably 3% by mass to 50% by mass, based on the total mass of the water-soluble resin layer. More preferred. 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. Oxygen blocking property is improved in the above range, good sensitivity can be obtained, and deterioration of inking property can be prevented.
  • the water-soluble resin layer may contain a hydrophobic resin.
  • the hydrophobic resin refers to a polymer that dissolves or does not dissolve in less than 5 g of pure water at 125 ° C. and 100 g.
  • examples of the hydrophobic resin include polyethylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, poly (meth) acrylate alkyl ester (for example, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, and poly (meth). ) Butyl acrylate, etc.), copolymers combining raw material monomers of these resins, and the like.
  • the hydrophobic resin preferably contains a polyvinylidene chloride resin. Further, the hydrophobic resin preferably contains a styrene-acrylic copolymer (also referred to as a styrene acrylic resin). Furthermore, the hydrophobic resin is preferably hydrophobic resin particles from the viewpoint of on-machine developability.
  • the hydrophobic resin may be used alone or in combination of two or more.
  • the content of the hydrophobic resin is preferably 1% by mass to 70% by mass and 5% by mass to 50% by mass with respect to the total mass of the water-soluble resin layer. It is more preferably%, and further preferably 10% by mass to 40% by mass.
  • the occupied area ratio of the hydrophobic resin on the surface of the water-soluble resin layer is preferably 30 area% or more, more preferably 40 area% or more, and further preferably 50 area% or more.
  • An upper limit of the occupied area ratio of the hydrophobic resin on the surface of the water-soluble resin layer is, for example, 90 area%.
  • the occupied area ratio of the hydrophobic resin on the surface of the water-soluble resin layer can be measured as follows.
  • the surface of the water-soluble resin layer is irradiated with a Bi ion beam (primary ion) at an acceleration voltage of 30 kV and emitted from the surface.
  • a Bi ion beam primary ion
  • the hydrophobic part is mapped and the area of the hydrophobic part occupying 1 ⁇ m 2 is measured.
  • the occupied area ratio of the hydrophobic portion is obtained, and this is referred to as the "occupied area ratio of the hydrophobic resin on the surface of the water-soluble resin layer".
  • the hydrophobic resin is an acrylic resin
  • the measurement is performed based on the peak of C 6 H 13 O ⁇
  • the hydrophobic resin is polyvinylidene chloride
  • the measurement is performed based on the peak of C 2 H 2 Cl + .
  • the occupied area ratio can be adjusted by the amount of the hydrophobic resin added or the like.
  • the water-soluble resin layer may contain a discoloring compound from the viewpoint of enhancing the visibility of the exposed portion.
  • a discoloring compound it becomes easy to set the brightness change ⁇ L in the lithographic printing plate original plate to 2.0 or more, which will be described later.
  • the brightness change ⁇ L is more preferably 3.0 or more, further preferably 5.0 or more, particularly preferably 8.0 or more, and most preferably 10.0 or more.
  • An upper limit of the brightness change ⁇ L is, for example, 20.0.
  • the brightness change ⁇ L is measured by the following method.
  • the "discolorable compound” refers to a compound whose absorption in the visible light region (wavelength: 400 nm or more and less than 750 nm) changes due to infrared exposure. That is, in the present disclosure, “discoloration” means that the absorption in the visible light region (wavelength: 400 nm or more and less than 750 nm) changes due to infrared exposure.
  • the discoloring compounds in the present disclosure are (1) a compound in which absorption in the visible light region is increased due to infrared exposure compared to before infrared exposure, and (2) absorption in the visible light region due to infrared exposure.
  • the infrared rays in the present disclosure are light rays having a wavelength of 750 nm to 1 mm, and preferably light rays having a wavelength of 750 nm to 1,400 nm.
  • the discoloring compound preferably contains a compound that develops color due to infrared exposure. Further, the discoloring compound is preferably an infrared absorber. Further, the discoloring compound preferably contains a degradable compound that decomposes due to infrared exposure, and more particularly, it may contain a degradable compound that decomposes due to heat, electron transfer, or both due to infrared exposure. preferable. More specifically, the discoloring compounds in the present disclosure are decomposed by infrared exposure (more preferably, by heat, electron transfer, or both due to infrared exposure) and before infrared exposure.
  • the compound has increased absorption in the visible light region, or the absorption has a shorter wavelength and has absorption in the visible light region.
  • “decomposition by electron transfer” means that an electron excited from HOMO (highest occupied orbital) to LUMO (lowest empty orbital) of a discoloring compound by infrared exposure is an electron accepting group (LUMO and potential) in the molecule. It means that the electron transfers in the molecule to a group close to), and the decomposition occurs accordingly.
  • the degradable compound may be a compound that absorbs and decomposes at least one part of light in the infrared wavelength range (wavelength range of 750 nm to 1 mm, preferably wavelength range of 750 nm to 1,400 nm), but may be 750 nm to 1, It is preferably a compound having maximum absorption in the wavelength range of 400 nm. More specifically, the degradable compound is preferably a compound that decomposes due to infrared exposure to produce a compound having a maximum absorption wavelength in the wavelength range of 500 nm to 600 nm.
  • the degradable compound may be a cyanine dye having a group (specifically, R 1 in the following formulas 1-1 to 1-7) that is decomposed by infrared exposure from the viewpoint of enhancing the visibility of the exposed portion.
  • R 1 in the following formulas 1-1 to 1-7
  • the degradable compound is more preferably a compound represented by the following formula 1-1 from the viewpoint of enhancing the visibility of the exposed portion.
  • R 1 represents a group represented by any of the following formulas 2 to 4, and R 11 to R 18 independently represent a hydrogen atom, a halogen atom, -R a , -OR b , and so on.
  • -SR c or represents -NR d R e, in each of R a ⁇ R e independently represents a hydrocarbon group, a 1, a 2 and a plurality of R 11 ⁇ R 18 are linked monocyclic or Polycycles may be formed, where A 1 and A 2 independently represent an oxygen atom, a sulfur atom, or a nitrogen atom, and n 11 and n 12 each independently represent an integer of 0 to 5.
  • n 11 and n 12 is 2 or more, n 13 and n 14 independently represent 0 or 1, L represents an oxygen atom, a sulfur atom, or -NR 10- , and R 10 represents a hydrogen atom, an alkyl group, or an aryl group, and Za represents a counterion that neutralizes the charge.
  • R 20 , R 30 , R 41 and R 42 independently represent an alkyl group or an aryl group
  • Zb represents a charge-neutralizing counterion
  • the wavy line represents the above formula 1-.
  • R 1 represents a group represented by any of the above formulas 2 to 4.
  • the group represented by the formula 2 the group represented by the formula 3, and the group represented by the formula 4 will be described.
  • R 20 represents an alkyl group or an aryl group, and the wavy line portion represents a binding site with a group represented by L in formula 1-1.
  • the alkyl group represented by R 20 an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 15 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms is further preferable.
  • the alkyl group may be linear, have a branch, or have a ring structure.
  • aryl group represented by R 20 an aryl group having 6 to 30 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, and an aryl group having 6 to 12 carbon atoms is further preferable.
  • the R 20 is preferably an alkyl group from the viewpoint of color development.
  • degradable and, from the viewpoint of coloring properties, be the alkyl group represented by R 20, is preferably a secondary alkyl group or a tertiary alkyl group, tertiary alkyl group preferable.
  • the degradability, and, from the viewpoint of coloring properties, the alkyl group represented by R 20, preferably an alkyl group having 1 to 8 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms It is more preferable to have a branched alkyl group having 3 to 6 carbon atoms, an isopropyl group or a tert-butyl group is particularly preferable, and a tert-butyl group is most preferable.
  • the alkyl group represented by R 20 may be a substituted alkyl group substituted with a halogen atom (for example, a chloro group) or the like.
  • ⁇ represents the binding site with the group represented by L in the formula 1-1.
  • R 30 represents an alkyl group or an aryl group, and the wavy line portion represents a binding site with a group represented by L in formula 1-1.
  • the alkyl group and aryl group represented by R 30 are the same as those of the alkyl group and aryl group represented by R 20 in Formula 2, and the preferred embodiment is also the same.
  • the alkyl group represented by R 30 is preferably a secondary alkyl group or a tertiary alkyl group, and preferably a tertiary alkyl group.
  • the alkyl group represented by R 30, preferably an alkyl group having 1 to 8 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms It is more preferable to have a branched alkyl group having 3 to 6 carbon atoms, an isopropyl group or a tert-butyl group is particularly preferable, and a tert-butyl group is most preferable.
  • the alkyl group represented by R 30 is preferably a substituted alkyl group, more preferably a fluorosubstituted alkyl group, and a perfluoroalkyl group. Is more preferable, and a trifluoromethyl group is particularly preferable.
  • the aryl group represented by R 30 is preferably a substituted aryl group, and the substituent is an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) or an alkoxy. Examples thereof include a group (preferably an alkoxy group having 1 to 4 carbon atoms).
  • ⁇ represents the binding site with the group represented by L in the formula 1-1.
  • R 41 and R 42 independently represent an alkyl group or an aryl group
  • Zb represents a charge-neutralizing counterion
  • the wavy line portion is a group represented by L in Formula 1-1. Represents the binding site with.
  • the alkyl group and aryl group represented by R 41 or R 42 are the same as those of the alkyl group and aryl group represented by R 20 in Formula 2, and the preferred embodiment is also the same.
  • the R 41 is preferably an alkyl group from the viewpoint of decomposability and color development.
  • R 42 is preferably an alkyl group from the viewpoint of decomposability and color development.
  • the alkyl group represented by R 41 is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. , Methyl group is particularly preferred.
  • the alkyl group represented by R 42 is preferably a secondary alkyl group or a tertiary alkyl group, and preferably a tertiary alkyl group.
  • the alkyl group represented by R 42 is preferably an alkyl group having 1 to 8 carbon atoms, and is a branched alkyl group having 3 to 10 carbon atoms.
  • a branched alkyl group having 3 to 6 carbon atoms an isopropyl group or a tert-butyl group is particularly preferable, and a tert-butyl group is most preferable.
  • Zb in the formula 4 may be a counterion for neutralizing the charge, and the compound as a whole may be contained in Za in the formula 1-1.
  • Zb is preferably a sulfonate ion, a carboxylate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a p-toluenesulfonate ion, or a perchlorate ion, and more preferably a tetrafluoroborate ion.
  • ⁇ represents the binding site with the group represented by L in the formula 1-1.
  • L is preferably an oxygen atom or ⁇ NR 10 ⁇ , and an oxygen atom is particularly preferable.
  • R 10 in ⁇ NR 10 ⁇ is preferably an alkyl group.
  • the alkyl group represented by R 10 an alkyl group having 1 to 10 carbon atoms is preferable.
  • the alkyl group represented by R 10 may be linear, have a branch, or have a ring structure.
  • a methyl group or a cyclohexyl group is preferable.
  • R 10 in ⁇ NR 10 ⁇ is an aryl group
  • an aryl group having 6 to 30 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, and an aryl group having 6 to 12 carbon atoms is further preferable.
  • these aryl groups may have a substituent.
  • R 11 ⁇ R 18 are each independently a hydrogen atom, -R a, is preferably -OR b, -SR c, or -NR d R e.
  • Hydrocarbon groups represented by R a ⁇ R e is preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably a hydrocarbon group having 1 to 15 carbon atoms, further a hydrocarbon group having 1 to 10 carbon atoms preferable.
  • the hydrocarbon group may be linear, have a branch, or have a ring structure.
  • an alkyl group is particularly preferable.
  • an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 15 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms is further preferable.
  • the alkyl group may be linear, have a branch, or have a ring structure. Specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group.
  • the alkyl group may have a substituent.
  • substituents include an alkoxy group, an aryloxy group, an amino group, an alkylthio group, an arylthio group, a halogen atom, a carboxy group, a carboxylate group, a sulfo group, a sulfonate group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and these. Examples include a group in which the above are combined.
  • R 11 to R 14 in the formula 1-1 are each independently preferably a hydrogen atom or —R a (that is, a hydrocarbon group), more preferably a hydrogen atom or an alkyl group, and the following Except for the case of, it is more preferably a hydrogen atom.
  • R 11 and R 13 bonded to the carbon atom to which L is bonded are preferably an alkyl group, and it is more preferable that both are linked to form a ring.
  • the ring formed may be a monocyclic ring or a polycyclic ring.
  • the ring formed include a monocycle such as a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring and a cyclohexadiene ring, and a polycycle such as an indene ring and an indole ring.
  • R 12 bonded to the carbon atom to which A 1 + is bonded preferably is linked to R 15 or R 16 (preferably R 16 ) to form a ring, and R is bonded to the carbon atom to which A 2 is bonded.
  • 14 is preferably linked to R 17 or R 18 (preferably R 18 ) to form a ring.
  • n 13 is preferably 1 and R 16 is preferably —R a (ie, a hydrocarbon group). Further, it is preferable that R 16 is linked to R 12 bonded to the carbon atom to which A 1 + is bonded to form a ring.
  • R 16 is linked to R 12 bonded to the carbon atom to which A 1 + is bonded to form a ring.
  • an indolium ring, a pyrylium ring, a thiopyrylium ring, a benzoxazoline ring, or a benzoimidazoline ring is preferable, and an indolium ring is more preferable from the viewpoint of enhancing the visibility of the exposed portion. These rings may further have a substituent.
  • n 14 is preferably 1 and R 18 is preferably —R a (ie, a hydrocarbon group). Further, it is preferable that R 18 is linked to R 14 bonded to the carbon atom to which A 2 is bonded to form a ring.
  • R 18 is linked to R 14 bonded to the carbon atom to which A 2 is bonded to form a ring.
  • an indole ring, a pyran ring, a thiopyran ring, a benzoxazole ring, or a benzimidazole ring is preferable, and an indole ring is more preferable from the viewpoint of enhancing the visibility of the exposed portion. These rings may further have a substituent.
  • R 16 and R 18 in the formula 1-1 are preferably the same group, and when they form a ring, it is preferable to form a ring having the same structure except for A 1 + and A 2 .
  • R 15 and R 17 in the formula 1-1 are the same group. Further, R 15 and R 17 are preferably —R a (that is, a hydrocarbon group), more preferably an alkyl group, and further preferably a substituted alkyl group.
  • R 15 and R 17 are preferably substituent alkyl groups from the viewpoint of improving water solubility.
  • Examples of the substituted alkyl group represented by R 15 or R 17 include a group represented by any of the following formulas (a1) to (a4).
  • R W0 represents an alkylene group having 2 to 6 carbon atoms
  • W is a single bond or an oxygen atom
  • n W1 represents an integer of 1 ⁇ 45
  • R W5 represents an alkyl group having 1 to 12 carbon atoms
  • R W2 ⁇ R W4 are each independently a single bond or 1 carbon atoms It represents an alkylene group of ⁇ 12
  • M represents a hydrogen atom, a sodium atom, a potassium atom, or an onium group.
  • alkylene group represented by RW0 in the formula (a1) examples include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, an isopentylene group, and n-.
  • examples thereof include a hexyl group and an isohexyl group, and an ethylene group, an n-propylene group, an isopropylene group, or an n-butylene group is preferable, and an n-propylene group is particularly preferable.
  • n W1 is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.
  • alkyl group represented by RW1 examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group and neopentyl.
  • a group, an n-hexyl group, an n-octyl group, an n-dodecyl group and the like can be mentioned, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group and a tert-butyl group are preferable.
  • Alkyl group represented by R W5 is the same as defined for the alkyl group represented by R W1, preferred embodiments are also the same as the preferred embodiment of the alkyl group represented by R W1.
  • Me represents a methyl group
  • Et represents an ethyl group
  • * represents a binding site
  • alkylene groups represented by RW2 to RW4 in the formulas (a2) to (a4) include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and an isobutylene group.
  • an ethylene group or an n-propylene group is particularly preferable.
  • the two existing Ms may be the same or different.
  • examples of the onium group represented by M include an ammonium group, an iodonium group, a phosphonium group, a sulfonium group and the like.
  • the CO 2 M in the formula (a2), the PO 3 M 2 in the formula (a 2), and the SO 3 M in the formula (a 4) may all have an anion structure in which M is dissociated.
  • Counter cation of the anion structure may be a A 1 +, may be a cation may be included in R 1 -L in Formula 1-1.
  • the group represented by the formula (a1), the formula (a2), or the formula (a4) is preferable.
  • n 11 and n 12 in the formula 1-1 are the same, and an integer of 1 to 5 is preferable, an integer of 1 to 3 is more preferable, 1 or 2 is further preferable, and 2 is particularly preferable.
  • a 1 and A 2 in the formula 1-1 independently represent an oxygen atom, a sulfur atom, or a nitrogen atom, and a nitrogen atom is preferable. It is preferable that A 1 and A 2 in the formula 1-1 are the same atom.
  • Za in Equation 1-1 represents a counterion that neutralizes the charge. If all of R 11 to R 18 and R 1- L are charge-neutral groups, Za is a monovalent counter anion. However, R 11 to R 18 and R 1 to L may have an anion structure or a cation structure. For example, when R 11 to R 18 and R 1 to L have two or more anion structures, Za Can also be a countercation. If the cyanine dye represented by the formula 1-1 has a charge-neutral structure as a whole except for Za, Za is not necessary.
  • Za is a counter anion
  • sulfonate ion carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, p-toluenesulfonate ion, perchlorate ion and the like
  • tetrafluoroborate ion is preferable.
  • alkali metal ion, alkaline earth metal ion, ammonium ion, pyridinium ion, sulfonium ion and the like can be mentioned, and sodium ion, potassium ion, ammonium ion, pyridinium ion or sulfonium ion is preferable, and sodium is preferable. Ions, potassium ions, or ammonium ions are more preferred.
  • the degradable compound is more preferably a compound represented by the following formula 1-2 (that is, a cyanine pigment) from the viewpoint of enhancing the visibility of the exposed portion.
  • R 1 represents a group represented by any of the above formulas 2 to 4, and R 19 to R 22 are independently hydrogen atom, halogen atom, -R a , -OR b , and so on.
  • -CN represents -SR c, or -NR d R e
  • R 23 and R 24 each independently represent a hydrogen atom, or represents a -R a, each is R a ⁇ R e independently, a hydrocarbon group
  • R 19 and R 20 , R 21 and R 22 , or R 23 and R 24 may be connected to form a monocyclic or polycyclic, and L may be an oxygen atom, a sulfur atom, or a sulfur atom.
  • R 10 represents a hydrogen atom, an alkyl group, or an aryl group
  • R d1 to R d4 , W 1 and W 2 each independently may have a substituent.
  • Za represents a counterion that neutralizes the charge.
  • R 1 in Equation 1-2 is synonymous with R 1 in Equation 1-1, and so is the preferred embodiment.
  • R 19 to R 22 are preferably hydrogen atoms, halogen atoms, -R a , -OR b , or -CN, respectively. More specifically, R 19 and R 21 are preferably hydrogen atom, or a -R a. Further, R 20 and R 22 are preferably hydrogen atoms, -R a , -OR b , or -CN. As —R a represented by R 19 to R 22 , an alkyl group or an alkenyl group is preferable. When all of R 19 to R 22 are ⁇ R a, it is preferable that R 19 and R 20 and R 21 and R 22 are connected to form a monocyclic or polycyclic ring. Examples of the ring formed by connecting R 19 and R 20 or R 21 and R 22 include a benzene ring and a naphthalene ring.
  • R 23 and R 24 are connected to form a monocyclic or polycyclic ring.
  • the ring formed by connecting R 23 and R 24 may be a monocyclic ring or a polycyclic ring.
  • Specific examples of the ring formed include a monocycle such as a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring and a cyclohexadiene ring, and a polycycle such as an inden ring.
  • R d1 to R d4 are preferably unsubstituted alkyl groups. Further, it is preferable that R d1 to R d4 are all the same group. Examples of the unsubstituted alkyl group include an unsubstituted alkyl group having 1 to 4 carbon atoms, and among them, a methyl group is preferable.
  • W 1 and W 2 are preferably substituted alkyl groups independently from the viewpoint of increasing water solubility in the compound represented by formula 1-2.
  • Examples of the substituted alkyl group represented by W 1 and W 2 include groups represented by any of the formulas (a1) to (a4) in the formula 1-1, and the preferred embodiment is also the same.
  • W 1 and W 2 are independently alkyl groups having a substituent from the viewpoint of on-machine developability, and the above-mentioned substituents include- (OCH 2 CH 2 )-, a sulfo group and a sulfo group.
  • a carboxy group, or a group having at least a salt of a carboxy group is preferable.
  • Za represents a counterion that neutralizes the charge in the molecule. If all of R 19 to R 22 , R 23 to R 24 , R d1 to R d4 , W 1 , W 2 , and R 1 to L are charge-neutral groups, then Za is a monovalent pair. It becomes an anion. However, R 19 to R 22 , R 23 to R 24 , R d1 to R d4 , W 1 , W 2 , and R 1 to L may have an anionic structure or a cation structure, for example, R.
  • Za can also be a counter cation if 19 -R 22 , R 23 -R 24 , R d1 -R d4 , W 1 , W 2 , and R 1- L have more than one anionic structure. If the compound represented by the formula 1-2 has a charge-neutral structure as a whole except for Za, Za is not necessary.
  • the example when Za is a counter anion is the same as that of Za in the formula 1-1, and the preferred embodiment is also the same. Further, the case where Za is a counter cation is the same as that of Za in the formula 1-1, and the preferred embodiment is also the same.
  • the cyanine dye as a degradable compound is more preferably a compound represented by any of the following formulas 1-3 to 1-7 from the viewpoint of degradability and color development.
  • the compound represented by any of the formulas 1-3, 1-5, and 1-6 is preferable.
  • R 1 represents a group represented by any of the above formulas 2 to 4, and R 19 to R 22 are independently hydrogen atom, halogen atom, and ⁇ R a. , -OR b, -CN, -SR c, or represents -NR d R e, each R 25 and R 26 independently represent a hydrogen atom, a halogen atom, or represents a -R a, R a ⁇ R e each independently represents a hydrocarbon group, and R 19 and R 20 , R 21 and R 22 , or R 25 and R 26 may be linked to form a monocyclic or polycyclic, and L is , Oxygen atom, sulfur atom, or -NR 10- , R 10 represents a hydrogen atom, an alkyl group, or an aryl group, and R d1 to R d4 , W 1 and W 2 are independent of each other.
  • Za represents a counteri
  • R 1, R 19 ⁇ R 22 in Formula 1-3 to Formula 1-7, R d1 ⁇ R d4, W 1, W 2, and L is, R 1 in Formula 1-2, R 19 ⁇ R 22, R d1 ⁇ R d4, W 1, W 2, and has the same meaning as L, and also the same preferred embodiment.
  • R 25 and R 26 in Formula 1-7 are each independently preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, and particularly preferably a methyl group.
  • the infrared absorbing compound described in International Publication No. 2019/219560 can be preferably used.
  • an acid color former as a discolorant compound.
  • the acid color former those described as the acid color developer in the image recording layer can be used, and the preferred embodiment is also the same.
  • the discoloring compound may be used alone or in combination of two or more kinds of components.
  • the above-mentioned acid coloring agent and a known acid generating agent may be used in combination.
  • the content of the discoloring compound in the water-soluble resin layer is preferably 0.10% by mass to 50% by mass, preferably 0.50% by mass to 30% by mass, based on the total mass of the water-soluble resin layer from the viewpoint of color development. % Is more preferable, and 1.0% by mass to 20% by mass is further preferable.
  • the ratio M X / M Y between the content M Y of the infrared absorber content M X and the image recording layer of the discoloring compound of the water-soluble resin layer is, in terms of color development property, 0.1 or higher Is more preferable, 0.2 or more is more preferable, and 0.3 or more and 3.0 or less is particularly preferable.
  • the water-soluble resin layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coatability, and inorganic particles for controlling the slipperiness of the surface. .. Further, the water-soluble resin layer may contain the oil-sensitive agent described in the image recording layer.
  • the water-soluble resin layer is applied by a known method.
  • the coating amount of the overcoat layer (solid content) is preferably from 0.01g / m 2 ⁇ 10g / m 2, more preferably 0.02g / m 2 ⁇ 3g / m 2, 0.02g / m 2 ⁇ 1g / m 2 is particularly preferred.
  • the thickness of the water-soluble resin layer in the planographic printing plate original plate according to the present disclosure is preferably 0.1 ⁇ m to 5.0 ⁇ m, and more preferably 0.3 ⁇ m to 4.0 ⁇ m.
  • the thickness of the water-soluble resin layer in the lithographic printing plate original plate according to the present disclosure is preferably 20% or more (that is, 0.20 times or more) with respect to the thickness of the image recording layer, and is 100% or more (that is, 1. It is more preferably 0 times or more, preferably 100% (that is, 1.0 times) to 500% (that is, 5.0 times), and 150% (that is, 1.5 times) to 300% (that is, that is). 3.0 times) is more preferable.
  • the aluminum support in the lithographic printing plate original plate according to the present disclosure can be appropriately selected from known aluminum supports for lithographic printing plate original plates and used.
  • the aluminum support is also simply referred to as a "support”.
  • an aluminum support having a hydrophilic surface (hereinafter, also referred to as “hydrophilic aluminum support”) is preferable.
  • the aluminum support in the lithographic printing plate original plate according to the present disclosure has a contact angle with water on the surface of the aluminum support on the image recording layer side by the aerial water droplet method of 110 ° or less from the viewpoint of suppressing scratches and stains.
  • the contact angle with water by the aerial water droplet method on the surface of the aluminum support on the image recording layer side shall be measured by the following method.
  • the lithographic printing plate original plate is immersed in a solvent capable of removing the image recording layer (for example, the solvent used in the coating liquid for the image recording layer), and the image recording layer is scraped off at least one of the sponge and cotton to obtain the image recording layer.
  • the surface of the aluminum support is exposed by dissolving it in a solvent.
  • a hydrophilic compound described later may be present on the surface of the aluminum support exposed by the above method. Therefore, for example, the contact angle with water on the surface may be adjusted by the hydrophilic compound remaining on the surface of the aluminum support.
  • the contact angle with water on the surface of the exposed aluminum support on the image recording layer side is measured on the surface at 25 ° C. by a fully automatic contact angle meter (for example, DM-501 manufactured by Kyowa Surface Chemistry Co., Ltd.) as a measuring device. It is measured as the contact angle of water droplets (after 0.2 seconds).
  • a fully automatic contact angle meter for example, DM-501 manufactured by Kyowa Surface Chemistry Co., Ltd.
  • the aluminum support in the present disclosure an aluminum plate that has been roughened and anodized by a known method is preferable. That is, the aluminum support in the present disclosure preferably has an aluminum plate and an anodized film of aluminum arranged on the aluminum plate.
  • the support (1) has an aluminum plate and an anodized film of aluminum arranged on the aluminum plate, and the anodized film is located closer to the image recording layer than the aluminum plate.
  • the anodic oxide film has micropores extending in the depth direction from the surface on the image recording layer side, and the average diameter of the micropores on the surface of the anodic oxide film is more than 10 nm and 100 nm or less, and the anodic oxidation.
  • the value of the brightness L * in the L * a * b * color system of the surface of the film on the image recording layer side is 70 to 100.
  • FIG. 1 is a schematic cross-sectional view of an embodiment of the aluminum support 12a.
  • the aluminum support 12a has a laminated structure in which an aluminum plate 18 and an anodized film 20a of aluminum (hereinafter, also simply referred to as “anodized film 20a”) are laminated in this order.
  • the anodized film 20a in the aluminum support 12a is located closer to the image recording layer than the aluminum plate 18. That is, it is preferable that the lithographic printing plate original plate according to the present disclosure has at least an anodized film, an image recording layer, and a water-soluble resin layer on an aluminum plate in this order.
  • the anodized film 20a is a film formed on the surface of the aluminum plate 18 by anodizing treatment, and this film is extremely fine micropores 22a which are substantially perpendicular to the film surface and are uniformly distributed among individuals.
  • the micropores 22a extend from the surface of the anodized film 20a on the image recording layer side (the surface of the anodized film 20a on the side opposite to the aluminum plate 18 side) along the thickness direction (aluminum plate 18 side).
  • the average diameter (average opening diameter) of the micropores 22a in the anodized film 20a on the surface of the anodized film is preferably more than 10 nm and 100 nm or less. Among them, from the viewpoint of the balance between printing resistance, stain resistance, and image visibility, 15 nm to 60 nm is more preferable, 20 nm to 50 nm is further preferable, and 25 to 40 nm is particularly preferable.
  • the diameter inside the pores may be wider or narrower than the surface layer. If the average diameter exceeds 10 nm, the printing resistance and image visibility are further excellent. Further, when the average diameter is 100 nm or less, the printing resistance is further excellent.
  • the average diameter of the micropores 22a is 400 ⁇ 600 nm in the four images obtained by observing the surface of the anodized film 20a with a field emission scanning electron microscope (FE-SEM) at a magnification of 150,000.
  • the diameter (diameter) of the micropores existing in the range of 2 is measured at 50 points and calculated as an arithmetic average value. If the shape of the micropore 22a is not circular, the diameter equivalent to the circle is used.
  • the "circle equivalent diameter” is the diameter of a circle when the shape of the opening is assumed to be a circle having the same projected area as the projected area of the opening.
  • the depth of the micropore 22a is not particularly limited, but is preferably 10 nm to 3000 nm, more preferably 50 nm to 2000 nm, and even more preferably 300 nm to 1600 nm.
  • the depth is an average value obtained by taking a photograph (150,000 times) of the cross section of the anodized film 20a and measuring the depths of 25 or more micropores 22a.
  • the shape of the micropore 22a is not particularly limited, and in FIG. 2, it is a substantially straight tubular (substantially cylindrical) shape, but it may be a conical shape whose diameter decreases in the depth direction (thickness direction).
  • the shape of the bottom of the micropore 22a is not particularly limited, and may be curved (convex) or flat.
  • the value of L * a * b * brightness L * in the color system of the surface of the aluminum support 12a on the image recording layer side (the surface of the anodized film 20a on the image recording layer side) is preferably 70 to 100. .. Among them, 75 to 100 is preferable, and 75 to 90 is more preferable, in that the balance between printing resistance and image visibility is more excellent.
  • the brightness L * is measured using a color difference meter Specro Eye manufactured by X-Light Co., Ltd.
  • the micropore communicates with the large-diameter hole extending from the surface of the anodic oxide film to a depth of 10 nm to 1,000 nm and the bottom of the large-diameter hole, and is deep from the communication position. It is composed of a small-diameter hole extending from 20 nm to 2,000 nm, and the average diameter of the large-diameter hole on the surface of the anodic oxide film is 15 nm to 100 nm, and the average diameter of the small-diameter hole at the communication position.
  • a mode in which the diameter is 13 nm or less (hereinafter, the support according to the above mode is also referred to as “support (2)”) is also preferably mentioned.
  • support (2) is also preferably mentioned.
  • the aluminum support 12b includes an aluminum plate 18 and an anodic oxide film 20b having a micropore 22b composed of a large-diameter hole portion 24 and a small-diameter hole portion 26.
  • the micropores 22b in the anodized film 20b communicate with the large-diameter hole portion 24 extending from the surface of the anodized film to a position at a depth of 10 nm to 1000 nm (depth D: see FIG. 2) and the bottom of the large-diameter hole portion 24.
  • the large-diameter hole portion 24 and the small-diameter hole portion 26 will be described in detail below.
  • the average diameter of the large-diameter pore portion 24 on the surface of the anodized film 20b is the same as the average diameter of the micropores 22a in the above-mentioned anodized film 20a on the surface of the anodized film, which is more than 10 nm and 100 nm or less, and the preferable range is also the same. Is.
  • the method for measuring the average diameter on the surface of the anodic oxide film 20b of the large-diameter hole portion 24 is the same as the method for measuring the average diameter on the surface of the anodic oxide film of the micropores 22a in the anodic oxide film 20a.
  • the bottom of the large-diameter hole portion 24 is located at a depth of 10 nm to 1,000 nm (hereinafter, also referred to as a depth D) from the surface of the anodized film. That is, the large-diameter hole portion 24 is a hole portion extending from the surface of the anodized film to a position of 10 nm to 1,000 nm in the depth direction (thickness direction).
  • the depth is preferably 10 nm to 200 nm.
  • the depth is an average value obtained by taking a photograph (150,000 times) of the cross section of the anodized film 20b, measuring the depths of 25 or more large-diameter hole portions 24, and averaging them.
  • the shape of the large-diameter hole portion 24 is not particularly limited, and examples thereof include a substantially straight tubular shape (substantially cylindrical) and a conical shape whose diameter decreases in the depth direction (thickness direction). preferable.
  • the small-diameter hole portion 26 is a hole portion that communicates with the bottom portion of the large-diameter hole portion 24 and extends further in the depth direction (thickness direction) from the communication position.
  • the average diameter of the small-diameter hole portion 26 at the communication position is preferably 13 nm or less. Of these, 11 nm or less is preferable, and 10 nm or less is more preferable.
  • the lower limit is not particularly limited, but it is often 5 nm or more.
  • the diameter (diameter) of the (small diameter hole) is measured and obtained as an arithmetic mean value. If the large-diameter hole is deep, the upper part of the anodic oxide film 20b (the region with the large-diameter hole) is cut (for example, cut with argon gas), and then the anodic oxide film 20b is cut.
  • the surface may be observed with the above FE-SEM to obtain the average diameter of the small-diameter holes.
  • the diameter equivalent to a circle is used.
  • the "circle equivalent diameter” is the diameter of a circle when the shape of the opening is assumed to be a circle having the same projected area as the projected area of the opening.
  • the bottom portion of the small-diameter hole portion 26 is located at a position extending 20 nm to 2000 nm in the depth direction from the communication position with the large-diameter hole portion 24 described above.
  • the small-diameter hole portion 26 is a hole portion that extends further in the depth direction (thickness direction) from the communication position with the large-diameter hole portion 24, and the depth of the small-diameter hole portion 26 is 20 nm to 2000 nm.
  • the depth is preferably 500 nm to 1500 nm.
  • the depth is an average value obtained by taking a photograph (50,000 times) of the cross section of the anodized film 20b and measuring the depths of 25 or more small-diameter holes.
  • the shape of the small-diameter hole portion 26 is not particularly limited, and examples thereof include a substantially straight tubular (approximately cylindrical) shape and a conical shape whose diameter decreases in the depth direction, and a substantially straight tubular shape is preferable.
  • -Roughening treatment step A step of roughening an aluminum plate-Anodization treatment step: A step of anodizing an aluminum plate that has been roughened-Pore wide treatment step: Anodizer obtained in an anodization treatment step Step of bringing an aluminum plate having an oxide film into contact with an acid aqueous solution or an alkaline aqueous solution to increase the diameter of micropores in the anodic oxide film.
  • the roughening treatment step is a step of applying a roughening treatment including an electrochemical roughening treatment to the surface of the aluminum plate. This step is preferably carried out before the anodizing treatment step described later, but it may not be carried out in particular as long as the surface of the aluminum plate already has a preferable surface shape.
  • the roughening treatment may be carried out only by the electrochemical roughening treatment, but is carried out by combining the electrochemical roughening treatment with the mechanical roughening treatment and / or the chemical roughening treatment. You may.
  • the electrochemical roughening treatment is preferably carried out using direct current or alternating current in an aqueous solution mainly containing nitric acid or hydrochloric acid.
  • the method of mechanical roughening treatment is not particularly limited, and examples thereof include the methods described in Japanese Patent Publication No. 50-40047.
  • the chemical roughening treatment is also not particularly limited, and known methods can be mentioned.
  • the chemical etching treatment performed after the mechanical roughening treatment smoothes the uneven edges on the surface of the aluminum plate, prevents ink from getting caught during printing, and improves the stain resistance of the printing plate. , It is performed to remove unnecessary substances such as abrasive particles remaining on the surface.
  • Examples of the chemical etching treatment include etching with an acid and etching with an alkali, and as a method particularly excellent in terms of etching efficiency, a chemical etching treatment using an alkaline aqueous solution (hereinafter, also referred to as “alkali etching treatment”) can be mentioned. Be done.
  • the alkaline agent used in the alkaline aqueous solution is not particularly limited, and examples thereof include caustic soda, caustic potash, sodium metasilicate, sodium carbonate, sodium aluminate, and sodium gluconate.
  • the alkaline aqueous solution may contain aluminum ions.
  • the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.01% by mass or more, more preferably 3% by mass or more, and preferably 30% by mass or less.
  • the alkaline etching treatment When the alkaline etching treatment is performed, it is preferable to perform a chemical etching treatment (hereinafter, also referred to as "desmat treatment") using a low-temperature acidic aqueous solution in order to remove the product generated by the alkaline etching treatment.
  • the acid used in the acidic aqueous solution is not particularly limited, and examples thereof include sulfuric acid, nitric acid, and hydrochloric acid.
  • the temperature of the acidic aqueous solution is preferably 20 ° C to 80 ° C.
  • (1) mechanical roughening treatment may be carried out before the treatment of (2) of the A aspect or (10) of the B aspect.
  • the amount of the aluminum plate dissolved in the first alkali etching treatment and the fourth alkali etching treatment is preferably 0.5 g / m 2 to 30 g / m 2, and more preferably 1.0 g / m 2 to 20 g / m 2 .
  • Examples of the nitric acid-based aqueous solution used in the first electrochemical roughening treatment in the A aspect include an aqueous solution used in the electrochemical roughening treatment using direct current or alternating current.
  • an aqueous solution obtained by adding aluminum nitrate, sodium nitrate, ammonium nitrate or the like to an aqueous nitric acid solution of 1 to 100 g / L can be mentioned.
  • the aqueous solution mainly containing hydrochloric acid used in the second electrochemical roughening treatment in the A aspect and the third electrochemical roughening treatment in the B aspect is an electrochemical rough surface using ordinary direct current or alternating current. Examples thereof include an aqueous solution used for the chemical treatment.
  • an aqueous solution obtained by adding 0 g / L to 30 g / L of sulfuric acid to a 1 g / L to 100 g / L hydrochloric acid aqueous solution can be mentioned.
  • nitrate ions such as aluminum nitrate, sodium nitrate and ammonium nitrate
  • hydrochloric acid ions such as aluminum chloride, sodium chloride and ammonium chloride may be further added to this solution.
  • FIG. 3 is a graph showing an example of an alternating current waveform diagram used in the electrochemical roughening process.
  • ta is the anode reaction time
  • ct is the cathode reaction time
  • tp is the time from 0 to the peak of the current
  • Ia is the peak current on the anode cycle side
  • Ic is the peak current on the cathode cycle side.
  • AA is the current of the anode reaction of the aluminum plate
  • CA is the current of the cathode reaction of the aluminum plate.
  • the time tp from 0 to the peak of the current is preferably 1 to 10 ms.
  • the conditions for one cycle of AC used for electrochemical roughening are that the ratio ct / ta of the anode reaction time ta and the cathode reaction time ct of the aluminum plate is 1 to 20, and the amount of electricity Qc and the anode when the aluminum plate is the anode.
  • the ratio Qc / Qa of the amount of electricity Qa at the time is in the range of 0.3 to 20 and the anode reaction time ta is in the range of 5 ms to 1000 ms.
  • the current density is preferably 10 A / dm 2 to 200 A / dm 2 for both the anode cycle side Ia and the cathode cycle side Ic of the current at the peak value of the trapezoidal wave.
  • Ic / Ia is preferably 0.3 to 20.
  • the total amount of electricity participating in the anode reaction of the aluminum plate at the time when the electrochemical roughening is completed is preferably 25 C / dm 2 to 1000 C / dm 2 .
  • FIG. 4 is a side view showing an example of a radial cell in an electrochemical roughening treatment using alternating current.
  • 50 is a main electrolytic cell
  • 51 is an AC power supply
  • 52 is a radial drum roller
  • 53a and 53b are main poles
  • 54 is an electrolytic solution supply port
  • 55 is an electrolytic solution
  • 56 is a slit
  • 57 is an electrolytic solution passage.
  • 58 is an auxiliary anode
  • 60 is an auxiliary anode tank
  • W is an aluminum plate.
  • the arrow A1 indicates the supply direction of the electrolytic solution
  • the arrow A2 indicates the discharge direction of the electrolytic solution.
  • the electrolysis conditions may be the same or different.
  • the aluminum plate W is wound around a radial drum roller 52 immersed in the main electrolytic cell 50 and is electrolyzed by the main poles 53a and 53b connected to the AC power supply 51 during the transfer process.
  • the electrolytic solution 55 is supplied from the electrolytic solution supply port 54 to the electrolytic solution passage 57 between the radial drum roller 52 and the main poles 53a and 53b through the slit 56.
  • the aluminum plate W treated in the main electrolytic cell 50 is then electrolyzed in the auxiliary anode tank 60.
  • An auxiliary anode 58 is arranged to face the aluminum plate W in the auxiliary anode tank 60, and the electrolytic solution 55 is supplied so as to flow in the space between the auxiliary anode 58 and the aluminum plate W.
  • the amount of the aluminum plate dissolved in the second alkali etching treatment is preferably 1.0 g / m 2 or more, and more preferably 2.0 g / m 2 to 10 g / m 2 in that a predetermined printing plate original plate can be easily produced.
  • the amount of the aluminum plate dissolved in the third alkali etching treatment and the fourth alkali etching treatment is preferably 0.01 g / m 2 to 0.8 g / m 2 and 0.05 g in that a predetermined printing plate original plate can be easily produced.
  • / M 2 to 0.3 g / m 2 is more preferable.
  • an acidic aqueous solution containing phosphoric acid, nitric acid, sulfuric acid, chromium acid, hydrochloric acid, or a mixed acid containing two or more of these acids is preferably used.
  • the acid concentration of the acidic aqueous solution is preferably 0.5% by mass to 60% by mass.
  • the procedure of the anodizing treatment step is not particularly limited as long as the above-mentioned micropores can be obtained, and known methods can be mentioned.
  • aqueous solutions of sulfuric acid, phosphoric acid, oxalic acid and the like can be used as the electrolytic bath.
  • the concentration of sulfuric acid is 100 g / L to 300 g / L.
  • the conditions for the anodic oxidation treatment are appropriately set depending on the electrolytic solution used, and for example, the liquid temperature is 5 ° C. to 70 ° C. (preferably 10 ° C. to 60 ° C.), and the current density is 0.5 A / dm 2 to 60 A / dm 2.
  • the pore-wide treatment is a treatment (pore diameter enlargement treatment) for enlarging the diameter (pore diameter) of micropores existing in the anodizing film formed by the above-mentioned anodizing treatment step.
  • the pore-wide treatment can be carried out by bringing the aluminum plate obtained by the above-mentioned anodizing treatment step into contact with an acid aqueous solution or an alkaline aqueous solution.
  • the method of contact is not particularly limited, and examples thereof include a dipping method and a spraying method.
  • the planographic printing plate original plate according to the present disclosure preferably has an undercoat layer (sometimes referred to as an intermediate layer) between the image recording layer and the support.
  • the undercoat layer strengthens the adhesion between the support and the image recording layer in the exposed area, makes it easy for the image recording layer to peel off from the support in the unexposed area, and develops while suppressing the deterioration of printing durability. May contribute to improving sex.
  • the undercoat layer may function as a heat insulating layer in the case of infrared laser exposure, and may also have an effect of preventing heat generated by the exposure from diffusing to the support and lowering the sensitivity.
  • the compound used for the undercoat layer may be a low molecular weight compound or a polymer.
  • 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.
  • the compound used for the undercoat layer is preferably a polymer having an adsorptive group and a hydrophilic group adsorbable on the surface of the support and further having a crosslinkable group.
  • two or more kinds may be mixed and used as needed.
  • 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.
  • Adsorbent groups that can be adsorbed on the surface of the support include phenolic hydroxy groups, carboxy groups, -PO 3 H 2 , -OPO 3 H 2 , -CONHSO 2- , -SO 2 NHSO 2- , -COCH 2 COCH 3 Is preferable.
  • As the 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 of the polar substituent of the polymer, a substituent having a pair charge with the polar substituent and a compound having an ethylenically unsaturated bond, and the above.
  • a monomer other than the above, preferably a hydrophilic monomer, may be further copolymerized.
  • a silane coupling agent having an addition-polymerizable ethylenic double bond reactive group described in JP-A-10-228679, JP-A-2-304441 Preferable examples thereof include phosphorus compounds having an ethylenic double bond reactive group described in Japanese Patent Publication No.
  • Crosslinkable groups preferably ethylenically unsaturated groups
  • support surfaces described in JP-A-2005-238816, JP-A-2005-125479, JP-A-2006-239867, and JP-A-2006-215263.
  • Low molecular weight or high molecular weight compounds having functional groups and hydrophilic groups that interact with are also preferably used. More preferred are polymer polymers having an adsorptive group, a hydrophilic group and a crosslinkable group that can be adsorbed on the surface of the support described in JP-A-2005-125794 and JP-A-2006-188038.
  • the content of the ethylenically unsaturated group in the polymer used for the undercoat layer is preferably 0.1 mmol to 10.0 mmol, more preferably 0.2 mmol to 5.5 mmol, per 1 g of the polymer.
  • the weight average molecular weight (Mw) of the polymer used in the undercoat layer is preferably 5,000 or more, and more preferably 10,000 to 300,000.
  • the undercoat layer preferably contains a hydrophilic compound in addition to the above polymer.
  • the hydrophilic compound is not particularly limited, and a known hydrophilic compound used for the undercoat layer can be used.
  • Preferred examples of the hydrophilic compound include phosphonic acids having an amino group such as carboxymethyl cellulose and dextrin, organic phosphonic acid, organic phosphoric acid, organic phosphinic acid, amino acids, and hydrochloride of amine having a hydroxy group.
  • hydrophilic compound a compound having an amino group or a functional group having a polymerization prohibitive ability and a group interacting with the surface of the support (for example, 1,4-diazabicyclo [2.2.2] octane (DABCO)).
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • 2,3,5,6-tetrahydroxy-p-quinone, chloranyl, sulfophthalic acid, ethylenediaminetetraacetic acid (EDTA) or its salt, hydroxyethylethylenediaminetriacetic acid or its salt, dihydroxyethylethylenediaminediacetic acid or its salt, hydroxy (Ethyliminodiacetic acid or a salt thereof, etc.) is preferably mentioned.
  • the hydrophilic compound hydroxycarboxylic acid or a salt thereof is preferably used from the viewpoint of suppressing scratches and stains.
  • the hydrophilic compound (preferably hydroxycarboxylic acid or a salt thereof) is preferably contained not only in the undercoat layer but also in the layer on the aluminum support from the viewpoint of suppressing scratches and stains.
  • the layer on the aluminum support is preferably a layer on the side where the image recording layer is formed, and is preferably a layer in contact with the aluminum support.
  • an undercoat layer or an image recording layer is preferably mentioned as a layer in contact with the aluminum support.
  • a layer other than the layer in contact with the aluminum support for example, a protective layer or an image recording layer may contain a hydrophilic compound (preferably hydroxycarboxylic acid or a salt thereof). That is, in the planographic printing plate original plate according to the present disclosure, it is also preferable that the image recording layer contains a hydroxycarboxylic acid or a salt thereof from the viewpoint of suppressing scratches and stains. Further, in the lithographic printing plate original plate according to the present disclosure, an embodiment in which the surface of the aluminum support on the image recording layer side is surface-treated with a composition containing at least hydroxycarboxylic acid or a salt thereof (for example, an aqueous solution) is also preferably mentioned. Be done.
  • a composition containing at least hydroxycarboxylic acid or a salt thereof for example, an aqueous solution
  • At least a part of the treated hydroxycarboxylic acid or a salt thereof is detected in a layer on the image recording layer side (for example, an image recording layer or an undercoat layer) in contact with the aluminum support. can do.
  • a layer on the image recording layer side for example, an image recording layer or an undercoat layer
  • the surface of the aluminum support on the image recording layer side can be made hydrophilic, and the image recording layer of the aluminum support can be made hydrophilic.
  • the contact angle with water on the side surface by the aerial water droplet method can be easily reduced to 110 ° or less, and as a result, a lithographic printing plate original plate having excellent scratch and stain suppression properties can be obtained.
  • hydroxycarboxylic acid is a general term for organic compounds having one or more carboxy groups and one or more hydroxy groups in one molecule, and is a hydroxy acid, an oxy acid, an oxycarboxylic acid, or an alcoholic acid. Also called (see Iwanami Physics and Chemistry Dictionary, 5th Edition, published by Iwanami Shoten Co., Ltd. (1998)).
  • the hydroxycarboxylic acid or a salt thereof is preferably represented by the following formula (HC).
  • R HC (OH) mhc ( COMM HC ) nhc formula (HC)
  • R HC represents a mhc + nhc valent organic group
  • M HC independently represents a hydrogen atom, an alkali metal, or onium
  • mhc and nhc each independently represent an integer of 1 or more. Represented, when n is 2 or more, M may be the same or different.
  • the organic group for mhc + NHC value represented by R HC includes mhc + NHC valent hydrocarbon group.
  • the hydrocarbon group may have a substituent and / or a linking group.
  • a group having a mhc + nhc valence derived from an aliphatic hydrocarbon for example, an alkylene group, an alcantryyl group, an alkanetetrayl group, an alcampentile group, an alkenylene group, an arcentryyl group, an alkentetrayl group.
  • Mhc + nhc valent groups derived from aromatic hydrocarbons such as groups, alkenylpentyl groups, alkynylene groups, alkyntriyl groups, alkynetetrayl groups, alkynpentyl groups, such as allylene groups, allenetriyl groups, Examples thereof include an arene tetrayl group and an allene pentayl group.
  • substituent that can be introduced into the hydrocarbon group include a substituent other than the hydroxyl group and the carboxyl group, such as an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and an aryl group.
  • substituents include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, Octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, Cyclopentyl group, 2-norbornyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, acetyloxymethyl
  • the linking group is composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom, and the number of atoms is preferably 1. ⁇ 50. Specific examples thereof include an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group and the like, and a plurality of these divalent groups are any of an amide bond, an ether bond, a urethane bond, a urea bond, and an ester bond. It may have a connected structure.
  • Examples of the alkali metal represented by MHC include lithium, sodium, potassium and the like, and sodium is particularly preferable.
  • M HC from the viewpoint of scratch stain inhibitory, preferably an alkali metal or an onium, and more preferably an alkali metal.
  • the total number of mhc and nhc is preferably 3 or more, more preferably 3 to 8, and even more preferably 4 to 6.
  • the hydroxycarboxylic acid or a salt thereof preferably has a molecular weight of 600 or less, more preferably 500 or less, and particularly preferably 300 or less.
  • the molecular weight is preferably 76 or more.
  • Specific examples of the hydroxycarboxylic acid constituting the hydroxycarboxylic acid or the salt of the hydroxycarboxylic acid include gluconic acid, glycolic acid, lactic acid, tartron acid, and hydroxybutyric acid (2-hydroxybutyric acid, 3-hydroxybutyric acid, ⁇ -Hydroxybutyric acid, etc.), malic acid, tartaric acid, citramal acid, citric acid, isocitrate, leucic acid, mevalonic acid, pantoic acid, ricinolic acid, ricineraidic acid, cerebronic acid, quinic acid, shikimic acid, monohydroxybenzoic acid derivative (Salicylic acid, cleosortic acid (homosalicylic acid, hydroxy (methyl) benzoic
  • hydroxycarboxylic acid or the hydroxycarboxylic acid constituting the salt of the hydroxycarboxylic acid a compound having two or more hydroxy groups is preferable from the viewpoint of suppressing scratches and stains, and a hydroxy group is preferable.
  • a compound having 3 or more hydroxy groups is more preferable, a compound having 5 or more hydroxy groups is further preferable, and a compound having 5 to 8 hydroxy groups is particularly preferable.
  • gluconic acid or shikimic acid is preferable as a substance having one carboxy group and two or more hydroxy groups.
  • Citric acid or malic acid is preferable as having two or more carboxy groups and one hydroxy group.
  • Tartaric acid is preferable as having two or more carboxy groups and two or more hydroxy groups.
  • gluconic acid is particularly preferable as the hydroxycarboxylic acid.
  • the hydrophilic compound may be used alone or in combination of two or more.
  • the content of the hydrophilic compound is 0.01 mass by mass with respect to the total mass of the undercoat layer. It is preferably% to 50% by mass, more preferably 0.1% by mass to 40% by mass, and particularly preferably 1.0% by mass to 30% by mass.
  • the undercoat layer may contain a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, etc. in order to prevent stains over time.
  • the undercoat layer is applied onto the aluminum support by a known method.
  • the coating amount (solid content) of the undercoat layer is preferably 0.1 mg / m 2 to 100 mg / m 2, and more preferably 1 mg / m 2 to 30 mg / m 2 .
  • the method for making a lithographic printing plate according to the present disclosure is not particularly limited as long as it is a method for making a lithographic printing plate using the lithographic printing plate original plate according to the present disclosure.
  • the method for producing a flat plate printing plate according to the present disclosure includes a step of exposing the flat plate printing plate original plate according to the present disclosure to an image (hereinafter, also referred to as an “image exposure step”) and a flat plate printing plate original plate after exposure.
  • a step of supplying at least one selected from the group consisting of printing ink and dampening water to remove the image recording layer of the non-image portion on the printing press (hereinafter, also referred to as "on-machine development processing step") is preferably included.
  • the above plate making method is also referred to as “on-machine development method” below.
  • the flat plate printing method according to the present disclosure is a method of making and printing a flat plate printing plate using the flat plate printing plate original plate according to the present disclosure, and is a step of exposing the flat plate printing plate original plate according to the present disclosure to an image (hereinafter referred to as an image).
  • image exposure process also referred to as “image exposure process”
  • at least one selected from the group consisting of printing ink and dampening water is supplied to the plate original plate after exposure to the image recording layer of the non-image area on the printing machine. It is preferable to include a step of removing the above (hereinafter, also referred to as “on-machine development processing step”) and a step of printing on the obtained flat plate printing plate (also referred to as “printing step”).
  • on-machine development processing step also referred to as “on-machine development processing step”
  • step of printing on the obtained flat plate printing plate also referred to as “printing step”.
  • the discard plate original plate is subjected to a development processing step without going through an image exposure step.
  • lithographic printing plate original plate according to the present disclosure can also be developed with a developing solution.
  • the step of exposing the lithographic printing plate original plate to the image can be performed according to the image exposure operation of the normal lithographic printing plate original plate.
  • Image-like exposure is performed by laser exposure through a transparent original image having a line image, halftone dot image, or the like, or laser light scanning with digital data.
  • the wavelength of the light source is preferably 700 nm to 1,400 nm.
  • a solid-state laser and a semiconductor laser that emit infrared rays are suitable.
  • the output is preferably 100 mW or more, the exposure time per pixel is preferably 20 ⁇ sec or less, and the irradiation energy amount is preferably 10 mJ / cm 2 to 300 mJ / cm 2 . It is preferable to use a multi-beam laser device in order to shorten the exposure time.
  • the exposure mechanism may be any of an inner drum method, an outer drum method, a flatbed method and the like. Image-like exposure can be performed by a conventional method using a platesetter or the like.
  • the development process for the lithographic printing plate original plate after exposure can be performed by a usual method.
  • on-machine development when at least one selected from the group consisting of printing ink and dampening water is supplied to the plate original plate after exposure on the printing machine, the exposed portion of the image recording layer is exposed by exposure.
  • the cured image recording layer forms a printing ink receiving portion (that is, an image portion) having a lipophilic surface.
  • the uncured image recording layer is dissolved or dispersed and removed by at least one selected from the group consisting of the supplied printing ink and dampening water, and a hydrophilic surface is formed on that portion. Is exposed.
  • the dampening water adheres to the exposed hydrophilic surface, and the printing ink is deposited on the image recording layer in the exposed area to start printing.
  • the surface of the lithographic printing plate original plate may be supplied with dampening water or printing ink first, but in order to permeate the dampening water and promote the on-machine developability, the dampening water is first supplied. Is preferably supplied.
  • Printing by the obtained lithographic printing plate can be performed by a usual method.
  • Printing can be performed by supplying the lithographic printing plate with the desired printing ink and, if necessary, dampening water.
  • the supply amounts of the printing ink and the dampening water are not particularly limited and may be appropriately set according to the desired printing.
  • the method of supplying the printing ink and the dampening water to the lithographic printing plate is not particularly limited, and a known method can be used.
  • the recording medium to be printed is not particularly limited, and a known recording medium can be used as desired.
  • the developer used in the developing process is not particularly limited, and a conventionally known developer may be used.
  • a developing solution for example, it is preferable to use a developing solution having a pH of 2 to 11, which may contain at least one compound selected from the group consisting of a surfactant and a water-soluble polymer compound.
  • the developing and gum solution treatment steps can be performed at the same time. Therefore, the post-washing step is not particularly required, and the drying step can be performed after the development and the gum liquid treatment are carried out in one step of one liquid. Therefore, as the developing treatment with a developing solution, it is preferable to develop the lithographic printing plate original plate after exposure with a developing solution having a pH of 2 to 11. After the development treatment, it is preferable to remove excess developer using a squeeze roller and then dry.
  • Performing development and gum liquid treatment in one step of one liquid means that development treatment and gum liquid treatment are performed in one step by one liquid, instead of performing development treatment and gum liquid treatment as separate steps. Means.
  • the developing process with a developing solution can be suitably carried out by an automatic developing processing machine having a developing solution supplying means and a developing processing means provided with a rubbing member.
  • An automatic developing machine using a rotating brush roll as the rubbing member is particularly preferable. Two or more rotary brush rolls are preferable.
  • the automatic developing processing machine is provided with a means for removing excess developing solution such as a squeeze roller and a drying means such as a warm air device after the developing processing means.
  • the automatic developing processing machine may be provided with a preheating means for heat-treating the lithographic printing plate original plate after exposure before the developing processing means.
  • the processing in such an automatic developing processing machine has an advantage that it is freed from dealing with the developing residue derived from the water-soluble resin layer and / or the image recording layer generated in the case of the so-called on-board developing processing.
  • a method of impregnating a sponge, absorbent cotton or the like with an aqueous solution, rubbing the entire plate surface, and drying after completion of the process is preferable.
  • a method of immersing the lithographic printing plate original plate in a vat containing an aqueous solution, a deep tank or the like for about 60 seconds, stirring the mixture, and then rubbing with absorbent cotton, a sponge or the like to dry the plate is preferable.
  • the developing process with a developing solution it is preferable to use an apparatus having a simplified structure and a simplified process.
  • the alkali development treatment the water-soluble resin layer is removed by the pre-washing step, then the development is carried out with a high pH alkaline developer, then the alkali is removed by the post-washing step, and the gum treatment is carried out in the gum pulling step. And dry in the drying process.
  • development and gumming can be performed simultaneously with one liquid. Therefore, the post-washing step and the gum treatment step can be omitted, and it is preferable to perform the development and gum pulling (gum liquid treatment) with one liquid, and then perform the drying step as necessary.
  • a method of immersing in the developing solution once or a method of immersing in the developing solution twice or more may be used.
  • the method of immersing in the developer once or twice is preferable.
  • the exposed lithographic printing plate original plate may be passed through a developing solution tank in which the developing solution is accumulated, or the developing solution may be sprayed onto the plate surface of the exposed lithographic printing plate original plate from a spray or the like.
  • the same developing solution or the developing solution in which the components of the image recording layer are dissolved or dispersed by the developing process (fatigue solution) is used twice.
  • a one-component development process one-component process
  • the developing treatment with a developing solution is carried out according to a conventional method, preferably at a temperature of 0 ° C. to 60 ° C., more preferably 15 ° C. to 40 ° C.
  • the treatment liquid charged in an external tank can be pumped up, sprayed from a spray nozzle, and rubbed with a brush.
  • the developer charged in the external tank can be pumped up, sprayed from the spray nozzle and rubbed with a brush, and then the developer is sprayed again from the spray nozzle and rubbed with a brush.
  • the developing process is performed using an automatic developing machine, the developing solution becomes fatigued due to the increase in the processing amount, so it is preferable to restore the processing capacity by using a replenishing solution or a fresh developing solution.
  • a gum coater or an automatic developing machine conventionally known for PS plate (Presensitized Plate) and CTP (Computer to Plate) can also be used.
  • an automatic developing machine for example, a method in which a developing solution charged in a developing tank or a developing solution charged in an external tank is pumped up by a pump and sprayed from a spray nozzle for processing, or in a tank filled with the developing solution. Both a method of dipping and transporting a printing plate with a guide roll in the liquid and processing, and a so-called disposable processing method of supplying and processing a substantially unused developer in the required amount for each plate can be applied. ..
  • any of the methods those having a rubbing mechanism with a brush, molton or the like are more preferable.
  • commercially available automatic developing machines (Clean Out Unit C85 / C125, Clean-Out Unit + C85 / 120, FCF 85V, FCF 125V, FCF News (made by Grunz & Jensen), Azura CX85, Azura CX85, Azura CX125, AZ
  • a device in which a laser exposure unit and an automatic developing unit are integrally incorporated can also be used.
  • the developer used in the developing process with a developing solution preferably has a pH of 2 to 11, more preferably 5 to 9, and even more preferably 7 to 9. From the viewpoint of developability and dispersibility of the image recording layer, it is advantageous to set the pH value higher, but it is more effective to set the pH value lower in terms of printability, especially stain suppression. is there.
  • the pH is a value measured at 25 ° C. using a pH meter (model number: HM-31, DKK-TOA CORPORATION).
  • the components contained in the developing solution used in the developing process with the developing solution include, for example, surfactants, water-soluble polymer compounds, wetting agents, preservatives, chelating compounds, defoaming agents, organic acids, organic solvents, and the like. Examples thereof include inorganic acids and inorganic salts.
  • the method for producing a lithographic printing plate according to the present disclosure and the lithographic printing method according to the present disclosure may include other known steps in addition to the above steps.
  • Other steps include, for example, a step of heating the entire surface of the lithographic printing plate original plate before exposure, during exposure, and at least between exposure and development, a position and orientation of the lithographic printing plate original plate before each step, and the like.
  • a confirmation step for confirming the printed image and the like can be mentioned.
  • the heating before development is preferably performed under mild conditions of 150 ° C. or lower from the viewpoint of suppressing the effect of the non-image area.
  • For heating after development it is preferable to use very strong conditions, and from the viewpoint of obtaining a sufficient image enhancement effect and suppressing problems such as deterioration of the support and thermal decomposition of the image portion, for example, 100 ° C. It is preferably in the heating range of about 500 ° C.
  • the molecular weight is the weight average molecular weight (Mw), and the ratio of the constituent repeating units is a molar percentage, except for those specified specifically.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) is a value measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
  • Resin particles (1) were synthesized by the following scheme.
  • the temperature was raised to 90 ° C., and the mixture was stirred for 2 hours.
  • the reaction solution was allowed to cool to room temperature (25 ° C., the same applies hereinafter) to obtain a dispersion of resin particles (1') containing the above resin (1').
  • the median diameter of the resin particles (1') in the dispersion was 100 nm.
  • 0.254 g of sodium hydrogen carbonate was added to adjust the pH of the system to 7.5, and then the temperature was raised to 90 ° C.
  • the ethylenically unsaturated bond value of the resin particles (1) is 2.5 mmol / g, which corresponds to the specific particles A.
  • the median diameter of the resin particles (1) was 100 nm, and the coefficient of variation was 25%.
  • the subscripts at the lower right of the parentheses of each structural unit represent the content ratio (mass ratio).
  • Resin particles (5) were synthesized by the following scheme.
  • the reaction solution was allowed to cool to room temperature (25 ° C., the same applies hereinafter) to obtain a dispersion of resin particles (5') containing the above resin (5').
  • the median diameter of the resin particles (5') in the dispersion was 130 nm.
  • 0.254 g of sodium hydrogen carbonate was added to adjust the pH of the system to 7.5, and then the temperature was raised to 90 ° C.
  • ⁇ Synthesis of resin particles (6) Synthesis of resin particles (1) except that the addition amounts of styrene, divinylbenzene, methyl methacrylate, and polyalkylene glycol monomethacrylate (Blemmer (registered trademark) PME-2000) were appropriately changed in the synthesis of the resin particles (1).
  • a dispersion liquid (solid content 10%) of the resin particles (6) containing the following resin (6) was obtained in the same manner as in the above.
  • the ethylenically unsaturated bond value of the resin particles (6) is 0.08 mmol / g, which does not correspond to the specific particles A.
  • the median diameter of the resin particles (6) was 120 nm, and the coefficient of variation was 24%.
  • the subscript at the lower right of the parentheses of each structural unit indicates the content ratio (mass ratio).
  • Resin particles (7) were synthesized by the following scheme.
  • the reaction solution was allowed to cool to room temperature (25 ° C., the same applies hereinafter) to obtain a dispersion of resin particles (7') containing the above resin (7').
  • the median diameter of the resin particles (7') in the dispersion was 130 nm.
  • 0.254 g of sodium hydrogen carbonate was added to adjust the pH of the system to 7.5, and then the temperature was raised to 90 ° C.
  • the dispersion liquid of the resin particles (1') containing the resin (1') obtained in the synthesis of the resin particles (1) was directly used as the dispersion liquid containing the resin particles (8) (solid content 5%).
  • the ethylenically unsaturated bond value of the resin particles (8) is 0 mmol / g, and does not correspond to the specific particles A.
  • the median diameter of the resin particles (8) was 98 nm, and the coefficient of variation was 26%.
  • Resin particles (2) were synthesized by the following scheme.
  • Neostan U-600 manufactured by Nitto Kasei Co., Ltd. was added to the three-necked flask, and the mixture was heated and stirred for 3 hours. Then, it cooled to room temperature, and the wall material a was obtained.
  • the oil phase component and the aqueous phase component were mixed and emulsified at 12000 rpm for 10 minutes using a homogenizer.
  • the obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 3 hours.
  • the microcapsule solution thus obtained was diluted with distilled water so that the solid content concentration was 15%.
  • the average particle size of the microcapsules was 0.2 ⁇ m.
  • the resin particles (3) are microcapsules containing pentaerythritol triacrylate and have an ethylenically unsaturated bond value of 0 mmol / g, and do not correspond to the specific particles A.
  • the ethylenically unsaturated bond value of the resin particles (9) was 0.10 mmol / g, the median diameter was 90 nm, and the coefficient of variation was 22%.
  • the ethylenically unsaturated bond value of the resin particles (10) was 0.33 mmol / g, the median diameter was 95 nm, and the coefficient of variation was 24%.
  • the ethylenically unsaturated bond value of the resin particles (11) was 0.50 mmol / g, the median diameter was 95 nm, and the coefficient of variation was 26%.
  • the ethylenically unsaturated bond value of the resin particles (12) was 1.00 mmol / g, the median diameter was 93 nm, and the coefficient of variation was 24%.
  • the ethylenically unsaturated bond value of the resin particles (13) was 1.50 mmol / g, the median diameter was 93 nm, and the coefficient of variation was 24%.
  • the resin particles (9) to (13) all correspond to the specific particles A.
  • the ethylenically unsaturated bond value of the resin particles (14) was 2.50 mmol / g, the median diameter was 95 nm, and the coefficient of variation was 23%.
  • the ethylenically unsaturated bond value of the resin particles (15) was 2.50 mmol / g, the median diameter was 101 nm, and the coefficient of variation was 25%.
  • the ethylenically unsaturated bond value of the resin particles (16) was 2.48 mmol / g, the median diameter was 98 nm, and the coefficient of variation was 22%.
  • the ethylenically unsaturated bond value of the resin particles (17) was 2.50 mmol / g, the median diameter was 110 nm, and the coefficient of variation was 25%.
  • the resin particles (14) to (17) all correspond to the specific particles A.
  • PETA penentaerythritol triacrylate, manufactured by s Sartomer
  • SR444 penentaerythritol triacrylate, manufactured by s Sartomer
  • Me represents a methyl group.
  • Resin particles (19) were synthesized by the following method.
  • Resin particles (20) were synthesized by the following method.
  • Resin particles (21) were synthesized by the following method.
  • the resin (21) contained in the resin particles (21) is shown below.
  • the subscripts under each compound (monomer) and the subscripts at the lower right of the parentheses indicate the content ratio (mass ratio).
  • Me represents a methyl group.
  • Resin particles (22) were synthesized by the following method.
  • the ethylenically unsaturated bond value of the resin particles (22) is 2.01 mmol / g, which corresponds to the specific particles A.
  • the median diameter of the resin particles (22) was 185 nm, and the coefficient of variation was 27.5%.
  • the resin (22) contained in the resin particles (22) is shown below. In the following resins, the subscripts under each compound (monomer) and the subscripts at the lower right of the parentheses indicate the content ratio (mass ratio).
  • Resin particles (23) were synthesized by the following method.
  • aqueous phase component was added to the oil phase component and mixed, and the obtained mixture was emulsified at 12,000 rpm for 16 minutes using a homogenizer to obtain an emulsion.
  • 16.8 g of distilled water was added to the obtained emulsion, and the obtained liquid was stirred at room temperature for 180 minutes.
  • the stirred liquid was heated to 45 ° C., and the mixture was stirred for 5 hours while maintaining the liquid temperature at 45 ° C. to distill off ethyl acetate from the above liquid.
  • the solid content concentration was adjusted to 20% by mass with distilled water to obtain an aqueous dispersion of resin particles (23).
  • the ethylenically unsaturated bond value of the resin particles (23) is 4.17 mmol / g, which corresponds to the specific particles A.
  • the median diameter of the resin particles (23) was 165 nm, and the coefficient of variation was 28.5%.
  • the resin (23) contained in the resin particles (23) is shown below. In the following resins, the subscripts under each compound (monomer) and the subscripts at the lower right of the parentheses indicate the content ratio (mass ratio).
  • the resin particles (24) are microcapsules containing SR399E, have an ethylenically unsaturated bond value of 0 mmol / g, and do not correspond to the specific particles A.
  • the median diameter of the resin particles (24) was 150 nm, and the coefficient of variation was 28.1%.
  • the resin (24) contained in the resin particles (24) is shown below. In the following resins, the subscripts under each compound (monomer) and the subscripts at the lower right of the parentheses indicate the content ratio (mass ratio).
  • Electrochemical roughening treatment an electrolytic solution having a hydrochloric acid concentration of 14 g / L, an aluminum ion concentration of 13 g / L, and a sulfuric acid concentration of 3 g / L is used, and an electrochemical roughening treatment is performed using an AC current. Processing was performed. The temperature of the electrolytic solution was 30 ° C. The aluminum ion concentration was adjusted by adding aluminum chloride.
  • the AC current waveform is a sinusoidal wave with symmetrical positive and negative waveforms, the frequency is 50 Hz, the anode reaction time and cathode reaction time in one AC current cycle are 1: 1, and the current density is the peak current value of the AC current waveform. It was 75 A / dm 2 .
  • the electric amount was 450C / dm 2 in terms of the total electric quantity aluminum plate participating in the anode reaction, electrolytic treatment was carried out four times to open the energization interval 112.5C / dm 2 by 4 seconds. A carbon electrode was used as the counter electrode of the aluminum plate. Then, it was washed with water.
  • Anodizing treatment was carried out using an anodizing treatment apparatus 610 by direct current electrolysis having the structure shown in FIG. 5 to form an anodizing film.
  • the anodizing treatment conditions were an electrolytic solution sulfuric acid concentration of 170 g / L, an electrolytic solution temperature of 50 ° C., a current density of 30 A / dm 2 , and a film amount of 2.4 g / m 2 .
  • the aluminum plate 616 is conveyed as shown by an arrow in FIG. The aluminum plate 616 is charged to (+) by the feeding electrode 620 in the feeding tank 612 in which the electrolytic solution 618 is stored.
  • the aluminum plate 616 is conveyed upward by the roller 622 in the power supply tank 612, is changed in the downward direction by the nip roller 624, and then is conveyed toward the electrolytic treatment tank 614 in which the electrolytic solution 626 is stored, and is conveyed by the roller 628. Turns horizontally.
  • the aluminum plate 616 is charged to (-) by the electrolytic electrode 630 to form an anodized film on its surface, and the aluminum plate 616 leaving the electrolytic treatment tank 614 is conveyed to a subsequent process.
  • the roller 622, the nip roller 624, and the roller 628 constitute the direction changing means, and the aluminum plate 616 is formed in the inter-tank portion between the power feeding tank 612 and the electrolytic treatment tank 614, and the rollers 622, 624 and 628 are Is transported in a chevron shape and an inverted U shape.
  • the feeding electrode 620 and the electrolytic electrode 630 are connected to the DC power supply 634.
  • Support A Average diameter of micropores on the surface of the anodized film: 12 nm, L * a * b * value of lightness L * on the surface of the anodized film: 81
  • Support B L * a * b * lightness L * value on the surface of the anodized film: 83, average diameter on the surface of the oxide film on the large-diameter pores in the micropores: 35 nm (depth 100 nm), micro Average diameter at the communication position of the small-diameter hole in the pore: 10 nm (depth 1,000 nm), ratio of the depth of the large-diameter hole to the average diameter of the large-diameter hole: 2.9
  • a desmat treatment was performed using an acidic aqueous solution.
  • an acidic aqueous solution used for the desmat treatment, an aqueous solution of 170 g / L of sulfuric acid was used. The liquid temperature was 30 ° C. An acidic aqueous solution was sprayed onto an aluminum plate to perform a desmat treatment for 3 seconds. Then, it was washed with water.
  • an electrochemical roughening treatment was performed using a hydrochloric acid concentration electrolytic solution and an alternating current.
  • the temperature of the electrolytic solution was 40 ° C.
  • the alternating current waveform is a sine wave with symmetrical positive and negative waveforms, and the frequency is 50 Hz.
  • the amount of electricity was 300 C / dm 2 , which is the total amount of electricity stored in the anodic reaction of the aluminum plate.
  • a carbon electrode was used as the counter electrode of the aluminum plate. Then, it was washed with water.
  • -Alkaline etching process An aqueous solution of caustic soda having a caustic soda concentration of 5% by mass and an aluminum ion concentration of 0.5% by mass is sprayed onto an electrochemically roughened aluminum plate at a temperature of 35 ° C. and the etching amount is 0.1 g / m 2 or less. Etching treatment was performed so as to be. Then, it was washed with water.
  • a desmat treatment was performed using an acidic aqueous solution.
  • an acidic aqueous solution used for the desmat treatment, an aqueous solution of 170 g / L of sulfuric acid was used. The liquid temperature was 30 ° C. An acidic aqueous solution was sprayed onto an aluminum plate to perform a desmat treatment for 3 seconds. Then, it was washed with water.
  • the preparation method of the inorganic layered compound dispersion liquid (1) used in the water-soluble resin layer coating liquid (1) is shown below.
  • Water-soluble resin layer coating liquid (2) -Polyvinyl alcohol (PVA-405, Kuraray Co., Ltd., saponification degree 81.5 mol%, degree of polymerization 500) 6% by mass aqueous solution: 0.03 part-Surfactant (polyoxyethylene lauryl ether, Emarex (registered trademark) ) 710, Nippon Emulsion Co., Ltd. 1% by mass aqueous solution: 0.86 parts, ion-exchanged water: 6.0 parts
  • An image recording layer coating liquid was prepared using the components described in the following image recording layer coating liquids (1) to (3).
  • the image recording layer coating liquid containing the resin particles was prepared by synthesizing the photosensitive liquid containing the components described in the following image recording layer coating liquids (1) to (3) other than the resin particles in the above synthesis example. ,
  • the dispersion liquid containing each resin particle was mixed and stirred immediately before coating so as to have the compositions shown in Tables 1 to 4.
  • -Resin particles (4) 5000 parts-Compound having an ethylenically unsaturated group (M-4): 2000 parts-Compound having an ethylenically unsaturated group (M-5): 3000 parts-Electron-accepting polymerization initiator (I-3): 800 parts, color former (H-2): 600 parts
  • Examples 1 to 35 and Comparative Examples 1 to 4 ⁇ Preparation of lithographic printing plate original plate>
  • the lithographic printing plate original plates of Examples 1 to 35 and Comparative Examples 1 to 4 were prepared by the following methods, respectively.
  • the undercoat layer coating solution (1) having the above composition was applied onto the supports shown in Tables 1 to 4 so that the dry coating amount was 20 mg / m 2 to form an undercoat layer.
  • One of the above-mentioned image recording layer coating liquids (1) to (3) is bar-coated on the undercoat layer, and dried in an oven at 120 ° C. for 40 seconds to obtain the dry film thicknesses shown in Tables 1 to 4.
  • An image recording layer (denoted as "thickness") was formed in the table.
  • lithographic printing plate original plate The lithographic printing plate original plate produced as described above is exposed (irradiation energy) on a Kodak Magnus 800 Quantum (plate setter) equipped with an infrared semiconductor laser under the conditions of an output of 27 W, an outer drum rotation speed of 450 rpm, and a resolution of 2,400 dpi. 110 mJ / cm 2 equivalent).
  • the exposed image includes a solid image and a chart of 3% halftone dots on the AM screen (Amplitude Modulation Screen).
  • the lithographic printing plate original plate according to the present disclosure can be obtained as a lithographic printing plate having high sensitivity and excellent printing durability.
  • the planographic printing plate original plates according to the present disclosure use the specific particles (18) to (21) as in Examples 30 to 35, it can be seen that they are also excellent in suppressing development residue during on-machine development.
  • Example 36 to 44 Preparation and evaluation of lithographic printing plate original plate>
  • An image recording layer coating liquid (1) was prepared in the same manner as in Example 1 except that the composition was changed to that shown in Table 5. Further, the obtained image recording layer coating liquid (1) was used to prepare a lithographic printing plate original plate in the same manner as in Example 1. The image recording layer coating liquid (1) was prepared by mixing and stirring a dispersion liquid containing resin particles and other components immediately before coating. Further, the obtained planographic printing plate original plate was evaluated in the same manner as in Example 1 in (1) to (4). The results are shown in Table 5.
  • the lithographic printing plate original plate according to the present disclosure can be obtained as a lithographic printing plate having high sensitivity and excellent printing durability.
  • the visibility changes greatly depending on the type of color former. For example, when (S-1), (S-4) or (S-6) is used as the color former, it can be seen that the visibility is particularly excellent.
  • Example 45 to 50 The planographic printing plate original plates of Examples 45 to 50 were prepared by the following methods.
  • Undercoat layer coating liquids (2) and (3) having the following compositions were prepared, respectively.
  • undercoat layer coating liquid (2)- -Polymer (UC-1) [the above structure]: 0.18 parts-Surfactant (Emarex (registered trademark) 710, Nippon Emulsion Co., Ltd .): 0.03 parts-Water: 28.0 parts
  • ⁇ Preparation of lithographic printing plate original plate> An undercoat layer coating solution of the type shown in Table 6 was applied onto the support A so that the dry coating amount was 20 mg / m 2 to form an undercoat layer (that is, a layer in contact with the support).
  • the image recording layer coating solution (1) having the composition shown in Table 6 was bar-coated on the undercoat layer and dried in an oven at 120 ° C. for 40 seconds to form an image recording layer having a dry film thickness of 1 ⁇ m.
  • the image recording layer coating liquid (1) was prepared by mixing and stirring a dispersion liquid containing resin particles and other components immediately before coating.
  • the water-soluble resin layer coating solution (1) having the above composition was bar-coated on the image recording layer, and dried in an oven at 120 ° C. for 60 seconds to obtain the water-soluble resin layer having the dry film thickness shown in Table 6. Formed.
  • the obtained planographic printing plate original plate was used with a Luxel PLATESETTER T-6000III manufactured by FUJIFILM Corporation equipped with an infrared semiconductor laser, and the outer surface drum rotation speed was 1,000 rpm, the laser output was 70%, and the resolution.
  • the exposure was performed under the condition of 2,400 dpi.
  • the lithographic printing plate obtained in an environment of a temperature of 25 ° C. and a humidity of 70% was scratched by a scratch tester.
  • HEIDON scratching Intersity TESTER HEIDEN-18 was used, and a sapphire needle having a diameter of 0.1 mm was used, and the scratch load was 50 (g).
  • the scratched plate was attached to the plate cylinder of a diamond IF2 printing machine manufactured by Mitsubishi Heavy Industries, Ltd. without developing.
  • Dia IF2 using IF102 (manufactured by FUJIFILM Corporation) / tap water 3/97 (capacity ratio) dampening water and Values-G (N) ink ink (manufactured by Dainippon Ink and Chemicals Co., Ltd.)
  • IF102 manufactured by FUJIFILM Corporation
  • tap water 3/97 (capacity ratio) dampening water
  • Values-G (N) ink ink manufactured by Dainippon Ink and Chemicals Co., Ltd.
  • the intermediate points such as 9 points and 7 points were evaluated as intermediate points when they were in the middle of the upper limit evaluation criteria.
  • the evaluation standard is preferably 10 to 6 points.
  • the results are shown in Table 6.
  • the "surface contact angle” shown in Table 6 represents the contact angle with water by the aerial water droplet method on the surface of the aluminum support on the image recording layer side. The contact angle was measured by the method described above. The details of the hydrophilic compounds shown in Table 6 are shown below.
  • Example 51 to 64 The planographic printing plate original plates of Examples 51 to 64 were prepared by the following methods.
  • [Water-soluble resin layer coating liquid (4)] -Polyvinyl alcohol (Gosenex (registered trademark) L-3266, manufactured by Mitsubishi Chemical Co., Ltd., sulfonic acid modification, saponification degree 86.5 to 89.0%): 50 parts-styrene acrylic resin particles (Finesphere (registered trademark)) LS-102, manufactured by Nippon Paint Industrial Coatings Co., Ltd., Tg 103 ° C): 17 parts, surfactant (EMALEX (registered trademark) 710, manufactured by Nippon Emulsion Co., Ltd.): 3.5 parts, water: 280 copies
  • the undercoat layer coating liquids of the types shown in Tables 7 to 9 are applied so that the dry coating amount is 20 mg / m 2 , and the undercoat layer (that is, the support). A layer in contact with) was formed.
  • the image recording layer coating liquid (4) was prepared by mixing and stirring a dispersion liquid containing resin particles and other components immediately before coating. Subsequently, the water-soluble resin layer coating liquids of the types shown in Tables 7 to 9 are bar-coated on the image recording layer, oven-dried at 120 ° C. for 60 seconds, and the dry films shown in Tables 7 to 9 are dried. A thick water-soluble resin layer was formed.
  • the lithographic printing plate original plate according to the present disclosure can be obtained as a lithographic printing plate having high sensitivity and excellent printing durability.
  • the compounds used in the image recording layer coating liquids (1) to (4) are as follows.
  • M-1 Urethane acrylate oligomer, U-15HA, weight average molecular weight 2078.15, manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • M-2 Compound with the following structure, molecular weight 302
  • M-3 Isocyanuric acid EO-modified diacrylate, Aronix M-215, manufactured by Toa Synthetic Co., Ltd.
  • M-4 Compound with the following structure, Aronix M-233, manufactured by Toa Synthetic Co., Ltd.
  • M-5 Pentaerythritol (tri) / Tetra) acrylate, manufactured by Sigma-Aldrich
  • M-6 compound synthesized by the following method
  • M-7 compound having the following structure, A-9300, manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • M-8 compound having the following structure, BPE-80N, manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • Neostan U-600 bismuth-based polycondensation catalyst, manufactured by Nitto Kasei Co., Ltd.
  • the reaction solution was cooled to room temperature (25 ° C.), and methyl ethyl ketone was added to synthesize a urethane acrylate solution having a solid content of 50% by mass.
  • the weight average molecular weight of Compound M-6 was measured by the following measuring instruments and methods.
  • GPC measuring device TOSOH HLC-8320 GPC, GPC flow phase: THF Inspector: Differential Refractometer (RI), Flow Velocity: 0.35 mL / min
  • Columns: TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperHZ3000, and TSKgel SuperHZ2000 were used in combination.
  • I-1 Compound with the following structure
  • I-2 Compound with the following structure
  • I-3 Compound with the following structure (3,3', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone)
  • I-1 is an electron-accepting polymerization initiator having an organic anion in which ⁇ d in the solubility parameter of Hansen is 16 or more, ⁇ p is 16 to 32, and ⁇ h is 60% or less of ⁇ p. is there.
  • I-4 Compound with the following structure
  • IS-1 Compound with the following structure
  • Me represents a methyl group and Ts represents a tosyl group.
  • IR-1 A compound having the following structure (HOMO: -5.35 eV)
  • IR-2 Compound with the following structure (HOMO: -5.45 eV)
  • IR-3 Compound with the following structure (HOMO: -5.44eV)
  • IR-4 A compound having the following structure (HOMO: -5.13 eV)
  • IR-5 Compound with the following structure (HOMO: -5.31 eV)
  • IR-1 is an infrared absorber having an organic anion in which ⁇ d in the solubility parameter of Hansen is 16 or more, ⁇ p is 16 to 32, and ⁇ h is 60% or less of ⁇ p.
  • Ph represents a phenyl group
  • Ts represents a tosyl group
  • Bu represents a butyl group.
  • H-1 Compound with the following structure H-2: 3,3'-carbonylbis (diethylaminocoumarin), manufactured by Tokyo Chemical Industry Co., Ltd.
  • H-3 Compound with the following structure S-1, S-4, S-6 , S-11 to S-14: The same compounds as S-1, S-4, S-6, and S-11 to S-14, which are specific examples of the leuco dye having the phthalide structure or the fluorane structure described above.
  • T-1 Compound with the following structure
  • Fluorosurfactant W-1 Compound with the following structure Fluorosurfactant W-2: Compound with the following structure Fluorosurfactant W-3: Compound with the following structure Fluorosurfactant W-4: Structure below Compound
  • the subscript at the lower right of the parentheses of each structural unit represents the content ratio (mass ratio), and the subscript at the lower right of the parentheses of the alkyleneoxy structure represents the number of repetitions.
  • BT-1 Compound with the following structure
  • BT-2 Compound with the following structure
  • BT-3 Compound with the following structure (polyvinyl butyral, l: 63 mol%, m: 1 mol%, n: 36 mol%, weight average molecular weight: 20,000 )
  • each structural unit (subscript in the lower right of the parentheses) represents the mass ratio
  • the subscript in the lower right of the parentheses of the ethyleneoxy structure represents the number of repetitions.

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  • Optics & Photonics (AREA)
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  • Materials For Photolithography (AREA)

Abstract

L'invention concerne une plaque originale d'impression planographique qui comprend séquentiellement un corps de support en aluminium, une couche d'enregistrement d'image et une couche de résine soluble dans l'eau, dans cet ordre, la couche d'enregistrement d'image contenant des particules A qui contiennent une résine comprenant un groupe à insaturation éthylénique, tout en ayant une valeur de liaison éthyléniquement insaturée de 0,10 mmol/g ou plus et un composé B autre que les particules A, ledit composé B comprenant un groupe éthyléniquement insaturé ; un procédé de production d'une plaque d'impression planographique faisant appel à ladite plaque originale d'impression planographique ; et un procédé d'impression planographique.
PCT/JP2020/025409 2019-06-28 2020-06-26 Plaque originale d'impression planographique, procédé de fabrication de plaque d'impression planographique, et procédé d'impression planographique WO2020262687A1 (fr)

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JP2019122477 2019-06-28
JP2019-122477 2019-06-28
JP2019158811 2019-08-30
JP2019-158811 2019-08-30
JP2019-169807 2019-09-18
JP2019169807 2019-09-18

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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63137226A (ja) * 1986-11-29 1988-06-09 Fuji Photo Film Co Ltd 光重合性組成物
JPS63202497A (ja) * 1987-02-18 1988-08-22 Fuji Photo Film Co Ltd 感光性平版印刷版用支持体の製造方法
JP2004341500A (ja) * 2003-04-21 2004-12-02 Fuji Photo Film Co Ltd 画像形成方法および画像露光装置
US20090269699A1 (en) * 2008-04-29 2009-10-29 Munnelly Heidi M On-press developable elements and methods of use
JP2011227311A (ja) * 2010-04-20 2011-11-10 Fujifilm Corp 着色感光性樹脂組成物、パターン形成方法、カラーフィルタの製造方法、カラーフィルタ及びそれを備えた表示装置
JP2012501878A (ja) * 2008-09-04 2012-01-26 イーストマン コダック カンパニー ネガ型画像形成性要素及び使用方法
WO2016027886A1 (fr) * 2014-08-22 2016-02-25 富士フイルム株式会社 Composition de développement de couleur, plaque d'original d'impression lithographique, procédé de fabrication de plaque d'impression lithographique et révélateur chromogène
WO2017141882A1 (fr) * 2016-02-19 2017-08-24 富士フイルム株式会社 Composition chromogénique, plaque originale d'impression planographique, procédé de production de plaque d'impression planographique, et composé chromogénique
WO2018159640A1 (fr) * 2017-02-28 2018-09-07 富士フイルム株式会社 Composition durcissable, plaque originale pour plaque d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, et composé
WO2018230412A1 (fr) * 2017-06-12 2018-12-20 富士フイルム株式会社 Plaque originale pour plaque d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, particules de polymère organique, et composition de résine photosensible
WO2019004471A1 (fr) * 2017-06-30 2019-01-03 富士フイルム株式会社 Plaque originale d'impression lithographique et procédé de production d'une plaque d'impression lithographique
WO2019013268A1 (fr) * 2017-07-13 2019-01-17 富士フイルム株式会社 Plaque originale de plaque d'impression lithographique, et procédé de fabrication de plaque d'impression lithographique
JP6461447B1 (ja) * 2017-09-29 2019-01-30 富士フイルム株式会社 平版印刷版原版、平版印刷版の作製方法及び平版印刷方法
WO2019150788A1 (fr) * 2018-01-31 2019-08-08 富士フイルム株式会社 Cliché matrice pour plaque lithographique, et procédé de production de plaque lithographique
WO2020045586A1 (fr) * 2018-08-31 2020-03-05 富士フイルム株式会社 Plaque originale d'impression à plat, procédé de fabrication d'une plaque d'impression à plat, procédé d'impression à plat et composition durcissable
WO2020045587A1 (fr) * 2018-08-31 2020-03-05 富士フイルム株式会社 Matrice de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, procédé d'impression lithographique et composition durcissable

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63137226A (ja) * 1986-11-29 1988-06-09 Fuji Photo Film Co Ltd 光重合性組成物
JPS63202497A (ja) * 1987-02-18 1988-08-22 Fuji Photo Film Co Ltd 感光性平版印刷版用支持体の製造方法
JP2004341500A (ja) * 2003-04-21 2004-12-02 Fuji Photo Film Co Ltd 画像形成方法および画像露光装置
US20090269699A1 (en) * 2008-04-29 2009-10-29 Munnelly Heidi M On-press developable elements and methods of use
JP2012501878A (ja) * 2008-09-04 2012-01-26 イーストマン コダック カンパニー ネガ型画像形成性要素及び使用方法
JP2011227311A (ja) * 2010-04-20 2011-11-10 Fujifilm Corp 着色感光性樹脂組成物、パターン形成方法、カラーフィルタの製造方法、カラーフィルタ及びそれを備えた表示装置
WO2016027886A1 (fr) * 2014-08-22 2016-02-25 富士フイルム株式会社 Composition de développement de couleur, plaque d'original d'impression lithographique, procédé de fabrication de plaque d'impression lithographique et révélateur chromogène
WO2017141882A1 (fr) * 2016-02-19 2017-08-24 富士フイルム株式会社 Composition chromogénique, plaque originale d'impression planographique, procédé de production de plaque d'impression planographique, et composé chromogénique
WO2018159640A1 (fr) * 2017-02-28 2018-09-07 富士フイルム株式会社 Composition durcissable, plaque originale pour plaque d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, et composé
WO2018230412A1 (fr) * 2017-06-12 2018-12-20 富士フイルム株式会社 Plaque originale pour plaque d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, particules de polymère organique, et composition de résine photosensible
WO2019004471A1 (fr) * 2017-06-30 2019-01-03 富士フイルム株式会社 Plaque originale d'impression lithographique et procédé de production d'une plaque d'impression lithographique
WO2019013268A1 (fr) * 2017-07-13 2019-01-17 富士フイルム株式会社 Plaque originale de plaque d'impression lithographique, et procédé de fabrication de plaque d'impression lithographique
JP6461447B1 (ja) * 2017-09-29 2019-01-30 富士フイルム株式会社 平版印刷版原版、平版印刷版の作製方法及び平版印刷方法
WO2019150788A1 (fr) * 2018-01-31 2019-08-08 富士フイルム株式会社 Cliché matrice pour plaque lithographique, et procédé de production de plaque lithographique
WO2020045586A1 (fr) * 2018-08-31 2020-03-05 富士フイルム株式会社 Plaque originale d'impression à plat, procédé de fabrication d'une plaque d'impression à plat, procédé d'impression à plat et composition durcissable
WO2020045587A1 (fr) * 2018-08-31 2020-03-05 富士フイルム株式会社 Matrice de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, procédé d'impression lithographique et composition durcissable

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